EP2811007A1 - Alkylene oxide and hydrocarbyl-substituted polycarboxylic acid quaternised alkylamine as additives in fuels and lubricants and their use - Google Patents

Abstract

The present invention relates to the use of quaternized alkylamine nitrogen compounds as a fuel and lubricant additive or kerosene additive, in particular as a detergent additive; 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, especially diesel engines with common rail injection systems, and for minimizing the power loss in direct injection Diesel engines, in particular in diesel engines with common-rail injection systems; and as an additive for gasoline fuels, in particular for the operation of DISI engines.

Description

The present invention relates to the use in a special manner of quaternized alkylamine-nitrogen compounds as a fuel and lubricant additive or kerosene additive, in particular as a detergent additive; 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, especially diesel engines with common rail injection systems, and for minimizing the power loss in direct injection Diesel engines, in particular in diesel engines with common-rail injection systems; and as an additive for gasoline fuels, in particular for the operation of DISI engines.

State of the art:

In direct-injection diesel engines, the fuel is injected through a directly into the combustion chamber of the engine reaching multi-hole injection nozzle and finely distributed (atomized), instead of being introduced into a pre-vortex or vortex chamber as in the classic (chamber) diesel engine. The advantage of direct-injection diesel engines lies in their high performance for diesel engines and yet low consumption. In addition, these engines achieve a very high torque even at low speeds.

There are currently three main methods used to inject the fuel directly into the combustion chamber of the diesel engine: the conventional distributor injection pump, the unit-injector system and the common-rail system ,

In the common-rail system, the diesel fuel is pumped from a pump with pressures up to 2000 bar into a high-pressure line, the common rail. Starting from the common rail, spur lines run to the various injectors, which inject the fuel directly into the combustion chamber. In this case, the full pressure is always applied to the common rail, which allows a multiple injection or a special injection form. In the other injection systems, however, only a smaller variation of the injection is possible. Injection in the common rail is essentially subdivided into three groups: (1) preinjection, which substantially achieves softer combustion, so that hard combustion noises ("nails") are reduced and engine running appears quiet; (2.) main injection, which is responsible in particular for a good torque curve; and (3.) post-injection, which provides in particular for a low NO _x value. In this post injection, the fuel is not burned in the rule, but evaporated by residual heat in the cylinder. The resulting exhaust gas / fuel mixture is transported to the exhaust system, where the fuel in the presence of suitable catalysts acts as a reducing agent for the nitrogen oxides NO _x .

Due to the variable, cylinder-specific injection of the common-rail injection system of the pollutant emissions of the engine, such as the emission of nitrogen oxides (NO _x ), carbon monoxide (CO) and in particular of particles (soot) are positively influenced. This allows, for example, that equipped with common-rail injection systems engines of Euro 4 standard can theoretically meet without additional particulate filter.

In modern common-rail diesel engines deposits can form under certain conditions, for example when using biodiesel-containing fuels or fuels with metal impurities such as zinc compounds, copper compounds, lead compounds and other metal compounds, the injection behavior of the Negatively affect the fuel and thereby affect the performance of the engine, ie In particular, reduce the power, but in part also deteriorate the combustion. The formation of deposits is further enhanced by structural developments of the injectors, in particular by the change in the geometry of the nozzles (narrower, conical openings with rounded outlet). For a permanently optimal functioning of engine and injectors such deposits must be prevented or reduced in the nozzle openings by suitable fuel additives

In the injection systems modern diesel engines cause deposits significant performance problems. The widespread recognition is that such deposits in the spray channels to a reduction of the fuel flow and thus to Loss of power (power loss). Deposits on the injector tip, on the other hand, impair the optimum formation of fuel spray and thus cause a deterioration in combustion and, as a result, higher emissions and increased fuel consumption. In contrast to these conventional "outward" deposition phenomena, "internal" deposits (collectively referred to as internal diesel injector deposits (IDID)) also create certain portions of the injectors, such as the nozzle needle, the spool, the valve piston, the valve seat the drive unit and the guides of these components increasingly performance problems. Conventional additives show insufficient activity against these IDIDs.

From the US 4,248,719 Quaternized ammonium salts are described which are prepared by reacting an alkenyl succinimide with a monocarboxylic acid ester and are used as dispersants in lubricating oils to prevent sludge formation. In particular, the reaction of polyisobutylsuccinic anhydride (PIBSA) with N, N-dimethylaminopropylamine (DMAPA) and quaternization with methyl salicylate is described, for example. However, an application in fuels, in particular diesel fuels, is not proposed therein. The use of PIBSA with low bis-malalination <20% is not described therein.

From the US 4,171,959 For example, quaternized ammonium salts of hydrocarbyl substituted succinimides are described which are useful as detergent additives for gasoline fuel compositions. For quaternization, alkyl halides are preferably used. Mention is also made of organic C ₂ -C ₈ hydrocarbyl carboxylates and sulfonates. Thus, the quaternized ammonium salts provided by the teachings have as counterion either a halide or a C ₂ -C ₈ hydrocarbyl carboxylate or a C ₂ -C ₈ hydrocarbyl sulfonate group. The use of PIBSA with low bis-malalination <20% is also not described therein.

From the EP-A-2 033 945 Cold flow improvers are known which are prepared by quaternization of special tertiary monoamines which carry at least one C ₈ -C ₄₀ alkyl radical with a C ₁ -C ₄ alkyl ester of special carboxylic acids. Examples of such carboxylic acid esters are dimethyloxalate, dimethyl maleate, dimethyl phthalate and dimethyl fumarate. Other applications than to improve the CFPP value of middle distillates are in the EP-A-2 033 945 not used.

The WO 2006/135881 describes quaternized ammonium salts prepared by condensation of a hydrocarbyl-substituted acylating agent and an tertiary amino group containing oxygen or nitrogen atom, followed by quaternization by means of hydrocarbyl epoxide in combination with stoichiometric amounts of an acid such as in particular acetic acid. Further in the WO 2006/135881 claimed quaternizing agents are dialkyl sulfates, benzyl halides and hydrocarbyl-substituted carbonates, with dimethyl sulfate, benzyl chloride and dimethyl carbonate being experimentally investigated.

The in the WO 2006/135881 However, preferably used quaternizing have serious disadvantages, such as: toxicity or carcinogenicity (eg dimethyl sulfate and benzyl halides), no residue combustion (eg dimethyl sulfate and alkyl halides), as well as insufficient reactivity leading to incomplete quaternization or non-economic reaction conditions (long reaction times , high reaction temperatures, excess of quaternizing agent, eg dimethyl carbonate) leads.

The EP-A-2 033 945 describes the preparation of halogen- and sulfur-free quaternary ammonium salts of organic carboxylic acids (such as oxalic acid, phthalic acid, salicylic acid, malonic acid and maleic acid and their alkyl esters) and their use for improving the CFPP value of diesel fuels.

Quaternary ammonium salts of alpha-hydroxycarboxylic acids are used in the EP-A-1 254 889 proposed as a cleaning agent for electronic components.

Furthermore, the Japanese patent application, application number describes 61-012197 , the use of quaternary ammonium salts of organic carboxylic acids as surface active agent or raw material for medicines or cosmetics.

It was therefore an object to provide further fuel additives which prevent deposits in the injector tip and internal Injektorablagerungen in the operation of common rail diesel engines.

Brief description of the invention:

It has now surprisingly been found that the above object is achieved by providing quaternized hydrocarbylamine compounds or fuel and lubricant compositions additized therewith.

Surprisingly, the additives according to the invention, as illustrated in particular by the enclosed application examples, are surprisingly effective in common rail diesel engines and are distinguished by their particular suitability as an additive for reducing powerloss by external and cold start problems due to internal deposits.

Brief Description:

FIG. 1 shows the sequence of a one-hour motor test cycle according to CEC F-098-08.

Detailed description of the invention: A1) Special embodiments

• 1. Kraftstoff- oder Schmierstoffzusammensetzung, enthaltend in einer Hauptmenge eines üblichen Kraftstoffs oder Schmierstoffs einen Anteil, insbesondere eine wirksame Menge, wenigstens eines eine quaternisierte Stickstoffverbindung umfassenden Reaktionsprodukts oder eine aus dem Reaktionsprodukt durch Aufreinigung erhaltene, eine quaternisierte Stickstoffverbindung enthaltende Teilfraktion davon, wobei das Reaktionsprodukt erhältlich ist durch Umsetzung eines quaternisierbaren Alkylamins, enthaltend wenigstens eine quaternisierbare, tertiäre Aminogruppe mit einem Quaternierungsmittel, das die wenigstens eine tertiäre Aminogruppe in eine quaternäre Ammoniumgruppe überführt,
  wobei das Quaternierungsmittel ein Hydrocarbylepoxid in Kombination mit einer freien Hydrocarbyl-substituierten Polycarbonsäure ist.
• 2. Kraftstoff- oder Schmierstoffzusammensetzung nach Ausführungsform 1, wobei das Alkylamin wenigstens eine Verbindung der folgenden allgemeinen Formel 3 umfasst,
  
           R_aR_bR_cN     (3)
  
  worin
  wenigstens einer der Reste R_a, R_b und R_c, wie z.B. einer oder zwei, für einen geradkettigen oder verzweigte, gesättigten oder ungesättigten C₈-C₄₀-Hydrocarbylrest (insbesondere geradkettigen oder verzweigte C₈-C₄₀-Alkyl) steht und die übrigen Reste für gleiche oder verschiedene, geradkettige oder verzweigte, gesättigte oder ungesättigten C₁-C₆-Hydrocarbylreste (insbesondere C₁-C₆-Alkyl) stehen; oder
• 2a. Kraftstoff- oder Schmierstoffzusammensetzung nach Ausführungsform 1, wobei
  das Alkylamin wenigstens eine Verbindung der folgenden allgemeinen Formel 3 umfasst,
  
           R_aR_bR_cN     (3)
  
  worin alle Reste R_a, R_b und R_c für gleiche oder verschiedene geradkettige oder verzweigte, gesättigten oder ungesättigten C₈-C₄₀-Hydrocarbylreste, insbesondere geradkettige oder verzweigte C₈-C₄₀-Alkyl-Reste stehen.
• 3. Kraftstoff- oder Schmierstoffzusammensetzung nach einem der Ausführungsformen 1 und 2, wobei das Quaternierungsmittel ein Epoxid der allgemeinen Formel 4 umfasst
  
  wobei die darin enthaltenen Reste R_d gleich oder verschieden sind und für H oder für einen Hydrocarbylrest stehen, wobei der Hydrocarbylrest für einen aliphatischen oder aromatischen Rest mit wenigstens 1 bis 10 Kohlenstoffatomen steht
• 4. Kraftstoff- oder Schmierstoffzusammensetzung nach einer der Ausführungsformen 1 bis 3, wobei die freie Säure des Quaternierungsmittels eine hydrocarbyl-substituierte C₃-C₂₈-Dicarbonsäure ist.
• 5. Kraftstoff- oder Schmierstoffzusammensetzung nach einer der Ausführungsformen 1 bis 4, wobei der Hydrocarbyl-Substituent der Carbonsäure ein Polyalkylenrest mit einem Polymerisationsgrad von 2 bis 100, oder 3 bis 50 oder 4 bis 25 ist.
• 6. Kraftstoff- oder Schmierstoffzusammensetzung nach einer der vorhergehenden Ausführungsformen, wobei das quaternisierbare tertiäre Amin eine Verbindung der Formel 3 ist, worin wenigstens zwei der Reste R_a, R_b und R_c gleich oder verschieden sind und für einen geradkettigen oder verzweigte, C₁₀-C₂₀-Alkylrest steht und der übrigen Rest für C₁-C₄-Alkyl steht.
• 7. Kraftstoff- oder Schmierstoffzusammensetzung nach einer der vorhergehenden Ausführungsformen, wobei das Quaternierungsmittel ausgewählt ist unter Niedrigalkylenoxiden in Kombination mit einer hydrocarbyl-substituierten Polycarbonsäure.
• 8. Kraftstoffstoff- oder Schmierstoffzusammensetzung nach einer der vorhergehenden Ausführungsformen, ausgewählt unter Dieselkraftstoffen, Biodieselkraftstoffen, Ottokraftstoffen, und Alkanol-haltigen Ottokraftstoffen., wie Bioethanolhaltige Kraftstoffe, insbesondere Dieselkraftstoffe.
• 9. Quaternisierte Stickstoffverbindung gemäß der Definition in einer der Ausführungsformen 1 bis 7.
• 10. Verfahren zur Herstellung einer quaternisierten Stickstoffverbindung nach Ausführungsform 9,
  umfassend die Umsetzung eines quaternisierbaren Alkylamins, enthaltend wenigstens eine quaternisierbare, tertiäre Aminogruppe mit einem Quaternierungsmittel, das die wenigstens eine tertiäre Aminogruppe in eine quaternäre Ammoniumgruppe überführt,
  wobei das Quaternierungsmittel ein Hydrocarbylepoxid in Kombination mit einer Hydrocarbyl-substituierten Polycarbonsäure ist.
• 11. Verwendung einer quaternisierten Stickstoffverbindung nach Ausführungsform 9 oder hergestellt nach Ausführungsform 10 als Kraftstoff- oder Schmierstoffadditiv.
• 12. Verwendung nach Ausführungsform 11 als Additiv zur Verringerung des Kraftstoffverbrauches von direkteinspritzenden Dieselmotoren, insbesondere von Dieselmotoren mit Common-Rail-Einspritzsystemen, und/oder zur Minimierung des Leistungsverlustes (powerloss) in direkteinspritzenden Dieselmotoren, insbesondere in Dieselmotoren mit Common-Rail-Einspritzsystemn (wie z.B. bestimmt in einem DW10 Test in Anlehnung an CEC F-098-08, wie unten im experimentellen Teil näher beschrieben).
• 13. Verwendung nach Ausführungsform 11 als Ottokraftstoffadditiv zur Verringerung von Ablagerungen im Einlasssystem eines Ottomotors, wie insbesondere DISI und PFI (Port Fuel Injector) -Motoren.
• 14. Verwendung nach Ausführungsform 10 als Dieselkraftstoffadditiv zur Verringerung und/oder Vermeidung von Ablagerungen in den Einspritzsystemen, wie z.B. bestimmt in einem XUD 9 Test, nach CEC-F-23-1-01), wie insbesondere der Internal Diesel Injector Deposits (IDID) und / oder von Ventilkleben in direkteinspritzenden Dieselmotoren, insbesondere in Common-Rail-Einspritzsystemen (wie z.B. bestimmt nach einer IDID Testprozedur, wie unten im experimentellen Teil näher beschrieben).
• 15. Additivkonzentrat, enthaltend in Kombination mit weiteren Diesel- oder Ottokraftstoffadditiven oder Schmierstoffadditiven wenigstens eine quaternisierte Stickstoffverbindung gemäß der Definition in Ausführungsform 9 oder hergestellt nach Ausführungsform 10.

The present invention particularly relates to the following specific embodiments:

• A fuel or lubricant composition comprising, in a majority of a conventional fuel or lubricant, a portion, particularly an effective amount, of at least one quaternized nitrogen compound-containing reaction product or a quaternized nitrogen compound-containing partial fraction thereof obtained from the reaction product, wherein the reaction product obtainable by reacting a quaternizable alkylamine containing at least one quaternizable tertiary amino group with a quaternizing agent which converts the at least one tertiary amino group into a quaternary ammonium group,
  wherein the quaternizing agent is a hydrocarbyl epoxide in combination with a free hydrocarbyl-substituted polycarboxylic acid.
• 2. A fuel or lubricant composition according to embodiment 1, wherein the alkylamine comprises at least one compound of the following general formula 3,
  
  R _a R _b R _c N (3)
  
  wherein
  at least one of the radicals R _a , R _b and R _c , such as one or two, is a straight-chain or branched, saturated or unsaturated C ₈ -C ₄₀ -hydrocarbyl radical (in particular straight-chain or branched C ₈ -C ₄₀ -alkyl) and the remaining radicals are identical or different, straight-chain or branched, saturated or unsaturated C ₁ -C ₆ -hydrocarbyl radicals (in particular C ₁ -C ₆ -alkyl); or
• 2a. A fuel or lubricant composition according to embodiment 1, wherein
  the alkylamine comprises at least one compound of the following general formula 3,
  
  R _a R _b R _c N (3)
  
  wherein all radicals R _a , R _b and R _{c are} identical or different straight-chain or branched, saturated or unsaturated C ₈ -C ₄₀ -hydrocarbyl radicals, in particular straight-chain or branched C ₈ -C ₄₀ -alkyl radicals.
• 3. A fuel or lubricant composition according to any one of embodiments 1 and 2, wherein the quaternizing agent comprises an epoxide of the general formula 4
  
  in which the radicals R _d contained therein are identical or different and represent H or a hydrocarbyl radical, where the hydrocarbyl radical is an aliphatic or aromatic radical having at least 1 to 10 carbon atoms
• 4. A fuel or lubricant composition according to any one of embodiments 1 to 3, wherein the free acid of the quaternizing agent is a hydrocarbyl-substituted C ₃ -C ₂₈ dicarboxylic acid.
• 5. A fuel or lubricant composition according to any one of embodiments 1 to 4, wherein the hydrocarbyl substituent of the carboxylic acid is a polyalkylene group having a degree of polymerization of 2 to 100, or 3 to 50 or 4 to 25.
• A fuel or lubricant composition according to any one of the preceding embodiments, wherein the quaternizable tertiary amine is a compound of formula 3 wherein at least two of R _a , R _b and R _{c are the} same or different and are straight or branched C ₁₀ C ₂₀ alkyl and the rest is C ₁ -C ₄ alkyl.
• A fuel or lubricant composition according to any one of the preceding embodiments, wherein the quaternizing agent is selected from lower alkylene oxides in combination with a hydrocarbyl-substituted polycarboxylic acid.
• 8. Fuel or lubricant composition according to one of the preceding embodiments, selected from diesel fuels, biodiesel fuels, gasoline fuels, and alkanol-containing gasoline fuels, such as bioethanol-containing fuels, in particular diesel fuels.
• 9. Quaternized nitrogen compound as defined in any one of Embodiments 1 to 7.
• 10. A process for producing a quaternized nitrogen compound according to Embodiment 9,
  comprising the reaction of a quaternizable alkylamine containing at least one quaternizable tertiary amino group with a quaternizing agent, which converts the at least one tertiary amino group into a quaternary ammonium group,
  wherein the quaternizing agent is a hydrocarbyl epoxide in combination with a hydrocarbyl-substituted polycarboxylic acid.
• 11. Use of a quaternized nitrogen compound according to embodiment 9 or prepared according to embodiment 10 as a fuel or lubricant additive.
• 12. Use according to embodiment 11 as an additive for reducing the fuel consumption of direct-injection diesel engines, in particular of diesel engines with common-rail injection systems, and / or for minimizing the power loss in direct-injection diesel engines, in particular in diesel engines with common rail injection systems (US Pat. as determined, for example, in a DW10 test following CEC F-098-08, as further described below in the experimental section).
• 13. Use according to embodiment 11 as a gasoline additive for reducing deposits in the intake system of a gasoline engine, in particular DISI and PFI (Port Fuel Injector) engines.
• 14. Use according to embodiment 10 as a diesel fuel additive for reducing and / or avoiding deposits in the injection systems, as determined, for example, in an XUD 9 test, according to CEC-F-23-1-01), in particular the Internal Diesel Injector Deposits (IDID ) and / or valve sticking in direct injection diesel engines, particularly in common rail injection systems (such as determined by an IDID test procedure, as further described below in the experimental section).
• 15. An additive concentrate containing in combination with further diesel or petrol additives or lubricant additives at least one quaternized nitrogen compound as defined in embodiment 9 or prepared according to embodiment 10.

Respective suitable test methods for checking the above-mentioned applications are known to those skilled in the art, or in the following experimental part, which is hereby expressly incorporated by reference, described.

A2) General definitions

Unless otherwise indicated, the following general meanings apply:

"Hydrocarbyl" is to be construed broadly and includes both long-chain and short-chain, straight or branched hydrocarbon radicals having 1 to 50 carbon atoms, which may additionally contain heteroatoms, such as. O, N, NH, S, may be included in their chain. A particular group of hydrocarbyl radicals includes both long and short chain, straight chain or branched alkyl radicals having 1 to 1000, 3 to 500, 4 to 400 carbon atoms.

"Long-chain" hydrocarbyl radicals are straight-chain or branched hydrocarbon radicals and have 7 to 50 or 8 to 50 or 8 to 40 or 10 to 20 carbon atoms, which may additionally contain heteroatoms, such as. O, N, NH, S, may be included in their chain. Furthermore, the radicals may be monounsaturated or polyunsaturated and one or more non-cumulated, e.g. 1 to 5, such as 1, 2 or 3 C-C double bonds or C-C triple bonds, in particular 1, 2 or 3 double bonds. They can be natural or synthetic.

They may also have a number average molecular weight (M _n ) of 85 to 20,000, such as 113 to 10,000, or 200 to 10,000 or 350 to 5,000, such as 350 to 3,000, 500 to 2,500, 700 to 2,500, or 800 to 1,500 are then in particular essentially composed of C _2-6 -, in particular C _2-4 monomer units, such as ethylene, propylene, n- or iso-butylene or mixtures thereof, wherein the various monomers may be randomly distributed or incorporated in units as blocks. Such long-chain hydrocarbyl radicals are also referred to as polyalkylene radicals or poly-C _2-6 or poly-C _2-4 -alkylene radicals. Suitable long-chain hydrocarbyl radicals and their preparation are for example also described in the WO2006 / 135881 and the literature quoted there.

Examples of particularly useful polyalkylene radicals are polyisobutenyl radicals derived of so-called "highly reactive" polyisobutenes, which are characterized by a high content of terminal double bonds. Terminal arranged double bonds are alpha-olefinic double bonds of the type

which together are also referred to as vinylidene double bonds. Suitable highly reactive polyisobutenes are, for example, polyisobutenes which have a proportion of vinylidene double bonds of greater than 70 mol%, in particular greater than 80 mol% or greater than 85 mol%. Particular preference is given to polyisobutenes which have uniform polymer skeletons. Uniform polymer skeletons have, in particular, those polyisobutenes which are composed of at least 85% by weight, preferably at least 90% by weight and more preferably at least 95% by weight, of isobutene units. Preferably, such highly reactive polyisobutenes have a number average molecular weight in the range mentioned above. In addition, the highly reactive polyisobutenes can have a polydispersity in the range of 1.05 to 7, more preferably from about 1.1 to 2.5, e.g. of less than 1.9 or less than 1.5. By polydispersity is meant the quotient of weight average molecular weight Mw divided by the number average molecular weight Mn.

Particularly suitable highly reactive polyisobutenes are e.g. the Glissopal grades of BASF SE, in particular Glissopal 1000 (Mn = 1000), Glissopal V 33 (Mn = 550) and Glissopal 2300 (Mn = 2300) and mixtures thereof. Other number-average molecular weights can be adjusted in a manner known in principle by mixing polyisobutenes of different number-average molecular weights or by extractive enrichment of polyisobutenes of specific molecular weight ranges.

A particular group of long chain hydrocarbyl radicals includes straight or branched chain alkyl radicals ("long chain" alkyl radicals) of 8 to 50, such as 8 to 40 or 8 to 30 or 10 to 20 carbon atoms.

Another group of special long-chain hydrocarbyl radicals comprises polyalkylene radicals which in particular consist essentially of C _2-6 , in particular C _2-4 monomer building blocks, such as ethylene, propylene, n- or iso-butylene or mixtures thereof are and have a degree of polymerization of 2 to 100, or 3 to 50 or 4 to 25,

"Short-chain hydrocarbyl" or "low molecular weight hydrocarbyl" in particular represents straight-chain or branched alkyl or alkenyl, optionally interrupted by one or more, such as e.g. 2, 3 or 4 heteroatom groups, such as -O- or -NH-. or optionally one or more times, e.g. 2, 3 or 4 times substituted.

"Hydrocarbylene" means straight chain or mono- or multi-branched bridging groups of 1 to 10 carbon atoms, optionally interrupted by one or more, e.g. 2, 3 or 4 heteroatom groups, such as -O- or -NH-. or optionally one or more times, e.g. 2, 3 or 4 times substituted.

"Alkyl" or "lower alkyl" in particular represents saturated, straight-chain or branched hydrocarbon radicals having 1 to 4, 1 to 5, 1 to 6, or 1 to 7, carbon atoms, such as. Methyl, ethyl, n -propyl, 1-methylethyl, n -butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, n -pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2, 2-trimethylpropyl, 1-ethyl-1-methylpropyl and 1-ethyl-2-methylpropyl; and n-heptyl, as well as the mono- or polysubstituted analogs thereof.

By "long-chain alkyl" is meant, for example, saturated, straight-chain or branched hydrocarbon radicals of 8 to 50, such as e.g. 8 to 40 or 8 to 30 or 10 to 20 carbon atoms, such as octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, hencosyl, docosyl, tricosyl, tetracosyl, pentacosyl, Hexacosyl, heptacosyl, octacosyl, nonacosyl, squalyl, constitutional isomers, especially one or more branched isomers and higher homologs thereof.

"Alkenyl" is mono- or polysubstituted, especially monounsaturated, straight-chain or branched hydrocarbon radicals having 2 to 4, 2 to 6, or 2 to 7 carbon atoms and a double bond in any position, e.g. C ₂ -C ₆ alkenyl such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1 propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3 Methyl 3-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2- propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl 1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1, 1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2 Dimethyl 2-butenyl, 1,2-dimethyl-3-butenyl, 1,3-dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 2.2 Dimethyl 3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl, 3.3 Dimethyl 2-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl 3-butenyl, 1,1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl and 1-ethyl-2-methyl-2 propenyl.

"Substituents" for radicals given herein are, in particular, unless otherwise specified, selected from keto groups, -COOH, -COO-alkyl, -OH, -SH, -CN, amino, -NO ₂ , alkyl, or alkenyl groups ,

"Mn" represents the number average molecular weight and is determined in a conventional manner; in particular, such data refer to Mn values determined by relative methods such as gel permeation chromatography with THF as the eluent and polystyrene standards or absolute methods such as vapor phase osmometry using toluene as a solvent.

"Mw" represents the weight average molecular weight and is determined in a conventional manner; in particular, such information refers to Mw values, determined by relative methods such as gel permeation chromatography with THF as eluent and polystyrene standards or absolute methods such as light scattering.

The "degree of polymerization" usually refers to the numerical average degree of polymerization (determination method gel permeation chromatography with THF as eluent and polystyrene standards, or GC-MS coupling).

A3) Tertiary amines of the formula (3)

Tertiary amines of the formula (3) are compounds known per se, as described, for example, in US Pat EP-A-2 033 945 ,

The tertiary amine starting material (3) preferably carries a segment of the formula NR _a R _b wherein one of the radicals has an alkyl group having 8 to 40 carbon atoms and the other an alkyl group having up to 40, particularly preferably 8 to 40 carbon atoms. The radical R _c is in particular a short-chain C ₁ -C ₆ -alkyl radical, such as a methyl, ethyl or propyl group. R _a and R _b may be straight or branched, and / or may be the same or different. For example, R _a and R _{b may be} a straight chain C ₁₂ -C ₂₄ alkyl group. Alternatively, only one of the two radicals may be long-chain (eg having from 8 to 40 carbon atoms) and the other may be a methyl, ethyl or propyl group.

Conveniently, the NR _a R _b segment is derived from a secondary amine such as dioctadecylamine, di-cocoamine, dihydrogenated tallowamine and methylbehenylamine. Amine compounds, such as those available from natural materials, are also suitable. For example, mention may be made of a secondary hydrogenated tallow amine wherein the alkyl groups are derived from hydrogenated tallow fat and have about 4 wt% C ₁₄ , 31 wt% C ₁₆ and 59 wt% C ₁₈ alkyl groups. Corresponding tertiary amines of the formula (3) are sold, for example, by Akzo Nobel under the name Armeen® M2HT or Armeen® M2C.

However, the tertiary amine starting material (3) can also be formed such that the radicals R _a , R _b and R _{c have the} same or different long-chain alkyl radicals, in particular straight-chain or branched alkyl groups having 8 to 40 carbon atoms.

However, the tertiary amine starting material (3) can also be formed such that the radicals R _a , R _b and R _{c are} identical or different short-chain alkyl radicals, in particular straight-chain or branched alkyl groups having 1 to 7 or especially 1 to 4 carbon atoms.

• N,N-Dimethyl-N-(2-ethylhexyl)amin, N,N-Dimethyl-N-(2-propylheptyl)amin, Dodecyldimethylamin, Hexadecyldimethylamin, Oleyldimethylamin, Cocoyldimethylamin, Dicocoylmethylamin, Talgfettdimethylamin, Ditalgfettmethylamin, Tridodecylamin, Trihexadecylamin, Trioctadecylamin, Sojadimethylamin, Tris(2-ethylhexyl)amin, sowie Alamine 336 (Tri-n-octylamin).

Other nonlimiting examples of suitable amines are:

• N, N-dimethyl-N- (2-ethylhexyl) amine, N, N-dimethyl-N- (2-propylheptyl) amine, dodecyldimethylamine, hexadecyldimethylamine, oleyldimethylamine, cocoyldimethylamine, dicocoylmethylamine, tallow fatty dimethylamine, ditallow fatty methylamine, tridodecylamine, trihexadecylamine, trioctadecylamine, Soyadimethylamine, tris (2-ethylhexyl) amine, and Alamine 336 (tri-n-octylamine).

Nonlimiting examples of short-chain tertiary amines are: trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, ethyldimethylamine, dimethylethylamine, n-propyldimethylamine, Isopropyldimethylamine, n-propyldiethylamine, isopropyldiethylamine, n-butyldimethylamine. n-butyldiethylamine,. n-Butyldipropylamin.

Short-chain triamines are particularly useful even when the quaternizing agent (see below) carries one or more alkyl radicals R _d with more than one carbon atom or one or more aromatic radicals R _d

A4) Quaternizing agent:

wobei die darin enthaltenen R_d Reste gleich oder verschieden sind und für H oder für einen Hydrocarbylrest stehen, wobei der Hydrocarbylrest wenigstens 1 bis 10 Kohlenstoffatome aufweist. Insbesondere sind dies aliphatische oder aromatische Reste, wie z.B. lineare oder verzweigte C_1-10-Alkylreste oder aromatische Reste, wie Phenyl oder C₁-₄-Alkylphenyl.In a further particular embodiment, the quaternization of the at least one quaternizable tertiary nitrogen atom is carried out with at least one quaternizing agent selected from epoxides, in particular hydrocarbyl epoxides.

wherein the R _d radicals contained therein are the same or different and are H or a hydrocarbyl radical, wherein the hydrocarbyl radical has at least 1 to 10 carbon atoms. In particular, these are aliphatic or aromatic radicals, such as for example, linear or branched C _1-10 alkyl radicals or aromatic radicals, such as phenyl or C _1-4 alkylphenyl.

Suitable hydrocarbyl epoxides are, for example, aliphatic and aromatic alkylene oxides, in particular C _2-12 -alkylene oxides, such as ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 2-methyl-1,2-propene oxide (isobutene oxide). , 1,2-pentene oxide, 2,3-pentene oxide, 2-methyl-1,2-butene oxide, 3-methyl-1,2-butene oxide, 1,2-hexene oxide, 2,3-hexene oxide, 3,4-hexene oxide , 2-methyl-1,2-pentene oxide, 2-ethyl-1,2-butene oxide, 3-methyl-1,2-pentene oxide, 1,2-decene oxide, 1,2-dodecene oxide or 4-methyl-1,2 -pentenoxid; and also aromatic-substituted ethylene oxides, such as optionally substituted styrene oxide, in particular styrene oxide or 4-methyl-styrene oxide.

In the case of using epoxides as quaternizing these are in the presence of free acids, especially in the presence of free hydrocarbyl-substituted unsaturated, especially saturated, optionally substituted, in particular unsubstituted protic acids, such as especially with hydrocarbyl-substituted C ₃ -C ₂₈ or C. _3- C ₁₂ dicarboxylic acids, in particular unsubstituted, saturated C ₃ -C ₆ dicarboxylic acid used ..

Suitable dicarboxylic acids are saturated acids, such as malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic, undecanedioic and dodecanedioic or higher molecular weight acids, such as tertiary, hexanoic or octadecanedioic acid, such as malic acid , α-ketoglutaric acid, oxaloacetic acid; glutamic acid; aspartic acid; and unsaturated acids such as maleic acid and fumaric acid; such as in particular malonic, succinic, glutaric, adipic and pimelic acid.

Also suitable are aromatic dicarboxylic acid, e.g. Phthalic acid.

If required or desired, hydrocarbyl-substituted dicarboxylic acids can also be used in their anhydride form. For the quaternization, the ring opening of the anhydride is then effected by the addition of water.

A5) Preparation of additives according to the invention: a) Quaternization

The quaternization with an epoxide of the formula (4) is basically based on known methods. If the boiling point of a component of the reaction mixture, in particular of the epoxide, at normal pressure above the reaction temperature, the reaction is conveniently carried out in an autoclave.

For example, in an autoclave, a solution of the tertiary amine with the organic hydrocarbyl substituted dicarboxylic acid (such as polyisobutene acid) is added in the required approximately stoichiometric amounts. For example, 0.1 to 2.0, 0.2 to 1.5, or 0.5 to 1.25 equivalents of dicarboxylic acid can be used per equivalent of quaternizable tertiary nitrogen atom. In particular, however, approximately approximately molar proportions of the dicarboxylic acid are used. The mixture is then sufficiently purged with N ₂ , and adjusted to a suitable form and the epoxide (eg propylene oxide) is metered in the required stoichiometric amounts at a temperature between 20 ° C and 180 ° C. For example, 0.1 to 4.0, 0.2 to 3, or 0.5 to 2 equivalents of epoxide can be used per equivalent of quaternizable tertiary nitrogen atom. In particular, however, about 1 to 2 equivalents of epoxide are used in relation to the tertiary amine to fully quaternize the tertiary amine group. In particular, a molar excess of alkylene oxide can be set, whereby the free carboxyl group of the dicarboxylic acid is partially or completely esterified. The mixture is then over a suitably long period of a few minutes to about 24 hours, such as stirred for about 10 h at a temperature between 20 ° C and 180 ° C (eg 50 ° C), cooled, such as to about 20 to 50 ° C. , purged with N ₂ and the reactor emptied.

The reaction can be at about 0.1 to 20 bar, such as. 1 to 10 or 1.5 to 5 bar pressure. The reaction can also be carried out at atmospheric pressure. In particular, an inert gas atmosphere, such as e.g. Nitrogen, appropriate.

If necessary, the reactants may be presented in a suitable inert organic aliphatic or aromatic solvent or mixture thereof for quaternization. Typical examples are, for example Solvesso series solvents, toluene or xylene or 2-ethylhexanol, or 2-propylheptanol, and also butyl diglycol, butyl glycol, methoxypropoxypropanol, butoxydipropanol or straight-chain and branched saturated hydrocarbons. The quaternization can also be carried out in the absence of a solvent.

The quaternization may be carried out in the presence of a protic solvent, optionally also in combination with an aliphatic or aromatic solvent. In particular, suitable protic solvents have a dielectric constant (at 20 ° C.) of greater than 7. The protic solvent may contain one or more OH groups and may also be water. Suitable solvents may also be alcohols, glycols and glycol ethers. In particular, suitable protic solvents may be those described in U.S. Pat WO 2010132259 are called. Particularly suitable solvents are methanol, ethanol, n-propanol, isoPropanol, all isomers of butanol, all isomers of pentanol, all isomers of hexanol, 2-ethylhexanol, 2-propylheptanol, as well as mixtures of different alcohols. The presence of a protic solvent can positively influence the conversion and reaction rate of quaternization.

b) work-up of the reaction mixture

The final reaction product thus formed can theoretically be further purified or the solvent removed. Optionally, excess reagent, such as excess epoxide, may be removed. This can be done for example by introducing nitrogen at atmospheric pressure or under reduced pressure. However, in order to improve the further processability of the products, solvents may also be added after the reaction, e.g. Solvesso series solvent, 2-ethylhexanol, or substantially aliphatic solvents. Usually, however, this is not absolutely necessary, so that the reaction product can be used without further purification as an additive, if appropriate after mixing with further additive components (see below).

B) Further additive components

The fuel additized with the quaternized additive according to the invention is a gasoline fuel or in particular a middle distillate fuel, especially a diesel fuel.

The fuel may contain other conventional additives to improve the effectiveness and / or wear suppression.

In the case of diesel fuels, these are primarily conventional detergent additives, carrier oils, cold flow improvers, lubricity improvers, corrosion inhibitors, demulsifiers, dehazers, defoamers, cetane improvers, combustion improvers, antioxidants or stabilizers, antistatic agents, metallocenes, metal deactivators, dyes and / or Solvent.

In the case of gasoline fuels, these are mainly friction modifiers, corrosion inhibitors, demulsifiers, dehazers, antifoams, combustion improvers, antioxidants or stabilizers, antistatic agents, metallocenes, metal deactivators, dyes and / or solvents.

Typical examples of suitable co-additives are listed in the following section:

B1) Detergent additives

• (Da) Mono- oder Polyaminogruppen mit bis zu 6 Stickstoffatomen, wobei mindestens ein Stickstoffatom basische Eigenschaften hat;
• (Db) Nitrogruppen, gegebenenfalls in Kombination mit Hydroxylgruppen;
• (Dc) Hydroxylgruppen in Kombination mit Mono- oder Polyaminogruppen, wobei mindestens ein Stickstoffatom basische Eigenschaften hat;
• (Dd) Carboxylgruppen oder deren Alkalimetall- oder Erdalkalimetallsalzen;
• (De) Sulfonsäuregruppen oder deren Alkalimetall- oder Erdalkalimetallsalzen;
• (Df) Polyoxy-C₂- bis C₄-alkylengruppierungen, die durch Hydroxylgruppen, Mono- oder Polyaminogruppen, wobei mindestens ein Stickstoffatom basische Eigenschaften hat, oder durch Carbamatgruppen terminiert sind;
• (Dg) Carbonsäureestergruppen;
• (Dh) aus Bernsteinsäureanhydrid abgeleiteten Gruppierungen mit Hydroxy- und/oder Amino- und/oder Amido- und/oder Imidogruppen; und/oder
• (Di) durch Mannich-Umsetzung von substituierten Phenolen mit Aldehyden und Mono- oder Polyaminen erzeugten Gruppierungen.

The usual detergent additives are preferably amphiphilic substances which have at least one hydrophobic hydrocarbon radical having a number-average molecular weight (M _n ) of from 85 to 20 000 and at least one polar group selected from:

• (Da) mono- or polyamino groups having up to 6 nitrogen atoms, wherein at least one nitrogen atom has basic properties;
• (Db) nitro groups, optionally in combination with hydroxyl groups;
• (Dc) hydroxyl groups in combination with mono- or polyamino groups, wherein at least one nitrogen atom has basic properties;
• (Dd) carboxyl groups or their alkali metal or alkaline earth metal salts;
• (De) sulfonic acid groups or their alkali metal or alkaline earth metal salts;
• (Df) polyoxy-C ₂ - to C ₄ -alkylene groups which are terminated by hydroxyl groups, mono- or polyamino groups, where at least one nitrogen atom has basic properties, or by carbamate groups;
• (Dg) carboxylic acid ester groups;
• (Ie) derived from succinic anhydride moieties having hydroxy and / or amino and / or amido and / or imido groups; and or
• (Di) by Mannich reaction of substituted phenols with aldehydes and mono- or polyamines generated groupings.

The hydrophobic hydrocarbon residue in the above detergent additives which provides sufficient solubility in the fuel has a number average molecular weight (M _n ) of from 85 to 20,000, preferably from 113 to 10,000, more preferably from 300 to 5,000, more preferably from 300 to 3,000, even more preferably from 500 to 2,500 and in particular from 700 to 2,500, especially from 800 to 1500. As a typical hydrophobic hydrocarbon radical, in particular in conjunction with the polar in particular polypropenyl, polybutenyl and polyisobutenyl radicals having a number average molecular weight M _n of preferably in each case 300 to 5,000, particularly preferably 300 to 3,000, more preferably 500 to 2,500, even more preferably 700 to 2,500 and in particular 800 to 1,500 into consideration.

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

Mono- or polyamino (Da) -containing additives are preferably polyalkene mono- or polyalkene polyamines based on polypropene or of highly reactive (ie predominantly terminal double bonds) or conventional (ie predominantly intermediate double bonds) polybutene or polyisobutene with M _n = 300 to 5000, especially preferably 500 to 2500 and in particular 700 to 2500. Such additives based on highly reactive polyisobutene, which from the polyisobutene, which may contain up to 20 wt .-% of n-butene units, by hydroformylation and reductive amination with ammonia, monoamines or polyamines such as dimethylaminopropylamine, ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine can be prepared, in particular from EP-A 244 616 known. If one proceeds in the preparation of the additives of polybutene or polyisobutene with predominantly intermediate double bonds (usually in the β and γ position), the preparation route by chlorination and subsequent amination or by oxidation of the double bond with air or ozone to carbonyl or Carboxyl compound and subsequent amination under reductive (hydrogenating) conditions. For amination here amines, such as. As ammonia, monoamines or the above polyamines, are used. Corresponding additives based on polypropene are especially in the WO-A 94/24231 described.

Other special monoamine (Da) containing additives are the hydrogenation of the reaction products of polyisobutenes having an average degree of polymerization P = 5 to 100 with nitrogen oxides or mixtures of nitrogen oxides and oxygen, as described in particular in WO-A 97/03946 are described.

Further special monoamino (Da) -containing additives are the compounds obtainable from polyisobutene epoxides by reaction with amines and subsequent dehydration and reduction of the amino alcohols, as described in particular in US Pat DE-A 196 20 262 are described.

Nitro groups (Db), optionally in combination with hydroxyl groups, containing additives are preferably reaction products of polyisobutenes of average degree of polymerization P = 5 to 100 or 10 to 100 with nitrogen oxides or mixtures of nitrogen oxides and oxygen, as described in particular in WO-A96 / 03367 and in the WO-A 96/03479 are described. These reaction products are generally mixtures of pure nitropolyisobutenes (eg, α, β-dinitropolyisobutene) and mixed hydroxynitropolyisobutenes (eg, α-nitro-β-hydroxy polyisobutene).

Hydroxyl groups in combination with mono- or polyamino (Dc) -containing additives are in particular reaction products of polyisobutene epoxides obtainable from preferably predominantly terminal double bonds having polyisobutene with M _n = 300 to 5000 with ammonia, mono- or polyamines, as in particular in the EP-A 476 485 are described.

Carboxyl groups or their alkali metal or alkaline earth metal salts (Dd) containing additives are preferably copolymers of C ₂ - to C ₄₀ olefins with maleic anhydride having a total molecular weight of 500 to 20,000, the carboxyl groups are reacted wholly or partially to the alkali metal or alkaline earth metal salts and a remaining group of the carboxyl groups with alcohols or amines. Such additives are in particular from the EP-A 307 815 known. Such additives are primarily for preventing valve seat wear and can, as in the WO-A 87/01126 described, be used with advantage in combination with conventional fuel detergents such as poly (iso) -butene amines or polyetheramines.

Sulfonic acid groups or their alkali metal or alkaline earth metal salts (De) containing additives are preferably alkali metal or alkaline earth metal salts of a Sulfobernsteinsäurealkylesters, as described in particular in EP-A 639 632 is described. Such additives are primarily used to prevent valve seat wear and can be used to advantage in combination with conventional fuel detergents such as poly (iso) butenamines or polyetheramines.

Polyoxy-C ₂ -C ₄ -alkylene (Df) containing additives are preferably polyether or polyetheramines, which by reaction of C ₂ - to C ₆₀ -alkanols, C ₆ -C ₃₀ alkanediols, mono- or di-C ₂ - to C ₃₀ -alkylamines, C ₁ - to C ₃₀ -alkylcyclohexanols or C ₁ - to C ₃₀ -alkylphenols with 1 to 30 mol of ethylene oxide and / or propylene oxide and / or butylene oxide per hydroxyl group or amino group and, in the case of polyetheramines, are obtainable by subsequent reductive amination with ammonia, monoamines or polyamines. Such products are used in particular in the EP-A 310 875 . EP-A 356 725 . EP-A 700 985 and US Pat. No. 4,877,416 described. In the case of polyethers, such products also meet carrier oil properties. Typical examples of these are tridecanol or Isotridecanolbutoxylate, Isononylphenolbutoxylate and Polyisobutenolbutoxylate and propoxylates and the corresponding reaction products with ammonia.

Carboxylic ester groups (Dg) containing additives are preferably esters of mono-, di- or tricarboxylic acids with long-chain alkanols or polyols, especially those having a minimum viscosity of 2 mm ² / s at 100 ° C, as in particular in DE-A 38 38 918 are described. As mono-, di- or tricarboxylic acids it is possible to use aliphatic or aromatic acids, especially suitable ester alcohols or polyols are long-chain representatives having, for example, 6 to 24 C atoms. Typical representatives of the esters are adipates, phthalates, isophthalates, terephthalates and trimellitates iso-octanol, iso-nonanol, iso-decanol and iso-tridecanol. Such products also meet carrier oil properties.

Derivatives derived from succinic anhydride with hydroxyl and / or amino and / or amido and / or imido (Dh) containing additives are preferably corresponding derivatives of alkyl- or alkenyl-substituted succinic anhydride and in particular the corresponding derivatives of polyisobutenyl succinic anhydride, which by reaction of conventional or highly reactive polyisobutene having M _n = preferably 300 to 5000, more preferably 300 to 3000, more preferably 500 to 2500, even more preferably 700 to 2500 and especially 800 to 1500, with maleic anhydride by thermal means in an ene reaction or via the chlorinated polyisobutene are available. The groups having hydroxyl and / or amino and / or amido and / or imido groups are, for example, carboxylic acid groups, acid amides of monoamines, acid amides of diamines or polyamines which, in addition to the amide function, still have free amine groups, succinic acid derivatives with a Acid and an amide, Carbonsäureimide with monoamines, Carbonsäureimide with di- or polyamines, which still have free amine groups in addition to the imide function, or diimides, which are formed by the reaction of di- or polyamines with two succinic acid derivatives. In the presence of imido groups D (h), however, the further detergent additive according to the present invention is used only up to a maximum of 100% of the amount by weight of compounds having betaine structure. Such fuel additives are well known and described, for example, in documents (1) and (2). Preference is given to the reaction products of alkyl- or alkenyl-substituted succinic acids or derivatives thereof with amines and particularly preferably to the reaction products of polyisobutenyl-substituted succinic acids or derivatives thereof with amines. Of particular interest here are reaction products with aliphatic polyamines (polyalkyleneimines), in particular ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine and hexaethyleneheptamine, which have an imide structure.

By Mannich reaction of substituted phenols with aldehydes and mono- or polyamines generated moieties containing (Di) additives are preferably reaction products of polyisobutene-substituted phenols with formaldehyde and mono- or polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine or dimethylaminopropylamine. The polyisobutenyl-substituted phenols may be derived from conventional or highly reactive polyisobutene having M _n = 300 to 5,000. Such "polyisobutene-Mannich bases" are particularly in the EP-A 831 141 described.

One or more of said detergent additives may be added to the fuel in such an amount that the metering rate of these detergent additives is preferably from 25 to 2500 ppm by weight, in particular from 75 to 1500 ppm by weight, especially from 150 to 1000% by weight . ppm.

B2) carrier oils

Co-used carrier oils may be mineral or synthetic. Suitable mineral carrier oils are fractions obtained in petroleum processing, such as bright stock or base oils having viscosities such as from class SN 500 to 2000, but also aromatic hydrocarbons, paraffinic hydrocarbons and alkoxyalkanols. It is also useful as a "hydrocrack oil" known and obtained in the refining of mineral oil fraction (Vakuumdestillatschnitt with a boiling range of about 360 to 500 ° C, available from high pressure catalytically hydrogenated and isomerized and dewaxed natural mineral oil). Also suitable are mixtures of the abovementioned mineral carrier oils.

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

Examples of suitable polyolefins are olefin polymers having M _n = 400 to 1800, especially based on polybutene or polyisobutene (hydrogenated or non-hydrogenated).

Examples of suitable polyethers or polyetheramines are preferably compounds containing polyoxy-C ₂ - to C ₄ -alkylene groups which are prepared by reacting C ₂ - to C ₆₀ -alkanols, C ₆ - to C ₃₀ -alkanediols, mono- or di-C ₂ - to C ₃₀ -alkylamines, C ₁ - to C ₃₀ -alkyl-cyclohexanols or C ₁ - to C ₃₀ -alkylphenols with 1 to 30 mol of ethylene oxide and / or propylene oxide and / or butylene oxide per hydroxyl group or amino group and, in the case of polyetheramines, are obtainable by subsequent reductive amination with ammonia, monoamines or polyamines. Such products are used in particular in the EP-A 310 875 . EP-A 356 725 . EP-A 700 985 and the US-A 4,877,416 described. For example, poly-C ₂ -C ₆ -alkylene oxide amines or functional derivatives thereof can be used as polyetheramines. Typical examples of these are tridecanol or Isotridecanolbutoxylate, Isononylphenolbutoxylate and Polyisobutenolbutoxylate and propoxylates and the corresponding reaction products with ammonia.

Examples of carboxylic acid esters of long-chain alkanols are, in particular, esters of mono-, di- or tricarboxylic acids with long-chain alkanols or polyols, as are described in particular in US Pat DE-A 38 38 918 are described. As mono-, di- or tricarboxylic acids it is possible to use aliphatic or aromatic acids, especially suitable ester alcohols or polyols are long-chain representatives having, for example, 6 to 24 carbon atoms. Typical representatives of the esters are adipates, phthalates, isophthalates, terephthalates and trimellitates of isooctanol, isononanol, isodecanol and of isotridecanol, eg. B. di- (n- or isotridecyl) phthalate.

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

Examples of particularly suitable synthetic carrier oils are alcohol-started polyethers having about 5 to 35, preferably about 5 to 30, particularly preferably 10 to 30 and in particular 15 to 30 C ₃ - to C ₆ -alkylene oxide units, for. For example, propylene oxide, n-butylene oxide and isobutylene oxide units or mixtures thereof, per alcohol molecule. Nonlimiting examples of suitable starter alcohols are long-chain alkanols or long-chain alkyl-substituted phenols, where the long-chain alkyl radical is in particular a straight-chain or branched C ₆ - to C ₁₈ -alkyl radical. Specific examples include tridecanol and nonylphenol. Particularly preferred alcohol-started polyethers are the reaction products (polyetherification products) of monohydric aliphatic C ₆ - to C ₁₈ -alcohols with C ₃ - to C ₆ -alkylene oxides. Examples of monohydric aliphatic C ₆ -C ₁₈ -alcohols are hexanol, heptanol, octanol, 2-ethylhexanol, nonyl alcohol, decanol, 3-propylheptanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, octadecanol and their constitution and position isomers. The alcohols can be in the form of pure isomers as well as in Form of technical mixtures are used. A particularly preferred alcohol is tridecanol. Examples of C ₃ - to C ₆ -alkylene oxides are propylene oxide, such as 1,2-propylene oxide, butylene oxide, such as 1,2-butylene oxide, 2,3-butylene oxide, isobutylene oxide or tetrahydrofuran, pentylene oxide and hexylene oxide. Among these, particularly preferred are C ₃ to C ₄ alkylene oxides, ie, propylene oxide such as 1,2-propylene oxide and butylene oxide such as 1,2-butylene oxide, 2,3-butylene oxide and isobutylene oxide. Specifically, butylene oxide is used.

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

Particular carrier oils are synthetic carrier oils, the alcohol-initiated polyethers described above being particularly preferred.

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

B3) cold flow improver

Suitable cold flow improvers are in principle all organic compounds which are able to improve the flow behavior of middle distillate fuels or diesel fuels in the cold. Conveniently, they must have sufficient oil solubility. In particular, the usually used for middle distillates of fossil origin, ie for conventional mineral diesel fuels, used cold flow improvers ("middle distillate flow improvers", "MDFI") come into consideration. However, it is also possible to use organic compounds which, when used in conventional diesel fuels, have in part or predominantly the properties of a wax anti-settling additive ("WASA"). Also, they can act partly or predominantly as nucleators. However, it is also possible to use mixtures of organic compounds which are active as MDFI and / or which act as WASA and / or as nucleators.

• (K1) Copolymeren eines C₂- bis C₄₀-Olefins mit wenigstens einem weiteren ethylenisch ungesättigten Monomer;
• (K2) Kammpolymeren;
• (K3) Polyoxyalkylenen;
• (K4) polaren Stickstoffverbindungen;
• (K5) Sulfocarbonsäuren oder Sulfonsäuren oder deren Derivaten; und
• (K6) Poly(meth)acrylsäureestern.

Typically, the cold flow improver is selected from:

• (K1) copolymers of a C ₂ to C ₄₀ olefin with at least one further ethylenically unsaturated monomer;
• (K2) comb polymers;
• (K3) polyoxyalkylenes;
• (K4) polar nitrogen compounds;
• (K5) sulfocarboxylic acids or sulfonic acids or their derivatives; and
• (K6) poly (meth) acrylic acid esters.

Mixtures of different representatives from one of the respective classes (K1) to (K6) as well as mixtures of representatives from different classes (K1) to (K6) can be used.

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

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

If further olefins are polymerized in, these are preferably higher molecular weight than the abovementioned C ₂ to C ₄₀ olefin base monomers. If, for example, ethylene or propene is used as the olefin base monomer, C ₁₀ - to C ₄₀ -α-olefins are particularly suitable as further olefins. Other olefins are polymerized in most cases only when monomers with carboxylic acid ester functions are used.

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

Suitable carboxylic alkenyl esters are, for example, C ₂ -C ₁₄ -alkenyl esters, for example the vinyl and propenyl esters, of carboxylic acids having 2 to 21 carbon atoms, whose hydrocarbon radical may be linear or branched. Preferred among these are the vinyl esters. Among the carboxylic acids with a branched hydrocarbon radical, preference is given to those whose branching is in the α-position to the carboxyl group, the α-carbon atom being particularly preferably tertiary, ie the carboxylic acid being a so-called neocarboxylic acid. Preferably, however, the hydrocarbon radical of the carboxylic acid is linear.

Examples of suitable carboxylic alkenyl esters are vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl neopentanoate, vinyl hexanoate, vinyl neononanoate, vinyl neodecanoate and the corresponding propenyl esters, with vinyl esters being preferred. A particularly preferred carboxylic acid alkenyl ester is vinyl acetate; typical resulting copolymers of group (K1) are the most commonly used ethylene-vinyl acetate copolymers ("EVA").

Particularly advantageous ethylene-vinyl acetate copolymers and their preparation are in the WO 99/29748 described.

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

Also, terpolymers of a C ₂ - to C ₄₀ -α-olefin, a C ₁ - to C ₂₀ alkyl ester of an ethylenically unsaturated monocarboxylic acid having 3 to 15 carbon atoms and a C ₂ - to C ₁₄ alkenyl ester of a saturated monocarboxylic acid having 2 to 21 Carbon atoms are suitable as copolymers of class (K1). Such terpolymers are in the WO 2005/054314 described. A typical such terpolymer is composed of ethylene, 2-ethylhexyl acrylate and vinyl acetate.

The at least one or more ethylenically unsaturated monomers are in the copolymers of class (K1) in an amount of preferably 1 to 50 wt .-%, in particular from 10 to 45 wt .-% and especially from 20 to 40 wt .-%, based on the total copolymer copolymerized. The majority by weight of the monomer units in the copolymers of class (K1) is thus usually derived from the C ₂ to C _{40 based} olefins.

The copolymers of class (K1) preferably have a number average molecular weight M _{n of} from 1000 to 20,000, particularly preferably from 1000 to 10,000 and in particular from 1000 to 8000.

Typical comb polymers of component (K2) are, for example, by the copolymerization of maleic anhydride or fumaric acid with another ethylenically unsaturated monomer, for example with an α-olefin or an unsaturated ester such as vinyl acetate, and subsequent esterification of the anhydride or acid function with an alcohol having at least 10 carbon atoms available. Further suitable comb polymers are copolymers of α-olefins and esterified comonomers, for example esterified copolymers of styrene and maleic anhydride or esterified copolymers of styrene and fumaric acid. Suitable comb polymers may also be polyfumarates or polymaleinates. In addition, homopolymers and copolymers of vinyl ethers are suitable comb polymers. As a component of class (K2) suitable comb polymers are, for example, those which are described in the WO 2004/035715 and in " Comb-like polymers. Structure and Properties ", NA Platé and VP Shibaev, J. Poly. Sci. Macromolecular Revs., 8, pp. 117-253 (1974 Also mixtures of comb polymers are suitable.

As the component of the class (K3), suitable polyoxyalkylenes are, for example, polyoxyalkylene esters, polyoxyalkylene ethers, mixed polyoxyalkylene ester ethers, and mixtures thereof. Preferably, these polyoxyalkylene contain at least one, preferably at least two linear alkyl groups each having 10 to 30 carbon atoms and a polyoxyalkylene group having a number average molecular weight of up to 5000. Such polyoxyalkylene compounds are for example in the EP-A 061 895 as well as in the U.S. 4,491,455 described. Particular polyoxyalkylene compounds are based on polyethylene glycols and polypropylene glycols having a number average molecular weight of 100 to 5000. Further, polyoxyalkylene mono- and diesters of fatty acids having 10 to 30 carbon atoms such as stearic acid or behenic acid are suitable.

Polar nitrogen compounds suitable as a component of class (K4) may be of both ionic and nonionic nature, and preferably have at least one, especially at least two, tertiary nitrogen substituent of the general formula> NR ⁷ wherein R ^{7 is} C ₈ - to C ₄₀ hydrocarbon radical stands. The nitrogen substituents may also be quaternized, that is in cationic form. Examples of such nitrogen compounds are ammonium salts and / or amides obtainable by reacting at least one amine substituted with at least one hydrocarbyl radical with a carboxylic acid having 1 to 4 carboxyl groups or with a suitable derivative thereof. The amines preferably contain at least one linear C ₈ - to C ₄₀ -alkyl radical. Examples of suitable primary amines for the preparation of said polar nitrogen compounds are octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tetradecylamine and the higher linear homologues, and suitable secondary amines are, for example, dioctadecylamine and methylbehenylamine. Also suitable for this purpose are amine mixtures, in particular industrially available amine mixtures such as fatty amines or hydrogenated tallamines, as described, for example, in US Pat Ullmanns Encyclopedia of Industrial Chemistry, 6th edition, in the chapter "Amines, aliphatic Suitable acids for the reaction are, for example, cyclohexane-1,2-dicarboxylic acid, cyclohexane-1,2-dicarboxylic acid, cyclopentane-1,2-dicarboxylic acid, naphthalenedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid and succinic acids substituted by long-chain hydrocarbon radicals ,

In particular, the component of class (K4) is an oil-soluble reaction product of at least one tertiary amino group-containing poly (C ₂ - to C ₂₀ -carboxylic acids) with primary or secondary amines. The poly (C ₂ - to C ₂₀ -carboxylic acids) which have at least one tertiary amino group and are based on this reaction product preferably contain at least 3 carboxyl groups, in particular 3 to 12, especially 3 to 5 carboxyl groups. The carboxylic acid units in the polycarboxylic acids preferably have 2 to 10 carbon atoms, in particular they are acetic acid units. The carboxylic acid units are suitably linked to the polycarboxylic acids, usually via one or more carbon and / or nitrogen atoms. Preferably, they are attached to tertiary nitrogen atoms, which are connected in the case of several nitrogen atoms via hydrocarbon chains. Preferably, the component of class (K4) is an oil-soluble reaction product based on at least one tertiary amino group-containing poly (C ₂ - to C ₂₀ -carboxylic acids) of the general formula IIa or IIb

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

and the variable B denotes a C ₁ - to C ₁₉ -alkylene group. The compounds of the general formula IIa and IIb have in particular the properties of a WASA.

Furthermore, the preferred oil-soluble reaction product of component (K4), in particular that of general formula IIa or IIb, is an amide, an amide ammonium salt or an ammonium salt in which no, one or more carboxylic acid groups are converted into amide groups.

Straight-chain or branched C ₂ -C ₆ -alkylene groups of the variable A are, for example, 1,1-ethylene, 1,2-propylene, 1,3-propylene, 1,2-butylene, 1,3-butylene, 1,4- Butylene, 2-methyl-1,3-propylene, 1,5-pentylene, 2-methyl-1,4-butylene, 2,2-dimethyl-1,3-propylene, 1,6-hexylene (hexamethylene) and in particular 1,2-ethylene. Preferably, the variable A comprises 2 to 4, in particular 2 or 3 carbon atoms.

C ₁ - to C ₁₉ -alkylene groups of the variables B are before, for example, 1,2-ethylene, 1,3-propylene, 1,4-butylene, hexamethylene, octamethylene, decamethylene, dodecamethylene, Tetradecamethylene, hexadecamethylene, octadecamethylene, nonadecamethylene and especially methylene. Preferably, the variable B comprises 1 to 10, in particular 1 to 4, carbon atoms.

The primary and secondary amines as reaction partners for the polycarboxylic acids to form the component (K4) are usually monoamines, in particular aliphatic monoamines. These primary and secondary amines may be selected from a variety of amines bearing hydrocarbon radicals, optionally linked together.

In most cases, these amines are secondary amines on which the oil-soluble reaction products of component (K4) are based and have the general formula HN (R ⁸ ) ₂ , in which the two variables R ⁸ are each independently straight-chain or branched C ₁₀ - to C ₃₀ -alkyl radicals, in particular C ₁₄ - to C ₂₄ -alkyl radicals. These longer-chain alkyl radicals are preferably straight-chain or only slightly branched. As a rule, the abovementioned secondary amines are derived, with regard to their longer-chain alkyl radicals, from naturally occurring fatty acids or from their derivatives. Preferably, the two radicals R ^{8 are the} same.

The abovementioned secondary amines can be bound to the polycarboxylic acids by means of amide structures or in the form of the ammonium salts, and only one part can be present as amide structures and another part as ammonium salts. Preferably, only a few or no free acid groups are present. Preferably, the oil-soluble reaction products of component (K4) are completely in the form of the amide structures.

Typical examples of such components (K4) are reaction products of nitrilotriacetic acid, ethylenediaminetetraacetic acid or propylene-1,2-diaminetetraacetic acid with in each case 0.5 to 1.5 mol per carboxyl group, in particular 0.8 to 1.2 mol per carboxyl group, dioleylamine , Dipalmitinamin, Dikokosfettamin, distearylamine, dibehenylamine or especially Ditalgfettamin. A particularly preferred component (K4) is the reaction product of 1 mole of ethylenediaminetetraacetic acid and 4 moles of hydrogenated ditallow fatty amine.

Further typical examples of the component (K4) include the N, N-dialkylammonium salts of 2-N ', N'-dialkylamidobenzoates, for example, the reaction product of 1 mole of phthalic anhydride and 2 moles of ditallow fatty amine, the latter may be hydrogenated or unhydrogenated, and the reaction product of 1 mole of a Alkenylspirobislactons with 2 moles of a dialkylamine, for example Ditalgfettamin and / or tallow fatty amine, the latter two may be hydrogenated or not hydrogenated, called.

Further typical structural 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 US Pat WO 93/18115 are described.

Sulfocarboxylic acids, sulfonic acids or their derivatives which are suitable as cold flow improvers of the component of class (K5) are, for example, the oil-soluble carboxamides and carboxylic acid esters of ortho-sulfobenzoic acid in which the sulfonic acid function is present as sulfonate with alkyl-substituted ammonium cations, as described in US Pat EP-A 261 957 to be discribed.

As cold flow improvers of the component of the class (K6) suitable poly (meth) acrylic acid esters are both homo- and copolymers of acrylic and methacrylic acid esters. Preferred are copolymers of at least two mutually different (meth) acrylic acid esters, which differ with respect to the fused alcohol. Optionally, the copolymer contains a further, different of which olefinically unsaturated monomer copolymerized. The weight-average molecular weight of the polymer is preferably 50,000 to 500,000. A particularly preferred polymer is a copolymer of methacrylic acid and methacrylic acid esters of saturated C ₁₄ and C ₁₅ alcohols wherein the acid groups are neutralized with hydrogenated tallamine. Suitable poly (meth) acrylic esters are, for example, in WO 00/44857 described.

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

B4) Lubricity improver

Suitable lubricity improvers (or friction modifiers) are usually based on fatty acids or fatty acid esters. Typical examples are tall oil fatty acid, such as in the WO 98/004656 described, and glycerol monooleate. Also in the US Pat. No. 6,743,266 B2 described reaction products of natural or synthetic oils, such as triglycerides, and alkanolamines are suitable as such lubricity improvers.

B5) Corrosion Inhibitors

Suitable corrosion inhibitors are e.g. Succinic esters, especially with polyols, fatty acid derivatives, e.g. Oleic acid esters, oligomerized fatty acids, substituted ethanolamines, and products sold under the trade name RC 4801 (Rhein Chemie Mannheim, Germany) or HiTEC 536 (Ethyl Corporation).

B6) Demulsifiers

Suitable demulsifiers are e.g. the alkali or alkaline earth salts of alkyl-substituted phenol and naphthalene sulfonates and the alkali or alkaline earth salts of fatty acids, as well as neutral compounds such as alcohol alkoxylates, e.g. Alcohol ethoxylates, phenol alkoxylates, e.g. tert-butylphenol ethoxylate or tert-pentylphenol ethoxylate, fatty acids, alkylphenols, condensation products of ethylene oxide (EO) and propylene oxide (PO), e.g. also in the form of EO / PO block copolymers, polyethyleneimines or polysiloxanes.

B7) Dehazer

Suitable dehazers are e.g. alkoxylated phenol-formaldehyde condensates such as the NALCO 7D07 (Nalco) and TOLAD 2683 (Petrolite) products available under the tradename.

B8) antifoam

Suitable antifoams are e.g. Polyether-modified polysiloxanes such as the TEGOPREN 5851 (Goldschmidt), Q 25907 (Dow Corning) and RHODOSIL (Rhone Poulenc) products available under the tradename.

B9) Cetane number improver

Suitable cetane number improvers are e.g. aliphatic nitrates such as 2-ethylhexyl nitrate and cyclohexyl nitrate and peroxides such as di-tert-butyl peroxide.

B10) Antioxidants

Suitable antioxidants are e.g. substituted phenols such as 2,6-di-tert-butylphenol and 6-di-tert-butyl-3-methylphenol and phenylenediamines such as N, N'-di-sec-butyl-p-phenylenediamine.

B11) Metal deactivators

Suitable metal deactivators are e.g. Salicylic acid derivatives such as N, N'-disalicylidene-1,2-propanediamine.

B12) Solvent

Suitable ones are e.g. non-polar organic solvents such as aromatic and aliphatic hydrocarbons, for example, toluene, xylenes, white spirit, and products sold under the trade name SHELLSOL (Royal Dutch / Shell Group) and EXXSOL (ExxonMobil), as well as polar organic solvents, for example, alcohols such as 2 Ethylhexanol, decanol and isotridecanol. Such solvents usually enter the diesel fuel together with the abovementioned additives and co-additives, which they are intended to dissolve or dilute for better handling.

C) fuels

The additive of the invention is outstandingly suitable as a fuel additive and can be used in principle in any fuels. It causes a whole series of advantageous effects in the operation of internal combustion engines Fuels. The quaternized additive according to the invention is preferably used in middle distillate fuels, in particular diesel fuels.

The present invention therefore also fuels, especially middle distillate fuels, with an effective as an additive to achieve beneficial effects in the operation of internal combustion engines, such as diesel engines, especially direct injection diesel engines, especially of diesel engines with common rail injection systems, effective content on the quaternized additive according to the invention. This effective content (metering rate) is generally from 10 to 5000 ppm by weight, preferably from 20 to 1500 ppm by weight, in particular from 25 to 1000 ppm by weight, especially from 30 to 750 ppm by weight, each based on the total amount of fuel.

Middle distillate fuels, such as diesel fuels or fuel oils, are preferably petroleum raffinates, which usually have a boiling range of from 100 to 400.degree. These are mostly distillates with a 95% point up to 360 ° C or even beyond. However, these may also be so-called "Ultra Low Sulfur Diesel" or "City Diesel", characterized by a 95% point of, for example, a maximum of 345 ° C and a maximum sulfur content of 0.005 wt .-% or by a 95% point of for example, 285 ° C and a maximum sulfur content of 0.001 wt .-%. In addition to the mineral middle distillate mineral fuels or diesel fuels available through refining, those produced by coal gasification or gas liquefaction [GTL] or by biomass to liquid (BTL) fuels are also included. are available, suitable. Also suitable are mixtures of the abovementioned middle distillate fuels or diesel fuels with regenerative fuels, such as biodiesel or bioethanol.

The qualities of the heating oils and diesel fuels are specified in greater detail in, for example, DIN 51603 and EN 590 (see also Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Volume A12, pp. 617 ff.).

In addition to its use in the abovementioned middle distillate fuels of fossil, vegetable or animal origin, which are essentially hydrocarbon mixtures, the quaternized additive according to the invention can also be used in mixtures of such middle distillates with biofuel oils (biodiesel) become. For the purposes of the present invention, such mixtures are also encompassed by the term "middle distillate fuel". They are commercially available and usually contain the biofuel oils in minor amounts, typically in amounts of 1 to 30 wt .-%, in particular from 3 to 10 wt .-%, based on the total amount of middle distillate of fossil, vegetable or animal origin and biofuel.

Biofuel oils are generally based on fatty acid esters, preferably substantially on alkyl esters of fatty acids derived from vegetable and / or animal oils and / or fats. Alkyl esters are usually lower alkyl esters, in particular C ₁ - to C ₄ -alkyl esters, understood by transesterification of occurring in vegetable and / or animal oils and / or fats glycerides, especially triglycerides, by means of lower alcohols, for example ethanol or especially methanol (" FAME ") are available. Typical lower alkyl esters based on vegetable and / or animal oils and / or fats which are used as biofuel oil or components thereof include, for example, sunflower methyl ester, palm oil methyl ester ("PME"), soybean oil methyl ester ("SME") and in particular rapeseed oil methyl ester ("RME"). ,

The middle distillate fuels or diesel fuels are particularly preferably those with a low sulfur content, ie with a sulfur content of less than 0.05% by weight, preferably less than 0.02% by weight, in particular less as 0.005 wt .-% and especially less than 0.001 wt .-% sulfur.

As gasoline fuels are all commercially available gasoline fuel compositions into consideration. A typical representative here is the market-standard basic fuel of Eurosuper according to EN 228. Furthermore, petrol fuel compositions of the specification are also according to WO 00/47698 Possible fields of use for the present invention.

The quaternized additive according to the invention is particularly suitable as a fuel additive in fuel compositions, especially in diesel fuels, to overcome the initially described problems in direct injection diesel engines, especially in those with common rail injection systems.

A turbine fuel composition contains a major amount of liquid turbine fuel, such as turbine fuel common in civil or military aviation. These include, for example, fuels named Jet Fuel A, Jet Fuel A-1, Jet Fuel B, Jet Fuel JP-4, JP-5, JP-7, JP-8 and JP-8 + 100. Jet A and Jet A-1 are commercially available turbine fuel specifications based on kerosene. The associated standards are ASTM D 1655 and DEF STAN 91-91. Jet B is a further cut fuel based on naphtha and kerosene fractions. JP-4 is equivalent to Jet B. JP-5, JP-7, JP-8 and JP-8 + 100 are military turbine fuels, such as those used by the Navy and Air Force. In part, these standards designate formulations which already contain other additives, such as corrosion inhibitors, anti-icing agents, static dissipators, etc.

Suitable additives which may be included in the turbine fuel composition of the present invention include, but are not limited to, detergents, corrosion inhibitors, antioxidants such as hindered tertiary butyl phenols, N-butylphenylendiamines or N, N'-diphenylamine and derivatives thereof, metal deactivators such as N, N'-disalicylidene derivatives. 1,2-diaminopropane, solubilizers, antistatics such as Stadis 450, biocides, anti-icing agents such as diethylene glycol methyl ether, as well as mixtures of these additives.

Preferred additives are the following specific classes of compounds (A), (B) and (C):

Preferred additives (A) are derived from succinic anhydride compounds with long-chain hydrocarbon radicals having usually 15 to 700, especially 30 to 200 carbon atoms. These compounds may have further functional groups which are preferably selected from hydroxy, amino, amido and / or imido groups. Preferred additives are the corresponding derivatives of polyalkenyl succinic anhydride, which z. Example, by reaction of polyalkenes with maleic anhydride by thermal means or via the chlorinated hydrocarbons are available. The number average molecular weight of the long-chain hydrocarbon radicals is preferably in a range of about 200 to 10,000, more preferably 400 to 5000, in particular 600 to 3000 and especially 650 to 2000. Preferably, these long-chain hydrocarbon radicals are derived from conventional and in particular from the aforementioned reactive polyisobutenes. Of particular interest as additives (A) are the derivatives of polyalkenyl succinic anhydrides with ammonia, monoamines, polyamines, monoalcohols and polyols. Polyamines preferred for derivatization include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, propylenediamine, etc. Suitable alcohols include monohydric alcohols such as ethanol, allyl alcohol, dodecanol and benzyl alcohol, polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, 1,2-butanediol, neopentyl glycol, Glycerol, trimethylolpropane, erythritol, pentaerythritol, mannitol and sorbitol.

Suitable as additives succinic anhydride derivatives (A) are for example in the US 3,522,179 . US 4,234,435 . US 4,849,572 . US 4,904,401 . US 5 569 644 and US Pat. No. 6,165,235 which is incorporated herein by reference.

Preferred additives (B) are polyalkenyl thiophosphonate esters. The polyalkenyl radical of these esters preferably has a number average molecular weight in the range from about 300 to 5000, particularly preferably 400 to 2000 and in particular 500 to 1500. The polyalkenyl radical is preferably derived from polyolefins, as described above for the component (A) as a long-chain hydrocarbon radical. These are in particular polyalkenyl radicals which are derived from conventional or reactive polyisobutenes. Suitable processes for preparing suitable polyalkenyl thiophosphonate esters by reacting a polyolefin with a thiophosphorylating agent are e.g. B. in the US 5,725,611 described, which is hereby incorporated by reference.

Preferred additives (C) are Mannich adducts. Such adducts are obtained in principle by Mannich reaction of aromatic hydroxyl compounds, in particular phenol and phenol derivatives, with aldehydes and mono- or polyamines. Preferably, it is the reaction products of polyisobutene-substituted phenols with formaldehyde and mono- or polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dimethylaminopropylamine, etc. Suitable Mannich adducts and processes for their preparation are, for. B. in the US 5,876,468 . EP-A 831 141 . EP-A 1 233 990 and EP-A 1 226 188 which is incorporated herein by reference.

The additives (A) to (C) and, if appropriate, further of the abovementioned additives can usually each be used in amounts of from 0.0001 to 1% by weight, preferably from 0.001 to 0.6% by weight and in particular from 0.0015 to 0 , 4 wt .-%, based on the total amount of the turbine fuel composition can be used.

The invention will now be described in detail with reference to the following embodiments. In particular, the test methods mentioned below are part of the general disclosure of the application and are not limited to the specific embodiments.

Experimental part: A. General testing methods engine test 1. XUD9 Test - Determination of Flow Restriction

The procedure is carried out according to the standard regulations according to CEC F-23-1-01.

2. DW10 test - Determination of power loss due to injector deposits in the common rail diesel engine 2.1. DW10-KC - Keep Clean Test

The Keep Clean Test is based on the CEC Test Procedure F-098-08 Issue 5. The same test setup and motor type (PEUGEOT DW10) are used as in the CEC procedure.

Change and special features:

Purified injectors were used in the experiments. The cleaning time in the ultrasonic bath in 60 ° C water + 10% Superdecontamine (Intersciences, Brussels) was 4h.

Test run times:

The test period was 12h without shutdown periods. The in FIG. 1 The one-hour test cycle from CEC F-098-08 was traversed 12 times.

Power determination:

The initial power P0, KC [kW] is calculated from the measured torque at 4000 rpm full load directly after the test start and warm-up of the engine. The procedure is described in issue 5 of the test procedure (CEC F-98-08). The same test setup and the PEUGEOT DW10 motor type are used.

The final power (Pend, KC) is determined in the 12th cycle in stage 12, (see table, Figure 2). Again, the operating point is 4000 / min full load. Pend, KC [kW] is calculated from the measured torque.

The power loss in the KC test is calculated as follows: $$\mathrm{Power\; loss}.\mathrm{KC}\left[\%\right]=\left(1-\frac{\mathit{Pend}.\mathit{KC}}{\mathit{P}\mathrm{0}.\mathit{KC}}\right)*100$$

2.2. DW10-Dirty Up - Clean Up- (DU-CU)

The DU-CU test is based on the CEC test procedure F-098-08 Issue 5. The procedure is described in issue 5 of the test procedure (CEC F-98-08). The same test setup and the PEUGEOT DW10 motor type are used.

The DU - CU test consists of two separate tests that are run one behind the other. The first test is for deposit formation (DU), the second for deposit removal (CU). After the DU, the power loss (powerloss) is determined. After the end of the DU run, the engine is not operated for at least 8 hours and cooled to ambient temperature. Thereafter, the CU fuel is used to start the CU without removing and cleaning the injectors. Deposits and powerloss ideally go back in the CU test history.

Change and special features:

Cleaned injectors were installed in the engine before each DU test. The cleaning time in the ultrasonic bath at 60 ° C, water + 10% Superdecontamine (Intersciences, Brussels) was 4h.

Test run times:

The test period was 12h for the DU and 12h for the CU. The engine was operated in the DU and CU test without shutdown phases.

The in FIG. 1 The one-hour test cycle from CEC F-098-08 was traversed 12 times in each case.

Power determination:

The initial power P0, du [kW] is calculated from the measured torque at 4000 / min full load directly after the test start and warm-up of the engine. The procedure is also described in Issue 5 of the test procedure.

The final power (Pend, du) is determined on the 12th cycle in step 12 (see table above). Again, the operating point is 4000 / min full load. Pend, du [kW] is calculated from the measured torque.

The power loss in the DU is calculated as follows $$\mathrm{Power\; loss}.\mathrm{you}\left[\%\right]=\left(1-\frac{\mathit{Pend}.\mathit{you}}{\mathit{P}\mathrm{0}.\mathit{you}}\right)*100$$

Clean up

The initial power P0, cu [kW] is calculated from the measured torque at 4000 rpm full load directly after the test start and warm-up of the engine in the CU. The procedure is also described in Issue 5 of the test procedure.

The final power (Pend, cu) is determined in the 12th cycle in stage 12, (see table Figure 2). Again, the operating point is 4000 / min full load. Pend, cu [kW] is calculated from the measured torque.

The power loss in the CU test is calculated as follows (negative powerloss count in the cu test means performance gain) $$\mathrm{Power\; loss}\left(\mathrm{YOU}\mathrm{CU}\right)\left[\%\right]=\left(\frac{\mathit{Pend}.\mathit{you}-\mathit{Pend}.\mathit{cu}}{\mathit{P}\mathrm{0}.\mathit{you}}\right)*100$$

The fuel used was a commercial diesel fuel from Haltermann (RF-06-03). To this was added 1 wt ppm zinc in the form of a zinc didodecanoate solution to artificially stimulate the formation of deposits on the injectors.

3. IDID test - Determination of the additive effect against internal injector deposits

The formation of deposits inside the injector was characterized by the deviations of cylinder exhaust temperatures at the cylinder exit during cold start of the DW10 engine.

To promote the formation of deposits, 1 mg / L Na of an organic acid salt, 20 mg / L dodecenylsuccinic acid and 10 mg / L of water were added to the fuel.

The test is performed as a dirty-up clean-up test (DU-CU).

DU-CU is based on the CEC Test Procedure F-098-08 Issue 5.

The DU - CU test consists of two separate tests that are run one behind the other. The first test is for deposit formation (DU), the second for deposit removal (CU).

After the DU run, a cold start of the engine is carried out after a shutdown phase of at least eight hours followed by a 10-minute idle period.

Thereafter, the CU fuel is used to start the CU without removing and cleaning the injectors. After the CU run over 8h, after a shutdown phase of at least eight hours, the engine will start cold with a 10-minute idle period carried out. The evaluation is done by comparing the temperature curves for the individual cylinders after a cold start of the du and the CU run.

The IDID test indicates internal deposit formation in the injector. The characteristic used in this test is the exhaust gas temperature of the individual cylinders. With an injector system without IDID, the exhaust gas temperatures of the cylinders increase evenly. If the IDID is available, the exhaust gas temperatures of the individual cylinders do not increase uniformly and deviate from one another.

The temperature sensors are located behind the cylinder head outlet in the exhaust manifold. Significant deviations of individual cylinder temperatures (e.g.,> 20 ° C) indicate the presence of internal injector deposits (IDID).

The tests (DU and CU) are carried out with 8h running time. The one-hour test cycle from CEC F-098-08 (see FIG. 3) is passed through 8 times in each case. In the case of deviations of the individual cylinder temperatures from greater than 45 ° C to the mean value of all 4 cylinders, the test is terminated prematurely.

Change and special features: Cleaned injectors were installed before each start of the DU test. The cleaning time in the ultrasonic bath at 60 ° C water + 10% Superdecontamine was 4h.

B. Production Examples: Preparation Examples 1 to 4: Quaternization of tertiary fatty amines with propylene oxide in the presence of various hydrocarbyl-substituted succinic acids

R₁ steht dabei für langkettiges Hydrocarbyl; R₂, R₃ und R₄ entsprechen R_a, R_b und R_c sind wie oben definiert; R₅ entspricht R_d wie oben definiert; und R steht für H oder ist ein durch Veresterung mit dem Epoxid erzeugter Rest wie z.B. -CH₂CH(R₅)OH

R ₁ stands for long-chain hydrocarbyl; R ₂ , R ₃ and R ₄ correspond to R _a , R _b and R _c are as defined above; R ₅ corresponds to R _d as defined above; and R is H or is a residue produced by esterification with the epoxide such as -CH ₂ CH (R ₅ ) OH

a) Reagents used:

Polyisobutylenesuccinic anhydride (PIBSA, Glissopal® SA, BASF): Prepared from maleic anhydride and polyisobutene 1000 in a known manner. Qualities with saponification numbers in the range of 84-95 mg KOH / g were used for the preparation examples according to the invention. To prepare polyisobutylenesuccinic acid, polyisobutylenesuccinic anhydride was mixed with the equimolar amount of water in accordance with the saponification number and hydrolyzed at a temperature of 100.degree. For example, the reaction of polyisobutylene succinic anhydride (saponification number 85.6 mg KOH / g) after 16 h reaction time at 100 ° C gave a reaction product having an acid number of 79.1 mg KOH / g. The formation of polyisobutylenesuccinic acid was confirmed by IR spectroscopy (1711 cm ^-1 ).

In an analogous manner, tetrapropenylsuccinic anhydride (CAS 26544-38-7) and a mixed i-hexadecenyl / i-octadecenylsuccinic anhydride (CAS 32072-96-1 and 28777-98-2) from Pentagon were hydrolyzed to the corresponding succinic acid derivatives.

Cocoyldimethylamine: (N, N-dimethyl-N-C12 / 14-amine, CAS 68439-70-3 or 112-18-5) with a total amine number of 246 mg KOH / g.
N-methyl-N, N-ditallow fatty amine: Armeen® M2HT from Akzo Nobel, CAS 61788-63-4, with a total amine number of 108 mg KOH / g

b) General Synthesis Instructions

In a 2 l autoclave, a solution of the tert. Amine (1 eq.) And the Alkylenbernsteinsäurederivats (1 eq.) Submitted in 2-ethylhexanol. The amount of 2-ethylhexanol and the batch size are chosen so that the final product has an active content of 50% and the reactor has a degree of filling of about 70%. Then it is rinsed three times with N ₂ , a pre-pressure of about 2 bar N _{2 is} set and the temperature is raised to 50 ° C. Propylene oxide (2 eq.) Is added within 1 h. The mixture is then stirred for 15 h at 50 ° C, cooled to 25 ° C, rinsed with N ₂ and the reactor emptied. The product is transferred to a ₂ L jacketed reactor and excess propylene oxide is removed by passing N ₂ flow (10 l / h) under vacuum (70 mbar) at 50 ° C for 6 h. ¹ H NMR (CDCl ₃ ) confirms the quaternization (δ = 3.3 ppm, singlet, R ₂ N (CH ₃ ) ₂ and R ₃ NCH _3, respectively).

c) Experiments performed

Following the above procedure, the following quaternizations were carried out with propylene oxide example tert. Amin Hydrocarbyl-substituted succinic acid 1 Cocoyldimethylamin polyisobutylene 2 Cocoyldimethylamin tetrapropenyl 3 Cocoyldimethylamin i-hexadecenyl / i-octadecenylsuccinic 4 N-methyl-N, N-di-tallow tetrapropenyl

Production Example 5:

Reagents: Dodecene oxide (CAS 2855-19-8) from Aldrich, trimethylamine (anhydrous, CAS 75-50-3) from BASF

In a ₂ l autoclave rendered inert with N ₂ , a solution of trimethylamine (47.2 g, 0.8 mol) and dodecene oxide (147.2 g, 0.8 mol) in 2-ethylhexanol (194.4 g) is introduced. Then the temperature is raised to 40 ° C. A solution of tetrapropenylsuccinic acid (252.8 g, 0.8 mol) in 2-ethylhexanol (252.8 g) is added within 1.5 h. The mixture is then stirred at 40 ° C for 15 h. Volatile components are removed by introducing an N ₂ stream at 40 ° C, then the reactor is emptied. ¹ H NMR (CDCl ₃ ) confirms quaternization (δ = 3.3 ppm, singlet, RN (CH ₃ ) ₃ ).

C. Application examples:

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

Application Example 1: Determination of the additive effect on the formation of deposits in diesel engine injection nozzles

DW10 test according to CEC F-098-08

Fuel: Aral summer diesel, unadditized EN 590

Part 1: Dirty up (DU)

Zn content in fuel: 3mg / ml,

Duration: 12 hours non-stop

Power (t = 0 h) = 98.2kW (at the beginning of the test)

Power (t = 12 h) = 89.9 kW (at the end of DU)

Power loss (t = 12h) = 8.5%

Part 2: Clean up (CU)

Zn content in the fuel: 1 mg / ml,

Duration: 6 hours non-stop

Additive: 50 ppm active ingredient of additive according to Preparation Example 2

Power (t = 0 h) = 89.2kW (at the beginning of the test)

Power (t = 6 h) = 97.5 kW (at the end of CU)

Based on the output value of the power (98.2 kW), one sees an increase in power after 6 hours from 90.8% to 99.3%.

Reference is expressly made to the disclosure of the references cited herein.

Claims (22)

Use of a quaternized nitrogen compound-comprising reaction product or a quaternized nitrogen compound-containing partial fraction thereof obtained from the reaction product, which reaction product is obtainable by
Reacting a quaternizable alkylamine containing at least one quaternizable tertiary amino group with a quaternizing agent which converts the at least one tertiary amino group into a quaternary ammonium group,
wherein the quaternizing agent is a hydrocarbyl epoxide in combination with a free hydrocarbyl-substituted polycarboxylic acid;
as a fuel or lubricant additive or kerosene additive. Use according to claim 1 as an additive for reducing the fuel consumption of direct injection diesel engines, in particular of diesel engines with common rail injection systems, and / or for minimizing the power loss in direct injection diesel engines, especially in diesel engines with common rail injection systems. Use according to claim 1 as a gasoline additive for reducing deposits in the intake system of a gasoline engine, in particular DISI and PFI (Port Fuel Injector) engines. Use according to claim 1 as a diesel fuel additive for reducing and / or avoiding deposits in the injection systems, such as in particular the Internal Diesel Injector Deposits (IDID) and / or valve sticking in direct-injection diesel engines, especially in common-rail injection systems. Use according to any one of the preceding claims, wherein the alkylamine comprises at least one compound of the following general formula 3,

R _a R _b R _c N (3)

wherein
at least one of the radicals R _a , R _b and R _{c is} a straight-chain or branched, saturated or unsaturated C ₈ -C ₄₀ -hydrocarbyl radical (in particular straight-chain or branched C ₈ -C ₄₀ -alkyl) and the remaining radicals are identical or different , straight-chain or branched, saturated or unsaturated C ₁ -C ₆ -hydrocarbyl radicals (in particular C ₁ -C ₆ -alkyl); or
wherein all radicals R _a , R _b and R _{c are} identical or different straight-chain or branched, saturated or unsaturated C ₈ -C ₄₀ -hydrocarbyl radicals, in particular straight-chain or branched C ₈ -C ₄₀ -alkyl radicals. Use according to any one of claims 1 to 5, wherein the quaternizing agent
an epoxide of the general formula 4

in which
the radicals R _d contained therein are identical or different and represent H or a hydrocarbyl radical, where the hydrocarbyl radical is an aliphatic or aromatic radical having 1 to 10 carbon atoms. Use according to any one of the preceding claims, wherein the free acid of the quaternizing agent is a hydrocarbyl-substituted C ₃ -C ₂₈ dicarboxylic acid. Use according to any preceding claim, wherein the hydrocarbyl substituent of the carboxylic acid has a number average molecular weight (M _n ) of from 85 to 20,000 or is a polyalkylene radical having a degree of polymerization of 2 to 100, or 3 to 50 or 4 to 25. OK?? Use according to any one of the preceding claims wherein the quaternizable tertiary amine is a compound of formula 3 wherein at least two of R _a , R _b and R _{c are the} same or different and are straight chain or branched, C ₁₀ -C ₂₀ -alkyl radical and the remaining radical is C ₁ -C ₄ -alkyl. Use according to any one of the preceding claims, wherein the quaternizing agent is selected from lower alkylene oxides in combination with a polyalkenyl-substituted dicarboxylic acid. Use according to one of the preceding claims, wherein the fuel is selected from diesel fuels, biodiesel fuels, gasoline, and alkanol-containing gasoline. A quaternized nitrogen compound as defined in any one of claims 1 to 10. A process for producing a quaternized nitrogen compound according to claim 12,
comprising the reaction of a quaternizable alkylamine containing at least one quaternizable tertiary amino group with a quaternizing agent which converts the at least one tertiary amino group into a quaternary ammonium group,
wherein the quaternizing agent is a hydrocarbyl epoxide in combination with a free hydrocarbyl-substituted polycarboxylic acid. Additive concentrate containing in combination with further diesel or petrol additives or lubricant additives at least one quaternized nitrogen compound as defined in claim 12 or prepared according to claim 13. A fuel or lubricant composition or kerosene composition comprising, in a majority of a conventional fuel or lubricant, a proportion of at least one reaction product comprising a quaternized nitrogen compound or one of the reaction product by purification a quaternized nitrogen compound-containing partial fraction thereof, wherein the reaction product is obtainable by
Reacting a quaternizable alkylamine containing at least one quaternizable tertiary amino group with a quaternizing agent which converts the at least one tertiary amino group into a quaternary ammonium group,
wherein the quaternizing agent is a hydrocarbyl epoxide in combination with a free hydrocarbyl-substituted polycarboxylic acid. A fuel or lubricant composition according to claim 15, wherein the alkylamine comprises at least one compound of the following general formula 3,

R _a R _b R _c N (3)

wherein
at least one of the radicals R _a , R _b and R _{c is} a straight-chain or branched, saturated or unsaturated C ₈ -C ₄₀ -hydrocarbyl radical (in particular straight-chain or branched C ₈ - C ₄₀ -alkyl) and the remaining radicals are identical or different , straight-chain or branched, saturated or unsaturated C ₁ -C ₆ -hydrocarbyl radicals (in particular C ₁ -C ₆ -alkyl); or
wherein all radicals R _a , R _b and R _{c are} identical or different straight-chain or branched, saturated or unsaturated C ₈ -C ₄₀ -hydrocarbyl radicals, in particular straight-chain or branched C ₈ -C ₄₀ -alkyl radicals. A fuel or lubricant composition according to any one of claims 15 and 16, wherein the quaternizing agent comprises an epoxide of general formula 4

in which the radicals R _d contained therein are identical or different and represent H or a hydrocarbyl radical, where the hydrocarbyl radical is an aliphatic or aromatic radical having 1 to 10 carbon atoms. A fuel or lubricant composition according to any one of claims 15 to 17, wherein the free acid of the quaternizing agent is a hydrocarbyl-substituted C ₃ -C ₂₈ dicarboxylic acid. A fuel or lubricant composition according to any one of claims 15 to 18, wherein the hydrocarbyl substituent of the carboxylic acid is a polyalkylene radical having a degree of polymerization of 2 to 100, or 3 to 50 or 4 to 25. OK?? A fuel or lubricant composition according to any one of claims 15 to 19 wherein the quaternizable tertiary amine is a compound of formula 3 wherein at least two of R _a , R _b and R _{c are the} same or different and are straight or branched C ₁₀ C ₂₀ alkyl and the rest is C ₁ -C ₄ alkyl. A fuel or lubricant composition according to any one of claims 15 to 20, wherein the quaternizing agent is selected from lower alkylene oxides in combination with a free hydrocarbyl-substituted polycarboxylic acid. A fuel or lubricant composition according to any one of the preceding claims 15 to 21 selected from diesel fuels, biodiesel fuels, gasoline fuels and alkanol-containing gasolines.

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