EP2540808A1 - Quaternised nitrogen compounds and their use as additives in fuels and lubricants - Google Patents

Abstract

Fuel composition comprises a conventional fuel containing a portion of at least one quaternized nitrogen containing compound comprising a reaction product, or a quaternized nitrogen compound of the reaction product obtained by purification, in which the reaction product is obtainable by (a) reacting a hydrocarbyl-substituted polycarboxylic acid compound with a compound comprising at least one polycarboxylic acid with the reactive, and (b) the subsequent reaction with a quaternizing agent, in which at least one tertiary amino group is converted into a quaternary ammonium group. Fuel composition comprises a conventional fuel containing a portion of at least one quaternized nitrogen containing compound comprising one reaction product, or a quaternized nitrogen compound of the reaction product obtained by purification, in which the reaction product is obtainable by (a) reacting a hydrocarbyl-substituted polycarboxylic acid compound with a compound comprising at least one polycarboxylic acid with the reactive, preferably addable or condensable oxygen or nitrogen group and containing at least one quaternizable amino group to obtain a quaternizable hydrocarbyl-substituted polycarboxylic acid compound, and (b) the subsequent reaction with a quaternizing agent, in which at least one tertiary amino group is converted into a quaternary ammonium group, where the quaternizing agent of alkyl esters is a cycloaromatic or cycloaliphatic mono- or polycarboxylic acid, preferably dicarboxylic acid. Independent claims are also included for: (1) the quaternized nitrogen compound as mentioned above; (2) producing the quaternized nitrogen compound comprising reacting the hydrocarbyl-substituted polycarboxylic acid compound quaternizable containing at least one tertiary, quaternizable amino group with the quaternizing agent, which converts at least one tertiary amino group into the quaternary ammonium group, where the quaternizing agent of the alkyl ester is the cyclic aromatic or cycloaliphatic mono-or polycarboxylic acid, preferably dicarboxylic acid; (3) use of the quaternized nitrogen compound as a fuel additive; and (4) an additive concentrate comprising at least one quaternized nitrogen containing compound as mentioned above in combination with other diesel or gasoline fuel additives, preferably diesel fuel additives.

Description

The present invention relates to novel quaternized nitrogen compounds, their preparation and use as a fuel and lubricant additive, in particular as a detergent additive additive packages containing these compounds; as well as with it additized fuels and lubricants. Furthermore, the present invention relates to the use of these quaternized nitrogen compounds as a fuel additive for reducing or preventing deposits in the injection systems of direct injection diesel engines, especially in common rail injection systems, to reduce the fuel consumption of direct injection diesel engines, especially diesel engines with common rail injection systems and minimizing powerloss in direct injection diesel engines, particularly in diesel engines with common rail injection systems.

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 as in the classic (chamber) diesel engine in a vortex or vortex chamber. 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.

Essentially, three methods are currently 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. 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. This is always the full on the common rail

Pressure, 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. Widely used is the realization that such deposits In the spray channels can lead to a reduction of the fuel flow and thus to power losses (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 a tertiary-amino-containing oxygen or nitrogen atom-containing compound, 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 in dimethyl sulfate and alkylene oxides and benzyl halides), no residue-free combustion (eg dimethyl sulfate and alkyl halides), as well as insufficient reactivity, resulting in incomplete quaternization or non-economic reaction conditions ( long reaction times, high reaction temperatures, excess of quaternizing agent, eg dimethyl carbonate).

It was therefore an object to provide improved quaternized fuel additives, in particular based on hydrocarbyl-substituted polycarboxylic compounds, which no longer have the disadvantages of the prior art mentioned.

Brief description of the invention:

It has now surprisingly been found that the above object is achieved by providing special quaternized nitrogen compounds and thus additized fuel and lubricant compositions.

Surprisingly, the additives according to the invention produced in this way are superior to the conventionally prepared additives according to the prior art in a number of respects: they have low toxicity (owing to the targeted choice of the quaternizing agent, incineration without residue (ashless), they show a high degree of toxicity Content of quaternized product, and allow an economic reaction during their production and surprisingly have improved HandlingEigenschaften, in particular improved solubility, in particular in diesel performance additive packages, on. At the same time, the additives according to the invention show an improved effect with respect to the prevention of deposits in diesel engines, as illustrated in particular by the enclosed application examples.

Detailed description of the invention: A1) Special embodiments

1. 1. Kraftstoff- oder Schmierstoffzusammensetzung, insbesondere Kraftstoffzusammensetzung, enthaltend in einer Hauptmenge eines üblichen Kraft- 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
   1. a. Umsetzung einer mit hochmolekularem Hydrocarbyl substituierten Polycarbonsäureverbindung, mit einer Verbindung umfassend wenigstens eine mit der Polycarbonsäure reaktiven (insbesondere addierbaren oder kondensierbaren) Sauerstoff-oder Stickstoffgruppe sowie enthaltend wenigstens eine quaternisierbare Aminogruppe, wobei man eine quaternisierbaren hydrocarbyl-substituierten Polycarbonsäureverbindung (durch Addition oder Kondensation) erhält, und
   2. b. deren anschließende Umsetzung mit einem Quaternisierungsmittel, das die wenigstens eine tertiäre Aminogruppe in eine quaternäre Ammoniumgruppe überführt, wobei das Quaternisierungsmittel der Alkylester einer cycloaromatischen oder cycloaliphatischen Mono- oder Polycarbonsäure (insbesondere einer Mono- oder Dicarbonsäure) oder einer aliphatischen Polycarbonsäure (insbesondere Dicarbonsäure) ist.
2. 2. Kraftstoff- oder Schmierstoffzusammensetzung, insbesondere Kraftstoffzusammensetzung, enthaltend in einer Hauptmenge eines üblichen Kraft- 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 einer quaternisierbaren mit hochmolekularem Hydrocarbyl substituierten Polycarbonsäureverbindung, enthaltend wenigstens eine quaternisierbare Aminogruppe mit einem Quaternisierungsmittel, das die wenigstens eine tertiäre Aminogruppe in eine quaternäre Ammoniumgruppe überführt,
   wobei das Quaternisierungsmittel der Alkylester einer cycloaromatischen oder cycloaliphatischen Mono- oder Polycarbonsäure (insbesondere einer Mono- oder Dicarbonsäure) oder einer aliphatischen Polycarbonsäure (insbesondere Dicarbonsäure) ist.
3. 3. Kraftstoff- oder Schmierstoffzusammensetzung, insbesondere Kraftstoffzusammensetzung, nach einer der vorhergehenden Ausführungsformen, wobei das Quaternisierungsmittel eine Verbindung der allgemeinen Formel 1 ist
   
            R₁OC(O)R₂     (1)
   
   worin
   R₁ für einen niedermolekularen Hydrocarbylrest, wie Alkyl- oder Alkenylrest, insbesondere einen Niedrigalkylrest, wie insbesondere Methyl oder Ethyl, steht und
   R₂ für einen gegebenenfalls substituierten einkernigen cyclischen Hydrocarbylrest, insbesondere einen Aryl- oder Cycloalkyl- oder Cycloalkenylrest , insbesondere Aryl, wie Phenyl, steht, wobei der Substituent ausgewählt ist unter OH, NH₂, NO₂, C(O)OR₃, und R₁OC(O)-, worin R₁ die oben angegebenen Bedeutungen besitzt und R₃ für H oder R₁ steht, wobei der Substituent insbesondere OH ist. Insbesondere ist das Quaternisierungsmittel ein Phthalat oder ein Salicylat, wie Dimethyl-Phthalat, oder Methylsalicylat.
4. 4. Kraftstoff- oder Schmierstoffzusammensetzung, insbesondere Kraftstoffzusammensetzung, nach einer der Ausführungsformen 1 und 2, wobei das Quaternisierungsmittel eine Verbindung der allgemeinen Formel 2 ist
   
            R₁OC(O)-A-C(O)OR_1a     (2)
   
   worin
   R₁ und R_1a unabhängig voneinander für einen niedermolekularen Hydrocarbylrest, wie einen Alkyl- oder Alkenylrest, insbesondere einen Niedrigalkylrest steht und
   A für Hydrocarbylen (wie insbesondere C₁-C₇-Alkylen oder C₂-C₇-Alkenylen) steht.
5. 5. Kraftstoff- oder Schmierstoffzusammensetzung, insbesondere Kraftstoffzusammensetzung, nach einer der vorhergehenden Ausführungsformen, wobei die quaternisierte Stickstoffverbindung ein zahlenmittleres Molekulargewicht im Bereich von 400 bis 5000 insbesondere 800 bis 3000 oder 900 bis 1500 aufweist.
6. 6. Kraftstoff- oder Schmierstoffzusammensetzung, insbesondere Kraftstoffzusammensetzung, nach einer der vorhergehenden Ausführungsformen, wobei das Quaternisierungsmittel ausgewählt ist unter Alkylsalicylaten, Dialkylphthalaten und Dialkyloxalaten; wobei Alkylsalicylate, insbesondere Niedrigalkylsalicylate , wie Methyl-, Ethyl- und n-Propylsalicylate besonders zu nennen sind.
7. 7. Kraftstoff- oder Schmierstoffzusammensetzung, insbesondere Kraftstoffzusammensetzung, nach Ausführungsform 1, wobei die mit der Polycarbonsäure reaktive (addierbare oder kondensierbare), eine Sauerstoff- oder Stickstoffgruppe sowie wenigstens eine quaternisierbare Aminogruppe enthaltende Verbindung ausgewählt ist unter
   1. a. Hydroxyalkyl-substituierten Mono- oder Polyaminen mit wenigstens einer quaternisierbaren, primären, sekundären oder tertiären Aminogruppe
   2. b. geradkettigen oder verzweigtem, cyclischen, heterocyclischen, aromatischen oder nichtaromatischen Polyaminen mit wenigstens einer primären oder sekundären Aminogruppe und mit wenigstens einer quaternisierbaren, primären, sekundären oder tertiären Aminogruppe;
   3. c. Piperazinen,
   wobei Gruppe a. besonders zu nennen ist
8. 8. Kraftstoff- oder Schmierstoffzusammensetzung nach Ausführungsform 7, wobei die mit Verbindung ausgewählt ist unter
   1. a. Hydroxyalkyl-substituierten primären, sekundären oder tertiären Monoaminen und Hydroxyalkyl-substituierten primären, sekundären oder tertiären Diaminen.
   2. b. geradkettigen oder verzweigten aliphatischen Diaminen mit zwei primären Aminogruppen; Di- oder Polyaminen mit wenigstens einer primären und wenigstens einer sekundären Aminogruppe; Di- oder Polyaminen mit wenigstens einer primären und wenigstens einer tertiären Aminogruppe; aromatischen carbo-cyclischen Diaminen mit zwei primären Aminogruppen; aromatischen heterocyclischen Polyaminen mit zwei primären Aminogruppen; aromatischen oder nichtaromatischen Heterozyklen mit einer primären und einer tertiären Aminogruppe;
   wobei Gruppe a. besonders zu nennen ist
9. 9. Kraftstoffstoffzusammensetzung nach einer der vorhergehenden Ausführungsformen, ausgewählt unter Dieselkraftstoffen, Biodieselkraftstoffen, Ottokraftstoffen, und Alkanol-haltigen Ottokraftstoffen.
10. 10. Kraftstoff- oder Schmierstoffzusammensetzung, insbesondere Kraftstoffzusammensetzung, nach einer der vorhergehenden Ausführungsformen, wobei die hydrocarbyl-substituierte Polycarbonsäureverbindung eine Polyisobutenylbersteinsäure oder ein Anhydrid (PIBSA) davon ist, wobei diese einen niedrigen Bismaleinierungsgrad, insbesondere von gleich oder weniger als 20%, wie z.B. 15, 13, 12 oder 11 % , insbesondere 10% oder weniger als 10% , wie z.B. 2 bis 9, oder 3 bis 7 %, aufweist. Insbesondere sind derartige PIBSAs von HR-PIB mit einem Mn im Bereich von etwa 400 bis 3000 abgeleitet.
    Insbesondere sind obige Zusammensetzungen Kraftstoffzusammensetzungen, wie vor allem Dieselkraftstoffe.
11. 11. Quaternisierte Stickstoffverbindung gemäß der Definition in einer der vorhergehenden Ausführungsformen, insbesondere gemäß Ausführungsform 3, 4 und vor allem Ausführungsform 6, 7 oder8.
12. 12. Verfahren zur Herstellung einer quaternisierter Stickstoffverbindung nach Ausführungsform 11,
    umfassend die Umsetzung einer quaternisierbaren hydrocarbyl-substituierten Polycarbonsäureverbindung, enthaltend wenigstens eine tertiäre, quaternisierbare Aminogruppe mit einem Quaternisierungsmittel, das die wenigstens eine tertiäre Aminogruppe in eine quaternäre Ammoniumgruppe überführt,
    wobei das Quaternisierungsmittel der Alkylester einer cycloaromatischen oder cycloaliphatischen Mono- oder Polycarbonsäure (insbesondere einer Mono- oder Dicarbonsäure) oder einer aliphatischen Polycarbonsäure (insbesondere Dicarbonsäure) ist.
13. 13. Verwendung einer quaternisierten Stickstoffverbindung nach Ausführungsform 11 oder hergestellt nach Ausführungsform 12 als Kraftstoffadditiv oder Schmierstoffadditiv insbesondere Kraftstoffadditiv, insbesondere Dieselkraftstoffadditiv,.
14. 14. Verwendung nach Ausführungsform 13 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-Einspritzsystemen.
15. 15. Verwendung nach Ausführungsform 13 als Ottokraftstoffadditiv zur Verringerung von Ablagerungen im Einlasssystem eines Ottomotors, wie insbesondere DISI und PFI (Port Fuel Injector) -Motoren.
16. 16. Verwendung nach Ausführungsform 13 als Dieselkraftstoffadditiv, insbesondere als Kaltfließverbesserer, als Wachs-Anti-Settling Additiv (WASA) oder als Additiv zur Verringerung und/oder Vermeidung von Ablagerungen in den Einspritzsystemen, wie insbesondere der Internal Diesel Injector Deposits (IDID) und / oder von Ventilkleben in direkteinspritzenden Dieselmotoren, insbesondere in Common-Rail-Einspritzsystemen.
17. 17. Additivkonzentrat, enthaltend in Kombination mit weiteren Diesel- oder Ottokraftstoffadditiven, insbesondere Dieselkraftstoffadditiven, wenigstens eine quaternisierte Stickstoffverbindung gemäß der Definition in Ausführungsform 11 oder hergestellt nach Ausführungsform 12.

The present invention particularly relates to the following specific embodiments:

1. A fuel or lubricant composition, in particular a fuel composition, containing in a majority of a conventional fuel or lubricant a proportion (in particular an effective amount) of at least one reaction product comprising a quaternized nitrogen compound (or a fraction obtained from the reaction product containing a quaternized nitrogen compound thereof), wherein the reaction product is obtainable by
   1. a. Reacting a high molecular weight hydrocarbyl-substituted polycarboxylic acid compound with a compound comprising at least one polycarboxylic acid-reactive (especially addable or condensable) oxygen or nitrogen group and containing at least one quaternizable amino group to obtain a quaternizable hydrocarbyl-substituted polycarboxylic acid compound (by addition or condensation) , and
   2. b. their subsequent reaction with a quaternizing agent which converts the at least one tertiary amino group to a quaternary ammonium group, wherein the quaternizing agent is the alkyl ester of a cycloaromatic or cycloaliphatic mono- or polycarboxylic acid (especially a mono- or dicarboxylic acid) or an aliphatic polycarboxylic acid (especially dicarboxylic acid).
2. 2. Fuel or lubricant composition, in particular fuel composition, containing in a main amount of a conventional fuel or lubricant, a proportion (in particular an effective amount) at least one of a quaternized Nitrogen compound comprising reaction product (or a obtained from the reaction product by purification, a quaternized nitrogen compound-containing fraction thereof), wherein the reaction product is obtainable by
   Reacting a quaternizable high molecular weight hydrocarbyl-substituted polycarboxylic acid compound containing at least one quaternizable 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 the alkyl ester of a cycloaromatic or cycloaliphatic mono- or polycarboxylic acid (especially a mono- or dicarboxylic acid) or an aliphatic polycarboxylic acid (especially dicarboxylic acid).
3. 3. Fuel or lubricant composition, in particular fuel composition, according to one of the preceding embodiments, wherein the quaternizing agent is a compound of general formula 1
   
   R ₁ OC (O) R ₂ (1)
   
   wherein
   R _{1 is} a low molecular weight hydrocarbyl radical, such as alkyl or alkenyl radical, in particular a lower alkyl radical, in particular methyl or ethyl, and
   R _{2 is} an optionally substituted mononuclear cyclic hydrocarbyl radical, in particular an aryl or cycloalkyl or cycloalkenyl radical, in particular aryl, such as phenyl, where the substituent is selected from OH, NH ₂ , NO ₂ , C (O) OR ₃ , and R ₁ OC (O) -, wherein R _{1 has} the meanings given above and R _{3 is} H or R ₁ , wherein the substituent is in particular OH. In particular, the quaternizing agent is a phthalate or a salicylate, such as dimethyl phthalate, or methyl salicylate.
4. 4. Fuel or lubricant composition, in particular fuel composition, according to any one of embodiments 1 and 2, wherein the quaternizing agent is a compound of general formula 2
   
   R ₁ OC (O) -AC (O) OR _1a (2)
   
   wherein
   R ₁ and R _1a independently of one another represent a low molecular weight hydrocarbyl radical, such as an alkyl or alkenyl radical, in particular a lower alkyl radical, and
   A is hydrocarbylene (in particular C ₁ -C ₇ -alkylene or C ₂ -C ₇ -alkenylene).
5. 5. Fuel or lubricant composition, in particular fuel composition, according to one of the preceding embodiments, wherein the quaternized nitrogen compound has a number average molecular weight in the range of 400 to 5000, in particular 800 to 3000 or 900 to 1500.
6. 6. A fuel or lubricant composition, in particular fuel composition, according to one of the preceding embodiments, wherein the quaternizing agent is selected from alkyl salicylates, dialkyl phthalates and dialkyl oxalates; wherein alkylsalicylates, especially Niedrigalkylsalicylate, such as methyl, ethyl and n-propyl salicylates are particularly mentioned.
7. 7. Fuel or lubricant composition, in particular fuel composition, according to embodiment 1, wherein the reactive with the polycarboxylic acid (addable or condensable), an oxygen or nitrogen group and at least one quaternizable amino group-containing compound is selected from
   1. a. Hydroxyalkyl-substituted mono- or polyamines having at least one quaternizable, primary, secondary or tertiary amino group
   2. b. straight-chain or branched, cyclic, heterocyclic, aromatic or nonaromatic polyamines having at least one primary or secondary amino group and having at least one quaternizable, primary, secondary or tertiary amino group;
   3. c. piperazines,
   where group a. especially to call
8. 8. A fuel or lubricant composition according to embodiment 7, wherein the compound is selected under
   1. a. Hydroxyalkyl-substituted primary, secondary or tertiary monoamines and hydroxyalkyl-substituted primary, secondary or tertiary diamines.
   2. b. straight-chain or branched aliphatic diamines having two primary amino groups; Di- or polyamines having at least one primary and at least one secondary amino group; Di- or polyamines having at least one primary and at least one tertiary amino group; aromatic carbo-cyclic diamines having two primary amino groups; aromatic heterocyclic polyamines having two primary amino groups; aromatic or non-aromatic heterocycles having a primary and a tertiary amino group;
   where group a. especially to call
9. 9. Fuel composition according to one of the preceding embodiments, selected from diesel fuels, biodiesel fuels, gasoline, and alkanol-containing gasoline.
10. 10. A fuel or lubricant composition, in particular fuel composition, according to any one of the preceding embodiments, wherein the hydrocarbyl-substituted polycarboxylic acid compound is a polyisobutenyl succinic acid or anhydride (PIBSA) thereof, which has a low Bismaleinierungsgrad, in particular equal to or less than 20%, such as 15, 13, 12 or 11%, in particular 10% or less than 10%, such as 2 to 9, or 3 to 7%. In particular, such PIBSAs are derived from HR-PIB having an Mn in the range of about 400 to 3,000.
    In particular, the above compositions are fuel compositions, especially diesel fuels.
11. 11. Quaternized nitrogen compound as defined in any one of the preceding embodiments, in particular according to embodiment 3, 4 and in particular embodiment 6, 7 or8.
12. 12. A method for producing a quaternized nitrogen compound according to Embodiment 11,
    which comprises reacting a quaternizable hydrocarbyl-substituted polycarboxylic acid compound containing at least one tertiary, quaternizable 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 the alkyl ester of a cycloaromatic or cycloaliphatic mono- or polycarboxylic acid (especially a mono- or dicarboxylic acid) or an aliphatic polycarboxylic acid (especially dicarboxylic acid).
13. 13. Use of a quaternized nitrogen compound according to embodiment 11 or prepared according to embodiment 12 as a fuel additive or lubricant additive, in particular fuel additive, in particular diesel fuel additive ,.
14. 14. Use according to embodiment 13 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 (powerloss) in direct-injection diesel engines, especially in diesel engines with common-rail injection systems.
15. 15. Use according to embodiment 13 as a gasoline additive for reducing deposits in the intake system of a gasoline engine, in particular DISI and PFI (Port Fuel Injector) engines.
16. 16. Use according to embodiment 13 as a diesel fuel additive, in particular as a cold flow improver, as a wax anti-settling additive (WASA) or as an additive for reducing and / or avoiding deposits in the injection systems, in particular the Internal Diesel Injector Deposits (IDID) and / or valve sticking in direct injection diesel engines, especially in common rail injection systems.
17. 17. Additive concentrate, containing in combination with other diesel or petrol additives, in particular diesel fuel additives, at least one quaternized nitrogen compound as defined in embodiment 11 or prepared according to embodiment 12.

A2) General definitions

A "condensation" or "condensation reaction" in the context of the present invention describes the reaction of two molecules with elimination of a smaller molecule, in particular a water molecule. Is such a cleavage analytically undetectable, especially in stoichiometric amounts undetectable, and the two molecules still react, for example under addition, the reaction of the two molecules takes place "without condensation".

• " Hydrocarbyl" ist breit auszulegen und umfasst sowohl langkettige als auch kurzkettige, gerade oder verzweigte Kohlenwasserstoffreste, welche ggf. zusätzlich Heteroatome, wie z.B. O, N, NH,S, in ihrer Kette enthalten können.
• " Langkettige" oder "hochmolekulare" Hydrocarbylreste haben ein zahlengemitteltes Molekulargewicht (M_n) von 85 bis 20.000, wie z.B. 113 bis 10.000, oder 200 bis 10.000 oder 350 bis 5.000, wie z.B. 350 bis 3.000, 500 bis 2.500, 700 bis 2.500, oder 800 bis 1.500. Sie sind insbesondere im Wesentlichen aus C_2-6-, insbesondere C_2-4-Monomerbausteinen, wie Ethylen, Propylen, n- oder iso-Butylen oder Mischungen davon aufgebaut, wobei die verschiedenen Monomere statistisch verteilt oder als Blöcke einpolymerisiert enthalten sein können. Derartige langkettige Hydrocarbylreste werden auch als Polyalkylenreste oder Poly-C_2-6- oder Poly-C_2-4-alkylenreste bezeichnet. Geeignete langkettige Hydrocarbylreste und deren Herstellung sind beispielsweise auch beschreiben in der WO2006/135881 und der dort zitierten Literatur.

Unless otherwise indicated, the following general meanings apply:

• "Hydrocarbyl" is to be interpreted broadly and includes both long-chain and short-chain, straight or branched hydrocarbon radicals, which may optionally contain additional heteroatoms, such as O, N, NH, S, in their chain.
• "Long chain" or "high molecular weight" hydrocarbyl radicals 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. They are 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 polymerized form 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.

welche zusammen auch als Vinyliden-Doppelbindungen bezeichnet werden. Geeignete hochreaktive Polyisobutene sind beispielsweise Polyisobutene, die einen Anteil an Vinyliden-Doppelbindungen von größer 70 Mol-%, insbesondere größer 80 Mol-% oder größer 85 Mol-% aufweisen. Bevorzugt sind insbesondere Polyisobutene, die einheitliche Polymergerüste aufweisen. Einheitliche Polymergerüste weisen insbesondere solche Polyisobutene auf, die zu wenigstens 85 Gew.-%, vorzugsweise zu wenigstens 90 Gew.-% und besonders bevorzugt zu wenigstens 95 Gew.-% aus Isobuteneinheiten aufgebaut sind. Vorzugsweise weisen solche hochreaktiven Polyisobutene ein zahlenmittleres Molekulargewicht in dem oben genannten Bereich auf. Darüber hinaus können die hochreaktiven Polyisobutene eine Polydispersität im Bereich von 1,05 bis 7, insbesondere von etwa 1,1 bis 2,5, wie z.B. von kleiner 1,9 oder kleiner 1,5, aufweisen. Unter Polydispersität versteht man den Quotienten aus gewichtsmittlerem Molekulargewicht Mw geteilt durch das zahlenmittlere Molekulargewicht Mn.Examples of particularly useful polyalkylene radicals are polyisobutenyl radicals derived from so-called "highly reactive" polyisobutenes (HR-PIB), which are distinguished by a high content of terminal double bonds (cf., for example, also US Pat Rath et al, Lubrication Science (1999), 11-2, 175-185 ). 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 wt .-%, preferably at least 90 wt .-% and particularly preferably at least 95 wt .-% 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 may have a polydispersity in the range of 1.05 to 7, in particular from about 1.1 to 2.5, such as 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, for example, the Glissopal brands from BASF SE, in particular Glissopal ^® 1000 (Mn = 1000), Glissopal ^® V 33 (Mn = 550), Glissopal ^® 1300 (Mn = 1300) and Glissopal ^® 2300 (Mn = 2300 ) and their mixtures. 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.

wobei wt-%(X) für den Gewichtsanteil der Komponente X (X = PIBSA oder BM PIBSA) im Umsetzungsprodukt von PIB mit MSA steht

PIBSA is prepared in a manner known in principle by reacting PIB with maleic anhydride (MSA), which in principle produces a mixture of PIBSA and bismaleinated PIBSA (BM PIBSA, see Scheme 1, below), which as a rule is not separated, but rather as such Follow-up reactions is used. The ratio of the two components to one another can be specified by the "degree of bismaleination" (BMG). The BMG is known (see also US 5,883,196 ). The BMG can also be determined according to the following formula: $$\mathrm{BMG}=100\%\times \left[(\mathrm{wt}-\%\left(\mathrm{BM\; PIBSA}\right)/\left(\mathrm{wt}-\%\left(\mathrm{BM\; PIBSA}\right)+\mathrm{wt}-\%\left(\mathrm{PIBSA}\right)\right)\right]$$

wherein wt -% (X) represents the weight fraction of component X (X = PIBSA or BM PIBSA) in the reaction product of PIB with MSA

Hydrocarbyl-substituted polycarboxylic acid compound having a "low degree of bismaleination", particularly corresponding polyisobutenylsuccinic acids or anhydrides thereof (also collectively referred to as PIBSA) are known in the art. Particularly advantageous are bis-maleination grades of 20% or less, or 15% or less, such as 14, 13, 12, or 10%; or 10% or less, such as 2-9, 3-8, 4-7, 5 or 6%. Their targeted production is described for example in the US 5,883,196 , Particularly suitable for their preparation are the above highly reactive polyisobutenes having an Mn in the range from about 500 to 2500, such as 550 to 3000, 1000 to 2000 or 1000 to 1500.

As a non-limiting example of such a PIBSA can Glissopal ^® SA derived from HR-PIB (Mn = 1000), are called with a Bismaleinierungsgrad of 9%.

"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.

"Alkyl" or "lower alkyl" in particular represents saturated, straight-chain or branched hydrocarbon radicals having 1 to 4, 1 to 6, 1 to 8, or 1 to 10 or 1 to 20 carbon atoms, 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, n-octyl, n-nonyl and n-decyl, as well as the mono- or polysubstituted analogs thereof.

"Hydroxyalkyl" is in particular the mono- or polysubstituted, especially monohydricated, analogs of the above-mentioned alkyl radicals, such as, for example, the monohydroxylated analogs of the above straight-chain or branched alkyl radicals, e.g. the linear hydroxyalkyl groups having primary hydroxyl group such as hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl.

"Alkenyl" is mono- or polysubstituted, in particular monounsaturated, straight-chain or branched hydrocarbon radicals having 2 to 4, 2 to 6, 2 to 8 2 to 10 or 2 or to 20 carbon atoms and a double bond in any position, for. 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.

"Alkylene" stands for straight-chain or mono- or poly-branched hydrocarbon bridging groups having 1 to 10 carbon atoms, such as, for example, C ₁ -C ₇ -alkylene groups selected from -CH ₂ -, - (CH ₂ ) ₂ -, - (CH ₂ ) ₃ -, -CH ₂ -CH (CH ₃ ) -, -CH (CH ₃ ) -CH ₂ -, - (CH ₂ ) ₄ -, - (CH ₂ ) ₂ -CH (CH ₃ ) -, -CH ₂ -CH (CH ₃ ) -CH ₂ -, (CH ₂ ) ₄ -, - (CH ₂ ) ₅ -, - (CH ₂ ) ₆ , - (CH ₂ ) ₇ -, -CH (CH ₃ ) -CH ₂ -CH ₂ -CH (CH ₃ ) - or - CH (CH ₃ ) -CH ₂ -CH ₂ -CH ₂ -CH (CH ₃ ) or C ₁ -C ₄ -alkylene groups selected from -CH ₂ -, - (CH ₂ ) ₂ -, - (CH ₂ ) ₃ -, -CH ₂ -CH (CH ₃ ) -, -CH (CH ₃ ) -CH ₂ -, - (CH ₂ ) ₄ -, - (CH ₂ ) ₂ -CH (CH ₃ ) -, -CH ₂ -CH (CH ₃ ) -CH ₂ -.

"Alkenylene" refers to the mono- or polysubstituted, in particular mono-unsaturated analogs of the above alkylene groups having 2 to 10 carbon atoms, in particular C ₂ -C ₇ -Alkenylene or C ₂ -C ₄ alkenylene, such as -CH = CH-, -CH = CH-CH ₂ -, - CH ₂ -CH = CH-, -CH = CH-CH ₂ -CH ₂ -, -CH ₂ -CH = CH-CH ₂ -, -CH ₂ -CH ₂ -CH = CH -, -CH (CH ₃ ) -CH = CH-, -CH ₂ -C (CH ₃ ) = CH-.

• Cycloalkyl: carbocyclische Reste mit 3 bis 20 Kohlenstoffatomen, wie z.B. C_3-C₁₂-Cycloalkyl, wie Cyclopropyl, Cyclobutyl, Cyclopentyl, Cyclohexyl, Cycloheptyl, Cyclooctyl, Cyclononyl, Cyclodecyl, Cycloundecyl und Cyclododecyl; bevorzugt sind Cyclopentyl, Cyclohexyl, Cycloheptyl, sowie Cyclopropyl-methyl, Cyclopropyl-ethyl, Cyclobutyl-methyl, Cyclobutyl-ethyl, Cyclopentyl-methyl, Cyclopentyl-ethyl, Cyclohexyl-methyl oder C_3-C₇-Cycloalkyl, wie Cyclopropyl, Cyclobutyl, Cyclopentyl, Cyclohexyl, Cycloheptyl, Cyclopropyl-methyl, Cyclopropyl-ethyl, Cyclobutyl-methyl, Cyclopentyl-ethyl, Cyclohexyl-methyl, wobei die Anbindung an den Rest des Moleküls über jegliches geeignetes C-Atom erfolgen kann.
• Cycloalkenyl: monocyclische, einfach ungesättigte Kohlenwasserstoffgruppen mit 5 bis 8, vorzugsweise bis 6 Kohlenstoffringgliedern, wie Cyclopenten-1-yl, Cyclopenten-3-yl, Cyclohexen-1-yl, Cyclohexen-3-yl und Cyclohexen-4-yl;
• Aryl: ein- oder mehrkernige, vorzugsweise ein- oder zweikernige, gegebenenfalls substituierte aromatische Reste mit 6 bis 20 wie z.B. 6 bis 10 Ring-Kohlenstoffatomen, wie z.B. Phenyl, Biphenyl, Naphthyl wie 1- oder 2-Naphthyl, Tetrahydronaphthyl, Fluorenyl, Indenyl und Phenanthrenyl. Diese Arylreste können gegebenenfalls 1, 2, 3, 4, 5 oder 6 gleiche oder verschiedene Substituenten tragen.

"Cyclic hydrocarbyl radicals" include in particular:

• Cycloalkyl: carbocyclic radicals having from 3 to 20 carbon atoms, such as, for example, C ₃ -C ₁₂ -cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; preferred are cyclopentyl, cyclohexyl, cycloheptyl and also cyclopropylmethyl, cyclopropylethyl, cyclobutylmethyl, cyclobutylethyl, cyclopentylmethyl, cyclopentylethyl, cyclohexylmethyl or C ₃ -C ₇ -cycloalkyl, such as cyclopropyl, cyclobutyl, Cyclopentyl, cyclohexyl, cycloheptyl, cyclopropyl-methyl, cyclopropyl-ethyl, cyclobutyl-methyl, cyclopentyl-ethyl, cyclohexyl-methyl, wherein the attachment to the rest of the molecule via any suitable carbon atom can take place.
• Cycloalkenyl: monocyclic, monounsaturated hydrocarbon groups having from 5 to 8, preferably to 6 carbon ring members, such as cyclopenten-1-yl, cyclopenten-3-yl, cyclohexen-1-yl, cyclohexen-3-yl and cyclohexen-4-yl;
• Aryl: mononuclear or polynuclear, preferably mononuclear or dinuclear, optionally substituted aromatic radicals having 6 to 20 such as 6 to 10 ring carbon atoms, such as phenyl, biphenyl, naphthyl such as 1- or 2-naphthyl, tetrahydronaphthyl, fluorenyl, indenyl and phenanthrenyl. These aryl radicals may optionally carry 1, 2, 3, 4, 5 or 6 identical or different substituents.

"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 ,

A3) Polycarboxylic acid compounds, and hydrocarbyl-substituted polycarboxylic acid compounds:

The polycarboxylic acid compounds used are aliphatic di- or polyvalent (such as 3- or 4-valent), in particular of di-, tri- or tetracarboxylic acids, and analogs thereof, such as anhydrides or lower alkyl esters (partially or completely esterified), and optionally one or more (such as 2 or 3), in particular a long-chain alkyl radical and / or a high molecular weight hydrocarbyl radical, in particular a polyalkylene radical substituted. Examples are C ₃ -C ₁₀ polycarboxylic acids, such as the dicarboxylic acids malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid, and their branched analogues; and the tricarboxylic acid citric acid; and anhydrides or lower alkyl esters thereof. The polycarboxylic acid compounds may also be prepared from the corresponding monounsaturated acids and addition of at least one long chain alkyl group and / or high molecular weight hydrocarbyl group. Examples of suitable monounsaturated acids are fumaric acid, maleic acid, itaconic acid.

The hydrophobic "long chain" or high molecular weight "hydrocarbyl moiety which provides sufficient solubility of the quaternized product in the fuel has 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 typical hydrophobic hydrocarbyl radicals include polypropenyl, polybutenyl and polyisobutenyl radicals, eg having a number average molecular weight M _n of 3,500 to 5,000, 350 to 3,000, 500 to 2,500, 700 to 2,500 and 800 to 1,500.

Suitable hydrocarbyl-substituted compounds are described, for example in the DE 43 19 672 and the WO2008 / 138836 ,

Suitable hydrocarbyl-substituted polycarboxylic acid compounds also include polymeric, especially dimeric, forms of such hydrocarbyl-substituted polycarboxylic acid compounds. Dimer forms contain e.g. two acid anhydride groups which can be reacted independently of one another in the production process according to the invention with the quaternizable nitrogen compound.

A4) Quaternizing agent:

Suitable quaternizing agents are in principle all suitable as such alkyl esters of a cycloaromatic or cycloaliphatic mono- or polycarboxylic acid (especially a mono- or dicarboxylic acid) or an aliphatic polycarboxylic acid (especially dicarboxylic acid) into consideration.

1. a) Verbindungen der allgemeinen Formel 1 ist
   
            R₁OC(O)R₂     (1)
   
   worin
   R₁ für einen Niedrigalkylrest steht und
   R₂ für einen gegebenenfalls substituierten einkernigen Aryl- oder Cycloalkylrest steht, wobei der Substituent ausgewählt ist unter OH, NH₂, NO₂, C(O)OR₃; R_1aOC(O)-, worin R_1a die oben für R₁ angegebenen Bedeutungen besitzt, und R₃ für H oder R₁ steht;
   oder
2. b) Verbindungen der allgemeinen Formel 2
   
            R₁OC(O)-A-C(O)OR_1a     (2)
   
   worin
   R₁ und R_1a unabhängig voneinander für einen Niedrigalkylrest steht und
   A für Hydrocarbylen (wie Alkylen oder Alkenylen) steht

In a particular embodiment, however, the quaternization of the at least one quaternizable tertiary nitrogen atom is carried out with at least one quaternizing agent selected from among

1. a) compounds of general formula 1 is
   
   R ₁ OC (O) R ₂ (1)
   
   wherein
   R _{1 is} a lower alkyl radical and
   R _{2 is} an optionally substituted mononuclear aryl or cycloalkyl radical, the substituent being selected from OH, NH ₂ , NO ₂ , C (O) OR ₃ ; R _{1a is} OC (O) -, wherein R _{1a has} the meanings given above for R ₁ , and R _{3 is} H or R ₁ ;
   or
2. b) Compounds of the general formula 2
   
   R ₁ OC (O) -AC (O) OR _1a (2)
   
   wherein
   R ₁ and R _1a independently of one another represent a lower alkyl radical and
   A represents hydrocarbylene (such as alkylene or alkenylene)

Particularly suitable compounds of formula 1, wherein
R _{1 is} a C ₁ -, C ₂ - or C ₃ -alkyl radical and
R _{2 is} a substituted phenyl radical, where the substituent for HO or an ester radical of the formula R _{1a is} OC (O) - which is in para, meta or in particular ortho to the radical R ₁ OC (O) - am aromatic ring is located.

Particularly suitable quaternizing agents are the lower alkyl esters of salicylic acid, such as methyl salicylate, ethyl salicylate, n- and i-propyl salicylate, and n-, i- or tert-butyl salicylate.

A5) Quaternized or quaternizable nitrogen compounds

1. a. Hydroxyalkyl-substituierten Mono- oder Polyaminen mit wenigstens einer quarternisierten (z.B. Cholin) oder quaternisierbaren, primären, sekundären oder tertiären Aminogruppe,
2. b. geradkettigen oder verzweigtem, cyclischen, heterocyclischen, aromatischen oder nichtaromatischen Polyaminen mit wenigstens einer primären oder sekundären (anhydridreaktiven) Aminogruppe und mit wenigstens einer quarternisierten oder quaternisierbaren, primären, sekundären oder tertiären Aminogruppe;
3. c. Piperazinen.

The quaternizable nitrogen compounds reactive with the polycarboxylic acid compound are selected from

1. a. Hydroxyalkyl-substituted mono- or polyamines having at least one quaternized (eg choline) or quaternizable, primary, secondary or tertiary amino group,
2. b. straight-chain or branched, cyclic, heterocyclic, aromatic or nonaromatic polyamines having at least one primary or secondary (anhydride-reactive) amino group and having at least one quaternized or quaternizable, primary, secondary or tertiary amino group;
3. c. Piperazines.

• d. Hydroxyalkyl-substituierten primären, sekundären, tertiären oder quartären Monoaminen und Hydroxyalkyl-substituierten primären, sekundären, tertiären oder quartären Diaminen.
• e. geradkettigen oder verzweigten aliphatischen Diaminen mit zwei primären Aminogruppen; Di- oder Polyaminen mit wenigstens einer primären und wenigstens einer sekundären Aminogruppe; Di- oder Polyaminen mit wenigstens einer primären und wenigstens einer tertiären Aminogruppe; Di- oder Polyaminen mit wenigstens einer primären und wenigstens einer quartären Aminogruppe; aromatischen carbo-cyclischen Diaminen mit zwei primären Aminogruppen; aromatischen heterocyclischen Polyaminen mit zwei primären Aminogruppen; aromatischen oder nichtaromatischen Heterozyklen mit einer primären und einer tertiären Aminogruppe;

In particular, the quaternizable nitrogen compounds are selected from

• d. Hydroxyalkyl-substituted primary, secondary, tertiary or quaternary monoamines and hydroxyalkyl-substituted primary, secondary, tertiary or quaternary diamines.
• e. straight-chain or branched aliphatic diamines having two primary amino groups; Di- or polyamines having at least one primary and at least one secondary amino group; Di- or polyamines having at least one primary and at least one tertiary amino group; Di- or polyamines having at least one primary and at least one quaternary amino group; aromatic carbo-cyclic diamines having two primary amino groups; aromatic heterocyclic polyamines having two primary amino groups; aromatic or non-aromatic heterocycles having a primary and a tertiary amino group;

Examples of suitable "hydroxyalkyl-substituted mono- or polyamines" are those endowed with at least one, such as 1, 2, 3, 4, 5 or 6, hydroxyalkyl substituents.

As examples of "hydroxyalkyl-substituted monoamines" may be mentioned: N-hydroxyalkyl-monoamines, N, N-dihydroxyalkyl-monoamines and N, N, N-trihydroxyalkyl-monoamines, wherein the hydroxyalkyl groups are the same or different and are also as defined above , Hydroxyalkyl stands in particular for 2-hydroxyethyl, 3-hydroxypropyl or 4-hydroxybutyl.

For example, the following "hydroxyalkyl-substituted polyamines" and especially "hydroxyalkyl-substituted diamines" may be mentioned: (N-hydroxyalkyl) -alkylenediamines, N, N-dihydroxyalkylalkylenediamines wherein the hydroxyalkyl groups are the same or different and are also as defined above. Hydroxyalkyl stands in particular for 2-hydroxyethyl, 3-hydroxypropyl or 4-hydroxybutyl; Alkylene stands in particular for ethylene, propylene or butylene.

Suitable "diamines" are alkylenediamines, as well as the N-alkyl substituted analogs thereof, such as N-monoalkylated alkylenediamines and the N, N or N, N'-dialkylated alkylenediamines. Alkylene in particular represents straight-chain or branched C _1-7 or C _1-4 -alkylene, as defined above. Alkyl is in particular C _1-4 -alkyl as defined above. Examples are, in particular, ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, 1,4-butylenediamine and isomers thereof, pentanediamine and isomers thereof, hexanediamine and isomers thereof, heptanediamine and isomers thereof, and mono- or polysubstituted, such as, for example - or double C ₁ -C ₄ -alkylated, such as methylated, derivatives of the aforementioned diamine compounds, such as 3-dimethylamino-1-propylamine (DMAPA), N, N-diethylaminopropylamine, and N, N-dimethylaminoethylamine.

Suitable straight-chain "polyamines" are, for example, dialkylenetriamine, trialkylenetetramine, tetraalkylenepentamine, pentaalkylenehexamine, and the N-alkyl-substituted analogs thereof, such as N-monoalkylated and the N, N or N, N'-dialkylated Alkylenpolyamine. Alkylene in particular represents straight-chain or branched C _1-7 or C _1-4 -alkylene, as defined above. Alkyl is in particular C _1-4 -alkyl as defined above.

Examples are in particular diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, dipropylenetriamine, tripropylenetetramine, tetrapropylenepentamine, pentapropylenhexamine, dibutylenetriamine, tributylenetetramine, tetrabutylenepentamine, pentabutylenehexamine; and the N, N-dialkyl derivatives thereof, especially the N, N-di-C _1-4 alkyl derivatives thereof. Examples which may be mentioned are: N, N-dimethyldimethylenetriamine, N, N-diethyldimethylenetriamine, N, N-dipropyldimethylenetriamine, N, N-dimethyldiethylene-1,2-triamine, N, N-diethyldiethylene-1,2-triamine, N, N-dipropyldiethylene-1,2-triamine, N, N-dimethyl-dipropylene-1,3-triamine (ie DMAPAPA), N, N-diethyl-dipropylene-1,3-triamine, N, N-dipropyl-dipropylene-1,3-triamine, N, N-dimethyldibutylene-1,4-triamine, N, N-diethyldibutylene-1,4-triamine, N, N-dipropyldibutylene-1,4-triamine, N, N-dimethyldipentylene-1,5-triamine, N, N-diethyldipentylene-1,5-triamine, N, N-dipropyldipentylene-1,5-triamine, N, N-dimethyldihexylene-1,6-triamine, N, N-diethyldihexylene-1,6-triamine and N, N- Dipropyldihexylen-1,6-triamine,

"Aromatic carbocyclic diamines" having two primary amino groups are the di-amino substituted derivatives of benzene, biphenyl, naphthalene, tetrahydronaphthalene, fluorene, indene, and phenanthrene.

• 5- oder 6-gliedriges gesättigtes oder einfach ungesättigtes Heterocyclen, enthaltend ein bis zwei Stickstoffatome und/oder ein Sauerstoff- oder Schwefelatom oder ein oder zwei Sauerstoff- und/oder Schwefelatome als Ringglieder, z. B. Tetrahydrofuran, Pyrrolidin, Isoxazolidin, Isothiazolidin, Pyrazolidin, Oxazolidin, Thiazolidin, Imidazolidin, Pyrrolin, Piperidin, Piperidinyl, 1,3-Dioxan, Tetrahydropyran, Hexahydropyridazin, Hexahydropyrimidin, Piperazin;
• 5-gliedrige aromatische Heterocyclen, enthaltend neben Kohlenstoffatomen ein, zwei oder drei Stickstoffatome oder ein oder zwei Stickstoffatome und ein Schwefel-oder Sauerstoffatom als Ringglieder, z. B. Furan, Thian, Pyrrol, Pyrazol, Oxazol, Thiazol, Imidazol und 1,3,4-Triazol; Isoxazol, Isothiazol, Thiadiazol, Oxadiazol
• 6-gliedrige Heterocyclen enthaltend neben Kohlenstoffatomen ein oder zwei bzw. ein, zwei oder drei Stickstoffatome als Ringglieder, z. B. Pyridinyl, Pyridazin, Pyrimidin, Pyrazinyl, 1,2,4-Triazin , 1,3,5-Triazin-2-yl;

"Aromatic or non-aromatic heterocyclic polyamines" having two primary amino groups are the derivatives of the following heterocycles substituted with two amino groups:

• 5- or 6-membered saturated or monounsaturated heterocycles containing one to two nitrogen atoms and / or an oxygen or sulfur atom or one or two oxygen and / or sulfur atoms as ring members, eg. Tetrahydrofuran, pyrrolidine, isoxazolidine, isothiazolidine, pyrazolidine, oxazolidine, thiazolidine, imidazolidine, pyrroline, piperidine, piperidinyl, 1,3-dioxane, tetrahydropyran, hexahydropyridazine, hexahydropyrimidine, piperazine;
• 5-membered aromatic heterocycles containing, in addition to carbon atoms, one, two or three nitrogen atoms or one or two nitrogen atoms and one sulfur or oxygen atom as ring members, e.g. Furan, thian, pyrrole, pyrazole, oxazole, thiazole, imidazole and 1,3,4-triazole; Isoxazole, isothiazole, thiadiazole, oxadiazole
• 6-membered heterocycles containing in addition to carbon atoms one or two or one, two or three nitrogen atoms as ring members, for. Pyridinyl, pyridazine, pyrimidine, pyrazinyl, 1,2,4-triazine, 1,3,5-triazin-2-yl;

"Aromatic or non-aromatic heterocycles having a primary and a tertiary amino group" are, for example, the abovementioned N-heterocycles, which are aminoalkylated on at least one ring N atom, and in particular carry an amino-C _1-4 -alkyl group.

"Aromatic or non-aromatic heterocycles having a tertiary amino group and a hydroxyalkyl group" are, for example, the abovementioned N-heterocycles which are hydroxyalkylated on at least one ring N-atom, and in particular carry a hydroxyC _1-4 -alkyl group.

The following groups of individual classes of quaternizable nitrogen compounds may be mentioned in particular:

Group 1:

SURNAME FORMULA Diamines with primary second N atom ethylenediamine

1,2-propylenediamine

1,3-propylene

Isomeric butylenediamines, e.g.

1,5-pentylene

Isomeric pentanediamines, e.g.

Isomeric hexanediamines, e.g.

Isomeric heptanediamines, e.g.

Di- and polyamines with secondary second N-atom Diethylenetriamine (DETA)

Dipropylenetriamine (DPTA), 3,3'-lminobis (N, N-dimethylpropylamine)

Triethylenetetramine (TETA)

Tetraethylenepentamine (TEPA)

pentaethylenehexamine

N-methyl-3-amino-1-propylamine

bishexamethylenetriamine

aromatics Diaminobenzenes, e.g.

Diaminopyridines, e.g.

Group 2:

SURNAME FORMULA heterocycles 1- (3-aminopropyl) imidazole

4- (3-aminopropyl) morpholine

1- (2-aminoethylpiperidine)

2- (1-piperazinyl) ethylamine (AEP)

N-methyl piperazine

Amines with tertiary second N atom 3,3-Diamino-N-methyldipropylamine

3-dimethylamino-1-propylamine (DMAPA)

N, N-diethylamino

N, N-Dimethylaminoethylamine

Group 3:

SURNAME FORMULA Alcohols with primary and secondary amine ethanolamine

3-hydroxy-1-propylam in

diethanolamine

diisopropanolamine

N- (2-hydroxyethyl) ethylenediamine

Alcohols with tertiary amine Triethanolamine, (2,2 ^I , 2 ^II- nitrilotriethanol)

1- (3-hydroxypropyl) imidazole

Tris (hydroxymethyl) amine

3-dimethylamino-1-propanol

3-diethylamino-1-propanol

2-dimethylamino-1-ethanol

4-diethylamino-1-butanol

A6) Preparation of additives according to the invention: a) Reaction with oxygen or nitrogen group:

The reaction of the hydrocarbyl-substituted polycarboxylic acid compound with the quaternizable nitrogen compound according to the present invention may be carried out under thermally controlled conditions, so that essentially no condensation reaction takes place. In particular, no formation of water of reaction is observed. In particular, such a reaction takes place at a temperature in the range of 10 to 80, in particular 20 to 60 or 30 to 50 ° C. The reaction time can be in the range of a few minutes or a few hours, such as about 1 minute to about 10 hours. The reaction can take place at about 0.1 to 2 atm pressure, but especially at about atmospheric pressure. For example, an inert gas atmosphere, such as nitrogen, is useful

In particular, the reaction can also be carried out under elevated, condensation-promoting temperatures, for. B. in the range of or 90 to 100 ° C or 100 to 170 ° C. The reaction time may be in the range of a few minutes or a few hours, e.g. about 1 minute to about 10 hours. The reaction can be carried out at about 0.1 to 2 atm pressure, but especially at about atmospheric pressure.

The reactants are presented in particular in approximately equimolar amounts, optionally a lower, z. 0.05 to 0.5 times, e.g. 0.1 to 0.3 times the molar excess of the polycarboxylic acid compound is desirable. If necessary, the reactants may be presented in a suitable inert organic aliphatic or aromatic solvent or a mixture thereof. Typical examples are e.g. Solvesso series solvent, toluene or xylene. The solvent can also serve, for example, azeotropically remove condensation water from the reaction mixture. In particular, however, the reactions are carried out without solvent.

The reaction product thus formed can theoretically be further purified or the solvent removed. Usually, however, this is not absolutely necessary, so that the reaction product can be converted into the next synthesis step, the quaternization, without further purification.

b) Quaternization

The quaternization according to reaction step (b) is now carried out in a conventional manner

To carry out the quaternization, the reaction product or reaction mixture from stage a) is mixed with at least one compound of the above formula 1 or 2, in particular in the required stoichiometric amounts, in order to achieve the desired quaternization. Per equivalent of quaternizable tertiary nitrogen atom can be e.g. 0.1 to 2.0, 0.2 to 1.5, or 0.5 to 1.25 equivalents of quaternizing agent. In particular, however, approximately equimolar proportions of the compound are used to quaternize a tertiary amine group. Correspondingly, higher amounts are required to quaternize a secondary or primary amine group.

In this case, one typically operates at temperatures in the range of 50 to 180 ° C, such. 90 to 160 ° C or 100 to 140 ° C. The reaction time may be in the range of a few minutes or a few hours, e.g. about 10 minutes to about 24 hours. The reaction may be carried out at about 0.1 to 20 bar, e.g. 1 to 10 or 1.5 to 3 bar pressure, but especially at about atmospheric pressure.

If necessary, the reactants may be presented in a suitable inert organic aliphatic or aromatic solvent or a mixture thereof for quaternization, or there may still be a sufficient amount of solvent from reaction step a). Typical examples are e.g. Solvesso series solvent, toluene or xylene. The quaternization can also be carried out in the absence of a solvent

To carry out the quaternization, the addition of catalytically effective amounts of an acid may be expedient. Aliphatic monocarboxylic acids, such as, for example, C ₁ -C ₁₈ monocarboxylic acids, in particular lauric acid, isononanoic acid or neodecanoic acid, are preferred. The quaternization can also be carried out in the presence of a Lewis acid. The quaternization can also be carried out in the absence of any acid.

c) work-up of the reaction mixture

The final reaction product thus formed can theoretically be further purified or the solvent removed. In order to improve the further processability of the products but can also be added after the reaction solvent, such as for example 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 with a number-average molecular weight (M _n ) of 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 terminated by hydroxyl groups, mono or polyamino groups, wherein at least one nitrogen atom has basic properties, or terminated 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 the 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.

• Mono- oder Polyaminogruppen (Da) enthaltende Additive sind vorzugsweise Polyalkenmono- oder Polyalkenpolyamine auf Basis von Polypropen oder von hochreaktivem (d.h. mit überwiegend endständigen Doppelbindungen) oder konventionellem (d.h. mit überwiegend mittenständigen Doppelbindungen) Polybuten oder Polyisobuten mit M_n = 300 bis 5000, besonders bevorzugt 500 bis 2500 und insbesondere 700 bis 2500. Derartige Additive auf Basis von hochreaktivem Polyisobuten, welche aus dem Polyisobuten, das bis zu 20 Gew.-% n-Buten-Einheiten enthalten kann, durch Hydroformylierung und reduktive Aminierung mit Ammoniak, Monoaminen oder Polyaminen wie Dimethylaminopropylamin, Ethylendiamin, Diethylentriamin, Triethylentetramin oder Tetraethylenpentamin hergestellt werden können, sind insbesondere aus der EP-A 244 616 bekannt. Geht man bei der Herstellung der Additive von Polybuten oder Polyisobuten mit überwiegend mittenständigen Doppelbindungen (meist in der β- und γ-Position) aus, bietet sich der Herstellweg durch Chlorierung und anschließende Aminierung oder durch Oxidation der Doppelbindung mit Luft oder Ozon zur Carbonyl- oder Carboxylverbindung und anschließende Aminierung unter reduktiven (hydrierenden) Bedingungen an. Zur Aminierung können hier Amine, wie z. B. Ammoniak, Monoamine oder die oben genannten Polyamine, eingesetzt werden. Entsprechende Additive auf Basis von Polypropen sind insbesondere in der WO-A 94/24231 beschrieben.

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-hydroxypolyisobutene).

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 polyisobutene having M _n = 300 to 5000 with ammonia, mono- or polyamines, as described in particular 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, their carboxyl groups wholly or partially to the alkali metal or alkaline earth metal salts and a remaining Rest of the carboxyl groups are reacted 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 for preventing valve seat wear and can be used to advantage in combination with conventional fuel detergents such as poly (iso) buteneamines 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 In the case of polyethers, such products also fulfill 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 of iso-octanol, iso-nonanol, iso-decanol and of isotridecanol. 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 an acid and an amide function, carboximides with monoamines, carboximides with di- or polyamines which, in addition to the imide function, still have free amine groups, or diimides which are formed by reacting 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 a 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 dosage 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 used both in the form of pure isomers and in the form of technical mixtures. 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 capable of the flow behavior of middle distillate fuels or diesel fuels to improve 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, preference is given to α-olefins, particularly preferably α-olefins having 2 to 6 carbon atoms, for example propene, 1-butene, 1-pentene, 1-hexene and, above all, 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.

Suitable copolymers of class (K1) are also those which contain two or more mutually different carboxylic acid alkenyl ester in copolymerized form, wherein these differ 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 the other ethylenically unsaturated monomers are present in the copolymers of class (K1) in an amount of preferably from 1 to 50% by weight, in particular from 10 to 45% by weight and especially from 20 to 40% by weight. %, 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. Other 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, pages 117 to 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 - 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 preparing said polar nitrogen compounds are octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tetradecylamine and the higher linear homologues; secondary amines suitable for this purpose 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 Ullmann's Encyclopedia of Industrial Chemistry, 6th edition, in the chapter "Amines, aliphatic". Suitable acids for the reaction are, for example, cyclohexane-1,2-dicarboxylic acid, cyclohexene-1,2-dicarboxylic acid, cyclopentane-1,2-dicarboxylic acid, naphthalenedicarboxylic acid, Phthalic acid, isophthalic acid, terephthalic acid and succinic acids substituted with 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 -C ₂₀ -carbonic 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

darstellt und die Variable B eine C₁- bis C₁₉-Alkylengruppe bezeichnet. Die Verbindungen der allgemeinen Formel IIa und IIb weisen insbesondere die Eigenschaften eines WASA auf.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 connections 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, for example, 1,2-ethylene, 1,3-propylene, 1,4-butylene, hexamethylene, octamethylene, decamethylene, dodecamethylene, tetradecamethylene, hexadecamethylene, octadecamethylene, nonadecamethylene and in particular 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 acid or from its 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 being 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, added.

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, for example, salicylic acid derivatives such as N, N'-disalicylidene-1,2-propanediamine.

B12) Solvent

Suitable ones are e.g. nonpolar 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 arrive together with the aforementioned additives and co-additives which they are intended to dissolve or dilute for better handling into the diesel fuel.

C) fuels

The additive of the invention is outstandingly suitable as a fuel additive and can be used in principle in any fuels. It has a number of beneficial effects on the operation of internal combustion engines with 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 sulfur content of at most 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 heating oils and diesel fuels are specified in greater detail in, for example, DIN 51603 and EN 590 (cf. Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Volume A12, p. 617 et seq. ).

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). 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.

The invention will now be described in more detail with reference to the following exemplary embodiments:

Experimental part: A. General testing methods engine test b1) XUD9 test - determination of flow restriction

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

b2) DW10 test - Determination of power loss due to injector deposits in the common rail diesel engine

To investigate the influence of the additives on the performance of direct injection diesel engines, the power loss was determined according to the official test method CEC F-098-08. The power loss is a direct measure of the formation of deposits in the injectors.

A direct injection diesel engine with common rail system was used according to test methods CEC F-098-08. 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.

B. Production Examples: Reactants used:

PIBSA: Made from maleic anhydride and PIB 1000 in a known manner. For the following preparation examples and comparative examples according to the invention, grades having saponification numbers in the range of 84-95 mg KOH / g were used. In this case, DMAPA was used with the respective PIBSA quality in a molar ratio of 1: 1 corresponding to the saponification number. The PIBSA grades used had bis-malalization (BMG) levels of less than 15%. DMAPA: M = 102.18 methyl salicylate: M = 152.14 dimethyl phthalate: M = 194.19 dimethyl oxalate: M = 118.09 dimethyl sulfate: M = 126.13 dimethyl M = 90.08

Preparation Example 1 Synthesis of a Quaternized Sucinimide According to the Invention (PIBSA / DMAPA / Dimethyl Phthalate)

Polyisobutylenesuccinic anhydride (1659 g) is dissolved in Solvent Naphta Heavy (SNH, Exxon Mobil, CAS 64742-95-5) (1220 g) and 3-dimethylamino-1-propylamine (DMAPA, 153 g) is added. The reaction solution is stirred for 8 h at 170 ° C, with formed condensation water is distilled off continuously. The PIBSA-DMAPA succinimide is obtained as a solution in Solvent Naphta Heavy (TBN 0.557 mmol / g).

A portion of this solution of PIBSA-DMAPA succinimide (181 g) is added to dimethyl phthalate (19.4 g) and the resulting reaction solution is stirred for 11 h at 120 ° C and then for 24 h at 150 ° C. After cooling to room temperature, the product obtained is the ammonium carboxylate as a solution in Solvent Naphta Heavy. ¹ H NMR analysis confirms quaternization.

Preparation Example 2 Synthesis of a Quaternized Succinimide According to the Invention (PIBSA / DMAPA / Methyl Salicylate)

Polyisobutylene succinic anhydride (PIBSA, 2198 g) is heated to 110 ° C and 3-dimethylamino-1-propylamine (DMAPA, 182 g) is added within 40 min. added, with the reaction mixture heated to 140 ° C. The reaction mixture is heated to 170 ° C and held for 3 h at this temperature, with 28 g of distillate are collected. The PIBSA-DMAPA succinimide is obtained as a viscous oil (TBN 0.735 mmol / g).

A mixture of this PIBSA-DMAPA succinimide (284.5 g), methyl salicylate (65.5 g) and 3,3,5 trimethylheptanoic acid (BASF) (0.75 g) is heated to 140-150 ° and the reaction mixture is stirred for 6 h at this temperature. After cooling to room temperature, the product obtained is the ammonium salicylate as a viscous oil. ¹ H NMR analysis confirms quaternization. By adding Pilot 900 Oil, Petrochem Carless Ltd., the active content of the solution is adjusted to 50% by weight.

Preparation Example 3 Synthesis of a Quaternized Succinimide According to the Invention (PIBSA / DMAPA / Dimethyloxalate)

Polyisobutylene succinic anhydride (PIBSA, 2198 g) is heated to 110 ° C and 3-dimethylamino-1-propylamine (DMAPA, 182 g) is added within 40 min. added, with the reaction mixture heated to 140 ° C. The reaction mixture is heated to 170 ° C and held for 3 h at this temperature, with 28 g of distillate are collected. The PIBSA-DMAPA succinimide is obtained as a viscous oil (TBN 0.735 mmol / g).

A mixture of this PIBSA-DMAPA succinimide (211 g), dimethyl oxalate (34.5 g) and lauric acid (4.9 g) is heated to 120 ° C and then for 4 h at this temperature touched. Excess dimethyloxalate is removed on a rotary evaporator in vacuo (p = 5 mbar) at 120 ° C. The product obtained is ammonium methyl oxalate as a viscous oil. ¹ H NMR analysis confirms quaternization.

For comparison with the prior art, Examples 2 and 4 of the WO 2006/135881 reworked.

Preparation Example 4 Synthesis of a Known Quaternized Succinimide (Comparative Example ) (Example 2 from WO 2006/135881)

A solution of PIBSA (420.2 g) in Pilot 900 Oil Petrochem Carless Ltd. , (51.3 g) is charged and heated to 110 ° C. Within 50 minutes, DMAPA (31.4 g) is metered in, with a slight exothermic reaction being observed. Within 80 minutes, the reaction mixture is heated to 150 ° C and the mixture is then held for 3 h at this temperature, wherein the resulting reaction water distilled off. After cooling to room temperature, the PIBSA-DMAPA succinimide is obtained as a solution in Pilot 900 oil (TBN 0.62 mmol / g).

A portion of the resulting PIBSA-DMAPA succinimide solution in Pilot 900 Oil, Petrochem Carless Ltd., (354 g) is charged and heated to 90 ° C. Dimethyl sulfate (26.3 g) is metered in, with the reaction temperature rising to 112.degree. Subsequently, the reaction mixture is stirred for 3 h at 100 ° C. After cooling to room temperature, the quaternized PIBSA-DMAPA succinimide is obtained as a solution in Pilot 900 oil. ¹ H NMR analysis confirmed the quaternization. The output was adjusted to an active ingredient content of 50% by weight by adding Pilot 900 oil.

Preparation Example 5 Synthesis of a Known Quaternized Succinimide (Comparative Example ) (Example 4 from WO 2006/135881)

A solution of PIBSA (420.2 g) in Pilot 900 Oil, Petrochem Carless Ltd. , (51.3 g) is charged and heated to 110 ° C. Within 50 minutes, DMAPA (31.4 g) is metered in, with a slight exothermic reaction being observed. Within 80 minutes, the reaction mixture is heated to 150 ° C and the mixture is then held for 3 h at this temperature, wherein the resulting reaction water distilled off. After cooling to room temperature, the PIBSA-DMAPA succinimide is obtained as a solution in Pilot 900 oil (TBN 0.62 mmol / g).

A portion of the resulting PIBSA-DMAPA succinimide solution in Pilot 900 Oil, Petrochem Carless Ltd., (130 g), dimethyl carbonate (20 g) and methanol (17.4) are charged to an autoclave, made inert with nitrogen, and introduced Pre-pressure of 1.3 bar set. Subsequently, the reaction mixture is stirred under autogenous pressure, first at 90 ° C. for 1 h, then at 140 ° C. for 24 h. After cooling to room temperature, the autoclave is depressurized and the contents are completely rinsed off with a little toluene as the solvent. All low boiling components are then removed on a rotary evaporator in vacuo to give the quaternized PIBSA-DMAPA succinimide solution in Pilot 900 oil. ¹ H NMR analysis confirmed the partial quaternization. The effluent is adjusted to an active ingredient content of 50% by weight by adding Pilot 900 oil.

C. Application examples:

• M1 : Additiv gemäß Herstellungsbeispiel 2 (Erfindung, mit Methylsalicylat quaterniert)
• M2 : Additiv gemäß Herstellungsbeispiel 4 (Vergleich, mit Dimethylsulfat quaterniert)
• M3 : Additiv gemäß Herstellungsbeispiel 5 (Vergleich, mit Dimethycarbonat quaterniert)

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.

• M1: additive according to preparation example 2 (invention, quaternized with methyl salicylate)
• M2: additive according to preparation example 4 (comparison, quaternized with dimethyl sulfate)
• M3: additive according to Preparation Example 5 (comparison, quaternized with dimethycarbonate)

Application Example 1: Determination of the additive effect on the formation of deposits in diesel engine injection nozzles a) XUD9 tests

Fuel used: RF-06-03 (Referenzdiesel, Haltermann Products, Hamburg) The results are summarized in Table 1. Table 1: XUD9 tests Ex. description Dosage acc. Preparation Example [mg / kg] Flow restriction 0.1 mm needle stroke [%] #1 M1, according to production example 2 30 10.7 # 2 M2, according to preparation example 4 30 48.5 # 3 M3, according to preparation example 5 30 20.8

It was found that the additive M1 according to the invention at the same dosage has an improved effect compared to the prior art (M2, M3).

b) DW10 test

To investigate the influence of the compound according to the invention on the performance of direct-injection diesel engines, the power loss was determined on the basis of the official test method CEC F-98-08. The power loss is a direct measure of the formation of deposits in the injectors. A common direct-injection diesel engine with common-rail system was used.

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.

The table below shows the results of relative power loss (powerloss) at 4000 rpm after 12 hours of continuous operation without interruption. The value P0 indicates the power after 10 minutes and the value Pend the power at the end of the measurement:

The test results are shown in Table 2. Table 2: Results of the DW10 test additive Dose [mg / kg] Time [h] P0 [KW] Pend [KW] Power loss basic value 0 12 99.3 94.3 5.0% M1, according to manufacturing example 2 160 12 98.7 97.4 1:32% M2, according to manufacturing example 4 160 12 99 98.1 0.9% M3, according to manufacturing example 5 160 12 98.1 95.7 2.4%

It can be seen that the additive M1 according to the invention has an improved effect compared to the base value and has an improved effect at least in comparison with the example M3.

Application Example 2: Determination of Solubility Properties

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

M 4 (invention)

substance Content [ppm] Additive acc. Production Example 2 80,00 Dehazer, commercial 3.00 Antifoam, silicone based, commercial 6.00 Pilot 900 80,00 Solvent Naphta Heavy 80,00 total 249.00

M 5 (comparison, dimethyl sulfate)

substance Content [ppm] Additive acc. Production Example 4 160.00 Dehazer, commercial 3.00 Antifoam, silicone based, commercial 6.00 Solvent Naphta Heavy 420.00 total 589.00

M 6 (comparison, dimethyl carbonate)

substance Content [ppm] Additive acc. Production Example 5 160.00 Dehazer (commercial) 3.00 Antifoam, silicone based, commercial 6.00 Solvent Naphta Heavy 150.00 total 319.00

The result of the solubility tests is summarized in the following table: The minimum necessary amount of solvent (Solvent Naphtha Heavy) is given in order to obtain a homogeneous, clear diesel performance package at room temperature with otherwise identical amounts of active substance, Pilot 900, Antifoam, Dehazer. Table 3: Determination of the solvent requirement additive Additive Package Minimum required amount of solvent for a homogeneous package PIBSA DMAPA-imide methyl salicylate M4 32% PIBSA DMAPA-imide dimethyl M5 71% PIBSA DMAPA-imide dimethyl M6 47%

Surprisingly, it was found that the additive according to Preparation Example 2 has the best solubility properties, that is, the least solvent required.

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

Claims (17)

A fuel composition comprising, in a majority of a common fuel, a proportion of at least one quaternized nitrogen compound-containing reaction product, or a quaternized nitrogen compound-containing partial fraction thereof obtained from the reaction product, the reaction product being obtainable by a) reacting a hydrocarbyl-substituted polycarboxylic acid compound with a compound comprising at least one polycarboxylic acid reactive, in particular addable or condensable, oxygen or nitrogen group and containing at least one quaternizable amino group to obtain a quaternizable hydrocarbyl-substituted polycarboxylic acid, and b) the subsequent reaction with a quaternizing agent which converts the at least one tertiary amino group into a quaternary ammonium group, the quaternizing agent being the alkyl esters of a cycloaromatic or cycloaliphatic monocarboxylic or polycarboxylic acid, in particular a mono- or dicarboxylic acid, or an aliphatic polycarboxylic acid, in particular dicarboxylic acid, is. A fuel composition comprising, in a majority of a conventional fuel, a portion of at least one quaternized nitrogen compound-containing 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 hydrocarbyl-substituted polycarboxylic acid compound containing at least a quaternizable 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 the alkyl ester of a cycloaromatic or cycloaliphatic mono- or polycarboxylic acid, in particular a mono- or dicarboxylic acid, or an aliphatic polycarboxylic acid, in particular dicarboxylic acid. A fuel composition according to any one of the preceding claims, wherein the quaternizing agent is a compound of general formula 1

R ₁ OC (O) R ₂ (1)

wherein
R _{1 is} a lower alkyl radical and
R _{2 is} an optionally substituted mononuclear aryl or cycloalkyl radical, wherein the substituent is selected from OH, NH ₂ , NO ₂ , C (O) OR ₃ , and R ₁ OC (O) -, wherein R _{1 has} the meanings given above and R _{3 is} H or R ₁ . A fuel composition according to any one of claims 1 and 2, wherein the quaternizing agent is a compound of general formula 2

R ₁ OC (O) -AC (O) OR _1a (2)

wherein
R ₁ and R _1a independently of one another represent a lower alkyl radical and
A represents hydrocarbylene, in particular alkylene or alkenylene. Fuel composition according to one of the preceding claims, wherein the quaternized nitrogen compound has a number average molecular weight in the range of 500 to 5000, in particular 800 to 3000 or 900 to 1500. A fuel composition according to any one of the preceding claims wherein the quaternizing agent is selected from alkyl salicylates, dialkyl phthalates and dialkyl oxalates. A fuel composition according to claim 1, wherein the polycarboxylic acid reactive, in particular addable or condensable, an oxygen or nitrogen group and at least one quaternizable amino group-containing compound is selected from a) hydroxyalkyl-substituted mono- or polyamines having at least one quaternizable, primary, secondary or tertiary amino group b) straight-chain or branched, cyclic, heterocyclic, aromatic or non-aromatic polyamines having at least one primary or secondary amino group and having at least one quaternizable, primary, secondary or tertiary amino group; c) piperazines. A fuel composition according to claim 7, wherein said compound is selected from a) hydroxyalkyl-substituted primary, secondary or tertiary monoamines and hydroxyalkyl-substituted primary, secondary or tertiary diamines. b) straight-chain or branched aliphatic diamines having two primary amino groups; Di- or polyamines having at least one primary and at least one secondary amino group; Di- or polyamines having at least one primary and at least one tertiary amino group; aromatic carbo-cyclic diamines having two primary amino groups; aromatic heterocyclic polyamines having two primary amino groups; aromatic or non-aromatic heterocycles having a primary and a tertiary amino group. Fuel composition according to one of the preceding claims, selected from diesel fuels, biodiesel fuels, gasoline fuels, and alkanol-containing gasolines. A fuel composition according to any one of the preceding claims, wherein the hydrocarbyl-substituted polycarboxylic acid compound is a polyisobutenyl succinic acid or anhydride thereof, which has a bismaleination level of less than 20%, e.g. 19, 18, 17, 16%, 15% or less than 15%, e.g. 14, 13, 12 or 11%, especially 10% or less than 10%, e.g. 2 to 9, or 3 to 7%. Quaternized nitrogen compound as defined in any one of the preceding claims. A process for producing a quaternized nitrogen compound according to claim 11,
which comprises reacting a quaternizable hydrocarbyl-substituted polycarboxylic acid compound containing at least one tertiary, quaternizable 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 the alkyl ester of a cycloaromatic or cycloaliphatic mono- or polycarboxylic acid, in particular a mono- or dicarboxylic acid, or an aliphatic polycarboxylic acid, especially dicarboxylic acid. Use of a quaternized nitrogen compound according to claim 11 or prepared according to claim 12 as a fuel additive. Use according to Claim 13 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. Use according to claim 13 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 13 as a diesel fuel additive, in particular as a cold flow improver, as a wax anti-settling additive (WASA) or as an additive for reducing and / or avoiding deposits in the injection systems, such as in particular the Internal Diesel Injector Deposits (IDID) and / or Valve bonding in direct-injection diesel engines, in particular in common-rail injection systems. Additive concentrate, containing in combination with other diesel or petrol additives, especially diesel fuel additives, at least one quaternized A nitrogen compound as defined in claim 11 or prepared according to claim 12.