AU2012277805C1 - Quaternized nitrogen compounds and use thereof as additives in fuels and lubricants - Google Patents

Abstract

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

Description

I

Quaternized nitrogen compounds and use thereof as additives In fuels and lubricants

The present invention relates to novel quatemized nitrogen compounds, to the preparation thereof and to the use thereof as a fuel and lubricant additive, more particularly as a detergent additive, to additive packages which comprise these compounds; and to fuels and lubricants thus additized. The presentinvention further relates to the use of these quaternized nitrogen compounds as a fuel additive for reducing or preventing deposits in the injection systems of direct-Injection diesel engines, especially in common-raiinjection 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 dies engines, especialy in diesel engines with common-raillinjection systems,

State of the art

in direct-injection diesel engines, the fuel is injected and distributed ultrafinely (nebulized) by a multihole injection nozzle which reaches directly into the combustion chamber of the engine, instead of being introduced into a prechamber or swir chamber as in the case of the conventional (chamber) diesel engine. The advantage of the direct-injection dieselengines lies in their high performance for diesel engines and nevertheless low fuel consumption. Moreover, these engines achieve a very high torque even at low speeds.

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

In the common-rail system, the diesel fuel is conveyed by a pump with pressures up to 2000 bar into a high-pressure line, the common rail. Proceeding from the common rail, branch lines run to the different injectors which inject the fuel directly into the combustion chamber. The ful pressure is always applied to the common rail, which enables multiple injection or a specific injection form, In the other injection systems, in contrast, only smaller variation in the injection is possible. The injection in the common

M/51320-PCT railisdivided essentially into three groups; (1, }pre-injection, by which essentially softer combustion is achieved, such that harsh combustion noises ("nailing") are reduced and theengineseemstorunquietly;(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, but instead evaporated by residual heat in the cylinder. The exhaust gas/fuel mixture formedistransportedtothe exhaust gas system, where the fuel, in the presence of suitable catalysts, acts as a reducing agent for the nitrogen oxides NO.

The variable, cyinder-individual'injection in the common-rail injection system can positively influence the pollutant emission of the engine, for example the emission of nitrogen oxides (NO,), carbon monoxide (O) and especially of particuiates (soot). This makes it possible, for example, that engines equipped with common-rali ejection particulate systems can meet the Euro 4 standard theoretically even without additional filters,

In modern common-rail diesel engines, under particular conditions, for example when biodiese-contaning 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, ,e, especially reduce the power, but in some cases also worsen the combustion. The formation of deposits is enhanced further by further developments in the injector construction, especially by the changein the geometry of the nozzles (narrower, conical orifices with rounded outlet). For lasting optimal functioning ofengine and injectors, such deposits in the nozzle orifices must be prevented or reduced by suitable fuel dditives,

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 inetor tip, in contrast, impair the optimal formation of fuel spray mist and, as a result, cause worsened combustion and associated higher emissions and increased fuel consumption. In contrast to these conventional "extemal' deposition phenomena, intemar deposits (referred to collectively as internal diesel injector deposits (DID)) in

M/51320-PCT particular parts of the injectors, such as at the nozzle needIe, at the control piston, at the valve piston, at the valve seat, in the control unit and in the guides of these components, also increasingly cause performance problems, Conventional additives exhibit inadequate action againstthese DIDs.

US 4,248,719 describes quatemized ammonium salts which arepreparedby reacting an alkenylsuccinimide with a monocarboxyic ester and find use as dispersants in lubricant oils for prevention of sludge formation, More particularly, for example, the reaction of polyisobutysuccinic anhydride (PIBSA) with NN-dimethylamnopropylaine (DMAPA) and quaternization with methyl salicyate is described. However, use in fuels, more particularly diesel fues, is not proposed therein. The use of PIBSA with low bismaleation levels of < 20% is not described therein.

US 4,171,959 describes quaternized arnmonium salts of hydrocarbyl-substituted succinimides, which are suitable as detergent additives for gasoline fuelcompositions. For quaternization, preference is given to using alkyl halides, Also mentioned are organic C-Chydrocarby carboxylates and suifonates. Consequently, the quaternized ammonium salts provided according to the teaching therein have, as a counterion, either a halide or a Cr-Chydrocarbyl carboxylate or a CrCrhydrocarbyl sufonate group, The use of PBSA with low bismaieation levels of < 20% is likewise not described therein

EP-A-2033 945 discloses cold flow improvers which are prepared by quaternizing specific tertiary monoamines bearing at least one C-04 -alkyi radical with a CC4-alkyl ester of specific carboxylic acids, Examples of such carboxylic esters are dimethyl oxalate, dimethyl maleate, dimethyl phthalate and dimethyl fumarate. Applications other than that of improving the CFPP value of middle distillates are not demonstrated in EP-A-2 033 945.

WO 2006/135881 describes quaternized ammonium saltsprepared by condensation of a hydrocarbyl-substituted acylating agent and of an oxygen or nitrogen atom-containing compound with a tertiary amino group, and subsequent quatemization by means of hydrocarbyl epoxide in the presence of stoichiometric amounts of an acid, especialy acetic acid. Further quaternizing agents claimed in WO 2006135881 are diakyl

M/51320-PCT sulfates, benzyl halides and hydrocarbyl-substituted carbonates, and dimethyl sulfate, benzyl chloride and dimethyl carbonate have been studied experimentally.

The quaternizing agents used with preference in WO 2006/135881, however, have serious disadvantages such as: toxicity or carcinogenicity (for example in the case of dimethyl sulfate and alkylene 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 quaternization or uneconomic reaction conditions (long reaction times, high reaction temperatures, excess of quaternizing agent; for example in the case of dimethyl carbonate).

Advantageously, the present invention may provide improved quaternized fuel additives, especially based on hydrocarbyl-substituted polycarboxylic acid compounds, which no longer have the disadvantages of the prior art mentioned.

Brief description of the invention:

The invention provides specific quaternized nitrogen compounds and fuel and lubricant compositions additized therewith.

Surprisingly, the inventive additives thus prepared are superior in several ways to the prior art additives prepared in a conventional manner: they have low toxicity (caused by the specific selection of the quaternizing agent, burn ashlessly, 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 regard to prevention of deposits in diesel engines, as especially illustrated by the use examples appended.

Detailed description of the invention:

A1) Specific embodiments

The present invention generally relates to the following embodiments:

8105639_1 (GHMatters) P95787.AU

1. A fuel or lubricant composition, especially fuel composition, comprising, in a majority of a customary fuel or lubricant, a proportion (especially an effective amount) of at least one reaction product comprising a quaternized nitrogen compound (or a fraction thereof which comprises a quaternized nitrogen compound and is obtained from the reaction product by purification), said reaction product being obtainable by a. reacting a high molecular weight hydrocarbyl-substituted polycarboxylic acid compound with a compound comprising at least one oxygen or nitrogen group reactive (especially capable of addition or condensation) with the polycarboxylic acid, and comprising at least one quaternizable amino group, to obtain a quaternizable hydrocarbyl-substituted polycarboxylic acid compound (by addition or condensation), and b. subsequent reaction thereof with a quaternizing agent which converts the at least one hereafter quaternizable, for example tertiary, amino group to a quaternary ammonium group, said quaternizing agent being the alkyl ester of a cycloaromatic or cycloaliphatic mono- or polycarboxylic acid (especially of a mono- or dicarboxylic acid) or of an aliphatic polycarboxylic acid (especiallydicarboxylic acid).

2. A fuel or lubricant composition, especially fuel composition, comprising, in a majority of a customary fuel or lubricant, a proportion (especially an effective amount) of at least one reaction product comprising a quaternized nitrogen compound (or a fraction thereof which comprises a quaternized nitrogen compound and is obtained from the reaction product by purification), said reaction product being obtainable by reacting a quaternizable high molecular weight hydrocarbyl-substituted polycarboxylic 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,

8105639_1 (GHMatters) P95787.AU said quaternizing agent being thealky ester of a cycloaromatcorcycloaliphaticmono or polycarboxyic acid especiallyy ofa mono- or dicarboxylic acid) or of an alphatic polycarboxylic acid (especially dicarboxylic acid).

3. The fuel composition according to either of the preceding claims, wherein about 1.1 to about 2.0 or about 1.25 to about 2.0 equivalents, for example 13, 1.4, 15, 1.6, 1,7, 1.8 or 1.9 equivalents, of quaternizing agent are used per equivalent of quaterizable tertiary nitrogen atom. By increasing the proportion of quaternizing agent within the range claimed, distinct improvements in product yields can be achieved,

4. The fuel composition according to any of the preceding claims, wherein the hydrocarby-substituted polycarboxylic acid compound is a polyisobutenylsuccinic acid or an anhydride thereof, said acid having a bismaleation level of equal to or less than about 20% or equal to or less than about 15%, for example 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1 or 0,1%,

Lower levels ofbismaleation can contributeto a distinct improvement in the solubility of the additive and/or compatibility of the constituents in the formulation of additive packages.

5. The fuel or lubricant composition, especially fuel composition, according to any of the preceding embodiments, wherein the quaternizing agent is a compound of the general formula 1

R 1 0C(O)R 2 (1)

in which R, is a low molecular weight hydrocarbyl radical, such as alky or akenyl radical, especialy a lower alkyl radical, such as especially methyl or ethyl, and R2 is an optionally substituted monocyclic hydrocarbyl radical, especially an aryl or cycloalkyl or cycloalkenyl radical ,especially aryl such as phenyl where the substituent is selected from OH, NH2 , NO2 , C(O)OR& and ROC(O), in which R 1 is as defined aboveand R9 is H or Ri where the substituent is especially OH. More particularly, the quaternizing agent is a phthalate or a salicylate, such as dimethyl phthalate ormethyl salicylate.

M/51320-PCT

6. The fuel orkubdcant composition, especially fuel composition, according to any of the preceding embodiments, wherein the quaternizing agent is a compound of the general formula 2

RiOC(O)-A-C(O)OR. (2)

in which R, and R, are each independently a low molecular weight hydrocarbyl radical, such as an alkyl or alkenyl radical, especially alower alkyl radical and A is hydrocarbylene (such as especially C-C7-alkyene or CrC7-alkenyene).

7. The fuel or lubricant composition, especially fuel composition, according to any of the preceding embodiments, wherein the quaternized nitrogen compound has a number-average molecular weight in the range from 400 to 5000, especially 800 to 3000 or 900 to 1500,

8. The fuel or lubrcant composition, especially fuel composition, according to any of the preceding embodiments, wherein the quaternizing agent is selected from alkyl salicylates, dialkyl phthalates and dialkyl oxalates; particular mention should be made ofalkyl salicylates, especially lower alkyl salicylates, such as methyl, ethyl and n propyl saicyiates,

9- The fuel or lubricant composition, especially fuel composition, according to embodiment 1, wherein the compound which is reactive (capable of addition or condensation) with the polycarboxylic acid and comprises an oxygen or nitrogen group and at least one quaternizabie amino group is selected from a. hydroxyaikyi-substituted mono- or polyamines having at least one quaternizable primary, secondary or tertiary amino group; b. straight-chain or branched, cyclic, heterocyclic, aromatic or nonaromatic polyamines having at east one primary or secondary amino group and having at least one quaternizable primary, secondary or tertiary amino group; c, piperazines, and particular mention should be made of group a.

M/51320-PCT a

10. The fuel or lubricant composition according to embodiment 9, wherein the compound which is reactive, especially capable of addition or condensation, with the polycarboxylicacid and comprises an oxygen or nitrogen group and at least one quaternizable amino group is selected from a. hydroxyalkyl-substituted primary, secondary or tertiary monoamines and hydroxyalkylsubstituted primary, secondary or tertiary diamines, b. straight-chain or branched aliphatic diamines having two primary amino groups; di- or polyamines having at least one primary and at least one secondary amino group; di- or polyamines having at least one primary and at least one tertiary amino group; aromatic carbocyclic diamines having two primary amino groups; aromatic heterocyclic polyamines having two primary amino groups; aromatic or nonaromatic heterocycles having one primary and one tertiary amino group; and particular mention should be made ofgroup a.

11. The fue' composition according to any of the preceding embodiments, selected from diesel fuels, biodiesel fuels, gasoline fuels and alkanoi-containing gasoline fuels

12. The fusi or lubricant composition, especially fuel composition, according to anyofthe preceding embodiments, wherein the hydrocarby-substituted polycarboxylic acid compound is a polyisobutenylsuccinic acid or an anhydride (PBSA) thereof, said acid having a low bismaleation level, especially 10% or less than 10%, for example 2 to 9 or 3 to 7%. More particularly, such PIBSAs are derived from HR-PIB with an Mn in the range from about 400 to 3000.

More particularly, the above compositions are fuel compositions, in particular diesel fuels,

13. The reaction product obtainable by a processas defined in any of the preceding embodiments, especially according to embodiment 3, 4, 5, 6 and in particular embodiment 8, 9 or 10, or quaernized nitrogen compound obtained from the reaction product by partial or full purification.

M/51320-PCT in a particular configuration (A) of the invention, quaternized reaction products which are prepared proceeding from polyisobutenylsuccinicacid or an anhydride thereof are provided, this compound having a bismaeaton levelof equal to or less than about 20% or equal to or less than about 15%, for example 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, or 0.1%, This polyisobutenyisuccinic acid compound is reacted (especially by addition or condensation) with a compound comprising at least one oxygen ornitrogen group reactive (addable or condensable) with the polyisobutenysuccinic acid compound and containing at least one quaternizable amino group, and then quaternized.

In a particular configuration (B) of theinvention, quatemized reaction products which are obtained by quaternization using an excess of quaternizing agent are provided. More particularly, about 1. 1 to about 2.0 or about 1.25 to about 2.0 equivalents, for example 13, 1,4A 1.5, 1.6, 1.7, 1.8 or 1.9, equivalents of quaternizing agent are used per equivalentof quatemizable tertiary nitrogen atoms. Particularly useful quaten[zing agents are those of the formula (1), especially the lower alkyl esters of saicylic acid, such as methyl salicylate, ethyl salicylate, n and i-propyl salicylate, and n I- or tert butyl salicylate.

In a further particular configuration (C), configurations (A) and (B) are combined, i,e. the quaternizable compounds prepared from the above polyisobutenylsuccinic acid compounds according to configuration (A) are quaternized according to configuration (B).

14. A process for preparing a quaternized nitrogen compound according to embodiment 13, comprising the reaction ofa quaternizable hydrocarbysubstituted polycarboxylic acid compound compising at least one tertiary quaternizable amino group with a quaternizing agent which converts the at least one tertiary amino group to a quaternary ammonium group, said quaternizing agent being the alkyl esterof a cycloaromatic or cycoaliphatic mono or polycarboxylic acid (especially of a rnono- or dicarboxylic acid) or of an alphatic polycarboxylic acid (especially dicarboxylic acid),

M/51320-PCT

15. The use of a reaction product or of a quaternized nitrogen compound according to embodiment 13 or of a compound prepared according to embodiment 14 as a fuel additive or lubricant additive, especially fuel additive, especially diesel fuel additive.

16. The use according to embodiment 15 as an additive for reducing the fuel consumption of direct-injection diesel engines, especially of diesel engines with common-rail injection systems, as determined, for example, in an XUD9 test to CEC-F 23-01, and/or for minimizing power loss in direct-injection diesel engines, especially in diesel engines with common-rail injection systems, as determined, for example, in a DW10 test based on CEC-F-098-08.

17. The use according to embodiment 15 as a gasoline fuel additive for reducing the level of deposits in the intake system of a gasoline engine, such as especially DISI (direct injection spark ignition) and PFI (port fuel injector) engines.

18. The use according to embodiment 15 as a diesel fuel additive, especially as a cold flow improver, as a wax antisettling additive (WASA) or as an additive for reducing the level of and/or preventing deposits in the intake systems, such as especially the internal diesel injector deposits (IDIDs), and/or valve sticking in direct-injection diesel engines, especially in common-rail injection systems.

19. An additive concentrate comprising, in combination with further diesel fuel or gasoline fuel additives, especially diesel fuel additives, at least one quaternized nitrogen compound as defined in embodiment 13 or prepared according to embodiment 14.

In particular, in one embodiment, the invention provides a fuel composition comprising, in a majority of a customary fuel, a proportion of at least one reaction product comprising a quaternized nitrogen compound, or a fraction thereof which comprises a quaternized nitrogen compound and is obtained from the reaction product by purification, said reaction product being obtainable by al) reacting a hydrocarbyl-substituted polycarboxylic acid compound with a compound comprising at least one oxygen or nitrogen group reactive, with the polycarboxylic acid, and comprising at least one quaternizable amino

8105639_1 (GHMatters) P95787.AU

10a

group, to obtain a quaternizable hydrocarbyl-substituted polycarboxylic acid compound, and a2) subsequent reaction thereof with a quaternizing agent which converts the at least one quaternizable amino group to a quaternary ammonium group, said quaternizing agent being the alkyl ester of a cycloaromatic or cycloaliphatic mono- or polycarboxylic acid, or of an aliphatic polycarboxylic acid; or

b) reacting a quaternizable hydrocarbyl-substituted polycarboxylic acid compound comprising at least one quaternizable amino group with a quaternizing agent which converts the at least one quaternizable amino group to a quaternary ammonium group, said quaternizing agent being the alkyl ester of a cycloaromatic or cycloaliphatic mono- or polycarboxylic acid, or of an aliphatic polycarboxylic acid

wherein about 1.1 to about 2.0 equivalents of quaternizing agent are used per equivalent of quaternizable tertiary nitrogen atom; and/or

the hydrocarbyl-substituted polycarboxylic acid compound is a polyisobutenylsuccinic acid or an anhydride thereof, said acid having a bismaleation level of 2 to 20% by weight, based in each case on the reaction product.

In another embodiment, the invention provides the use of a reaction product obtainable by a process of the invention or of a quaternized nitrogen compound obtained from the reaction product; or of a quaternized nitrogen compound prepared by a process comprising the reaction of a quaternizable hydrocarbyl-substituted polycarboxylic acid compound comprising at least one tertiary quaternizable amino group with a quaternizing agent which converts the at least one tertiary amino group to a quaternary ammonium group, said quaternizing agent being the alkyl ester of a cycloaromatic or cycloaliphatic mono- or polycarboxylic acid or of an aliphatic polycarboxylic acid; as a fuel additive, and wherein about 1.1 to about 2.0 equivalents of quaternizing agent are used per equivalent of quaternizable tertiary nitrogen atom.

8105639_1 (GHMatters) P95787.AU

1Ob

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 relatively small molecule, especially of a water molecule. When such an elimination is not detectable analytically, more particularly not detectable in stoichiometric amounts, and the two molecules react

8105639_1 (GHMatters) P95787.AU nevertheless, for example with addition, the reaction in question of the two molecules is "without condensation".

In the absence ofstatements to the ontrary the following general conditions apply:

"Hydrcarby ' can be interpreted widely and comprises both long-chain and short chain, straight-chain and branched hydrocarbon radicals, which may optionally additionally comprise heteroatoms, for example 0, N, NH, S, in the chain thereof.

"Long-chain" or "high molecular weight' hydrocarbyl radicals have a number-average molecular weight (M) of 85 to 20 000, for example 113 to 10 000, or 200 to 10 000 or 350 to 5000, for example 350 to 3000, 500 to 2500, 700 to 2500, or 800 to 1500. More particularly, they are formed essentially from especially C, monomer units such as ethylene, propylene, n- or isobutylene or mixtures thereof, where the different monomers may be copolymerized in random distribution or as blocks. Such long-chain hydrocarbyl radicals are also referred to as polyakylene radicals or poly-C or poly C2 4-alkylene radicals. Suitable long-chain hydrocarbyl radicals and the preparation thereof are also described, for example, in WO2006/135881 and the literature cited therein.

Examples of particularly useful poiyakylene radicals are polyisobutenyi radicals derived from "high-reactivity" polyisobutenes (HR-PIB) which are notable for a high content of terminal double bonds (cf, for example, also Rath et al, Lubrication Science (1999), 1IH2, 175-185). Terminal double bonds are alpha-olefinic double bonds of the type

Polymer

which are also referred to collectively as vinylidene double bonds. Suitable high reactivity polyisobutenes are, for example, polyisobutenes which have a proportion of vinyidene double bonds of greater than 70 mol%, especially greater than 80 mol% or greater than 85 mol%. Preference is given especially to polyisobutenes which have homogeneous polymer structures, Homogeneous polymer structures are possessed

M/51320-PCT 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 atleast 95%by weight Such high-reactivity polyisobutenes preferably have a number-average molecular weight within the abovementioned range. in addition, the high-reactivity polysobutenesmay have a polydispersity in the range from 105 to 7, especially of about 11 to 2.5, for example of less than 1.9 or less than 1.5. Polydispersity is understood to mean the quotient of weight-average molecular weight Mw divided by the number-average molecular weight Mn.

Particularly suitable high-reactivity polyisobutenes are, for example, the Glissopal brands from BASF SE, espeialy Gissopal 1000 (Mn =1000), Giissopail V33 (Mn = 550), GlissopaP 1300 (Mn = 1300) and Giissopal 2300 (Mn = 2300), and mixtures thereof. Other number-average molecular weights can be established in a manner known in principle by mixing polysobutenes of different number-average molecular weights or by extractive enrichment of polyisobutenes of particular molecular weightranges,

PIBSA is prepared in a manner known in principle by reacting PIB wth malec anhydride (MAA), in principle forming a rmxture of PIBSA and bismaleated PIBSA (BM PIBSAf.scheme 1, below,which is generally not separated but used as such in further reactions. The ratio of the two components to one another can be reported via the "b1 smaleation lever (BML). The BML is known per se (see also US 5,883,196). The BML can also be determined by the following formula:

BML = 100% x (wt-%(BM PSSA))/(wt-%(BM PIBSA)+wt-%(PIBSA))

where wt-% (X) represents the proportion by weight of component X (X = PIBSA or BM PIBSA) in the reaction product of PIwith MSA,

Scheme I

N/51320-PCT

P 0 +N

PIB MSA PIBSA BM PBSA

Hydrocarbyisubstituted polycarboxylicacid compound with a "low bismaleation level" especially corresponding polysobutenylsuccinic acids or anhydrides thereof (also referred to overall as PIBSA) are known from the prior art. Especially advantageous are bismaleation levels of 20% or less, or 15% or less, for example 14, 13, 12 or 10%; or 10% or less, for example 2-9, 3-8, 4-7, 5 or 6%, The controlled preparation thereof is described, for example, in US 5,883,196. Suitable for preparation Thereof are especially the above high-reactivity polyisobutenes with anMn in the range from about 500 to 2500, for example 550 to 3000, 1000 to 2000 or 1000 to 1500

A nonlimiting example of a corresponding PIBSA is Glissopal* SA, derived from HR-PiB (Mn = 1000), with a bismaleation level of 9%.

"Short-chain hydrocarbyl" or "low molecular weight hydrocarbyl" is especially straight chain or branched alkyl or alkenyl, optionally interrupted by one or more, for example 2, 3 or 4heteroatom groups such as -- or -NH-, or optionally mono- or polysubstituted, for example di-, tri- or tetrasubstituted.

"AlkyP or "lower alkyl" represents especially saturated, straight-chain or branched hydrocarbon radicals having 1 to 4, 1 to 6, 1 to 8, or 1 to 10 or 1 to 20, carbon atoms, for example methyl, ethyl, n-propy, 1-methylethyl, n-butyl, 1-methypropy. 2 methylpropy,1i-dimethylethyi n-pentyti 1-methylbutyl, 2-methybutyt 3-methybutyl, 2,2-dimethylpropyl i-ethylpropyl, n-hexyl,1,1-dimethylpropyl 1,2-dimethylpropyl, 1 methylpentyl 2-rnethylpentyl, 3-methylpentyi 4-methylpentyl 1,1-dimethybuty, 1,2 dimethylbutyl,1,3-dimethylbutyl,2,2-dimethylbutyl,2,3-dirnethylbutyi,3,3-direthylbutyl, 1-ethybuty, 2-ethylbuty, 1,1,2-trimethylpropy, -1,2,2-trimethylpropy. 1-ethyl-I methylpropyl and 1-ethyl-2-methylpropyl; and also n-heptyi, n-octyl, n-nonyl and n decyl, and the singly ormultiply branched analogs thereof.

M/51320-PCT

"HydroxyalkyP represents especially the mono- or polyhydoxylated, especially monohydroxyrated, analogs of the above akyl radicals, for example the monohydroxylated anaogs of the above straight-chain or branched alkyl radcals, for 5 examplethe linear hydroxyakyl groups with aprimaryhydroxyl group, such as hydroxymethylt2-hydroxyethy 3-hydroxypropyl 4 -hydroxybutyt

"Alkeny" represents mono- or poyunsaturated, especially monounsaturated, straeght chain or branched hydrocarbon radicals having 2 to 4, 2 to 6, 2 to 8, 2 to 10 or.2 or to 10 20 carbon atoms and a double bond in any position, for example C2-Ce-afkeny such as ethenyl, 1-propenyt 2-propeny, 1-methylethenyr 1-buteny, 2-butenyl 3-butenyl, 1 methy-1-propeny, 2-methyl-1-propeny, 1-methyl-2-propenyl, 2-methy2-propeny 1 penteny, 2-penteny!, 3-pentenyt4-pentenyl, 1-methy-Ibutenyl, 2-methy.1-butenyl 3 methykl-butenyl, 1-rnethyl-2-butenyl, 2-methyk2-buteny 3-methy-2-butenyl, 1-methyl 15 3-butenyi, 2 -methyk3-buteny 3 -methyl-3-butenyl, 11-dimethyl-2-propeny 1,2 dimethy1--propenyw 1,2-ditethyl2-propenyi1-ethyl-i-propenyf, 1-ethyk2-propenyl, I hexenyl, 2-hexeny 3-hexeny, 4-hexenyt 5-hexenyt 1-methyl-1-pentenyl, 2-methyl-1 pentenyi, 3-methy--i-pentenyl 4-rnethyl-I-pentenyl, 1-methy-2-penteny, 2-methyl2 pentenyl, 3-methy-2-penteny 4 -methyl-2-pentenyl -methyl-3-penteny, 2-methy4l pentenyl 3-methyI-Spenteny 4-rnethy-3-penteny -methyl4-penteny 2-methy-4 pentenyl, 3-methy-4-pentenyi, 4-methy14-pentenyl, 1,1-dimethyi-2-butenyt 1,1-dimethyk3-butenyr 1,2-dimethyk1-buteny. 1,2-dimethy2-butenyl, ,2-dimethy-s3 butenyt 1,3-dimethyl-1-buteny, I.3-dimethyl-2-buteny% 1,3-dimethyl-3-butenyl, 2,2 dimethy'3-buteny', 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-buteny, 2,3-dimethy-3 butenyl 3,3-dimethyl- n 3-butenylbuteny 1-ethyl-1-butenyl, I-ethyk2 butenyl, 1-ethyl-3-butenyt 2-ethyi-l-butenyl, 2-ethy-2-butenyl, 2 -ethyi-3-butenyl 1,1,2 trimethyl-2-propeny 1-ethyl-m-rethyl-2-oropenyl, 1-ethyl-2-methy-I-propenyl and I-ethyl-2-methyl-2-propenyt

"Alkylene" representsstraight-chain or mono- or polybranched hydrocarbon bridge groups having I to 10carbon atoms, for example C--alkylene groups selectedfrom -CH 2- -(CH2) 2-,~(CH) -CH-CH(C-))-, CH - , (CH 2) 4 - -(CH2) 2-CH(CH 3 3 -C(0H -CH2-CH(CH 3 )-CH, (CH2 )n--(CH2), -(CH )r -(CH2)-,-CH(CH3)-CH-CHrCH(CH)~ )

2 or -CH(CH)-CH-CHrCHrCH(CH) or CCpakyene groups selected f.rom -

M/51320-PCT

(CH2-, -(CH2h, -CHrCH(CH3), ~CH(CH)-CHr, -(CH 2) 4 -, -(CH 2 $)CH(CH),-CH CH(CH 3)-CHt.

"Akenylene" representsthe mono- or polyunsaturated, especially monounsaturated, analogs of the above alkylene groups having 2 to 10 carbon atoms, especially C2C7 alkenyenes or O - C,-akenylenes, such as -CH=CH, -CH=CH-CH), -CHrCH=CH-, -CH=CH-CH-2CHr2, -CH 2-CH=CH-CH2-, -CHCH2-0HzCH-, -CH(CH)-CH=CH-, -CH 2 -C(CH,)=CH-.

"Cycic hydrocarbyl radicals" comprise especially: - cycloalkyl: carbocycic radicals having 3 to 20 carbon atoms, for example C-C cycloalkyl such as cyclopropyt cyclobutyl, cyclopenty, cydlohexyl, cycloheptyl, cyclooctyl,dcyconony cyclodecyl,cycloundecyl and cyclododecyl; preference is given to cyclopenty, cycohexyl cycloheptyt and also to cyclopropylmethyi, cydopropylethyl, cyclobutylmethyi, cyclobutylethyl, cyclopentylmethyl, cycliopentylethy], cyclohexymethyl, or C 3 -Ccycoalkyl such as cyclopropyl, cyclobuty cyclopentyl, cydohexyl, cycloheptyl, cyclopropylmethy, cyclopropylethyl, cyclobutylmethyl, cyclopentylethyl, cyclohexylmethyl, where the bond to the rest of the molecule may be via any suitable carbon atom. - cycloalkenyl: monocycic, monounsaturated hydrocarbon groups having 5 to 8, preferably up to 6, carbon ring members, such as cyclopenten-1-yl, cyclopenten3>yl, cyclohexen-1-yl, cyclohexen-3-yi and cyoohexen-4-yl; - aryt mono- or polycylic, preferably mono- or bicyclic, optionally substituted aromatic radicals having 6 to 20, for example 6 to 10, ring carbon atoms, for example pheny, biphenyl, naphthyl such as 1- or 2-naphtyl, tetrahydronaphthyt, fluorenyl, indenyl and phenanthrenyl These arylradicals may optional bear 1, 2, 3, 4, 5 or 6 identical or different substituents.

"Substituents" for radicals specified herein are especially, unless stated otherwise, selected fromketo groups, -COOM, -COO-alkyl, -OH, -SH, -CN, amino, -NO 2 , alkyl, or alkenyl groups.

The term "about" in the context of a stated figure or of a value range denotes deviations from the specifically disclosed values, These are usually customary deviations. These

M/51320-PCT may differ, for example, by ± 10% to 0.1% from the specific values. Typicaly, such deviations are about ±8% to ±1% or 5%, ± 4%, ± 3% or ±2%.

A$) Polycarboxylic acid compounds and hydrocarby-substituted polycarboxylic acid compounds:

The polycarboxylic acid compounds used are aiphatic di- or polybasic (for example tri or tetrabasic), especially from di-, tri- or tetracarboxylic acids and analogs thereof, such as anhydrides or lower aikyl esters partiallyy or completely esterified), and is optionally substituted by one or more (for example 2 or 3), especially along-chain alkyl radical and/or a high molecular weight hydrocarbyl radical, especially a polyalkylene radical Examples are Crew polycarboxylic acids, such as the dicarboxylic acids maonic acid, succinic add, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebadic acid, and the branched analogs thereof; and the tricarboxylic acid tric acid; and anhydrides or lower alkyl esters thereof of. The polycarboxylic acid compounds can also be obtained from the corresponding monounsaturated acids and addition of at least one long-chain alky radical and/or high molecular weight hydrocarby radical. Examples of suitable monounsaturated acids are fumaric acid, maleic add, itaconic acid.

The hydrophobic long-chain" or "high molecular weight" hydrocarbyl radical which ensures sufficient solubility of the quaternized product in the fuel has a number average molecular weight(Ma) of 85 to 20 000, for example 113 to 10 000, or 200 to 10 000 or 350 to 5000, for example 350 to 3000, 500 to 2500, 700 to 2500, or 800 to 1500, Typical hydrophobic hydrocarbyl radicals include polypropenyl, polybutenyl and poyisobutenyl radicals, for example with a number-average molecular weight M of 3500 to 5000, 350 to 3000, 500 to 2500, 700 to 2500 and 800 to 1500.

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

Suitable hydrocarbyl-substituted polycarboxyic acid compounds also comprise polymeric, especially dimeric, forms of such hydrocarbyksubstituted polycarboxylic acid compounds. Dimeric forms comprise, for example, two acid anhydride groups which

M/51320-PCT can be reacted independently with the quaterizable nitrogen Compound In the preparation process according to the invention.

A4) Quatemizing agents: 5 Useful quatemizing agents are in principle a! alkyl esters which are suitable as such and are thse of a cycloaromai or cycoaliphatic mono- or polycarboxyic acid (especially of amono- or dicarboxyic acid) or of an aliphatic polycatboxyic acid (especially dicarboxylic acid). 10 Ina particular embodiment, however, the at least one quaterizable tertiary nitrogen atom is quaternized with at least one quatemizing agent selected from

a) compounds of the general formula 1 15

R 10C(Q)R 2 (1)

in which R, isa lower ekyl radical and R2 is an optionally substituted monocycic aryl or cycoalkyi radical, where the subsfituent is selected from OH, NH , NOr 2 C(O)OR, and R 3 fOC(O) in which Ra s as defined above for R, and Rs is H or R ; 1

and b) compounds of the general formula 2

RtOC(Q)-A-C(O)OR* (2)

in which R 1 and Ria are each independently a lower alkyl radical and A Is hydrocarbylene (such as alkylene or akenyene).

Particularly suitable compounds of the formula I are thosein which

M/51320-PCT

R1 isa C, C-or Cralkyl radicaand R2 isa substituted phenyl radical, where the substituent is HO- or an ester radical of the formula RiOC(O)- which is in the para, meta or especially ortho position to the R10C(O)- radical on the aromatic ring, 5 Especially suitable quaternizing agents are the lower alkyl esters of salcylic acid, such as methylsaicylate, ethyl saficylate, n- and i-propyl salicylate, and n-, or tert-buty saliloylate,

10 A5) Quatemized or quatemizable nitrogen compounds:

The quaternizable nitrogen compounds reactive wIth the polycarboxylic acid compound are seected from a, hydroxyakyl-substituted mono or polamines having at least one 15 quatemized(e.g.chcline)orquaternizabe primary, secondary or tertiary amino group; b. straight-chain or branched, cyclic, heterocyclic, aromatic or nonaromatic polyarnines having at least one primary or secondary (anhydride-reactive) amino group and having atleast one quatemized or quatemizabe primary, secondary or tertiary amino group; c. piperazines,

The quaternizable nitrogen compound is especially seected from di hydroxyaikylsubstituted primary, secondary, tertiary or quaternary monoamines and hydroxyalkyl-substituted primary, secondary, tertiary or quaternary diamines; e, straight-chain or branched aliphatic diamines having two primary amino groups; di- or polyamines having atleastone primary and at least one secondary amino group; di- or polyamines having at least one primaryand at least one tertiary amino group; di- or polyarnines having at least one primary and at least one quatemary amino group; aromatic carbocyclic diamines having two primary aminogroups; aromatic heterocyclic polyamrines having two primary amino groups; aromatic or nonaromatic heterocycles having one primary and one tertiary arino group.

M/51320-PCT

Examples of suitable "hydroxyakyl-substtuted mono- or polyamines" are those provided with at least one hydroxyaikyl substituted, for example 1, 2, 3, 4, 6 or 6 hydroxyalkyl substituted.

Examples of "hydroxyalkyl-substituted monoamines" include: N-hydroxyalkyl monoamines, N,N-dihydroxyalkyl moncamines and N,N,Ntrihydroxyalkyl monoamines, where the hydroxyakylgroups are the same or differentand are also asidefined above, Hydroxyalkyl is especially 2-hydroxyethy, 3-hydroxypropyl or 4-hydroxybutyl

For example, the following "hydroxyalkysubstituted polyamines" and especially "hydroxyakylsubstituted diamines" may be mentioned: (N-hydroxyakyI)alkylene diarnines, NN-dihydroxyakylakylenediamines, where the hydroxyakyl groups are the same or different and are also as defined above. Hydroxyakyl is especially 2 hydroxyethyl, 3-hydroxypropyl or 4-hydroxybutyl; alkylene is especially ethylene, propylene or butylene.

Suitable "dlamines" are alkylenediamines, and the N-alkyksubstituted analogs thereof., such as N-monoaikyiated alkylenediamines and the NN- or N,N-dialkylated alkylenediamines. Alkylene is especially straight-hain or branched Cwor alkylene as defined above. Alkyl is especially0 4 -alkyl as defined above, Examples are especially ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, 1,4 butylenediamine and isomers thereof, pentanediamine and isomers thereof, hexanediamne and isomers thereof, heptanediamine and isomers thereof, and singly or multiply, for example singly or doubly, -C,4 alkylated, for example methylated, derivatves of the aforementioned diamine compounds such as 3-dmethylaino propylamine (DMAPA), N,N-diethylaminopropylamine and N,N-dimethylamino ethylamine.

Suitable straight-chain "polyamines" are, for example, dialkylenetriamine, trialkylenetetramine, tetraakyienepentamine, pentaalkylenehexamine, and the N-alkyk substituted analogs thereof,such as N-monoalkylated and the N:N- or N,N-dlialkylated alkylenepolyamnes. Alkylene is especially straight-chain or branched CO- or C.4. alkylene as defined above. Akyl is especially C 4 -aiky as defined above.

M/51320-PCT

Examples are especially diethylenetriamine, triethylenetetramine tetraethylenepentamine, pentaethylenehexamine, dipropylenetlamine, trpropylenetetramneI tetrapropyIenepentamIne, pentapropylenehexamine 5 dibutylenetriarine, tributylenetetramine, tetrabutylenepentamine pentabutylenehexamine; and the NN-diaikyi derivatives thereof, especiallytheNN-d C14-alkyl derivatves thereof. Examples include:N.N-dimethyidimethylenetriamine N,N-diethyldimethylenetTiamine, NN-dipropyidimethylenetriamine, N,N dimethydiethylene1,2riamine, NN-diethyidiethylene-1,2riamine, NN 10 dipropyldethylene-1.,2-triamine,N,N-dimethyidipropylene-,3-triamine(i.eDMAPAPA), N,N-diethyldipropylene-1,3-4riamine, N,N-dipropyidipropylene-1,3riamine, N,N dimethyidibutylene-1,4-4ramine, N,N-diethyidibutylene-1,4-triamine, N,N dipropyidibutylene-A1,4riamine, N,N-dimethyldipentylene-1,5-riamie, NN diethyidipentyiene-1,5-triamine, N,N-dipropyldipentylene-1,Siriamine, N, 15 dimethyldihexylene.-1Adriamine, N,N-diethyldihexylene-1,6-triamlne and N,N dipropyldihexylene-1.,6-triamine.

"Aromatic carbocyclic diamines" having two primary amino groups are the diamino substituted derivatives of benzene, bipheny, naphthlene, tetrahydronaphthaene, fluorene, mdene and phenanthrene.

"Aromatic or nonaromatic hetercyclic polyamines" having two primary aminogoup are the derivatives, substituted by two amino groups, of the following heterocycles:

- 5- or 6-membered, saturated or monounsaturated heterocycles comprising one to two nitrogen atoms and/or one oxygen or sulfur atom or one or two oxygen and/or sulfur atoms as ring members, for example tetrahydrofuran, pyrrolidine,isoxazolidine, isothiazolidine, pyrazolidine, oxazolidine, thiazolidine, imidazolidine, pyrrolme, piperidine, piperidinyl, 1,3-dioxane, tetrehydropyran, hexahydropyridazine, hexahydropyrimidine, piperazine;

- 5-membered aromatic heterocycles comprising, in addition to carbon atoms, two or three nitrogen atomsorone ortwo nitrogen atomsand one sulfur or oxygen atom as ring members, for example furan, thiane, pyrroe, pyrazole, oxazoe, thiazoie,imidazoie and 1,3,4riazole;isoxazoie, isothiazole, thiadiazole, oxadiazole;

M/5I320-PCT

- 6-membered heterocycles comprising, in addition to carbon atoms, one or two, or one, two or three, nitrogen atoms as ring members, for example pyridinyi, pyridazine, pyriniidine, pyrazinyi, 1,2,4-triazne, 1 3S4riazin-2-yL

"Aromatic or nonaromatic heterocycles having one primary and one tertiary amino group" are, for example, the abovementioned N-heterocycles which are amnoalkyiated on at least one ring nitrogen atom, and especially bear anmi ano-C 4-alkyl group.

"Aromatic or nonaromatic heterocycies having a tertary amino group and a hydroxyakyl group' are, for example, the abovementioned N-heterocycles which are hydroxyakylated on at east one ring nitrogen atom, and especially bear a hydroxy-C, 4-alkyi group.

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

M/51320-PCT

Group 1:

NAME FORMULA Diamines with pimarysecondnitr gatom Ethytenediamne H2N x NH2 NH2

1 2Propytened m e N M1

1HPropyenediamne H2 N- ,NH 2

Isomeric butyenediamines for example

5-Pentylenediami~ne H2 N t~'~NH2

somerk pentanadIaminea, for example 2

HN NH lsomer heixanedamines, for example

H. someric heptanediamnes, for examp le NH 2

and pwth a sonr cn nitrogen atom

Diethylenekramne (DETA)

Dipropyenetriamne (DPTA), 3,HNH minobis(NN-dimethyprpyamine) 2-NH 2

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

Tetraethylenepentamine (TEPA) H N N N H H

Pentaethylenehexamnee H N N H H

M/51"I320-PCT

N-Met hy amino-1-propy niN HNH H

t slhexamethyrenetrtamne NNH

NH2

Aoinobus ls ,

Diaminobenzenes forexample H2

H 2N N

Group 2:

He~cyNs NAME FORMULA

1(3 Aminopropy) midazone H I

N

4 2Aminro~py )mrphne~/> /H N-N

2-(l-Ppemaziny NH2 )ethyamrne (AEP) 2 !L--- IN "/ NI,

N-Methylpperazine / N

Aomin-N-thydrtiqeonydniQnat H N- N

NH2 3mthm Ap (DAP) H2

M/51320-PCT

NN4) ethylaqmjnopropy am ne

N

NM-D methylaminoethyIar~ H2 N

Group 3:

NA NAME - -- Alcohols with aprmary andsecondaryamine FORMULA

IEthanolami~ne 2 OH 3-Hydroxy-1-propy~ai Hns H2 >O

Dthanan mine HO

OH H Disopropanciamine N

-OH H N -H

Alcots tertia vamine OH

Triethanoamine22'NJttr ethanol i )

HN

0OH 3-Hydroxyp ropyj,,)m dHazo eHN > -N

M/51320-POT

H / OH Tris(hydroxymethyl)amne -N

\--OH

3-DImethyamino-1-propano

3DYethylamin-~propanoi HO N

2-Dimethylamino-I-ethanol N

40iethlarnioIbutanol HO N N

A) Preparation of Inventive additives:

a) Reaction with oxygen ornitrogen group

The hydrocarbyl-substituted polycarboxyli acid compound can be reacted with the quatemizable nitrogen compound according to the present invention under thermaly controlled conditions, such that there is essentially no condensation reaction. More particularly, no formation of water of reaction is observed in that case, More partculariy, such a reaction is effected at a temperature in the range from 10 to 8°C, especially 20 to 60°C or 30 to 50°C, The reaction time may be in the range from a few minutes or afew hours, for example about 1 minute up to about 10 hours. Thereaction can be effected at a pressure of about A to 2 atm, but especially at approximately standard pressure. For example, an inert gas atmosphere, for example nitrogen, is appropriate,

More particularly, the reaction can also be effected at elevated temperatures which promote condensation, for example in the range from 90 to 100°C or 100 to 170°C,

M/51320-PCT

The reaction time may be in the region of a few minutes or a few hours, for example about minute up to about 10 hours, The reaction can be effectedatpressureatabout 0 1 to 2 atm, but especially at about standard pressure

S The reactants are initially charged especiayin about equimolar amounts; optionally, a small molar excess of the polycarboxylic acid compound, for example a 0.05- to 0.5 fold, for example a 0.1- to 0.3-old, excess, is desirable. If required, the reactants can be initially charged in a suitable inert organic aliphatic or aromatic solvent or a mixture thereof. Typical examples are, for example, solvents of the Solvesso series, toluene or 10 xylene. The solvent can also serve, for example, to remove water of condensation azeotropically from the reaction mixture. More particularly, however, the reactions are performed without solvent,

The reaction product thus formed can theoretically be purfied further, or the solvent 15 can be removed. Usually, however, this is not absolutely necessary, such that the reaction step can be transferred without further purification into the next synthesis step, the quaternmization.

b) Quaternization

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

To perform the quaternization, the reaction product or reaction mixture from stage a) is admixed wIth at least one compound of the above formula I or 2, especially in the stoichiometric amounts required to achieve the desired quaternization. It is possible to use, for example, 0.1 to 20, 0.2 to15 or 0.5 to 1.25 equivalents, of quatemizng agent per equivalent of quaternizabte tertiary nitrogen atom, More particularly, however, approximately equimolar proportions of the compound are used to quatermze a tertiary amine group, Correspondingly higher use amounts are required to quaternize a secondary or primary amine group, in a further variant, the quaternizing agent is added in excess, for example 1.1 to 2.0, 1.25 to 2 or 1,25 to 175 equivalents of quaternizing agent per equivalent of quaternizable tertiary nitrogen atom,

Typical working temperatures here are in the range from 50 to 180°C, for example from 90 to 160°C or 100 to 140°C, The reaction time may be in the range of a few minutes M/51320-PCT or a few hours, for example about 10 minutesup to about 24 hours, The reaction can be effected at a pressure ofabout 0 to 20 bar, for example Ito 10 or 1,5 to 3 bar, but especially at about standard pressure.

5 If required, the reactants can be initially charged for the quaternization in a suitable inert organic 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 or xylene. The quatemization can, however, also be performed in the absence of a solvent 10 To perform ithe quatemization, the addition of catalyticaly active amounts of an acid may be appropriate. Preference is given to aliphatic monocarboxylic adds, for example CIrCemonocarboxyil acids such as especially lauric acid, isononanoic acid or neodecanoic acid. The quaternization can also be performed in the presence of a 15 Lewis acid,The quaternizaton can, however, also be performed in the absence of any acid.

c) Workup of the reaction mixture

The reaction end product thus formed can theoretically be purified further, or the solvent can be removed, in order to improve the further processabiiity of the products, however, it is also possible to add solvent after the reaction, for example sovents from the SoIvesso series, 2-ethyhexanoi, or essentially aliphatic sovents. Usually, however, this is not absolutely necessary, and 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 additized with the inventive quaternized additive is a gasoline fuel or especially a middle distillate fuel, in particular a diesel fuel,

The fuel may comprise further customary additives to improve efficacy and/or suppress wear.

M/51320-PCT

In the case of desel fuels, these are primary customary detergent additives, carrier st, cold flow improvers, lubricity iprovers, corrosion inhibitors, denuisifers, dehazers, antifoams, cetane number improvers, combustion improvers, antioxidants or 5 stabilizers, antistats, metallocenes, metal deactivators, dyes and/or sovents,

In the case of gasoline fueis, these are in particular lubricity improvers (friction modifiers), corrosion inhibitors, demulsifiers, dehazers, antifoams, combustion improvers, antioxidants or stablizers, antistats, metallocenes, metal deactivators, dyes 10 and/or solvents.

Typical examples of suitable coadditives are listed in the following section:

81) Detergent additives 15 The customary deterrent additives are preferably amphiphilic substances which possess atleast one hydrophobic hydrocarbon radical with a number-average molecular weight (Mn) of 85 to 20 000 and at least one polar moietyselectedfrom

(Da) mono- orpolyamino groups having up to 6 nitrogen atoms, at least one nitrogen atom having basic properties;

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

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

(Dd) carboxy groups or their aIkal metal oralkalne earth metal sats;

(De) sufonic acid groups or their aikali metal or alkaline earth metal saits;

(Df) polyoxy-C to C-alkylene moieties terminated by hydroxyl groups, mono- or poiyamno groups, at least one nitrogen atom having basic properties, or by carbamate groups;

M/51320-PCT

(Dg) carboxylic ester groups;

(Dh) moleties derived from succinic anhydride and having hydroxyl and/or amino 5 and/or amido andfor imido groups; and/or

(D) moieties obtained by Mannich reaction of substituted phenols with aldehydes and mono- or polyamines,

10 Thehydrophobic hydrocarbonradical in the above detergent additives, which ensures the adequate solublity in the fuel, has a number-average molecular weight (M,) of 85 to 20 000, preferably of 113 to 10 000, more preferably of 300 to 5000, even more preferably of 300 to 3000, even more especially preferably of 500 to 2500 and especially of 700 to 2500, in particular of 800 to 1500. As typical hydrophobic 15 hydrocarbon radicals, especially in conjunction with the polar especially polypropenyi, polybutenyi and polyisobutenyl radicals with a number-average molecular weight M of preferably in each case 300 to 5000, more preferably 300 to 3000, even more preferably 500 to 2500, even more especially preferably 700 to 2500 and especially 800 to 1500 into onsideration.

Examples of the above groups of detergent additives include the llowing;

Additives comprising mono- or polyamino groups (Da) are preferably polyalkenemono. or polyalkenepolyamines based on polypropene or on high-reactivity (i.e. having: predominantly terminal double bonds) or conventional (i.e, having predominantly internal double bonds) poiybulene or polyisobutene having M,= 300 to 5000, more preferably 500 to 2500 and especially 700 to 2500, Such additives based on high reactivity polyisobutene, which can be prepared from thepolyisob.utene which may comprise up to 20% byweight of n-butene units by hydroformylation andreductive amination with ammonia, monoarines or polyamines such as dimethylaminopropylamine,ethylenediamine, diethylenetriamine, triethylenetetramne or tetraethylenepentaminej are known especially from EP-A 244 616. When poybutene orpolyisobutene having predominantly internal double bonds (usually in the 8 and V positions) are used as starting materials in the preparation of the additives, a possible

M151320-PCT preparative route is by chlorinton and subsequent amination orbyoxidationofthe double bond with air or ozone to give the carbonyl or carboxyl compound and subsequent amination under reductive (hydrogenating) conditions, The amines used herefor the amination may be, for example, ammonia, monoamines or the 5 abovementioned polyamines, Corresponding additives based on polypropene are described in particular in WO-A 94,24231.

Further particular additives comprising monoamino groups (Da) are the hydrogenation products of the reaction products of polyisobutenes having an average degree of 10 polymerization P = 5 to 100 with nitrogen oxides or mixturesof nitrogen oxides and oxygen, as describedin paricular inWO-A 97/03946.

Further particular additives comprising monoamino groups (Da) are the compounds obtainable from polyisobutene epoxides by reaction with amines and subsequent 15 dehydration and reduction of the amino alcohols, as described in particular in DE-A 19620262,

Additives comprising nitro groups (Db), optionafly in combination with hydroxyl groups, are preferably reaction products of polylsobutenes having an average degree of polymerization P = 5to 100 or 10 to 100with nitrogen oxides or mixtures of nitrogen oxides and oxygen, asdescribedinparticular inWO-A 96/03367 and in WO-A 96/03479. These reaction products are generally mixtures of pure nitropoyisobutenes (e.g. or-dinitropolyisobutene) and mixed hydroxynitropolyisobutenes (e.g, a-nitro hydroxypolyisobutene)

Additives comprising hydroxy groups in combination with mono- or polyamino groups (Dc) are in particular reaction products of polyisobutene epoxides obtainable from polyisobutene having preferably predominantly terminal double bonds and M, = 300 to 5000, with ammonia or mono- or poyarnines, as described in particular in EP-A 476 485.

Additives comprising carboxyl groups or their alkali meta or alkaline earth metal salts (Dd) are preferably copolymers of C to CO-olefins with maleic anhydride which have a total moar mass of 500 to 20 000 and some or all ofwhose carboxyl groups have been

M/51320-PCT converted to the alkali metal or alkaine earth metal salts and any remainder of the carboxyl groups has been reacted with alcohols or amines. Such additives are disclosed in particular by EP-A 307 815. Such additives serve mainly to prevent valve seat wear and can, as described inWO-A 87/01126, advantageously be used in combination with customary fuel detergents such as poly(iso)buteneamines or polyetherarnines.

Additives comprising sulfonic acid groups or their alkali metal or alkaline earth metal salts (De) are preferably alkall metal or alkaline earth metal sats of an alkyl sulfosuccinate, as described in particular in EP-A 639 632. Such additives serve mainly to prevent valve seat wear and can be used advantageously in combination with customary fuel detergents such as poy(iso)butenamines or polyetheramines.

Additives comprising polyoxy-CC 4-alkylene moieties (Df are preferably polyethers or polyetheramnes which are obtainable by reaction of Cr to Cwalkanols, Ce- toCw alkanedials, mono- or di-Cr toC-alkylamines, C- toC-alkyicyclohexanols or Ce to C03-alkylphenols with 1 to 30 mo of ethylene oxide and/orpropylene oxide and/or butylene oxide per hydroxyl group or amino group and, in the case of the polyetheramines, by subsequent reductive amination with ammonia, monoamines or polyamines, Such products are described in particular in EP-A 310 875, EP-A 356 725, EP-A 700 985 and US-A 4 877 416. in the case of polyethers, such products also have carrier oil properties, Typical examples of these are tridecanol butoxylates, isotridecanolbutoxylates, isononylphenol butoxylates and poyisobuteno butoxylates and propoxyates and also the corresponding reaction products with ammonia.

Additives comprising carboxylic ester groups (Dg) are preferably esters of mono-, di- or tricarboxylicacids with long-chain alkanols or polyos, in particular those having a minimum viscosity of 2 mmIs at I00OC, as described in particular in DE-A 38 38 918. The mono-, di- ortricarboxylic acids used may be aliphatic or aromatic acids, and particularly suitable ester alcohols or ester poyos are long-chain representatives having, for example, 6 to 24carbon atoms. Typical representatives of the esters are adipates, phthalates, isophthalates, terephtha[ates and trimellitates of isooctanol, of isononanol, of isodecanol and ofisotridecanol.Such products also have carrieroil properties.

M/51320-PCT

Additives comprisingmoieties derived from succinicanhydride andhaving hydroxyl and/or amino and/or amido and/or especially Imido groups(0h) are preferably corresponding derivatives of alkyl or alkeny-substtuted succinic anhydride and S especially the corresponding derivatives of polyisobutenyisucciniC anhydride which are obtainable by reacting conventional or high-reactivity polyisobutene having M= preferably 300 to 5000, more preferably 300 to 3000, even more preferably 500 to 2500, even more especially preferably 700 to 2500 and especially 800 to 1500, with maleic anhydride by a thermal route in an ene reaction or viath chlorinated 10 polyisobutene. The moieties having hydroxyl and/or amino and/or amido and/orimido groups are, for example, carboxyflc acid groups, acid amides of monoarnines, acid amides of di- or polyamines which, in addition to the amide function, also have free amine groups, succinic acid derivatives having an acid and an amide function, carboximides with monoamines, carboximides with di- or polyamines which, in addition 15 to the imide function, also have free amine groups, or diimides which are formed by the reaction of di- or polyamines with two succinic acid derivatives. in the presence of imido moieties D(h), the further detergent additive in the context of the present invention is, however, used only up to a maximum of 100% of the weight of compounds with betaine structure. Such fuel additives are common knowledge and are described, 20 for example, in documents (1) and (2). They are preferably the reaction products of alky- or alkenyisubsdtuted succinic acids or derivatives thereof with mines and more preferably the reaction products of poilyisobutenyi-substituted succinic acids or derivatives thereof with mines. Of particular interest in this context are reaction products with aliphaticpolyamines (poiyalkyleneimines) such as especially ethylenediamine, diethylenetriamie, triethylenetetramine, tetraethylenepentamine, pentaethyenehexamine and hexaethyleneheptanine, which have an imide structure.

Additives comprising moieties (Di) obtained by Mannich reaction ofsubstitutedphenols with aldehydes and mono- or polyamines are preferably reaction products of phyisobutene-substituted phes wth formaldehyd yde and mono- or polyamines such as ethylenediamine, diethyenetriamie, triethylenetetraminetetraethyenepentamine or dimethylaminopropyjamine The polyisobutenyi-substtted phenos may stem from conventional or high-reactivity polyisobutene having M = 300 to 5000, Such "polyisobutene Mannich bases" are described in particular in EPA 831 141

M/51320-PCT

One ormore of the detergent additives mentioned can be addedto the fuel in such an amount thatthe dosage of these detergent additives is preferably 25 to 2500 ppm by weight, especially 75 to 1500 ppm by weight, in particular 150 to 1000 ppm by weight.

B2) Carrier oils

Carrier oils additionally usedmay be of mineral or synthetic nature, Sutable mineral carrier oils are the fractions obtained in crude oil processing, such as brightstock or 10 base oils having viscosities, for exampe, fromthe SN 500 to 2000 class; but also aromatic hydrocarbons, paraffinic hydrocarbons and akoxyaikanols. Likewise useful is a fraction which is obtained in the refining of mineral oil andis known as "hydrocrack oil (vacuum distillate cut having a boiling range from about 360 to 500°C, obtainable from natural mineral oil which has been catalytically hydrogenated and isomerized 15 under high pressure and also deparaffinized), Likewise suitable are mixtures ofthe abovementioned mineral carrier oils.

Examples of suitable synthetic carrier oils are polyolefins (polyalphaoiefins or polyintemaiolefins), (poly)esters, (poly)akoxylates, polyethers, aliphaicpoyether 20 amines, alkylphenol-started polyethers, alkyphenoi-started polyetheramines and carboxylic esters oflong-chain alkanols.

Examples of suitable polyolefins are olefin polymers having M, = 400 to 1800, in particular based on poybutene orpolyisobutene (hydrogenated or unhydrogenated).

Examples of suitable polyethers or polyetheramines are preferably compounds comprising potyoxy-C2 to Calkylene moieties which are obtainable by reacting C2 to Calkanos,C to Cao-aikanedos, mono- or di-C- to Cwalkylamines, C- to C alkyicycohexanols or Cs to C-alkyphenois with I to 30 mol of ethylene oxide and/or propylene oxide and/or butylene oxide per hydroxyl group or amino group, and, in the case of the polyetheramines, by subsequent reductive anination with ammonia, monoamines or polyaminesa Such products are described in particularin EP-A 310 875, EP-A 356 725, EP-A 700 985 and US-A 4,877,416. For example, the polyetheramines used may be poly C2 to C-aikylene - oxide amines or functional

NI/51320-PCT derivatives thereof, Typical examples thereof are tridecano butoxylates or isotridecanol butoxylates, isononylphenol butoxylatesand alsoPolyiSobutenolbutoxylates and propoxylates, and also the corresponding reaction products with ammonia.

5 Exampes of carboxylic esters of long-chain alkanols are in particular esters of mono-, di- or tricarboxylic acids with long-chain aikanols or polyois, as described in palicularin DE-A 38 38 918. The mono-, di- or trcarboxyic acids used may be aliphatic or aromatic acids: suitabe ester alcohols or polyos are in particular long-chain representatives having, for example, 6 to 24 carbon atoms. Typical representatives of 10 the esters are adipates, phthalates,isophthalates, terephthalates and trmelitates of isOocano isononanol,isodecanol and isotridecano, forexample di(n- or isotridecyl) phthalatei

Further suitable carrier oil systems are described, for example, in DE-A 38 26 608, 15 DE-A 41 42 241, DE-A 43 09 074, EP-A 452 328 and EP-A 548 617

Examples of particularly suitable synthetic carrier oils are alcohol-started polyethers having about 5 to 35, preferably about 5 to 30, more preferably 10 to 30 and especially 15 to 30 C- to Cr-alkylene oxide units, for example selected from propyene oxide, n 20 butylene oxide and isobutylene oxide units, or mixtures thereof, per alcoho molecule. Nonlimiting examples of suitable starter alcohols are iong-chain alkanols or phenols substituted by long-chain alkyl in which the long-chain alkyl radical is in particular a straight-chain or branched Ce to C-alkyl radical Particular examples include trIdecanol andnonylphenol. Particularly preferred alcohokstarted polyethers are the reaction products (polyetherification products) of monohydric aliphatic Cr toC, alcohols with Ca to C-alkylene oxides. Examples of monohydric aphatic0-Cr alcohols are hexanol, heptano, octanot 2-ethylhexanol nonyl alcohol, decanol,3 propyiheptanol undecanoi, dodecanol, tridecanol, teradecanolpentadecanol, hexadecanoi, octadecanol and the constitutional and positional isomers thereof. The alcohols can be used either in the form of the pureisomers or in the form of technical grade mixtures. A particularly preferred alcohol is tridecanol Examples of C to C alikylene oxides are propylene oxide, such as 1,2-propylene oxide,butyene oxIde, such as 1,2-butylene oxide, 2,3-butyleneoxide, isobutylene oxide or tetrahydrofuran, pentylene oxide and hexylene oxide. Particular preference among these is given to C

M/51320-PCT to Cealkylene oxides, i.e.propylene oxide such as 1 2 -propylene oxide and butylene oxide such as 1,2-butylene oxide, 2,3-butylene oxide andisobutylene oxide, Especially butylene oxide is used.

o Further suitable synthetic carrier oils are alkoxylated alkylphenols, as described in DE-A 10 102 913.

Particular carrier oils are synthetic carrier oils, particular preference being given to the above-desoibed alcohol-started polyethers, 10 The carrier oil or the mixture of different carrier oils is added to the fuel in an amount of preferably i to 1000 ppm byweight, more preferably of 10 to 500 ppm by weight and especially of 20 to 100 ppm by weight.

15 B3) Cold flow improvers

Sutable cold flow improvers are in principle all organic compounds which are capable of improving the flow performance of middle distillate fuels or diesel fuels under cold conditions. For the intended purpose, they must have sufficient oil solubility. in particular, useful cold flow improvers for this purpose are the cold flow improvers (middle distillate flowimprover, MDos) typically used in the case of middle distilfates offossil origin, i.e.in the case of customarymineral diesel fuels. Howeveritis also possible to use organic compounds which partly orPredominantly have the properties of a wax antisettling additive (WASA) when used in customary diesel fuels. They can also act partly or predoninanly as nucleators, Itis, though, also possible to use mixtures of organic compounds effective as MODFis and/or effective asWASAs and/or effective as nucleators,

The cold flow Improver is typically selected from (KI) copolyrners of a Cz to ,colefin with atleast one further ethylenicaly unsaturated monomer; (K2) comb polyrners; (K3) polyoxyakylenes; (K4) polar nitrogen compounds;

M/51320-PCT

(K5) suifocarboxyic acid or sulfonicacids.or derivatives there; and (K6) poly(meth)acrylic esters..

It is possible to use either mixtures of different representatives from one of the 5 particular classes (K1) to (K6) or mixtures representatives from different classes (K1) to (K6).

Suitable C to 04Colefin monomers for the copolymers of class(K) are, for example, those having 2 to 20 and especaly 2 to 10 carbon atoms, and I to 3 and preferably I 10 or 2 carbon-carbon double bonds, especially having one carbon-carbon double bond. in the latter case, the carbon-carbon double bond may be arranged either terminally (a olefins) or internally. However, preference is given to a-olefins, more preferably a olefins having 2 to 6 carbon atoms, for example propene, 1-butene, 1-pentene, 1 hexene and in particular ethylene.

In the copolymers of class (K1), the at least one further ethylenically unsaturated monomer is preferably selected from alkenyl carboxylates, (meth)acrylic esters and further olefins,

When further olefins are also opolymerized, they are preferably higher inmolecular weight than the abovementioned C2- to Caroefin base monomer, When, for example, the olefin basemonomer used is ethylene or propene, suitable further olefins are in particular C to C4a-olefins, Further olefins are in most cases only additionally copolymerizedwhen monomers with carboxylicester functions are also used.

Suitable (meth)acrylic esters are, for example, esters of (meth)acrylicacid with C- to Cr-aikanos, especially C to C-alkanols, in particular with methanol, ethanol, propanot, isopropanol, n-butanol, sec-butanol, isobutanol. tert-butano, pentanoi, hexanol, heptanol, octanci 2-ethylhexanol, nonanol and decano and structural isomers thereof.

Suitable alkenyl carboxylates are, for example, C to C akenyl esters,for example w the vinyl and propenyl esters, of carboxylic acids having 2 to.21 carbon atoms, whose hydrocarbon radicalmay belinearorbranched.Amongthese, preference is given to

M/51320-PCT the vinyl esters. Among the carboxylic acids with a branched hydrocarbon radical, preference is given to those whose branch is in the a-position to the carboxy group, the o-carbon atom more preferably being tertiary, i.e. the carboxylic acid being a so called neocarboxylic acid. However, the hydrocarbon radical of the carboxylic acid is preferably linear.

Examples of suitable alkenyl carboxylates are vinyl acetate, vinyl proponate, vinyl butyrate, vinyl 2-ethylhexancate, vinyl neopentanoate, vinyl hexanoate, vinyl neononanoate, vinyl neodecanoate and the corresponding propenyl esters, preference being given to the viny esters, A particularly preferred alkenyl carboxylate is vinyl acetate; typical copolymers of group (KI) resulting therefrom are ethylene-vinyl acetate copolymers ("EVAs"), which are some of the most frequently used, Ethylene-viny acetate copolymers usable particularly advantageously and their preparation are described in WO 99/29748.

Suitable copolymers of class (K1) are also those which comprise two or more different alkenyl carboxylates in copolymerized form, which differ in the alkenyl function and/or in the carboxylic acid group. Likewise suitable are copolymers which, as welas the alkenyl carboxylatess, comprise at.least one olefin and/or at least one (meth)acrylic ester incopolymerized form

Terpolymers of a Cr to Cji-olefin, a Cr to C&alky ester of an ethylenically unsaturated monocarboxylic acid having 3 to 15 carbon atoms and a02- to Cwakenyl ester of a saturated monocarboxylic acid having 2 to 21 carbon atoms are also suitable as copolymers of class (K1). Terpolymers ofthis kind are described in WO 200&/054314. A typical terpolymer of this kind is formed from ethylene, 2-ethylhexyl acrylate and vinyl acetate.

The at least one or thefurther ethylenically unsaturated monomer(s) are copolymerized in the copolymers of class (KI) in an amount of preferably I to 50% by weight, especially 10 to 45% by weight and in particular 20 to 40% by weight, based on the overall copolymer. The main proportion In terms of weight of the monomer units in the copolymers of class (KI) therefore originates generally from the C2 toC4 base olefins.

M/513.20-PCT

$8 The copoymers offclass (KI) preferably have a number-avrage molecular weight M, of 1000 to 20 000, morepreferably 1000 to 10 000 andin particular 1000 to 8000.

Typical comb polymers of component (K2) are, for example, obtainable by the 5 copolymerizationofmaleic anhydrideor fumaricacid with another ethylenically unsaturated monomer, for example with ana-oefin or an unsaturated ester, such as vinyl acetate, and subsequent esterification of the anhydride or acid function with an alcohol having atleast 10 carbon atoms. Further suitable comb polymers are copolymers ofa-olefins and esterified cornonomers, for example esterified copolymers 10 of styrene and maleic anhydride or esterified copolymers of styrene and fumaric acid., Suitable combpolymers may also bepolyfumarates or polymaleates. Homo- and copolymers of vinyl ethers are also suitable comb polymers. Combpoymers suitable as components of class (K2) are, for example, also those described in WO 2004/035715 and in "Comb-Like Polymers. Structure and Properties", N. APlate and 15 V. P. Shibaev, J. Poly, Sl Macronolecular Revs. 8, pages 117 to 253 (1974)". Mixtures of comb polymers are also sutable,

Polyoxyalkylenes suitable as components of class (K3) are, for exampe, polyoxyaikylene esters, pofyoxyalkylene ethers, mixed polyoxyalkylene ester/ethers andmixtures thereof. These polyoxyalkylene compounds preferably comprise at least one linear alkyl group, preferably at least two linear alkyl groups, each having 10 to 30 carbon atoms and a poyoxyalkylene group having anumber-average molecular weight of up to 5000. Such polyoxyalkylene compounds are described, for example, in EP-A 061895 and also in US 4,491,455. Particular polyoxyakylene compounds are based on polyethylene glycols and polypropylene glycols having a number-average molecular weight of 100 to 5000,Additionaly suitable are polyoxyafkylene mono- and diesters of fatty acids having 10 to 30 carbon atoms, such as stearic acid or behenic acid

Polarnitrogen compounds suitable as components offclass (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 teriary nitrogen atom of the general formula >NR in which R 7 is aG toC hydrocarbonradical The nitrogen substituentsmayalsobe quaternized, Le. be in cationic form,.An example ofsuch nitrogen compounds is that of ammoniurn salts and/or amides which are obtainable by the reaction of at least one

M/51320-PCT amine substituted by at least one hydrocarbon radical with a carboxylicadd having 1 to 4 carboxyl groups or with a suitable derivative thereof. The amines preferably comprise at least one linear C8 to C40-akyl radical. Primary amines suitable for preparing the polar nitrogen compounds mentioned are, for example, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tetradecylamine and the higher linear homologs, Secondary marines suitable for this purpose are, for example, dioctadecylamine and methybehenylamine, Also suitable for this purpose are amine mixtures, in Particular amine mixtures obtainable on the industrial scale, such as fatty marines or hydrogenated tallamines, as described, for example,in Ullmann's Encyclopedia of IndustrialChemistry, 6th Edition, NAminesaliphaticchapter.Adds suitable for the reaction are, for example, cyclohexane1 24icarboxylic acid, cydlohexene-1,2-dicarboxylic acid, cyclopentane-1,2-dicarboxylic acid, naphthalenedicarboxylic acid, phthalic acid, isophthaic acid, terephthatic acid, and succinic acids substituted by long-chain hydrocarbon radicals, in particular, the component of class (K4) is an ol-soluble reaction product of poly(C to Cw-carboxylic acids) having at least one tertiary amino group with primary or secondary amines.The poly(Cr to C2 -carboxylic acids) which have at least one tertary amino 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 polycarboxylic acids have preferably 2 to 10 carbon atoms, and are especially acet acid units. The carboxylic acid units are suitably bonded to the polycarboxylic acids, usually via one or more carbon and/or nitrogen atoms. They are preferably attached to tertiary nitrogen atoms which, in the caseof a plurality of nitrogen atoms, are bonded via hydrocarbon chains.

The component of class (K4) is preferably an oil-soluble reaction product based on poly(C- to C-carboxylic acids) which have at least one tertiary amino group and are of the general formula Ila or lib

HOOC'B B'COOH HOOC, NA' ',COOH B A . M53-a

MJS5132 0 -P CT

BaB HOOC' 'N' W',COOH C COOH ~(lib)

in which the variable A is a straighhain or branched C2 toCalkylene grouporthe moiety of the formula ill

HOOC'B'N'C12CF2 CH2-CHfC

and the variable B is a Ceto C-alkylene group. The compounds of the general formulae la and |b especially have the properties of aWASA. 10 Moreover, the preferred oil-soluble reactionproduct of component (K4), especially that of the general formula Ila or b,is an amde, an amide-ammonium salt or an ammonium salt in which no, one or more carboxyllc acid groups have been converted to amide groups,

Straight-chainor branched C2- to C-alkylene groups of the variable A are, for example, 1,1-ethylene, 1, 2 -propylene, 1,3-propylene, 1,2-butylene, 1,3-butylene, 1,4-butylene, 2-methyl-1, 3 -propylene, 1,5-pentylene, 2-methyb1,4-butylene, 2,2-dimethyl-1,3 propylene, 1hexylene (hexamethylene) and in paricular 1,2-ethylene. The variable A comprises preferably 2 to 4 and especially 2or 3 carbon atoms

Cr to Cialkylene groups of the variable 8 are, for example, 1,2-ethylene, 1,3-propylene, i4-butylene, hexamethylene, octamethylene, decamethylene, dodecamethylene, tetradecamethylene, hexadecamethylene, ocadecamethylene, nonadecamethylene and especially methylene. The variable 8 comprises preferably 1 to 10 and especially I to 4 carbon atoms,

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

M/51320-PCT

These parent aminesof the oilsoluble reaction products of component (K4) are usually secondary amines and have the general formula HN(R%2 in which the twovariabies RA are each independently straight-chain or branched C- to Craky radicals, especially 5 01W to C4-alky radicals. These relatively long-chain alkyl radicals are preferably

straight-chain or only slightly branched. In general, the secondary amines mentioned, with regard to their relatively long-chain alkyl radicals, derve from naturaly occurring fatty acid and from derivatives thereof. The two R radicaIs are preferably identica

The secondary amines mentioned may be bonded to the polycarboxylic acids by means of amide structures or in the form ofthe ammonium salts itisalsopossible for only a portion to be present as amnide structures and anoter portion as ammoniurn salts. Preferably only few, if any, free acid groups are present. The oil-soluble reaction products of component (K4) are preferaby present completely in the formof the amide structures.

Typical examples of such components (K4) are reactionproducts of nitriotracetic acid, of ethylenediaminetetraacetic acid or of propylene-1,2-diaminetetraacetic acid with in each case 0,5 to 1,5 mo per carboxyl group, especially 08 to 1.2moi per carboxyl group, of dioeylamine, dipalmitinamine, dicoconut fatty amine, distearyiamine, dibehenylamine or especially ditalow fatty amine. A particularly preferred component (K4) is the reaction product of I mo ofethyenediaminetetraacetic acid and 4 mol of hydrogenated ditallow fatty amine.

Further typical examples ofcomponent (K4) includethe N,N-dialkylammonium salts of 2-ttN'-dialkylamidobenzoates, for example the reaction product ofI mo of phthalic anhydride and 2 mol of ditailow fatty amine, the latter being hydrogenated or unhydrogenated, and the reaction product of I mo of an akenyspirobisactone with 2 mol ofadiaikylamine, for example ditallow fatty amine and/or tallow fatty amine, the last two being hydrogenated or unhydrogenated

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

M/51320-PCT

Sulfocarboxylic acids, sulfonic acids or derivatives thereof which are suitable as cold flow improvers of cass (K5) are, for example, the oil-soluble carboxamides and carboxyic esters of ortho-suifobenzoic acid, in which the sulfonic acid function is present as asulfonatewith alkyksubstituted ammonium cations, as described in EP-A 261 957.

Poiy(meth)acryli esters suitable as cold fiow improvers of class (K6) are eitherhomo or copolyrners of acrylic and methacrylic esters. Preferenceis given to copolymers of at leasttwo different (rneth)acrylic esters which differwith regard to the esterified alcohoL The copolymer optionaHy comprises another different olefinic-ally unsaturated monomer in copolymerized form. The weight-average molecular weight of the polymeris preferably 50 000 to 500 000. A particularly preferred polymer is a copolymer of methacrylic acid and methacryicesters offsaturated Cu and Cys alcohols, the acid groups having been neutralized with hydrogenated tallamine. Suitable poly(meth)acrylicesters are described, for example, in WO 0044857,

The cold flow improver or the mixture of different cold flow improvers is added to the middle distillate fuel or diesel fuel in a total amount of preferably 10 to 5000 ppm by weight, more preferably of 20 to 2000 ppm by weight, even more preferably of 50 to 1000 ppm by weight and especially of 100 to 700 ppm by weight, for example of 200 to 500 ppm by weight.

B4) Lubricity improvers

Suitable lubricity improvers or friction modifiers are based typically on fatty acids or fatty acid esters. Typical examples are tail ol fatty acid, as described, for example, in WO 98/004666, and glyceryl monooleate. The reaction products, described in US 6 743 26682,of natural or synthetic oils, for example triglycerides, and alkanolamines are also suitable as such lubricity improvers.

M/5$1320-PCT

B5) Corrosion inhibitors

Suitable corrosion inhibitors are, for example, succinic esters, in particular with polyols, fatty acid dedvatives, for example oleic esters, oigomerzed fatty acids, substituted 5 ethanolamines, and products sold under the trade name RC 4801 (Rhein Chemie Mannheim, Germany) or HiTEC 536 (Ethyl Corporation),

B6) Demusifiers

10 Suitable demulsifiers are, for example, the alkali metal or alkaline earth metal salts of alkyl-substituted phenol- and naphthalenesulfonates and the alkalmetal oralkaline earth retail salts of fatty acids, and also neutra compounds such as alcohol alkoxylates, e.g. alcohol ethoxylates, phenol alkoxylates, eg. tert-butypheno ethoxylate or ter-pentylpheno ethoxylate, fatty acds, akylphenols, condensation 15 products of ethylene oxide (EO) and propylene oxide (PO), for example including infthe form of E/PO block cpolymers, polyethyleneimines or else poysiloxanes.

87) Dehazers

Suitable dehazers are, for example, alkoxylated phenol-formaldehyde condensates, for example the products available under the trade names NALCO 7DO7 (Nalco) and TOLAD 2683 (Petrolite).

88) Antifoams

Suitable antifoams are, for example, polyether-modified polysiloxanes, for example the products available under the trade arnes TEGOPREN 5851 (Goldschmidt), Q 25907 (Dow Coming) and RHODOSIL (Rhone Poulenc).

89) Cetane number improvers

Suitable cetane number improvers are, for example, aiphaticnItrates such as 2-ethylhexyl nitrate and cyciohexyl nitrate and peroxides such as di-tert-buty peroxide.

M/51320-PCT

B10) Antioxidants

Suitable antioxidants are, for example substituted phenols, such as 2,6-di-tert~ butyphenol and 6-di-tert-butyl-3.methylphenl*, and alsophenylenediamnessuchas 5 Nt'-d-ser-butyi-p-pheryienediamine,

11) Metal deactivators

Suitable metal deactivators are, for example, salicylic acid derivatives such as 10 NK-disalicyidene-1,2-propsnediamine.

812) Solvents

Suitable solvents are, for example, nonpolar organic solvents such as aromatic and 15 aliphate hydrocarbons, for example toluene, xylenes, white spirit and products sold under the trade names SHELLSOL (Roya Dutch/Shel Group) and EXXSOL (ExxonMobil), and also polar organic solvents, for example, alcohols such as 2-ethyhexanol, decanoland isotridecanol.Such solvents are usually added to the diesel fuel together with the aforementoned additives and coaddfives, which they are intended to dissolve or dilute for better handling.

C) Fuels

The inventive additive isoutstandingly suitable as a fuel additive and can be used in principle in any fuels.I It brings about a whole series of advantageous effects in the operation of internal combustion engines with fuels. Preference is given to using the inventive quatemized additive in middle distillate fuels, especially diesel Fuels.

The present invention therefore also provides fuels, especially middle distillate fuels, with a content of the inventive quatemized additive which is effective as an additive for achieving advantageous effects in the operation of internal combustion engines, for example of diesel engines, especially of direct-injection diesel engines, in particular of diesel engines with common-rail injection systems, This effective content (dosage) is generally 10 to 5000 ppm by weight, preferably 20 to 1500 ppm by weight, especially

M/51320-PCT

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 fuelssuch as diesel fuels or heating oils are preferably mineral oil 5 raffinates which typically have a boiling range from 100 to 400 T , These are usually distillates having a 95% point up to 360°C or even higher. These may also be socalled "ultra low sulfur diesel" or "city diesel" characterized by a 95% point of, for example, notmore than 345°C and a sulfur content of not more than 0-005% by weight or by a 95% point of, for example, 285T and a sulfur content of notmore than0.001% by 10 weight. In additon to the mineral middle distillate fuels or diesel fuels obtainable by refining, those obtainable by coa gasificationorgaslquefactionjgastoliquid"(QTL)

fuels] or by biomass liquefaction ["biomass to liquid (BTL) fueis] are also suitable. Also suitable are mixtures of the aforementioned middle distillate fuels or diesel fuels with renewable fuels, such as biodiese or boethano 15 The qualitiesof the heating ols and diesel fuels are laid down in detail, for example, in DIN 51603 and EN 590 (of. also Ullmann's Encyclopedia ofIndustrial Chemistry, 5th edition, Volume A12, p. 17 ff),

in addition to the use thereof in the abovementioned middle distillate fuels of fossil, vegetable or animal origin, which are essentially hydrocarbon mixtures, the inventive quaterized additive can also be used in mixtures of such middle distillates with biofuel oils (biodiesel). Such mixtures are also encompassed by the term "middledistillate fuel" in the context of the present invention. They are commercially available and usually comprise the biofuel oils in minor amounts, typically in amounts of I to 30% by weight, especially of 3 to 10% by weight, based on the total amount of middle distillate of fossil, vegetable or animal origin andbiofuel ol.

Biofuel ols are generally based on fatty acid esters, preferably essentiallyon alky esters of fatty acidswhich derivefrom vegetable andor animal oils andor fats. Alkyl esters are typically understood to mean lower alkyl esters, especially CrC4-alkyl esters, which are obtainable by transesterifying the glycerides which occur in vegetable and/or animal oils and/or fats, especially triglycerides, by means of lower alcohols, for example ethanol or in particular methanol ("FAME"). Typical lower alkyl estersbased

M/51320-PCT on vegetable and/or animal ols and/or fats, which tind use as a biofuel oi or components thereof, are, for example, sunflower methyl ester, palm oil methyl ester ("PME"), soya 6 methyl ester (sME") and especially rapeseed oilmethyl ester ("RME"). 5 The middle distillate fuels or diesel fuels are more preferably those having a low sulfur content, i.e, having a sulfurcontent of less than 0.05% byweight, preferably of less than 0.02% by weight, more particularly of less than 0,005% byweightand esecialy of less than 0,001% by weight of sulfur, 10 Useful gasoline fuels include all commercial gasoline fuel compositions. One typical representative which shall be mentioned here is the Eurosuperbase fuel to EN 228, which is customary onthe market. In addition, gasoline fuel compositions of the specification according to WO 0047698 are also possible fields of use for the present 15 invention.

The inventive quaternized additive is especially suitable as afueladditiveinfuel compositions, especially in diesel fuels, for overcoming the problems outlinedat the outset in direct-injection diesel engines, inparticularIn those with common-rail iriection systems.

The invention is nowillustrated in detail by the working examples which follow. The test methods described herein are not restricted to the specific working examples, but are part of the general disclosure of the description and can be employed generally in the context of the present invention,

Experimentalisection:

A. General test methods

Engine test b1) XUD9 test - determination of flow restriction The procedure was according to the standard stipulations of CEC F-23-01,

M/51320-PCT b2) DW10 - keep clean test

To examinethe influence of the inventive compounds on the performane of direct ijection diesel engines, the power loss was determined on the basis of the official test method CEC F-098-08. The power loss is a diect measure of formation of deposits in the inectors,

The keep clean test is based on CEC test procedure F-098-08 Issue 5, The same test setup and engine type (PEUGEOT DW10) as in the CEC procedure are used, 10 Special features of the test used:

a) Injectors in the tests, cleaned injectors were used. The cleaning time in an ultrasound bath in water at 60C + 10% Superdecontamine (Interscienes, Brussels) was 4 h.

b) Test run times the test perod was 12 h without shutdown phases. The one-hour test cycle (see table below) from CEC F-98-08 was rn through 12 times,

ag D E'gine Load TOrUe Charge air nues) (rpm) (%) (Nm) temperature +1-20 +/-15 downstream of charge run cooler

1 2 1750 (20) 462

12 7 30,00 (60) 2123

5 2 1750 (20) 62 45 4 1 40 180) 50 26 1 400t-10 150 ) 5 606-s

2 1250 (10) 25 M/51320-PCT

2 ~ 1250 -- -- 14000 1 50

for range to be expected see CEC-96-08 target value

c) Power determination

The initial power (P0o, KC [W) is calculated from the measured torque at fu load 4 000 /min directly after the test has started and the engine has warmed up The procedure is described in Issue 5 of the test proedure CECF-98-0& The same test setup and the PEUGEOT DVV10 engine type are used, 10 The final power (P, KC) is determined in the 12th cycle in stage 12, (see table above). Here too, the operating point is full load 4 000/mir, Pa KC [kW) is calculated from the measured torque,

15 The power loss in Kiscalculated as follows:

power loss, KC [%] = (1 - PmKC / PtKC) x 100

The fuel used was a commercial diesel synthetically induce the formation of deposits fuel from Haltermann (RF-06-03) To at theinjectors,ppmofzincwasadded thereto in the form of a zinc neodecenoatesolution.

B. Preparation examples:

Reactants used:

PIBSA: Prepared from maleic anhydride and PS 1000 in a known manner. For the inventive preparation examples and comparative examples which follow, qualities with hydrolysis numbers in the region of 84-95 mg KOH/p were used, DMAPA was used with the particular PIBSA quality in a molar ratio of 1:1 according to the hydrolysis number. The PBSA quaiies used had bismaleation levels (BML) of less than 15%, M/51320-PCT

DMAPA: M 102.18 methyl salicytate: M = 152.14 dimethyl phthalate: MI=194.19 5 dimethyl oxaiate: M 11809 dimethyl sufate: M 126.13 dimethyl carbonate MN 90.08

Preparation example 1: Synthesis of an inventive quatemized succinimide 10 (PIBSADJMAPAdimethyi phthalate)

Polyisobutylenesuccinic anhydride (1659 g) is dissolved in Solvent Naphtha Heavy (SNH, Eon Mobi4 CAS64742-955) (1220g), and 3-dimethylamino-1-propyamine (DMAPA; 153 g) is added, The reaction solutionis stirred at 170°C for 8 h, in the 15 course of which water of condensation formed is distiled off continuously. This affords the PBSA-DMAPA succinimde as a solution in Sovent Naphtha Heavy (TBN 0.557 mnolg),

A portion of this solution of the PIBSA-DMA succinimide (181 g) is added to dimethyl phthalate (19A g), and the resulting reaction solution is stirred at 120°C for 11 h and then at 150°C for 241h After cooling to room temperature, the product obtained is the ammonium carboxylate as a solution in Solvent Naphtha Heavy. IH NMR analysis confirms the quatemization.

Preparation example 2: Synthesis of an inventive quatemtzed succinimide (PBSADMAPA/methyl salicylate)

Polyisobutylenesuccinic anhydride (PIBSA; 2198g) is heated to 110C, and 3 dimethylarino-i-propylamine (DMAPA; 182 g)is added within 40 min, in the course of which the reaction mixture heats up to 140°C. The reaction mixture is heated to 170°C and held at this temperature for 3h, in the course of which 28g of distillate are collected. This affords the PIBSA-DMAPA succinimide as a viscous ol (TBN 0,735 mmok/g).

M/51320-PCT

A mixture of this PIBSA-DMAPA succinimide (284,5 g), methyl salicylate (65,5 g) (i.e about 2 equivalents of methyl salicylate per equivalent of tertiary amino group) and 3,3,5-trimethyiheptanoic acid (from BASF) (0-75g) is heated to 140-150 and the reaction mixtureisstirredatthistemperature for 6 h, After cooling to room temperature, 5 the product obtained is the ammonium salicylate as a viscous oIL 'H NMR analysis confirms the quaternization. By adding Pilot 900 oil, Petrochem Carless Ltd, the active ingredient content of the solution is adjusted to 50% by weight,

Preparationexample 3: Synthesis of an inventive quatemized suocinimide 10 (PIlSA/DMAPNdimetfiyl oxalate)

Polyisobutylenesuccinicanhydride (PIBSA;2198g) is heated to 110C, and 3 dimethylamino-1-propylamine (DMAPA; 182 g) isadded within 40 min, in the course of which the reaction mixture heats up to 140°C. The reaction mixtureis heated to 170C and held at this temperature for 3 h,in the course of which 28 g of distillate are collected, This affords the PIBSA-DMAPA sucinimide as a viscous oil (TBN 0.735 mmol/q).

Mixture of this PISSA-DMAPA succinimide (211 g), dimethyl oxalate (345 g) and auric acid (4.9 g) is heated to 120°C and then stirred at this temperature for 4 h. Excess dimethyi oxalate is removed on a rotary evaporator under reduced pressure (p = 5 mbar) at 120°, The product obtained is the ammonium methyl oxalate as a viscous oil, 1H NMR analysis confirms the quaternization,

For comparison with the prior art, Examples 2 and 4 from WO 2006/135881 were worked up.

Preparation example 4: Synthesis of a known quaternized succinimide (comparative example) (Example 2 from WO 2006/135881)

A solution of PIBSA (420.2 g) in Pilot 900 oil, Petrochem Carless Ltd, (51,3 g) is initially charged and heated to 110°C, DMAPA (31.4 g) is metered in within 50 minutes, in the course of'which aslightly exothermic reaction is observed. Within 80 minutes, the reaction mixture is heated to 150°C and the mixture is then kept at this temperature

M/51320-PCT for3 h, in the course of which the waterof reaction whch forms is distifed off. After coohng to room temperature, the PBSA-DMAPA succinimide is obtained as a solution in Pilot 900 oil (TBN 0.2 mnmo/g),

5 A portion of the PIBSA-DMAPA succinimide thusobtained as a solution in Pilot 900 oil Petrochern Carless Ltd, (354 g) is initally charged and heated to 90C. Dirnethy sulfate (26,3 g) is metered in, in the course of which the reaction temperature rises to 11.2°C Subsequenty, the reaction mixture stirred at I1C for 3 h. After cooling to room temperature, the quaternized PIBSA-DMAPA succinimide is obtainedasa 10 soluton in iot 900 oiH NMR confirmed the quaternization. The output was adjusted to an active ingredient content of 50% byweight by adding Pilot 900 oi

Preparation example 5: Synthesis of a known quatemized succinimide (comparative example) (Example 4 from WO 2006/135881) 15 A solution of PIBSA (420.2 g) in Rlot 900 oil, Petrochem Caness Ltd, (5.3 g) is initially charged and heated to 1IOC DMAPA (31.4 g) is meteredin within 50 minutes, in the course of which a slightly exothermic reaction is observed Within 80 minutes, the reaction mixture is heated to 150T and the mixture is then kept at this temperature for 3 h, in the course of whic the water of reaction which forms is dised off, After cooling to room temperature, the PIBSA-DMAPA succinimide is obtained as a solution in Pilot 900 oil (TBN 0.62 mmo/g).

A portion of the PIBSA-DMAPA succinimide thus obtained as a solution in Plot 900 oil, Petrochem Cariess Ltd, (130 g), dimethyl carbonate (20 g) and methanol (17.4) are charged into an autoclave and inertized with nitrogen, and a starting pressure of 13 bar is established. Subsequently, the reaction mixture is stirred under autogenous pressure first at 90oC for 1 h, then at 140°C for 24h. After cooling to room temperature, the autoclave isdecompressed and the contents are rinsed out completely with a little toluene as a solvent Alll ow-boiling constituents are subsequently removed on a rotary evaporator under reduced pressure to obtain the quaternized PIBSA-DMAPA sucinimide as a solution in Pilot 900 oil. 1 H NMR analysis confirmed the partial quatemization, The output is adjusted to an active ingredient content of 50% by weight by adding Pilot 900 oil

M/51320-PCT

C. Use examples:

in the use examples which follow, the additives are used either as a pure substance 5 (as synthesized in the above preparation examples) or in the form ofan additive package!

M1: Additive according to preparation example 2 (inventive, quaternized with methyl salicylate) 10 M2: Additive according to preparation example 4 (comparative, quatemized with dimethyl sulfate) M3: Additive according topreparation example 5 (comparative, quatemized with dimethyl carbonate)

15 Use example 1: determination of the additive action on the formation of deposits in diesel engine injection nozzles

a) XUD9 Tests

Fuel used: RF-06-03 (reference diesel, Haltermann Products, Hambur)

The results are compiled in table 1:

Table 1: XUD9 tests . Name Osagiccording to Flow restriction preparation example 0.1 mm needle

[mg/kgh Strokse %

#1 1, according to 30 10. 7 preparation example 2 #2 M2, according to 30 48,5 preparation example 4 #3 M, according to 30 20,8 Preparation example 5

M/51320-PCT

It was found that theinventive additive M, with the same dosage, has an improved effect compared to the prior art (M2, M3),

b) DWIE test

To study the influence of the inventive compound on the performance of direct-injection diesel engines, the power loss was determined based on the official test method CEC F-098-08 as described above. The power loss is a direct measure of formation of deposits in the injectors. A conventional direct-injection diesel engine with a common 10 rai system was used,

The fuel used was a commercial dieselfuel from Hatermann (R-s063) To syntheticay induce the formation of deposits at the injectors, 1I ppm by weight of zinc in the form of a zinc didodecanoate solution was added thereto. 15 The tablebelow shows the results of the determinations of the relative power loss at 4000 rpm after 12 hours of sustained operation without interruption. The value Pn gives the power after 10minutes and the value Ped the power at the end of the measurement: 20 The test results are shown in table 2

Table 2: Results of the DW10 test Addi ive Dose Tie p K K Pw loss '

- [mki ~ _[ 0 12 99.39+3 50% M1 according to preparation 1600example2 12 98,7 97.4 1,32% M2, according to preparation 10 12 9 981 0% example 1 example54 M3, according to prelparation ----- - example 5 1160 12 98.1 95,7 2,4%

it was found that the inventive additive M1 has an improved effect compared to the base value and has animproved effect atleast compared to example M3.

M/51320-POT

Use example 2: Determination of thesolubity properties

To determine the solubility properties, the following additive packages were produced and tested:

M 4 (inventive) Substance Content [ppm] Additive acc. to preparation example 2 160.0 Dehazer commercial 30 Antifoam, silicone-based commercial 6'00

Sovent Naphtha Heavy ______I

1Tota 249.00

M 5 (comparative dmethy sufate) Substance Content [ppm] Additive aco to preparation example 4 160.00 Dehazer, commercial 30 Antfoam, siicone-based, commercial Solvent Naphtha Heavy 420,00 Total590

M 6 (comparative, dimethyl carbonate) Substance Content [ppm] ddtive acc. to preparation example 5 160.00 Dehazer (commercial) 3.0 Antifoam, silicone-based commercial 60 Solvent Naphtha Heavy 150M Total 319-00

The result of the soubdty tests is compiled in the table below. Theminimum amount of solvent (Solvent Naphtha Heavy) needed to obtain a homogeneous, clear diesel

M/51320-PCT performance package at room temperature with otherwise identical amounts of active substance, Pilot 900, antifoam and dehazer is reported.

Table 3: Determination of the solvent requirement

Additive Additive Minimum amount of solvent needed for a homogeneous package PIBSA-DMAPA-imide-methyl salicylate M4 32% PIBSA-DMAPA-imide-dimethyl sulfate M5 71% PIBSA-DMAPA-imide-dimethyl carbonate M6 47%

It was found 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.

It is to be understood that, if any prior art publication is referred to herein, such reference does not constitute an admission that the publication forms a part of the common general knowledge in the art, in Australia or any other country.

In the claims which follow and in the preceding description of the invention, except where the context requires otherwise due to express language or necessary implication, the word "comprise" or variations such as "comprises" or "comprising" is used in an inclusive sense, i.e. to specify the presence of the stated features but not to preclude the presence or addition of further features in various embodiments of the invention.

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Claims (20)

Claims

1. A fuel composition comprising, in a majority of a customary fuel, a proportion of at least one reaction product comprising a quaternized nitrogen compound, or a fraction thereof which comprises a quaternized nitrogen compound and is obtained from the reaction product by purification, said reaction product being obtainable by al) reacting a hydrocarbyl-substituted polycarboxylic acid compound with a compound comprising at least one oxygen or nitrogen group reactive, with the polycarboxylic acid, and comprising at least one quaternizable amino group, to obtain a quaternizable hydrocarbyl-substituted polycarboxylic acid compound, and a2) subsequent reaction thereof with a quaternizing agent which converts the at least one quaternizable amino group to a quaternary ammonium group, said quaternizing agent being the alkyl ester of a cycloaromatic or cycloaliphatic mono- or polycarboxylic acid, or of an aliphatic polycarboxylic acid; or

b) reacting a quaternizable hydrocarbyl-substituted polycarboxylic acid compound comprising at least one quaternizable amino group with a quaternizing agent which converts the at least one quaternizable amino group to a quaternary ammonium group, said quaternizing agent being the alkyl ester of a cycloaromatic or cycloaliphatic mono- or polycarboxylic acid, or of an aliphatic polycarboxylic acid

wherein 1.1 to 2.0 equivalents of quaternizing agent are used per equivalent of quaternizable tertiary nitrogen atom; and/or the hydrocarbyl-substituted polycarboxylic acid compound is a polyisobutenylsuccinic acid or an anhydride thereof obtained via the conversion of polyisobutene and maleic anhydride, said acid having a bismaleation level of 2 to 20% by weight, based in each case on the conversion product of polyisobutene and maleic anhydride.

11998048_1 (GHMatters) P95787.AU

2. The fuel composition according to claim 1, wherein the compound comprising at least one oxygen or nitrogen group is reactive with the polycarboxylic acid by addition or condensation.

3. The fuel composition according to claim 1 or 2, wherein said quaternizing agent is an alkyl ester of a cycloaromatic or cycloaliphatic mono- or dicarboxylic acid, or of an aliphatic polycarboxylic acid.

4. The fuel composition according to any one of claims 1 to 3, wherein about 1.25 to about 2.0 equivalents of quaternizing agent are used per equivalent of quaternizable tertiary nitrogen atom.

5. The fuel composition according to any one of claims 1 to 4, wherein the hydrocarbyl-substituted polycarboxylic acid compound is a polyisobutenylsuccinic acid or an anhydride thereof obtained via the conversion of polyisobutene and maleic anhydride, said acid having a bismaleation level of 2 to 15% by weight, based in each case on the conversion product of polyisobutene and maleic anhydride.

6. The fuel composition according to any one of the preceding claims, wherein the quaternizing agent is a compound of the general formula 1

R10C(O)R 2 (1)

in which R1 is a lower alkyl radical and R2 is an optionally substituted monocyclic aryl or cycloalkyl radical, where the substituent is selected from OH, NH 2 , NO 2 , C(O)OR 3 , and R1 0C(O)-, in which R1 is as defined above and R 3 is H or R1 .

7. The fuel composition according to any one of the preceding claims, wherein the quaternizing agent is a compound of the general formula 2

RiOC(O)-A-C(O)OR1i (2)

11998048_1 (GHMatters) P95787.AU in which R 1 and Ri are each independently a lower alkyl radical and A is hydrocarbylene.

8. The fuel composition according to any one of the preceding claims, wherein the quaternized nitrogen compound has a number-average molecular weight in the range from 500 to 5000.

9. The fuel composition according to any one of the preceding claims, wherein the quaternized nitrogen compound has a number-average molecular weight in the range from 800 to 3000.

10. The fuel composition according to any one of the preceding claims, wherein the quaternized nitrogen compound has a number-average molecular weight in the range from 900 to 1500.

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

12. The fuel composition according to any one of claims 1 to 11, wherein the compound which is reactive with the polycarboxylic acid and comprises an oxygen or nitrogen group and at least one quaternizable amino group is selected from a. hydroxyalkyl-substituted mono- or polyamines having at least one quaternizable primary, secondary or tertiary amino group; b. straight-chain or branched, cyclic, heterocyclic, aromatic or nonaromatic polyamines having at least one primary or secondary amino group and having at least one quaternizable primary, secondary or tertiary amino group; c. piperazines.

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13. The fuel composition according to claim 12, wherein the compound which is reactive with the polycarboxylic acid and comprises an oxygen or nitrogen group and at least one quaternizable amino group is selected from a. hydroxyalkyl-substituted primary, secondary or tertiary monoamines and hydroxyalkyl-substituted primary, secondary or tertiary diamines, b. straight-chain or branched aliphatic diamines having two primary amino groups; di- or polyamines having at least one primary and at least one secondary amino group; di- or polyamines having at least one primary and at least one tertiary amino group; aromatic carbocyclic diamines having two primary amino groups; aromatic heterocyclic polyamines having two primary amino groups; aromatic or nonaromatic heterocycles having one primary and one tertiary amino group.

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

15. The use of a reaction product obtainable by a process as defined in any one of the preceding claims or of quaternized nitrogen compound obtained from the reaction product; or of a quaternized nitrogen compound prepared by a process comprising the reaction of a quaternizable hydrocarbyl-substituted polycarboxylic acid compound comprising at least one tertiary quaternizable amino group with a quaternizing agent which converts the at least one tertiary amino group to a quaternary ammonium group, said quaternizing agent being the alkyl ester of a cycloaromatic or cycloaliphatic mono- or polycarboxylic acid or of an aliphatic polycarboxylic acid; as a fuel additive, and wherein 1.1 to 2.0 equivalents of quaternizing agent are used per equivalent of quaternizable tertiary nitrogen atom.

16. The use according to claim 15 as an additive for reducing the fuel consumption of direct-injection diesel engines, or diesel engines with common-rail injection systems, and/or for minimizing power loss in direct-injection diesel engines, or in diesel engines with common-rail injection systems.

11998048_1 (GHMatters) P95787.AU

17. The use according to claim 15 as a gasoline fuel additive for reducing the level of deposits in the intake system of a gasoline engine, or DISI (direct injection spark ignition) and PFI (port fuel injector) engines.

18. The use according to claim 15 as a diesel fuel additive, as a cold flow improver, as a wax antisettling additive (WASA) or as an additive for reducing the level of and/or preventing deposits in the intake systems, the internal diesel injector deposits (IDIDs), and/or valve sticking in direct-injection diesel engines, or in common-rail injection systems.

19. The use according to any one of claims 15 to 18, wherein about 1.25 to about 2.0 equivalents of quaternizing agent are used per equivalent of quaternizable tertiary nitrogen atom.

20. The use according to any one of claims 15 to 19, wherein said quaternizing agent is the alkyl ester of a cycloaromatic or cycloaliphatic mono- or dicarboxylic acid, or of an aliphatic polycarboxylic acid.

11998048_1 (GHMatters) P95787.AU