HUE030070T2 - Quaternised nitrogen compounds and their use as additives in fuels and lubricants - Google Patents

Description

Qnatemsset! nitrogen compounds a»<t their «sè M additives m ftiéls and hrt?rkants

The present invention relates to novel qaâtemized nitrogen compounds, to the preparation thereof and to the use thereof as a fuel additive, more particularly as a detergent additi ve, to additive packages which comprise these compounds; and to fuels thus additized, The present invention further relates to the use of these guaternized nitrogen compounds as a feel: additive for reducing or preventing deposits in the injection systems of direct-injection diesel engines, especially in common-rail injection systems, for reducing the fuel consumption of direct-injection diesel engines, especially of diesel engines with common-rail injection systems, and for minimizing power loss in direct-injection diesel engines, especially in diesel engines with common -rail injection systems.

State of the art;

In direct injection diesel engines, the fuel is injected and distributed ultrafinely (nebulized) by a tnultlhole 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 direct-injection diesel engines lies in their high performance for diesel engines and nevertheless low tool 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 combustion chamber of the diesel engine: the eommntional distributor injection pump, the pump-nozzle system (unit-injector system or umt-pnmp system) and the common» rail system,. ih the common-rail system, the diesel fuel is conveyed hy a pump with pressures up to 2()00 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 full pressure is always applied to Ute common rail, which enables multiple injection or a specific injection form, ln the other injection systems, in contrast, only smaller variation in the .injection is possible. The injection In the common rail is divided essentially into three groups: (1.) pro-injection, by which essentially softer combustion is achieved, such that harsh combustion noises {"nailing") arc 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. In this post-injection, the fuel is generally not combusted, hut 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 NOx,

The variable, cylinder-individual injection in the common-rail injection system can positively influence the pollutant emission of the engine, for example the emission of nitrogen oxides (NOx}, carbon monoxide (CO) and especially of particulates (soot). T his makes it possible, for example, that engines equipped with common-rail, injection systems can meet the Euro 4 standard theoretically even without additional particulate fitters. in modem common-rail diesel engines, under particular conditions, for example when hiodiesel-eordaining fuels or -fuels with metal impurities such as zinc compounds, copper compounds, lead compounds and other metal compounds are used, deposits can form on the Injector orifices, which adversely affect the injection performance of the fuel and hence impair the performance of the engine, he. especially reduce the power, hut 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 optimal functioning of engine and injectors, such deposits in the nozzle orifices must he 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 channels can lead to a decrease in the fuel flow and hence to power loss. Deposits at the injector 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 “external” deposition phenomena, “internal” deposits (referred to eoleetiveiy as internal diese! injector deposits (IDO.'))) in particular parts of the injectors, such as at the nozzle needle, at the control piston, at the valve piston, id 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 IDIDs. US 4,248,71 p describes qnahmùmi ammonium salts which are prepared hv reacting an alben>dsueeimm!de with a monoearboxylie ester and find use as dispersants in lubricant oils for prevention of sludge formation. More particularly, lor example, the reaction of polyisobutylsuccinic anhydride {PIBSA ) with RN-dimeíhyíaminopropyiamíne { DM AP A) and quatendzation with methyl sali cylate is described. However, use in fuels, more particularly diesel fuels, is not proposed therein. The use of PIBSA with low hismafeation levels of < 20%> is not described therein, US 4,171,959 describes quaternized ammonium salts ofhydröcarbyl-súbstíMed saeehhmidcs, which arc suitable as deterpnt additives for gasoline fuel compositions. For quatern.izat.iou, preference is given to using alkyl halides. Also mentioned are organic Cb-CVhydrocarbyl carboxylai.es and sulfonates. Consequently, the quaternized ammonium salts provided according to the teaching therein have, as a counterion, either a halide or a Cy-Cydiydrocarhyl earhoxylate or a Cg-Gg-hydroearbyl sulfonate group. The use of PIBSA with low bismaleation levels of < 20% is likewise not described, therein. EP- A -2 033 945 discloses cold flow inaprovers which are prepared by quatemlzlng specific tertiary -monoamines bearing at least one CrCkralkyi radical with a Ct-Cr alkyl ester of spéciik carboxylic acids. Examples of such carboxylic esters are dimethyl oxalate, dimethyl maleate, dimethyl pb thai ate and dimethyl iuraarate. Applications other than that of improving die OFPP value of middle distillates arc not demonstrated in BP-A-2 033 '945, WO 2006/135881 describes quaternized ammonium salts prepared by condensation of a hydrocarbyS-siihstlmied acylating agent and of an oxygen or nitrogen atom-containing compound with a tertiary amino group, and subsequent q natural za iron by means of hydrocarbyl epoxide in the presence of stoichiometric amounts of an acid, especially acetic acid. Further quatemtzing agents claimed in WO 2006/1358:81 are dtaihyl sulfates, benzyl halides and hydroeafbyi-substituted carbonates, and dimethyl sulfate, benzyl chloride and dimethyl carbonate have been studied experimentally.

The quaiemizing agents used with preference in WÔ 2006/135881, however, have serious disMvantaps such as: toxicity or carcinogenicity (for example In the ease of dimethyl sulfate and alkyiene oxides and benzyl halides), no residue-free combustion (for example in the case of dimethyl sulfate and alkyl halides), and inadequate reactivity which leads to incomplete qnatemizafion or uneconomic reaction conditions (long reaction times, high reaction temperatures, excess of quaternixing agent; for example in the case of dimethyl carbonate). WO 2011/141731 A1 describes a gasoline fuel composition comprising a quaternary ammonium sail as additive. This additive is prepared by the reaction of a carboxylic ester with a reaction product obtainable by reacting a hydrocarbyh-substituted acylating agent with a compound comprising an oxygen group or nitrogen group and a quaternizable ammonium group. The additive is used to reduce the level of deposits in intake valves or injection nozzles of a. gasoline engine. WO 2011/095819 Â1 describes a diesel fuel eomposition comprising a quaternary ammonium salt as additive. The additive is used to minimize power loss in direct injection diesel engines or to reduce deposits in injection nobles in direct injection diesel engines. The additive is prepared by the reaction of a carboxylic ester with a reaction product obtainable by reacting a hydmcarbyd-snbstitutcii acylating agent with a compound comprising m oxygen group or nitrogen group and a quatemizable ammonium group.

It was therefore an object of the present invention to provide improved quatprn&amp;ed fuel additives, especially based on hydrocarbyl-substituted polyearboxylic acid compounds, which no longer have the disadvantages of the prior art mentioned.

It has now been round tbdt, surprisingly, the above object is achieved by providing spec? lie quatemixed nitrogen compounds and fuel compositions addittzed 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 quatemizing agent, burn ashiessly, exhibit a high content of quaternized product, and allow an economic reaction regime in the preparation thereof, and surprisingly have improved handling properties, such as especially improved solubility, such as especially in diesel performance additive packages. At the same time, the inventive additives exhibit improved action with regal'd to prevention of deposits ip diesel engines, as especially illustrated by the use examples appended.

Detailed description of the invention: AI) Specific embodiments

The present invention relates especially to the following specific embodiments: 1 < A fuel composition, especial 1 y fuel composition, comprising, in a majority of a customary fuel, a proportion (especially an effective amount} of at least one reaction product comprising a quaternmed nitrogen compound (or a fraction thereof winch comprises a quatermxcd nitrogen compound and is obtained from the reaction product by purification), said reaction product being obtainable by a 1 > reacting a high molecular weight hyclmcarbyl-substituted polycarboxylic acid compound with a compound comprising at least one oxygen or nitrogen group reactive (especially capable of addition or condensation) with the polyearhoxylic acid, and comprising at least one quatendxable amino group, to obtain a quatemizahle hydrocarbyl-substituted polycarboxylic acid compound (by addition or condensation), and a 2) subsequent reaction thereof with a quaternizing agent which converts the at least one hereafter quaternizable, for example tertiary, amino group to a quaternary ammonium group, said quatemizing agent being the alkyl ester of a eyeioaromatie or cycloaliphatic mono·' or polyearhoxylic acid (especially of a mono- or dicarhoxylle acid) or of an aliphatic polyearhoxylic acid (especially diearhoxylie acid); or b) reacting a quaternizable high molecular weight hydrocarbyh substituted polyearhoxylic acid compound comprising at least one quaternizable amino group with a quaternizing agent which converts the at least one hereafter quaternizable, for example tertiary, amino group to a quaternary ammonium group, said quatemiziog agent being the alkyl ester of a eyeioaromatie or cycloaliphatic mono- or polyuarboxylic aeld {especially of a mono- or diearhoxylie acid) or of an aliphatic* polyearhoxylic acid (especially dtcarboxylic acid), wherein about 1.1 to about 2.0 or about 1.25 to about 2.0 equivalents of quatemhdng agent are used per equi valent of qMiocnixahle tertiary nitrogen atom; and/or the hydroearhyl-substitufed polyearboxylie acid compound is a polyisobutenylsueeinie aeld or an anhydride thereof, said acid having a bismaleation level of 2 to 20% by weight or 2 to 151¾ by weight, based in each case on the reaction product, 2. The fuel composition according to embodiment 1, wherein about 1,1 to about 2,0 or about 1,25 to about 2,0 equivalents, for example 1.3, 1.4, 1.5, Lé, L7, 1,8 or 1,9 equivalents, of quatem bring agent are used per equivalent of quaternixable tertiary nitrogen atom* By increasing the proportion of quatemking agent within the range claimed, distinct improvements; in product yields can be achieved. 3. The fuel composition according to either of the preceding embodiments; wherein the hydrocarbyl-suhstituted polyearboxylie acid compound is a polyisohutenylsuccimc acid or an anhydride thereof, said acid having a hismaleation level of 2 to 20% or 2 to 15%, for example 15,14, 13,12, ! 1, 10, % 8, 7, 6, 5,4,3 or 2%, based in each case on the reaction product.

Lower levels of hismaleation can contribute to a distinct improvement in the solubility of the additive and/or compatibility of the constituents in the formulation of additive packages. 4. The -fuel composition according to any of the preceding embodiments, wherein the quatemking agent is a compound of the general formula 1 R50C(0)R2 (1) in which

Rj is a low molecular weight hydrocarhyl radical, such as alkyl or alkenyl radical, especially a lower alkyl radical, such as especially methyl or ethyl, and R-2 is an optionally substituted monocyclic hydroearhyl radical, especially an aryl or cycloalkyl or cycioalkenyl radical, especially aryl such as phenyl, where the •Siibâtituent is selected from OH, MhL, NO?, C'tO)ORg and RjOCfO}-, in which Rj. is as defined above and Rí is H or Bq, where the substituent is especially OH. More particularly, the quaieroking agent is a phthaiate or a salicylate, such as dimethyl phthalate or methyl salicylate. 5. The fuel composition according to any of the preceding embodiments, wherein the quaternkmg agent is a compound of the general formula 2 R ! (.)('{Ö }··A - (3(0)0R ;,, (2) in which

Rj and Ria are each independently a lew molecular weight hydrocarhyl radical, such äs an alkyl or alkenyl radical, especially a lower alkyl radical and A is hydrocarbylene (such as especially CyC j-alkylerse or CrC?-a!kenylene). 6, The fuel composition according to any of the preceding embodiments, wherein the quaternixed nitrogen compound has a number-average molecular weight in the range from 400 to 5000, especially 800 to 3000 or 900 to 1500. 7, The fuel composition according to any of the preceding embodiments, wherein the quatemixing agent is selected from alkyl salicylates, dialkyl phthalates and dialkyl oxalates; particular mention should be made of alkyl salicylates, especially lower alkvl salicylates, such as methyl, ethyl and n-propyl salicylates, 8, The fuel composition according to eudxxhmeot I, wherein the compound which is reactive (capable of addition or condensation} with the polycarboxylie acid and comprises an oxygen or nitrogen group and at least one quaterniaablc amino group is selected from a. hydroxyalkyl-^hstltutod mono- or polyamines having at least one quatenhkahle primary, secondary or tertiary amino group; 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 quatemizahle primary, secondary or tertiary amino group; e, piperidines, and particular mention should be made of group a, 9, The fuel composition according to embodiment 8, wherein the compound which is reactive, especially capable of addition or condensation, with the poiycarhoxylie acid and comprises ait oxygen or nitrogen group and at least one quaternixabie amino group is selected from <t hydroxyaikyl-substiUued primary, s§eo$d$ry of tertiary rnortoamioes and hydiokyalkybsubstitutod primary, secondary or tertiary diamines, straight-chain or branched aliphatic diamines having two primary amino groups; di - or poiyamüms having at least one primary and at least one secondary amino group; di- or polyamines having at least one primary and at least one tertiary amino group; aromatic carboeydie 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,

Kh The fuel composition according to any of the preceding embodiments, selected from diesel fuels, biodiesel fuels, gasoline fuels and alkmtol “Containing gasoline fuels. 11« The fitei composition according to any of the preceding embodiments, wherein the hydrocarbyrtsuhshtuted polycarhoxylic add compound is a polyisobutenylsueclnlc acid or an anhydride (PjBSA) thereof; said acid having a low hismaleation level, especially 10% or less than 10%, for example 2 to 9 or 3 to 7%. More particularly, such FIBS As are derived from HR-PIB with an Mn in the range Írom. about 400 to 3000.

More particularly, the above .fuel compositions -are in particular diesel fuels. 12. The use of a reaction product obtainable by a process as defined in any of the preceding embodiments, especially according to cmbodirtient 2, 3, 4, 3 and in particular embodiment 7, 8 or 9, or quatemlxed nitrogen compound obtained horn the reaction product by partial or full purification as a fuel additive.

In a particular configuration (Ai of the invention, quai errs ized reaction products which are prepared proceeding horn polyisohtdenylsnecinic add or an anhydride thereof are provided, this compound having a bismaleation level of 2 to 20% or 2 to 15%, for example 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3 or 2%. This polyisobufenylsuecinic acid compound is reacted (especially by addition or condensation) with a compound ooinpri sing at kast one oxygen or nitrogen group reactive (addable or condensable) with the polyisobutenyisueernie acid compound and containing at least one quatemizabie amino group, and then quaiernixed.

In a particular configuration (B) of the invention, qnateruized reaction px'odiscts which are obtained by qnaiernization using an excess of qtxatemizing 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, 1,4, 1,5, 1.6, 1,7, 1.8 or 1.9, equivalents of quatemlzing agent are used per equivalent of quaternixabie tertiary nitrogen atoms. Particularly useful quatemizing agents are those of the formula (i), especially die lower alkyl esters of salicylic acid, such as methyl salicylate, ethyl salicylate, n~ and bpropyl salicylate, and η-, or tort-butyl, salicylate.

In a further particular configuration (€), configurations (A) and (B) are combined, ie, the quaternixahle compounds prepared from the above polyisobutenylsuoeink acid compounds according to configuration (Â) are quaternixed according to configuration (B). 13. The use of a quai emi zed nitrogen compound according to embodiment. 12, prepared by a process comprising the reaction of a qxxateroixable hydrocarbyl-substituled polycarboxylic acid compound comprising at least one tertiary qnatemizable amino group with a quaternizmg agent which converts the at least one tertiary amino group to a qnaterriitry ammonium group, said quatemizixig agent being the alky! ester of a cyeloaromatio or cycloaliphatic mono- or polycarboxylic acid (especially of a mono- or dicarhoxylie acid) or of an aliphatic polycarboxylic acid (especially diearboxyiic acid) and wherein about 1.1 to about 2,0 or about 1,25 to about 2,0 equivalents of quatemizing agent are used per equivalent of quaternizabie tertian·' nitrogen atoms as a fuel additive. 14, The use of a reaction product or of a quaternixed nitrogen coffipoimd according to embodiment ! 3 or of a compound prepared according to embodiment 13 as a fuel additive, especially diesel fuel additive, 15, The use according to embodiment 14 as an additive lor reducing the Idei consumption of direct-injection diesel engines, especially of diesel engines with, common-rail injection systems, as determined, for example, in an XÖD9 test to CBC-F-23-0I, and/or for minimizing power loss in direct-injection diesel engines, especially in diesel engines with common-rail injection systems, as determined, for example, in a DW!0 test based on CEC-F-098-Ö8, 16, The use according to embodiment .14 as a gasoline fuel additive for reducing the level of deposits in the intake system of a gasoline engine, such as especially DIS! (direct inieetion spark ignition) and PFJ (port fuel injector} engines, 17, Tbe use according to embodiment 14 as a diesel fuel additive, especially as a cold flow improver, as a wax anti settling additive (WÄSA) or as an additive for reducing the level of and/or preventing deposits In the intake systems, such as especially the internal diesel injector deposits (IDIDs), and/or valve sticking in direct-injection diesel engines, especially in common-rail injection systems.

Also described herein are: 18, An additive concentrate comprising, in combination with further diesel fuel or gasoline fuel additives, especially diesel fuel additives, at least one reaction product or a quatemixed nitrogen compound as defined ini embodiment 12 or prepared according to embodiment 13, A2} General definitions A "condensation' or ’Condensation reaction*' in the context of the present invention describes the reaction of two molecules with elimination of a rclativelv small •y molecule, especially of a water molecule. When such an elimination Is not detectable analytically, more particularly not detectable in stoichiometric amounts, and tbc two molecules react nevertheless, ter 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: "Hydroearhyl" 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 Ö, N, NIL S. in the chain thereof, ”Long-ehain” 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, lor example 350 to 3000. 500 to 2500, 760 to 2500, or 800 to 1500. More particularly, they are fonnod essentially from CL.?,, especially C;m, monomer units such as ethylene, propylene, n- or isobutylene or mixtures thereof, where the différent monomers may he copoiymermxl in random distribution or as blocks. Such long-chain hydrocarbyl radicals are also referred to as polyalkylsns radicals su ροίν-C- 6~ or poly-C>.,i-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.

Examples of particularly useful polyalkyleoe radicals are polyisobntsnyl radicals derived -from "high-reactivity* polyasohuten.es (IfR-PiB) which tire notable for a high content of terminal double bonds (ef., for example, also Rath et al,, Lubrication Science (1999k 11 -2, 175-185). Termina! double bonds are alpha oiefmie double bonds of the type

which arc also referred to collectively m vinylidene double bonds. Suitable high-reactivity poiyisohutenes are, for example, poiyisohutenes which feme a proportion of vinylidene double bonds of greater than especially greater than 80 mol% or greater than 85 mo)%, Preference is given especially to polyisobutenes which have homogeneous polymer structures. Homogeneous polymer structures are possessed 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 pelyisohuterms preferably have a number-average molecular weight within the ahovementioned range. In addition, the high-reactivity polyisobutenes may have a polydispersity in the range from 1.05 to 7, especially of about L i to 2.5, for example of less than 1.9 or less than L5. Polydispersity Is understood to mean the quotient of weight-average molecular weight Mw divided by the «umher-average molecular weight Mn. •Particularly suitable high-reactivity polyisobutenes are, for example, the GHssopal brands from BASF SE, especially Giissopal® 1000 (Mn “ ÍÖÖÖ), Glissopal® V 33 (Mn- 550), GHssopal^ 1300 (Mn™i300) and CilissopaF 2300 (Mn ^2300), and mixtures thereof. Other number-average molecular weights can be established in a marmer known in principle by mixing polyisobutenes of different number-average molecular weights or by extractive enrichment of poîyisotsuîenes of particular molecular weight ranges, FIBS A is prepared in a manner known in principle by reacting FIB with maleic anhydride (MAA), in principle forming a mixture of PIBSA and Msmaieaied PIBSA (BM PIBSA, cf, scheme 1, below), which is generally not separated hid used as such in further reactions. The ratio of the two components to one another can be reported via the ^blsmaleation level'* (3BML). The BML Is known per se (see also US 5,883,196). The BML can also he determined hv the following formula: BML - 100% s [(wt-%(BM FIBSA))/(wt-%(BM F!BSA)t-wt~%(PIBSA))j where wt~% (X) represents the proportion by weight of component X (X PiBSA or BM FIB'S Λ) in the reaction product of PIB with MSA,

Scheme 1

FÍ8 MSA P'BSA 8MÍPSBSÁ

Hydrocarbyl-subsümted polycatboxylie acid mxtipamê with a “low bismaleatlon level”, especially corresponding polyisobutenylsuceinic acids or anhydrides thereof (also referred to overall as PÎBSA) are known from the prior art. Especially advantageous are bismaleatiön levels of 20% of 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 the above high-reactivity poiyisobmenes with an Mn in the range from about $00 to 2500, for example 550 to 3000, 1000 to 2000 or 1.000 to 1500. À nonlimiting, example of a corresponding PIBSA is inrisopal'8 SA, derived from HR-FIB (Mn ~ 1000), with a bismalcation level of 9%< "Shorf-ehain hydroearbyl” or "low molecular weight hydrooarbyr is especially straight-chain or branched alkyl or alkenyl, optionally interrupted by one or more, for example 2, 3 or 4, heieroatom groups such as -0- or -NH-, or optionally mono- or polysubstituted, for example di-, tri~ or tetrasubsfituted. "Alkyl'' or "lower alky!" 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, «-propyl, 1-methyieihyl n-boiyl 1--methyipropyl 2-methyipropyl, 1,1-dimethylethyl n-pentyi 1-methylhutyl 2~metby!hutyl 3-methyibuiyl 2,2-dimeihyiptopyL 1-ethyl propyl, «-hexyl, 1., 1.-4hnethylpropyi, 1,2--dimethylpropyl, 1-methylpentvL 2-meîhylperttyL 3-methylpentyl, 4-methyipentyl 1,1-dimethylbutyh 1,2-dhnethylbutyl, L3-dhnethyibutyl 2,2--dimethylhutyl 2,3-dimethylhutyl, 3,3-dimethylhulyl l~ethylhutyl 2-eihyÍbutyl, l,l,2~trim®thyipropyl, i,2,2--trimethylpropyl I -ethyl· 1.-methyipropyl and X-ethyb2-methyipropyl; and also n-heptyi n-oetyi, nmonyi and n-dceyl and the singly or Multiply branched analogs thereof; "Hydioxyalkyl* represents especially the mono- or polyhydroxyl a ted, especially monohydroxylated, analogs of the above alkyl radicals, for example the. mo no h yd ro x y ! at ed analogs of the above straight-chain or branched alkyl radicals, for example the linear hydroxyalkyl groups with a primary hydroxyl poop, such as hydroxymethyl 2-hydroxyethyi, 3-hydrox>propyl, 4-hydroxybulyl "Alkenyl" represents mono- or polyunsaturated, especially monounsaturated. straight-chain or branched hydrocarbon radicals having 2 to 4, 2 to 6, 2 to 8, 2 to 10 or 2 or to 20 carbon atoms and a double bond in any position, for example C:3 -C6-alkcnyi such as ethenyl, l-propenyi, 2-propenyl l-methyleihenyl Lhutohyl 2~butenyl 3-hltiênyl, I-methyl-1 -prepenyi, 2-mefhyl-l -ptopenyl, I -toethyl-2-propeny 1, 2-metbyl-2-popenyh t -pentenyl 2-pentenyl 3-pentenyl 4-pentenyl, 1 -methyl-1 -butenyl 2-methyl-]-buieny!, 3-methyl-1 -butenyl, I -metbyI-2-butenyi, 2-methy!»2-butenyi, 3-methyl-2-buteny!, \-metbyl-3-butcnyl, 2-methyl~3-buteny|, 3-methyl-3-butenyi, Ll-dimethyl-2-propenyl, 1,2-dimefhyl-1 -propenyl 1,2-dlutet|vy|-2-prc^cnyi! 1 -ethyl-1 -propenyi, I -ethybS-propenyi, I-teenyl 2~hexenyl, 3~hexenyi, 4-hex.eayl, S-hexenyl, l-methyl-L pentenyl, 2-.methyl-1 -pentenyl, 3-methyl-1 -pentenyl, 4-methyl-1 -pentenyl I -methyl-2-penlenvl, 2-methyl-2-penîenyl 3-methy!-2-pentenyl, 4-methyl-2-pentenyl, 1 -methyl-3-pentenyl, 2-methyi-3-pentenyL 3-methyl-3-pentenyl, 4-methyl-3~pentenyl, I -methyl-4-pentenyl, 2-Methyi-4-penie«yl, 3-methyl -4-pentenyl 4~methyl-4~pentenyl 1,1 -dimethyl-2-huterty I, 1, l -dimethyl-3-butenyl 1,2-dimetbyl-1 -buiettyi .1,2-dirnethyl~2~ butenyl, 1,2-dimethyl-3-butenyl 1,3-dimethyl-i -butenyl 1,3 -dim et by I ~2 -b u terry 1, 1,3- dlme&amp;^-S^ùenyt, 2,2~dimeíhyI--3-hntenyh ’feiimyl* 2,3foimethyb2*· hutenyl, 2,3-dimethyl-3-butenyl, 3.3*dimeî.hyl·· 1 ~butenyl, 3,3 -dimethyl-2 butenyl, 1 -ethyl-}--butenyl, 1 -Gthyl-2-butenyi, 1 -ethyl - 3 - b u ten y! » 2~ethyl~ 1 -butenyl, 2~gthyl-2-butenyl, 2--eih.yi-3--bntenyi, 1 J^-trimethyldbpropenyl, i -ethyl-1 -methyl-2-propenyh 1 ~ethyl~2~methyl~ i -propenyl and 1 -ethyh-2--metliyl--2--propenyh "Alkylene" represents sfraigld-ehain or mono- or polybranehed hydrocarbon bridge groups having 1 to 10 carbon atoms, for example CrOj-alkylene groups selected from •Clir. -(Cl-bb·, -(CHp)?··, CiirCH(aifK -CH(CHfhCHr, (Ob)4·, -(CHa)2-CH(CH.O-, -CH2-CH(CH3)-CH2-, (€H>)4~, ~{CH>)5-, -(CH2)6, (CH.>}?··, -CH(Cti5}-CllrCflrCll(Clh}- or ~Ce(CHj)-CHrCHrCHrCH(CH3)~ or C,-CV alkylene .groups selected bom -(CH2)2~, -(CM>)r> -CB2-CM(CH3)-, -CH(CH.*)~CHï-, -(CH2)4-, -(CHí)rCH(CH.î)-, -CH;-C'H(CH3)-CH2-. "Alkeuyleoe” represents the mono- or polyunsaturated, especially mononnsatnrated, analogs of the above alkylene groups having 2 to 10 carbon atoms, especially €>-€·;--alkenyl ones or CrOalkenylenes, such äs »CH-CH-. -CH=CH-CH?-, ~CH.rCfi-CH-, -CH-CH~CHra-h-, -CH2”C 11 :::Q1 *C'lb-CHrCMrCM-CH-, ~CH(CH5)-CH-CH-, -CfI;:-C(CH3l=<'H·. "Cyclic hydrocarbyi radicals" comprise especially; eyeloaikyl: egrbocyciie radicals having 3 to 20 carbon atoms, for example €r Cj2-cycloalky 1 such as cyclopropyl, cyclobutyl, cyclopentyl, eyeiohexyi, cycloheptyl, eyciooeCyi, cyciononyl, eyelodecyk cycioundecyl and cyclododecyl; preference is given to cyclopentyl, eyeiohexyi, cycloheptyl, and also to eyelopropyltnethyL eyclopropylebtyl, eyclobutylmethyl, cyelobutylethyb eyelopentyhnethyl, eyedopenty! ethyl, cyclohexyimethyl, or Ch-Crcycloalkyl such as cyclopropyl, cyelobutyl, cyclopentyl, eyefohexyl, cycloheptyl. cyelopropylmethyl, cyefopropylefhyk cyclohuiylmethyh eyelopentylcthyL c>clohexyimethyl, where the bond to the rest of the molecule may be via any suitable carbon atom. eydoalkenÿî: monocyclic, monounsaturated hydrocarbon groups having 5 to 8, preferably up to 6, carbon ring members, such as eydopeofen~l~yh cyclopeníen-3-yl, cydohesen-1 -yk eyelohexen-3-y! and cydohcxen-4-yl; aryl: mono- or polycyclic, preferably mono» or Mcyelle, optionally substituted somatic radicals having 6 to 20, for example 6 to 10, ring carbon atoms, for example phenyl, biphenyl, naphthyl such as 1- or 2-naphthyL tetrahydronaphlhyl, fluorenyi, indenyl and phenamhrenyî. These aryl radicals nmy optionally bear 1, 2, 3, 4, 5 or 6 identical or different substituents. ''Substituants" fer radicals specified herein are especially, unless stated otherwise, selected ltom keto groups, -Cööil, »C'QO-alkyl, --OH, -SB, -CM, amino, -NOg 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 may differ, for example, by &amp; 10% to *0.1% front the specific values. Typically, such deviations are about ·.♦.· 8% to ± 1% or « 5%, &amp; 4%, * 3% or *2%. A3) Poly carboxylic acid compounds amd pölyearboxybe acid compounds;

The polycarboxylic acid compounds used are aliphatic éb or polybasic (for example tri- or tetrabasie), especially írom di-, tri- or ietracarhoxylie acids and analogs thereof such as anhydrides or lower alkyl esters (partially or completely esterlfted), and is optionally substituted by one or more (tor example 2 or 3), especially a long-chain alkyl radical and/or a high molecular weight liydroearbyi radical, especially a polyalkylenc radical. Examples are CY-Cks polycarboxylic acids, such as the diearhoxylie acids malonie acid, succinic acid, glutarie add, adipic acid, pimelle acid, suberic acid, axelaie acid and schade acid, and the branched analogs thereof and the tricarboxylic acid citric acid; and anhydrides or lower alkyl esters thereof of, The polycarboxylic acid compounds can also be obtained from the corresponding monounsaiurated acids and addition of at least one iong-eham alkyl radical and/or high molecular weight hydrocarhyl radical. Examples of suitable monounsaturated adds are fumaric acid, maleic acid, ilaconic acid.

The hydrophobie "k>ng~ehain" or ”high molecular weight" hydroearhyi radical which ensures Sufficient solubility of the quaiernized product in the fuel has a number-average molecular weight iMn) 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. Typical hydrophobic hydroearhyi radicals include polypropenyi, polybuleny! and polyisobPtdiyl radicals, for example with a number-average molecular weight Mt, of 3500 to 5000, 350 to 3000, 500 to 2500, 700 to 2500 and 800 to 1500.

Suitable hydrocarhyTsuhstituted compounds are described, for example, in DE 43 19 672 and WO 2008/138836.

Suitable hydrocarbyhsubstituted poly-carboxylic acid compounds also comprise polymeric, especially dimeric, forms of such hydrocarhyi-substituted polycarboxylie acid compounds. Dimeric forms comprise, for example, two acid anhydride groups which can be reacted independently with the quaterni zahle nitrogen compound in the preparation process according to the invention, A4) QtMteramîng agents:

Useful quaternizing agents are in principle all alky! esters which are suitable as such and are those of a cycloaromatic or cycloaliphatic mono- or polyeafhoxylic acid (especially of a mono- or dicarhoxyiic add) or of an aliphatic polycarboxylic acid (especially dicarhoxyiic acid).

In a particular -embodiment, however, the at least one quatermzäMe tertiary nitrogen atom is quaiernized with at least one quaternizing agent selected from a) compounds of the general formula 1

RiOC(0)Ro (1) in which

Ri .is a lower alkyl radical, and

Rj is an optionally substituted monocyclic aryl or cycloalkyl radical, where the substituent is selected front OH, NIL·, NO* C(0)0R.u and RSsO€(O.K in which R,a is as defined above for Rj and R3 is H or Rs : and b) compounds of the general, formula 2 R Oü(Ofr A~C(0)ÖRfa (2) in which R; and R.ia are each independently a lower alkyl radical and A is hydroenrbylene (such as alkylene or alkenyfone).

Particularly suitable compounds of the formula 1 are those in which Rj is a Cfo, €fo or €5-alkyl radical and 1½ is a substituted phenyl radical, where the substituent is HO- or an ester radical of the formula R^OCCÔ)- which is in the para» tueta or especially ortho position to the R îOC(0}~ radical on the aromatic ring.

Especially suitable quateraizmg agents are the lower alkyl esters of salicylic acid, such as methyl salicylate, ethyl salicylate, n- and i-propyl salicylate, and η-, i- or terEhuty! salicylate. AS) Qnsitcrsiized or quaíertózalbie ölfrogéS CöMpäuftds:

The quateorfoabte nitrogen compounds reactive with the poiyeafboxylie acid compound are selected from a> bydroxyaikyl-substituted fnOao or polyarnmes having M least one quateraixed (e,g< dióiké) or quuternizable primary, secondary or tertiary amino group: b. straight-cham or branched, cyclic, heterocyclic, aromatic or nonaromatic polyamines having at least one primary or secondary (anhydride-reactive) amino group and having at least one quatermxed or quaternixable primary, secondary or tertiary amino group; e. piperazines.

The quatemizable nitrogen compound is especially selected torn d. hydmxyalkyl-substituted primary, secondary, tertiary or quaternary monoamines and hydroxyalkyj-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 tertiary amino group; di- or polyamines having at least one primary and at least one quaternary amino group; aromatic earhoeyelie diamines having two primary amino groups; aromatic heterocyclic polyamines having two primary amino groups; aromatic or nonaromatie heterocycles having one primary and one tertiary amino group.

Examples of suitable "hydroxyalkyl-suhstituted mono- Of poiyamtnes" are those provided with at least one bydroxyaikyl substituted, for example 1, 2, 3, 4, 5 or 6 bydroxyaikyl substituted.

Examples of ^hydroxyalkyl-suhstituted monoamines” include: N-ltydroxyalkyl monoamines, N.M-dihydtxjxyalkyi monoamines and Ν,Ν,Ν-trihydroxyalkyl monoamines, where the bydroxyaikyl groups are the same or different and are also as defined above. Hydroxvalkyl is especially 2-hydroxyetbyl, 3-hydroxypropyl or 4-liydroxyhuty!.

For example, the following "hydmxyalkyl-suhsfiiided polyamines" and -espeeiafty "hydroxyalkyl-substiinted' diamines" may he mentioned; (N~l)ydroxyalkyi}a!kylene·-diamiites, N,N"dillydroxyalkyialkyleneiliajnineSs where the hydroxyalkyl groups· are the same or different and are also as defined above. Hydroxyalkyl is espeuaPv 2-hydroxyethyl, 3-hydroxypropyl or 4~hydroxybntyl; aikylefte is especially ethylene, propylene or butylene.

Suitable "diamines" are alkyienedianrines, and the N- alkyl-substituted analogs thereof, such as N-monoalkylated alkylenexharninex and the N.N» or RN'-dialkvlated alkylenediamines, Alkylene is especially straight-chain or branched Cfor or alkylene as defined above. Alkyl is especialiy CM-alkyl as defined above. Examples are especially ethyienediannne, l,2~po]ydenediamme, 1,3 · propylenediarnine, 1,4-butylenediamine and isomers thereof, perstanediamine and isomers thereof hexanediamine and isomers thereof heptanediamine and isomers titerenfi and singly or multiply, for example singly or doubly. CrCf-alkylated, for example methylated, derivatives of the aforementioned diamine compounds such as S-dimethylamino- l·· propylamine (PMAFA), Ν,Ν-diethyläminopropylannne and Ν,Ν-dunethylammo·-ethyiamme.

Suitable straight-chain "polyamines" are, for example, dialkyieneiriamine, trialkyienetetramine, teiraaikylenepeniatnine. pentaálkylenehexannne, and the N-aikyl-suhstiiuted analogs thereof, such as N-racmoalkylated and the N,N~ or M,N'~ dialkylaied alkyienepolyamines, Alkylene A especially siraighf-ehain or branched Co 7™ or C{4-âikylene as defined above. Alkyl is especially Cj-4~alkyl as defined above,

Examples are especially diethylenetriamlne, tneibylenetetrantlne, tetraethylenepentamme, pen taethy I en eh ex am ine, dipropylenetriamine, tripropylenetetramine, teirapropylenepentamine, pentapropylenehexamine, dibutyUmeiri amine, t ri but y I en eieir am me, tetrabuiylenepermunme, pentabutylenehexamine; and the K,hf-dia1kyl derivatives thereof especially the N,N-dl~Ci„j-alkyi derivatives thereof Examples Include: N,N~ dimeUyyjdimeihylenetriamiuc, NfN-(licthyldimethylenetriamine, N,N~ dipropyldimethyî enetriamine, N ,N-dimetiyMiefeyíeü«·-1,2-tf iamine, N ~ diêÂyliiêiiytoe-t;?24B8friiiîie? N,N-dipropyÍdiethykne~lJ~tóaník©s N>N* dimethyldipropyieneA3driarn!oe (te. DMAPAPA), N,NAliethyldipr<.>py{ene-î,3-tíaffime, N ,N -clîpropyidipfopy|ene> .1 ,3-triatmne, Ν,Ν-dimeîhyldibuty lene-1,4- triamine, N\N-diethyk1ibutylene4,4dmrnine, N,N-dípröpyWlb«tyle«tó-î,4-triarairie, N, N-dinieiîiy!d|periiyiane-1 ,5-triamine, N,N~di eihyldipeniylotte" lySAriítóm, N,H~ dlpropyldipentylonê·* î ,5-trîâîÂiôê, N>N-dimet'hyldihexÿieae~î,b-triamin05 N,H~ diethyI4lhdx:yknö-l,b-ímmipe and N ,N mipfopyMihexyleue-1 ,6dnamine. "Aromatic carhoeyelic diamines'' having two primary amino groups are the diamino·· substituted derivatives of benzene, biphenyl, naphthalene, ietiahydronapMhalene, fluorene, indene and phenanthrene, "Aromatic or nonaromatic heterocyclic polyamines” having two primary amino groups are the derivatives, substituted by two ammo groups, of the following heteroeydes: S* or dnnembered, saturated or nmnomtsafufated Imteroeycles 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, Lsoxazolidine, isothiazolidlne, pyrazolidine, oxazolldine, thiazolidine, imidazolldine, pyrroline, piperidine, piperidinyl, 13 -dioxane, tetrahydronyran, hexahydropyridamne, hex almlropyrim kirne, piperazine; S-menibered aromatic heteroeyeles comprising, in addition to carbon atoms, two or three nitrogen atoms or one or two nitrogen atoms and ope sulfur or oxygen atom as ring members, Ihr example fhran, thiane, pyrrole, pyrazole, oxazole, tldazole, imidazole and hixf-triazole; isoxazoie, isoihiazoie, tlhadiazole, oxadiazole; d-menfbered lieterocycles comprising, in addition to carbon atoms, one or two, of one, two or three, nitrogen atoms m ring members, for example pyridinyl, pyridarine, pyrimidine, pyrarinyl 1,2,4-trtanine, 13,5-driazin-2-yl. "Aromatic or nonaromatic heterocycles having one primary anti one tertiary amino group" are, for example, the aboxemcntioned N-heterocycies which are amínoalkylatéd on at least one ring nitrogen atom, and especially hear an amino-Cy*-alkyl group. "Aromatic or nonaromafic heterocycles having a tertiary amino group and a hydroxyaikyi group" are, for example, the ahovementioned N-heterocycies which are hydroxyalkylaled on at least one ring nitrogen atom, and especially bear a hydroxy-CS ralkyl group.

Mention should be made especially of the following groups of individual classes of quatenhuahle nitrogen compounds:

Group 1:

Group 2;

Group 3:

A6) Preparation of lovent Ive additives; a) Eeaatiotï with oxygen or nitrogen group

The hydroearhyl-substiMed polyearboxylie add compound can be reacted with the quatemixabfo nitrogen compound according to the present invention undor thermally controlled conditions, such that there is essentially no condensation reaction. More particularly,, no formation of water of reaction is observed in that ease. More particularly, such a. reaction is effected at a temperature in the range from 10 to S0*C, especially 2D to 60°C or 30 to SD°C, The reaction time may he in the range from a few minutes or a few hours, for example about 1 minute up to about I D hours, The reaction can he effected at a pressure of about 0,1 to 2 atm, hut especially at approximately standard pressure. For example, an inert gas atmosphere, for example nitrogen, is appropriate.

More particularly, the reaction can also he effected at elevated temperatures which promote condensation, for example in the range from 90 to HKPC or 10D to 3?{i°C, The reaction tune may be in the region of a few minutes or a tow hours, for example about 1 minute up to about 10 hours. 1'he reaction can he effected at pressure at about 0.1 to 2 atm, but especially at about standard pressure.

The reactants are initially charged especially in about equimolar amounts; optionally, a small molar excess of the polyearboxylie acid compound, tor example a 0,05- to 0,5-fold, for example a 0.1- to 0.3-fold, excess, Is desirable, ff required, the reactants can be initially charged In a suitable inert organic aliphatic or aromatic solvent or a mixture thereof. Typical examples are, fer example, solvents of fee So! vesse aeries, toluene or xylene. Tim 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 purified further, or the solvent can he removed. Usually, however, this is not absolutely necessary, such that the reaction step can be tmnsferred without fitriher purification info the next synthesis step, the quaternisation, b) Quaternkation

The quaternkation in reaction step (b) is then carried out in a manner known per se.

To perform the qnaternixation, the reaction product or reaction mixture from stage a) is admixed with at least one compound of the above formula 1 or 2, especially in the stoichiometric amounts required to achieve the desired quaternkation. The quatemking agent is added in excess per equivalent of quaternkable tertiary nitrogen atom, for example 1.1 to 2,0, 1,25 to 2 or 1,25 to 1.75 equivalents of quatemking agent per equivalent of quaternkable tertiary nitrogen atom.

Typical working temperatures here are in the range from 50 fo 180°€, ihr example from 00 to 160°C or 100 to 140°C, The reaction time may be in fee range of a few minutes or a few hours, for example about 10 minutes up to about 24 hours. The reaction can he effected at a pressure of about 0.1 to 20 bar, for example 1 to 10 or 1.5 to 3 bar, but especially at about standard pressure, if required, the reactants can be initially charged for fee qua terni xa lion In a suitable inert organic aliphatic 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 nr xylene. The quaternkation can, however, also be perfenned in the absence of a solvent.

To perform the ^«afernizatkm, foe addition of eatalytlcally active amounts of an add may he appropriate. Preference is given to aliphatic monoearhoxylic acids, for example Os-Cis-monoearboxylie acids such as especially laurie acid, isonoaanoic acid or neodeeanoio add. The quatemization can also he performed in the presence of a Lewis acid. The qnatemistation can, however, also he performed in the absence of any acid, c) Workup of the reaction mixture

The reaction end product thus formed can theoretically be purified further, or the solvent can be removed. In order to improve the further processability of the products, however, it is also possible to add solvent after the reaction, for example solvents from the Solvesso series, 2~ethylhexa«ol, or essentially aliphatic solvents, Usually, however, this is pot absolutely necessary, arid so the reaction product is usable without further purification as an additive, optionally after blending with further additive components (see below}, B> Further additive components

The fuel addhfoed with the inventive quaternized additive is a gasoline fuel or especially a middle distillate foci, in particular a diesel fuel.

The fuel may comprise further customary additives to improve efficacy and/or suppress wear. la the ease of diesel fuels, these are primarily customary detergent additives, carrier oils, cold flow improvers, lubricity improvers, corrosion inhibitors, demulsifiers, dehazers, antifoams, cetane number improvers, combustion improvers, antioxidants or stabilizers, antistats, metallocenes, metal deactivators, dyes and/or solvents.

In foe ease of gasoline fuels, these are in particular lubricity improvers (friction modifiers), corrosion inhibitors, demulsifiers, dehazers, antifoams, combustion improvers, antioxidants or .stabilizers, aatistats, metallocenes, metal deaetivators, dyes and/or solvents.

Typiea! examples of suitable coadditives are listed in the following section: B l ) Detergent additives

The customary detergent additives are preferably amphiphilic substances which possess at least one hydrophobic hydrocarbon radical with a mitaben-average molecular weight (Ms) of 85 to 20 000 and at least one polar moiety selected from: (Da) mono- or polyamino groups having up to 6 nitrogen atoms, at least one nitrogen atom having basi c properlies; (Db) nitro groups, optionally is combination with hydroxyl groups; (Do) hydroxyl groups is combination with mono- or polvamino groups, at least one nitrogen atom having basic properties; (Dd) carboxyl groups or their alkali metal or alkaline earth metal salts; (De) sulfonic acid groups or their alkali metal or alkaline earth metal salts; (DÍ) polyoxy-Ca- to €h~alkylesie moieties terminated by hydroxyl groups, mono- or polya.rn.ino groups, at least one nitrogen atom having basic properties, or fey carbamate groups; (Dg) carboxylic ester groups; (Dh) moieties derived fi'om succinic anhydride and having hydroxyl and/or amino and/or ami do and/or irnido groups; and/or (Di) mobfies obtained by Mamhch reaction of substituted phenols with aldehydes and 01000- or polyamides.

The hydrophobic hydrocarbon radical in the above detergent additives, which ensures the adequate solubility in the fuel, has a number-average molecular weight (Ma) of 85 to 20 000, preferably of 113 to 10 000, more preferably of 300 to 50()0. even more preferably of 3 00 to 3000, even more especially preferált! y of 500 to 2500 and especially of 700 to 2500, in particular of 800 to 1500. äs typical hydrophobic hydrocarbon radicals, especially in conjunction with the polar especially polypropenyl, polybutOnyl and polyisobnteny! radicals with a »umber-average molecular weight ME of preferably in each ease 300 to 500(1, 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.

Examples of the abo ve gro ups of detergent additi ves include the following:

Additives comprising mono- or poiyamino groups (Da) are preferably polyalkencmono- or polyalkeoepolyamines baaed on polypropene or on high-reactivity (i.e. having predominantly terminal double bonds) or conventional (i,e, having predominantly internal double bonds) polybutene or polyisobuiene having M» ~ 300 to 5()00, more preferably 500 to 2500 and especially 700 to 2500. Such additives based on high-reactivity polyisobutme, which can be prepared from the polyisobuteue which may comprise up to 20% by weight of n~hutene units by hydroformylation and reductive amination with ammonia, monoamines or polyamines such as dimetbyhuTiinopropylaniine, ethyienedimmoe, diethylenehimnioe, íriethylenefeíranhne or tetraethylenepeniamine, are known especially from EP-A 244 6ib, When polyhutcne or poíyisobutene having predominantly internal double bonds (usually in the p and γ positions) are used as starting materials in the preparation of the additives, a possible preparative route is by chlorination and subsequent amination or by oxidation of the double bond with air or oxone to gi ve the carbonyl or carboxyl compound and subsequent amination under reductive (hydrogenating) conditions. The amines used here tor the amination may be, for example, ammonia, monoamines or the áhovemeniioned polyamrn.es, Corresponding additives based on polypropene are described in particular in WOA 94/24231,

Further particular additives comprising monoamino groups (Da) are die hydrogenation products of the reaction products of polyisobutenes having an average degree of polymerfeation P S: 5 to IQO with nitrogen oxides or mixtures of ni trogen oxides and oxygen, as described in particular in WCAÀ 97/03946,

Further particular -additives eotnpmhg monoamino groups (Da) are the compounds obtainable from polyisobutene epoxides by reaction with amines and subsequent dehydration and reduction of the amino alcohols, as described in particular in DP.-A 19b: 20 262,

Additives comprising nitro groups (Db), optionally in combination with hydroxyl groups, are preferably reaction products ot'polyisobntenes having an average degree of polymerization P 5 to 100 or 10 to 100 with ni trogen oxid es or mixtures o f nitrogen oxides and oxygen, as described in particular in WÇKA 96/03367 and in WO-A 96/03479. These reaction products are generally mixtures of pure nitropolyisobntcues (e.g, α,β-dinitropolyisobutene) and mixed hydroxynitropoiyisobutenes (e.g. a-miro-p·-b ydroxypolyi sobiiíene).

Additives comprising hydroxyl groups in combination with mono- or poly ami no groups (Dc) arc in particular reaction products of polyisobutene epoxides obtainable from polyisobutene having preferably predominantly terminal double bonds and Mf,:::: 300 to 5000, with ammonia or mono-- or polyaniines, as described in particular in BP~A 476 485.

Additives comprising carboxyl groups or their alkali metal or alkaline earth metal salts ( Dd) are preferably döpolymers of Ci- to C^-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 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 3()7 8'IS, Such additives serve mainly to prevent valve seat wear and can, as described in WO-A 87/0112b, advantageously be used in combination with customary fuel detergents such as poIy( iso}but uneamdies or polyedteramines,

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 sidtosueeinate, as described vn particular in EP-A 639 632, Such additives serve mainly to prevent valve seat wear and can be used advarhageonsly in combination with customary fnel detergents such as pol:y(iso)buteneamines or polyetheramimes.

Additives comprising polyoxy-Cs-Ci-alkylene moieties (Df) are preferably polyethers or polyethcraïnines which are obtainable by reaction of (A- to €«ralkanols, CV to CV alkancdlols, mono- or di-Cb- to CValky I amines, CV to C^AÍkyleyxdohexamxls or Cr to Cbo-aikylphenols with 1 to 30 mol of ethylene oxide and/or propylene oxide and/or butylene ox ide per hydroxyl group or amino group and, in the ease of the polyetheramines, by subsequent reduotive amination with ammonia, monoamines or polyamines, Such products arc described in particular in EP-A 310 875, EP- A 356 725, EP-A 700 985 and ÜS-A 4 877 4.16.,. In.the case of polyethers, such products also have carrier oil properties. Typical examples of these are trideeanol buioxylates, isoiridecanol buioxylates, isononylphenol hutoxylates and polyisobntenol hutoxylates and propoxylaies and also the corresponding reaction products with ammonia.

Additives comprising carbokylie ester groups (Dg) are preferably esters erf mono-, di-or tricarboxylic adds with long-chain alkanois or polyols, in particular those having a minimum viscosity of 2 mm2/s at 100¾ m described in particular in DE-A 38 38 918, The mono-, di- or tricarboxylic adds used may be aliphatic, or aromatic adds, and: particularly suitable ester alcohols or ester polyols are long-chain representatives having, for example, 6 to 24 carbon atoms. Typical representatives of the esters are adipates, phthalaîes, isophthalates, terephthalates and trimellitates of tsooctool, of isononanol, of isodecancd and of isotridecanoL Such products also have carrier oil properties.

Additives comprising moieties derived Ûom suectate anhydride avid having hydroxy! and/or amino and/or antido and/or especially imido groups (Dh) art preferably corresponding derivatives of alkyl - or alkenyl-substituted succinic anhydride and especially the corresponding derivatives of polyisobuteoylsuceinie anhydride which are obtainable by reacting conventional or high-reactivity polyisobutene having «* preferably 300 to 5600, 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 polyisobutene. The moieties having hydroxyl and/or amino and/or arnido and/or iniido groups are, for example, earhoxyhc acid groups, add amides of monoamines, acid amides of di- or polyamines ’which, in addition to the amide fonction, also have free amine groups, succinic add derivatives having an acid and an amide function, earboxkTMd.es with monoamines, carboximides with di-- or polyamines which, in addition to the imide function, also have tree amine groups, or diimides which arc formed by the reaction o f di - or polyamines with two succinic acid derivatives, lu the presence of imido moieties D(h), the further deterpnt addi tive in the context of the present invention is, however, used only up to a maximum oil 00% of the weight of compounds with betame structure. Such fuel additives are common knowledge and are described, for example, in documents {i) and :(2-). They are preferably the reaction products of alkyl- or alkenyl-substituted succinic acids or derivatives thereof with amines and more preferably the reaction products of poljdsohutenyl-substituted succinic acids or derivatives thereof with amines. Of particular interest in this context are reaction products with aliphatic polyamines (polyalkylenenmnes) such as especially efhyienediamiue, diethylenetriarnine, iriethyleneieimmine, tctraethylenepentamine, peniaethyfonehe.xanrine and hcxacthyleneheptamine, 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 polyisohuteue-substltuted phenols with formaldehyde and mono- or polyamines such as ethylenediamine, diethylenetriamine, triethylenetotramine, tetracthylenopentamine or dimel:hykí«ínopropy!amínöv The polyisobutcmyi-subsiituted phenols may stem from conventional or higk-reactivfly pelyfsohutene having M8 = 300 to 501)0. Such "polyisobutene Mannieh bases” are described in particular in BP-A 831 141..

One or more of the detergent additives mentioned can be added to the fuel in such m amount that the dosage of these detergent additives is preferably 25 to 2500 ppm hy weight, especially 75 to 1500 ppm by weight, in particular 150 to 1000 ppm hy weight. 82} Carrier oils

Carrier oils additionally used maybe of mineral or synthetic nature. Suitable mineral earner oils are the fractions obtained in crude oil processing, such as hrightstoek or base oils having viscosities, for example, horn the SN 500 to 2000 class; but also aromatic hydrocarbons, paraffinic hydrocarbons and alkoxyalkanoLs. Likewise useful is. a fraction which is obtained in the refining of mineral oil and is known as "hydröefack oil" (vacuum distillate cut having a boiling range from about 360 to 500CC, obtainable from natural mineral oil which has been catalytic-ally hydrogenated and isomerized under high pressure and also deparafhmxed). Likewise suitable are mixtures of the a ho vemes m oned mineral carrier ods.

Examples of suitable· synthetic carrier oils are polyolefins (poiyalphaoleflus or polyintemalolefms), (poiyiesters, (poly)alkoxylates, polyethers, aliphatic polyether-amines, alkyl phenol- started poiyethers, alkylphenol-stmted polyetherammes and carboxylic esters of long-chain alkanols,

Exatoples of suitable polyolefins are olefin polymers having M« ™ 4(10 to 18(10, in particular based on poly-butene or polyisobuteue (hydrogenated, or unhydrogenated}.

Examples of suitable polyethers or polyetherammes are preferably compounds comprising poiyoxy-C;·- to Cs-alkylene .moieties which are obtainable hy reacting Cato C$o-alkanoisx CV to Cio-alkanediols, mono- or di-Ch- to (ijo-alkylamines, Cj- to Cíq~ alkylcyelohexanols or CV to C.hí-alky (phenols with 1 to 30 mol of ethylene oxide and/or propylene oxide and/or butylene oxide per hydroxyl group or amino group, and, in the ease of the polyetheramines, by subsequent reductive amination with ammonia, monoamines or polyamines. Such products are described in particular in EP--Â 310 873, EP-Â 356 725, BF-A 700 985 and US-Λ 4,877,416. For example, the polyetheramines used may he poiy-Cr to CValkylene oxide amines or ftmetfonal deri vatives thereof, Typical examples thereof are tridecanol butoxyiates or isotridecanol butoxyiates, isononylphenol butoxyiates and also polylsobutenoi butoxyiates and propoxyhUes, and also the corresponding reaction products with ammonia.

Examples of earhoxylic esters of long-chain alkanols are in particul ar esters of mono-, di- or tricarboxylic acids with long-chain alkanols or polyols, as described in particular in DÎUA 38 38 918, Thé mono-, di- or tricarboxyl ic acids used may be aliphatic or aromatic acids; suitable ester alcohols or polyols are in particular long-chain representatives having, tor example, 6 to 24 carbon atoms, Typical representatives of the esters are adipates, phihalates, isophibalates, terephthalates and trlmeOitates of isooctanoh isononanol, isodecanol and isotrideeanoL for example di(m or isotrideeyl) phthalate,

Further suitable carrier oil systems are described, lor example. In DE~A 38 26 608, DB«Ä 41 42 241, DE~A 43 09 074, IP-Á 452 328 and EP-A 548 617.

Examples of particularly suitable synthetic carrier oils are alcohol-slatted polyethers having about 5 to 35, preferably about S to 30, more preferably 10 to 30 and especially 15 to 30 €3- to C(j-alkylene oxide units, for example selected from propylene oxide, n~ butylene oxide and isobutylene oxide units, or mixtures thereof, per alcohol molecule. Notilimiting examples of suitable starter alcohols are long-chain alkanols or phenols substituted by long-chain alkyl in which the long-chain alkyl radical is in particular a straight-chain or branched C6- to C(s~alkyl radical. Particular examples include tridecanol and nonylphenol. Particularly preferred alcohol-started polyethers are the reaction products {polyéthérification products} of monohydrie aliphatic C$* to €;r alcohols with Cr to Cräihyteue oxides. Examples of monohydrie aliphatic Q-Cik- alcohols are hexánok heptane}, oetanol, 2-eihylhexanol, nonyl alcohol, decanoi, 3~ prapylheptano!, undecimoh dodeeanot, Iridecanol, tetradeeanol, pentadeeahoi, hexadecanol, octadeeanol and the constitutional and positional isomers thereof, The alcohols can he used either itt the form of the pure isomers or in the form of technical grade mixtures, Λ particularly preferred alcohol is tridecanol. Examples of Ch- to CV atkylene oxides are propylene oxide, such as 1,3-propylene oxide, butyl ette oxide, such as 1,2-hutyiene oxide, 2,3-bufylene oxide, isobutylene oxide or tetrahydrofuran, perUylene oxide and hexylene oxide. Particular preference among-these is given to Cr to Ci-alkvlene oxides, i.e. propylene oxide such as 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.

Further suitable synthetic carrier oils are aikoxylated alkyl phenols, as described in DB A 10 102 913.

Particular carrier oils are synthetic carrier oils, particular preference being given to the above-described alcohol-started pnlyetbers.

The carrier oil or the mixture of different carrier oils is added to the fuel in an amount of preferably 1 to 10ÖÖ ppm by wei ght, more preferably of 10 to 500 ppm by weight and especially of 20 to 100 ppxn by weight, B3 ) Cold flow improvers

Suitable cold flow improvers are in principle all organic compounds which are capable of íínpröving the how performance of middle distillate fuels or diesel fuels under cold conditions. For the intended purpose, they must have sufficient oil solubility, in particular, useful cold flow improvers for this purpose are the cold flow improvers (middle distillate How improvers, MDFls) typically used in the case of middle distillates 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 die properties of 8 Wax antisettling additive (WASA) when used in customary diesel fuels.

They can also act partly or predominantly as nucleators. It is, though, also possible to use mixtures of organic compounds effective as MDFIs and/or effective as WASÂs and/or effective as nucleators.

The cold flow improver is typically selected from (Kl) copolymers of a Cr to C^ydeirt with at least one further ethylenically urssafurated monomer; i K2) comb polymers; (K 3 ) po i y oxyalkylenes; (K.4) polar nitrogen compounds; (&amp;5) sulfoearhoxylie acids or sulfonic acids or derivatives thereof; and (Kd) po 1 y (meth)a cryl ic esters.

It is possible to use either mixtures of different representatives from one of the particular classes {K1 ) io (K6) or mixtures of representatives from different classes (KI)to(K6).

Suitable Cfo to €#-olcfin monomers for the copolymers of class (Kl) are, for example, those having 2 to 20 and especially 2. to 10 carbon atoms, and 1 to 3 and preferably 1 or 2 earbon-earhon double bonds, especially having one eurbomearhon double bond. In the latter case, the carbon-carbon double bond may he arranged either terminally («.-olefins) or internally. II owe ver, preference is given to a-oleflns, more preferably a-oiefms having 2 to 6 carbon atoms, for example propene, I -butene, l-peniene, l· hexene mid in particular ethylene. 1rs the copolymers of class (Kl), the at least one further ethylenically unsaturaied monomer is preferably selected from alkenyl carboxylatcs, (meth)acrylió esters and further olefins.

When further Olefins are also eopolynterfeed, they are preferably higher in molecular weight than the abovententtoned €y to C^-ofefin base monomer. When, for example, the olefin base monomer used is ethylene or propene, suitable further olefins are in particular Cur to C^-etfokfms. further oleins are in most casus only additionally eopolymerixed when monomers with carboxylic ester feoetions arc also used,

Suitable (meth)acrylic esters are, for example, esters of (meih)acrylie add with C> to Cjo^alkaaols, especially €V to Qo-alkanols, in particular with methanol, ethanol, propanol, isopropanol, ndmtannL sec-butanol, isobutanol, tert-butanoL pentanol, hexanol, hoptanol, ootanol, 2-ethylhexanol, nouanol and decanol, and structural isomers thereof.

Suitable alkenyl earboxylates are, for example, €2- to C ^-alkenyl esters, tor example the vinyl and propen y I esters, of carboxylic acids having 2 to 21 carbon atoms, whose hydrocarbon radical may he linear or branched, Among these, preference is given to 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 a-earbon atom more preferably being tertiary, i.e, the carboxylic acid being a so-called OiXKxrrhoxyhe add. However, the hydrocarbon radical of the carboxylic acid is preferably linear.

Examples of suitable alkenyl earboxylates are -vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-etbyihexanoaie, vinyl neopentanoate, vinyl hexanoate, vinyl neononanoate, vinyl neodeeanoat© and the corresponding propenyI esters, preference being given to the vinyl esters, A particularly preferred alkenyl carboxyl ate is vinyl acetate; typical copolymers of group {Kl} resulting therefrom are ethylene-vinyl acetate copolymers f'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,

Suitable copolymers of class f K.1) are also those which comprise two Or more different alkenyl earboxylates in eopolymerixed form, which differ in the alkenyl function and/or in the catboxyie add group. Likewise suitable are copolymers which, as well as the alkenyl earboxylaiuCs), comprise at least one olefin and/or at least one (meth)acrylic ester in arpolymerfoed form.

Terpolymers of a CV to Q{1-«~olefin5 a Cj- to Cao-alkyi ester of an ethylemeally unsaturated monocarboxylic add having 3 to 15 carbon atoms and a CS~ to (.'n-alkenyl ester of a saturated monocarboxylie acid having 2 to 21 carbon atoms are also suitable as copolymers of class (Kl ), Terpolymers of this kind are described in WO 2005/054314, 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 monomerts) are eopolymerized in the copolymers of class < K1 ) in an amount of preferably 1 to 50% by weight, especially 10 to 45% by weight and in particular 20 to 40% by weight, based ön the overall copolymer. The main proportion in terms of weight of the monomer units itt the copolymers of class (Ki) therefore originates generally from the 0¾ to C40 base olefins.

The copolymers of dass (K i ) preferably have a numhewaverage molecular weight Mr of 1000 to 20 000, more preferably 1000 to 10 000 and in particular 1000 to 8000,

Typical comb polymers of component (K.2) are, for example, obtainable by the copolym creation of maleic anhydride or fumarie acid with another ethylemeally unsaturated monomer, for example with an «-olefin or an unsaturated ester, such as vinyl aeciate, and subsequent esterification of the anhydride or acid function with an alcohol having at least Î0 carbon atoms. Further suitable comb polymers are copolymers of α-olefms and esterified comonomers, for example esterified copolymers of styrene and maleic anhydride or esterified copolymers of styrene and fumaric acid. Suitable' comb polymers may also he polyfumaraf.es or polymaleates. Homo- and copolymers of vinyl ethers .are also suitable comb polymers. Comb polymers suitable as components of dass (K2) are, for example, also those described in WO 2ÖÖ4/CJ3571S and in "Comb-Like Polymers, Structure and Properties”, N. A. Plate and V. P. Shihaev, 1. Poly, lei. Maerornoleeular Revs. 8, pages 117 to 253 (1974)”, Mixtures of comb polymers are also suitable. ïfolyoxyalkylenes suitable as components of eláss (KJ) are, for example, polyoxyatkylene esters, polyoxyalkyiene ethers, mixed polyoxyalkyiene ester/ethers {«id mixtures thereof. These polyoxyalkyiene compounds preferably comprise at least one linear alkyl group, preferably at least two linear alkyl groups, each having 10 to 30 carbon Moms and a polyoxyalkyiene group having a number-average molecular weight of up to 5000. Such polyoxyalkyiene compounds are described, for example, in EP-A 061 §95 and also in US 4,491,455. Particular polyoxyalkyiene compounds are based on polyethylene glycols and polypropylene glycols having a. number-average molecular weight of 100 to $000> Additionally suitable are polyoxyalkyiene mono- and diesters of fatty acids having 10 to 30 carbon atoms, such as Stearic acid or behenie acid.

Polar nitrogen compounds tótable as components of Class (K4) may be either ionic or 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 >NK ' in which K' is a CVto CiO'-bydrocarhon radical. The nitrogen substituents may also be quatemized, i.e, be in cationic form. An example of such nitrogen compounds is that of ammonium salts and/or amides which are obtainable by the reaction of at least one 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 €r to C^-alkyl radical. Primary amines suitable for preparing the polar nitrogen compounds mentioned are, for example, octylamine, nonylamine, decylamine, undecylamine. dodceylamine, tetradecylamine and the higher linear homologs. Secondary amines suitable for this : purpose are, for example, dioetadeeylamine and methylbehenylamine. Also suitable for this purpose are amine mixtures, in particular amine mixtures obtainable on the industrial scale, such as laity amines or hydrogenated tall amines, as described, for example, in Uilmarm’s Encyclopedia of Industrial Chemistry, 6th Edition, ’’Amines, aliphatic" chapter. Acids suitable for the reaction are, for example, eyc!ohexane-l,2-dicarboxyiie acid, cyciohexene-l,2-dicarboxyiie acid, eyclopentane-l,2-diearhoxylie acid, naphthalenedieatboxylte acid, phthalic acid, isophthalic acid, terephthalie add, and succinic adds-substituted by longwham hydroeatlmo radicals.

In particular, the component of class (K4) is an oil-soluble reaction product of polvfCy to C?.o-carboxylic acids) having at least one tertiary amino group with primary or secondary aminos, The poly(€y~ to (To-earhoxylie acids) which hay© at least one tertiary marine group and form the basis of this reaction product comprise preferably at least 3 carboxyl groups, especially 3 to 12 and in particular 3 to 5 carboxyl groups. The carboxylic acid units in the polycarboxylie acids have preferably 2 to 10 carbon atouts, and arc especially acetic acid units. The carboxylic acid units are suitably bonded to the polyearboxylic 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 nitrogen atoms, are bonded via hydrocarbon chains.

The component of class (K4> is preferably an oil-soluble react?cm product based on poIy(ü2~ to Cao-carboxyhc acids) which have at least one tertiary amino group and are of the general formula 11a or lib

(11a) (fib) in which the variable A is a straight-chain or branched <Y io C0-a!kylenC group or the moiety of the formula 111

(II) and the variable B is a CV to Cf<ralkylene group. The- compounds of the general formula© fia and Uh especially have the properties of a WAS A.

Moreover, the preferred oil-soluble reaction product of component (K.4), especially that of the general formula lia or Ob, is an amide, an amide-ammonium salt or an atnmonium salt in; which no, one or more carboxylic acid groups have been converted to araidé groups.

Straight -chain or branched Cy to Q-alkylene groups of the -variable A are, for example, 1,. 3 -ethylene, 1,2-propylene, 1,3-propylene, I „2-butylene, Î ,3-butyIeoe, 1,4-hntylene, 2-rnethyM ,3-propyleoe, 1,5-pentylene, 2«raethyW $4<hutyle»es '2»M«ôeifcÿh< 1,3-propylene, 1,6-hexylene (hexamethylene) and in. particular 1,2-ethylene, The variable A comprises preferably 2 to 4 and especially 2 or 3 carbon atoms. €r to C^mlkyleae groups of the variable B arc, for example, 1,2--eihyiene, 1 3-propyien©, 1,4-butylene, Iiexamethylene, oetameihylene, deeametbylene, dodecamethylenc, tetradecamethyiene, 1 wxadeeamothylene, oetadecamethyiene, nonadeearnethylene and especially methylene. The variable B comprises preferably 1 to 10 and especially ! to 4 carbon atoms.

The primary1 abd secondary amines as a reaction partner for the polyearhoxyiie acids to form component (K4) are typically monoamines, especially aliphatic monoamines. These primary and secondary amines may be selected from a multitude of amir,es which bear hydrocarbon radicals which may optionally be bonded to one another.

These purem amines of the oil-soluble reaction products of component (K4) are usually secondary amines and have the general formula HN(R*h hi which the two variables R* are each independently straight-chain or branched Cur to Cho-aikyi radicals, especially €h- to CSraikyi radicals. These relatively long-chain alkvi radicals are preferably stmight-chain or only slightly branched, In puerai, 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 Es radicals are preferably identical

The secondary amines mentioned may he bonded to the polyearboxylic 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 amide structures and another portion as ammonium salts. Preferably only few, if any, free acid groups arc present. The oihsoiuble reaction produois of component (K4) ate preferably present completely in the fenn of the amide structures.

Typical examples of such components (K.4) are reaction products of nifriiotriacetk acid, of cthylenediaminctetraacetie acid or of propylene-1,2-äiarainetetraaceiie acid with in each ease 0,5 to ! .5 mo! per carboxyl group, especially 0,8 to 1,2 mol per carboxyl group, of dioleylamme, dipalmtt.ina.minc, dicoconut fatty amine, distearylamme, dibehenylamine or especially dltallow fatty amine. A particuiafly preferred component (K4) is the reaction product of 1 mol of ethylenediaminetelxaaeetie acid and 4 mol of hydrogenated dltallow laity amine.

Further typical examples of component (K.4) include the N.N-dialkylammorbum salts of 2~N5,N,-dialky!amidobenK'oates, for example the reaction product of 1 mol of phthalic anhydride and 2 mol of ditallow fatty amine, the latter being hydrogenated or unhydrogenated, arid the reaction product of ! mol of an alkenylspirobislactonc with 2 mol of a dialkylamiae, for example dltallow fatty amine and/or tallow fatty amine, the last two being hydrogenated or unhydrogenated.

Further typical structure types lor the component of eláss (K4) are cyclic compounds with tertiary amino groups or condensates of long-chain primary or secondary amines with carboxylic acid-containing polymers, as described in WO 93/18115.

Sullbcarboxylic acids, sulfonic adds or derivatives thereof which are suitable m cold How improvers of class (KS) arc, for example, the oil -soluble carboxamides and carboxylic esters of ortho-sulfohenzoie aeid, in which the sulfonic acid function: is present as a sulfonate with alky!-substituted ammonium cations, as described in ΕΡ-Λ 261 957,

Polyfmeih)acrylie esters suitable as cold flow improvers of class (Kb) are either homo or copolymers of acrylic and methacrylic esters. Preference is given to copolymers of at least two different (meth)acryiie esters winch differ with regard to the esters.tied alcohol. The copolymer optionally comprises another different oldlnically 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 Cj4 and Ci5 alcohols, the acid groups having been neutralized with hydrogenated tallasoine. Suitable po!y(meth)acrylic esters arc described, for example, in WO-00/443:57,

The cold flow improver or the mixture of different cold flow improvers is added to the middle distillate feel or diesel fuel in a total amount of "preferably '10 to 5000 ppm by weight, more preferably of 20 to 2ÖCK) 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. E4) Lubricity improvers

Suitable lubricity improvers or friction modi fiers are based typically on felly acids or fatty acid esters. Typical examples are tall oil fatly acid, as described, for example, in WO 98/004656, and glyceryl monooleate. The reaction products, described in US 6 743 266 B2, of natural or synthetic oils, for example triglycerides, and alkanolamines are also suitable as such lubricity improvers. R5) Corrosion inhibitors

Suitable corrosion inhibitors are, for example, succinic esters, in particular with polyols, fatty acid derivative®, for example oleic esters, oligomerized fatty acids, substituted ethanolanunes, and products sold under the trade name RC 4801 (Rhein Chemie Mamtheim, Germany) or HiTEC 536 (Ethyl evaporation). B6) Demulsifiers

Suitable demulsifiers are, for example, the alkali metal or alkaline earth metal salts of alkyl-substituted phenol- and naphihalenesulfonaies and the alkali metal or alkaline earth metal salts of fatty acids, and also neutral compounds such m alcohol alkoxylat.es, e<g, alcohol ethoxylates, phenol alkoxylates, e,g. teit^hutylphénol ethoxylate or tert-pemvlphenol ethoxviate, fatty acids, alkylphenols, condensation products of ethylene oxide (BO) and propylene oxide (PO), for example includingm the form Of 3EQ/PÖ block copolymers, polyethylenelmiBes or else polysiloxanes, B7> Debaters

Suitable debaters are, for example, aikoxylated phenol Aonnaldehyde condensates, for example the products available under the trade names NALCO 7DÖ7 (Naieo) and TOLAD 2683 (PetrolUe). Ö8) Anti foams

Suitable antifoiuns are, for example, polyether-modifted polysiloxanes, for example the products available under the trade names TEGOPREN 3851 (Goldschmidt), Q 25907 (Dow Corning) and RHODOS II. (Rhone Poulenc). B9) Cetane number improvers

Suitable cetane number improvers are, for example, aliphatic nitrates such as 2~ethyíbexy1 nitrate and cyclohexyl nitrat© and peroxides such as di-tert-butyl peroxide. BIO) Antioxidants

Suitable antioxidants are, for example substituted phenols, such as 2,6-di-tert-butyl phenol, and b-di-teri-butyl-Bmiethyiphenol, and also phenylenediamines such as N,N'-di-seo4>utyl~p-pheny!enediamine, B11} Medal deactivators

Suitable metal deaetivators are, tor example, salicylic add derivatives such as N ,Ν'χΙΐΧΰΙίονΙίάδηη-1 iS-propanediatnine, B12) Solvents

Suitable solvents are, for example, nonpolar organic solvents such as aromatic and aliphatic hydrocarbons, for example toluene, xylenes, white spirit and products sold under the trade names SHELLSOL (Royal Duieh/Sbell Group) and EXXSÖL (Exxm5M0b.il), and also polar organic solvents, for example, alcohols such as 2-etiiylis.cxanoI, decanol and isotrideeanol. Such solvents are usually added to the diesel fuel together with the aforementioned additives and coadd hives, which they are intended to dissolve or dilute for better handling. C) Fuels

The inventive additive is outstandingly suitable as a fuel additive and can he Used in 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 quaternked additive in middle distillate fuels, especially diesel fuels.

The present invention therefore also provides fuels, especially middle distillate fuels, with a content of the inventive qaaterrtixed additive which is effective as an additive for achieving advantageous effects in the operation of intenta! combnstion engines, for example of diesel engines, especially of direct-injection diesel engines, hi particular of diese! engines with commonuail in]eetiôn systems. This effective content (dosage) is generally 10 to 5000'ppm· by weight, preferably 20 to 1500 ppm by weight, especially 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 feels or beating oils are preferably mineral oil raffinates which typically have a boiling range from 100 to 4(K)°C. These are usually distillates having a 95% point up to 360°C or even higher, These may also be so -called "ultra low sulfer diesel” Of ”eity diesel", characterized by a 95% point of, tor example, not more than 345°C and a sulfur content of not more than 0,0053¾ by weight or by a 95% point of, for example, 285CC and a suffer content of not more than (».00 ! % by weight. In addition to the mineral middle distillate feels or diesel feels obtainable by refining, those obtainable by coal gasification or gas liquefaction ["gas to liquid” (GTL) feels] or by biomass liquefaction fehiotoMs to liquid" (BTL) fuels] are also suitable. Also suitable are mixtures of the aforementioned middle distillate feels or diesel feels with renewable feels, such as biodiesel or bioethanol.

The qualities of the heating oils and diesel feds are laid down in detail, tor example, in DIM 51603 and EN 590 (of, also Ultra arm's Encyclopedia of Industrial Chemistry, 5th edition. Volume A12, p, 617 if).

In addition to the use thereof in (he ahovemeniioned middle distillate feels of fossil, vegetable or animal origin, which are essentially hydrocarbon mixtures, the inventive quatemized 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 feel" iti the context of the present invention. They are commercially available and usually comprise fee biofeel oils in minor amounts, typically in amounts of 1 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 oil.

Biofuel oils are generally based on fatty acid esters, preferably essentially on alkyl esters of fatty acids which derive from vegetable and/or animal oils and/or fats. Alkyl ©sters are typically understood to mean lower alky! esters, especially CytV 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 on vegetable and/or animal oils and/or fats, which lind use as a biofuel oil or components thereof, are, for example, sunflower methyl ester, paint oil methyl ester pPMB?i), soya oil methyl ester ("SME”) and especially rapèseed oil methyl ester CRME”),

The middle distillate fuels or diesel fuels are more preferably those having a low sulfur content f e, ha ving a sulfur erraient of less than 0,05% by weight, preferably of less than 0.-02% by weight,. more partieniafly of less than (),005% by weight and especially oil ess than 0.001% by weight of sulfur.

Useful gasoline fuels include ail. commercial gasoline fuel compositions. One typical representative which shall he mentioned here is the Ëurosuper 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 tor the present invention.

The inventive qnatemked additive is especially suitable as a fuel additive hi fuel compositions, especially in diesel fuels, for overcoming the problems outlined at the outset in directdnjcction diesel engines, in particular in .those with common-rail injection 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, hut are part of the general disclosure of the description and can be employed generally in the context of the present invention. A. General test, methods Engine tmt bl) XU:D9 test --- deterMination of flow restriction

The procedure was according to the standard stipulations of CEC F-23-OL b2) DW10 - keep dean test

To examine the influence of the inventive compounds on the pesfiofmattee of direct-injection diesel engines, fee power loss was determined on the basis of the official test method CEC F-098-08, The power loss is a direct 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 DW:lO) as in the CEC procedure are used.

Special features of the test used: a) Injectors in the tests, cleaned injectors were used. The cleaning time in an ultrasound bath in water at 60°C + 10% Superdecontamine (interseiences, Brussels) was 4 h, h) Test run times the test period was 12 h without shutdown phases. The one-hour test cycle (see table below) from CEC F-098-08 was run through 12 times.

* for range to be expected see CEC-098-08 ** target value e) Power determination

The initial power (¾ &amp;Ü [kW]) is calculated; from the measured torque at fell load 4000/min directly alter the test has started and the engine has wanned up. The procedure is described its Issue 5 of the test procedure CEC F-98-08. The same test setup and the PEUGEOT DW 10 engine type are used.

The final power (Ρ«*η KO) is detenníned in the 12th cycle in stage 12, (see table above). Here too, the operating point is full load 4000/mim ífem K.C (kW'l is calculated from the measured torque.

Tfee power loss io KC Is calculated as follows: power loss, KC [%] - (1 * Pmd,K€ / P0,KC) x 100

The fiel used was a commercial diesel fuel from H alien naun (RF~(K>-03). To synthetically induce the format ion of deposits ál the injectors, 1 ppm of zinc was added thereto in the form of a zinc neodeeapoate solution, B. Preparation examples:

Reactants used: PIES A: Prepared from maleic anhydride and ΡΪΒ 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 ROH/g were used. DMAPA was used with the particular PIBSA quality in a molar ratio of 1:1 according to the hydrolysis number. The PIBSA qualities used had feismaíeatiqa levels (BML) of less than 15%,

DMAPA: M - 102. IE methyl salicylate: M s: 152.14 dimethyl phthalate: M ~ 194,19 dimethyl oxalate: M:::: 118,09 dimethyl sulfate: M ~ 126.13 dimethyl carbonate M ~ 90.08

Preparation example 1: Synthesis of an Iitveative quaterntzed suecinlmMe (PIBSA/PMAPAAftaethÿl pfathalate)

Polyisobufylenesucehne anhydrides (1659 g) is dissolved in Solvent Naphtha Heavy (SNH, Exxon Mobil, ÇÂS64?42~9$:*$) (1220 g), and d'-dimcthylammo-l-propylatnine (DM APA; 153 g) is added. The reaction solution is stirred át Í?Ö°C for 8 h, in the course of which water of condensation formed is distilled off oonfinpqusíy. This affords the P1BSA-D.MAPA succiuimide as a solution in Sol vem Naphtha Heavy (TEN 0.557 raraol/g). A portion of this solution of the PÏBSA-DMAPA succinimide (181 g) is added to dimethyl phthalate (19.4 g), and the resulting reaction solution is stirred at 120°€ for Î1 h and then at 150:iC for 24 In After cooling to room temperáimé, the product obtained is the ammonium earhoxylaie as a solution In Solvent Naphtha Heavy, lH NMR analysis confirms the quaternixation.

Pi'eparatton example 2: Synthesis of an mvetttive quatenuxed succinimide ( PIBSA/ÖMAF A,'' m ethy I salicylate)

Polyisobutyienesuccinie anhydride (PIBSA; 2198 g) is heated to Î T0°C, and 3~ dimetiiylarnino-1-propylanùne (DMAPA; 182 g) is added within 40 min, hi the course of Which the reaction mixture heats up to 140°C The reaction mixture is heated to 170a€ and held at this temperature for 3 h, in the course of which 28 g of distillate are collected. This affords the PiBSA-DMAPÁ succinimide as a viscous oil (TEN 0, 735 mmol/g), A mixture of this P1BSA-DMAPÀ sueeinlmide (2,84,5 g), methyl salicylate (65.5 g) (i.e, about 2 equivalents of methyl salicylate per equivalent of tertiary amino group) and 3j,5“trimethyihepímtöie acid (from BASF) (0.75 g) is heated to 140-150° and the reaction mixture is stirred at this temperature for 6h, After cooling to room temperature, the product obtained is the ammonium salicylate as a viscous oil. H NMli analysis confirms the quaforaixation, By adding Pilot 900 oil, Pelrochem Cariess Ltd,, the active ingredient content of the solution is adjusted to 50% hy weight.

Preparailon example 3t Synthesis of m inventive qnmerufxed sncelnimide (PIES A/DMAPA/dlmcthyi oxalate)

Polyisohutylenesuecinle anhydride (PIBSA: 2198 g) is heated to IICPC, and 3-dlmethyiamino^l-propylamine (DMAPA; 182 g) is added within 4(1 mkv in the course of which the reaction mixture heats up to 140*C. The reaction mixture is heated to 1?0°C and held at this temperature tor 3 h, in thé course of which 28 g of di stillate are collected. This affords the PIÖSA-DMAPA succinimide as a viscous oil (TBN 0.735 mmoi/g). A mixture of this PIBSA-DMAPA succmimide (211 g), dimethyl oxalate ('34.5 g) and lanfic acid (43) g) is heated to 120"€ and then stirred at this temperature for 4h„ Excess dimethyl oxalate is removed on a rotary evaporator under reduced pressure (p ~ 5 mbar) at 120°€. The product obtained is the ammonium methyl oxalate as a viscous oil. SH NMR analysis confirms the quateraixatlom

For comparison with the prior art. Examples 2 and 4 from WO 20()4/135881 were worked up.

Preparation example 4? Synthesis of a known qaaternfeed sueelnimide (comparative example) (Example 2 írom WO 2000/135831 ) A solution of PISS A (420,2 g) in Pilot 900 oil, Petroehem Carless Ltd.. (51,3 g) is initially charged and heated to 11 (PC, 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°C and the mixture is then kept at this temperature for 3 h, 1» the course of which the water of reaction which forms is distilled off, After cooling to room temperature, the F1BBA-DMAPA succimmide is obtained as a solution in Pilot 900 oil (TBN 0.62 mmol/g). A portion of die PIBSA-DMAPA succinimide thus obtained as a solution in Pilot 90(1 oil, Petroehem Carless Ltd., (354 g) is initially charged and heated to 90°C. Dimethyl sulfate (26.3 g) is metered in, in the course of which foe reaction temperature rises to 112°C, Subsequently, the reaction mixture is stirred at 100' (; for 3 h. After coaling to room temperature, the quai enured PIBSA-PMÂPA succinimide is obtained as a solution in Pilot 900 oil. Ή NMR confhmed the quaternization. The output was adjusted to an active ingredient content of 50% by weight by adding Phot 900 oil.

Preparation example 5; Synthesis ef a known quate.rateed s»«ciaimiáe (comparative example) (Example 4 from WO 2006/135881 ) A solution of P1BSA (4.20.2 g) in Pilot 900 oil, Petroehem Carless Ltd., (31,3 g) is initially charged arid heated to I I0°C. DMA PA (31,4 g) is metered 1« within 30 minutes, in the course of which a slightly exothermic reaction is observed. Within 80 minutes, the reaction mixture is heated to 150°C and the mixture is then kept at this temperature for 3 h, in the course of which the water of reaction which forms is distilled 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, Petroehem Carless Ltd,, (130 g), dimethyl carbonate (20 g) and methanol (17,4) are charged into an autoclave and inetfixed with nitrogen, and a starting pressure of 13 bar is established. Subsequently, the reaction mixture is stirred under autogenous pressure first at 90*€ for 1 h, then at 14(EC for 24 h. Affér cooling to room temperature, the autoclave is decompressed and the contents are rinsed out completely with a little toluene as a solvent. All low-hoiling constituents are subsequently removed on a rotaiy evaporator under reduced pressure to obtain the quateruized PIBSA-DMAPA succinimide as a solution in Pilot 900 oil, *H NMR analysis confirmed the partial quatemization. The output is adjusted to art active ingredient content of 50% by weight by adding Pilot 900 oil, C< Use examples'

In the use examples which follow, the additives are used either m a pure substance (as synthesized in the above preparation, examples) or in the form of an additive package.

Ml : Additive according to preparation example 2 (inventive, quaternized with methyl salicylate) M2: Additive according to preparation ex&amp;tnpî$ 4 (comparative, tpuiiernized with dimethyl sulfate) M3: Additive according to·preparation example 5 (comparative, quatemized with dimethyl carbonate}

Use example U determination of the additive &amp;mlm m the forMatioa of deposits ist diesel engine Injeetloo nnzsdes a) XI'DO Tests

Fuel used: RF 4)6-03 (reference diesel, Habcnnanu Products, .Hamburg)

The results are compiled in table 1:

Table 1 : XUD9 tests

It was found that the inventive additive SV11, with the same dosage, has an improved effect compared to the prior art (M2, M3). b) DW10 test

To study the influence of the inventive compound m the performance of direct-injection diesel engines, the power loss was determined based on the official test method ÇBC F-09ÍM18 as described above. The power loss is a direct measure of formation of deposits in ilte Ipjectors, Â conventional direct-injection diesel engine with a common-rail system was used.

The fuel used was a commercial diesel foe! from Hal term ann (RF-06-03). To synthetically induce the formation of deposits at the injectors* 1 ppm by weight of zinc in the form of a mxt didodecanoate solution was added thereto.

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 P0 gives the power after 10 minutes and the value the power at the end of the measurement;

The test results are shown In table 2.

Table 2; Results of the DWÍÖ test

It was found that the inventive additive Ml has an improved effect compared to the base value and has an improved effect at least compared to example M3.

Use example 2 ; Betermlnation of the soiuhilrty properties

To determine the solubility properties, the following additive packages were produced and tested; M 4 (Inventive)

M S (comparative, dhnethyl sulfate)

M 6 (comparative, dimethyl carbonate)

Th» result of the solubility tests is compiled in the table below. The minimum amount of solvent (Solvent IN aphtha Heavy) needed to obtain a homogeneous* eiear diesel performance package at room temperature with otherwise identical amounts of active substance. Pilot 90(), amifoam and debater is reported.

Table 3; Determination of the solvent requirement

It was Ibund that, surprisingly, the additive according to preparation example 2 has the best solubility properties, i.e, requires the least solvent

Reference is made explicitly to the disclosure of the publications cited herein.

Claims (3)

KmtmmÆî nttragene glass for use as fuel and additives in fuels 'and lubricants' FREE SHEET ITEMS A fuel composition comprising, in most cases, a conventional fuel, a fraction of at least one reaction product comprising a quaternized nitrogen compound, or a partial fraction thereof containing a quaternized nitrogen compound, which is obtained from the reaction product by purification, where the reaction product can be prepared al. by reacting a hydrocarbyl-substituted polaric acid compound with a compound containing at least one polycarboxylic acid-reactive, particularly additive or condensable, oxygen or nitrogen group, and comprising at least one quaternizable amino group with a polycarboxylic acid having a quaternizable chlorocarbyl group; and a2) following this quatemization agent! converting the at least one quaternizing amino group into a quaternary amino group, wherein the quatemerisation agent is a cycloaromatic or cycloaliphatic mono- or polycarboxylic acid, in particular an alkyl ester of a mono- or dicarboxylic acid or an aliphatic polycarboxylic acid; or b) reacting a quaternizing chlorocarboxylated polycarboxylic acid compound containing at least one quaternizable amino group with a quaternizing wax that converts the at least one quaternizing amino group to a quaternary amino group, wherein the quatemerisation agent is a cycloaromatic or cycloaliphatic mono- or polycarboxylic acid; in particular, an alkyl ester of a mono- or dicarboxylic acid or an aliphatic polycarboxylic acid, wherein the quaternizable tertiary is about 1.140 equivalent to nitrogen. about 2.0 to about 1.25 equivalents to about 2.0 equivalents of quatemizer! is used: and / or the hydrocarbyl-substituted polycarboxylic acid compound is a polyisobutenyl succinic acid or an anhydride thereof, where it is based on the reaction product, in each case 2-20% by weight or 2-15% by weight of the hesine digestion cock. A fuel composition according to any one of the preceding claims, wherein the quaternizing agent is a compound of the general formula R 1, C (O) R 2 (1) wherein R 1 is a lower alkyl group and R 2 is an optionally substituted monocyclic aryl or cycloalkyl wherein the substituent is selected from the group consisting of ÖH, NHg, NDg * C (O) 0R3 and RiOC (O), wherein R1 is as defined above, and R * * is H or Rj, 3 »The fuel according to one of the preceding claims Composition, wherein the quaternizing agent is a compound of the formula R0C (O) -AG (O) DRia (2), wherein R1 and Ris are independently selected from the group consisting of a lower alkyl group and a tetrahydrocarbylene; The fuel composition according to any one of the preceding claims, wherein the number-weighted molecular weight of the quaternized nitrogen compound is in the range 500-5000, 000-3000, or 900-1500. Hydrocarbylene. 5v Fuel composition according to one of the preceding claims, wherein the quaternizing agent is. selected from the group consisting of alkyl-terminals, d1a-α1-ions and diaicyl-oxalates. i. The fuel composition of claim 1, wherein the compound reactive with the polycarbonic acid, in particular additive or condensable, comprises an oxygen or nitrogen group and at least one quaternizable amino group is a) the at least one quaternizable, primary, secondary or tertiary amino group bridged hydroxyalkyl-substituted mono- or polyamines h) straight or branched chain radicals having at least one primary or cortical amino group and at least one quaternizable, primary, secondary or tertiary amino group, such as polysaccharides, heterocyclic, aromatic or non-aromatic polyamines. the fuel composition according to claim 6, wherein the polycarboxylic acid reactive, in particular adductive or condensable, oxygen or nitrogen group and at least brain quaternizable amine group compound is a) the hydroxyalkyl substituted primary, secondary or tertiary monoamnins and hyphenates-coupled primary, secondary or tertiary diamines b) straight or branched aliphatic diamines having two primary amine groups: dk 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 tertiary amino group: aromatic carbocyclic diamines having two primary amino groups; aromatic heterocyclic polyimides having two primary amino groups; it is selected from aromatic or non-aromatic heterocycles having one primary and one tertiary amino group. A fuel composition according to any one of the preceding claims, selected from Diesel fuels, Biodesel fuels, Otto fuel oils, and Otto-fueled Otto fuels, $ k One of the reaction products produced by the process as defined in one of the preceding claims, or a quaternized nitrogen compound obtained from the reaction product; or a quaternizable nitrogen compound produced by a process comprising reacting a quaternizable hydrocarbyl substituted polycarboxylic acid compound of at least one tertiary quaternizable amino group with a quaternizing agent to convert the at least one tertiary amino group to a quaternary ammonium moiety. wherein the quaternizing agent is a cycloornoric or cycloaliphatic mono- or polycarboxylic acid, especially an alkyl ester of a mono- or dicarboxylic acid or an aliphatic polycarboxylic acid; and wherein the quaternizable tertiary nitrogen is equivalent to 1.1 to about 2.0 or about 1.25 to the equivalent of nitrogen. an equivalent quaternizer of about 2; Use as a fuel additive, 10, The use according to claim 9 as an additive for reducing the fuel consumption of Diesel engines with direct injection or Diesel engines with a common rail injection system and / or direct injection diesel engines or common rail. to minimize the power loss of diesel engines with an injection system. 11- Use according to claim 9 for supplying Otio Fuel Sulfur Sulfur, a Ottomotor or DISI (Direct Injection Spark Ignition) and PFI (port fuel injection) motors! to reduce deposits in your system. 12L Use according to claim 9 as a diesel fuel adjuvant cold wax antisettling additive (WASA) or injection system deposition, internal diesel injector deposits (I DID) and / or direct injection. Injection Diesel Motorbike or common-rail injection systems for reducing and / or preventing valve jams.