EP2773729B1 - The use of quaternized polyetheramines as additives in fuels and lubricants - Google Patents

Description

Described here are novel quaternized polyether amines and their preparation, and the use of these compounds as a fuel and lubricant additive. 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, for reducing the fuel consumption of direct injection diesel engines, especially diesel engines with common rail injection systems, and to minimize the power loss in direct injection diesel engines, especially in diesel engines with common rail injection systems. Also described herein are additive packages containing these polyetheramines; as well as with it additized fuels and lubricants. The invention also relates to the use of these quaternized nitrogen compounds as an additive for gasoline fuels, in particular for improving the intake system cleanliness of gasoline engines.

State of the art:

In direct-injection diesel engines, the fuel is injected through a directly into the combustion chamber-reaching multi-hole injection nozzle of the engine and finely distributed (nebulized), 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.

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

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

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

In modern common-rail diesel engines deposits can form under certain conditions, for example when using biodiesel-containing fuels or fuels with metal impurities such as zinc compounds, copper compounds, lead compounds and other metal compounds, the injection behavior of the Negatively affect the 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 the engine and injectors, such deposits in the nozzle orifices must be prevented or reduced by suitable fuel additives.

Carburetors and intake systems of gasoline engines, as well as injectors Fuel metering systems are contaminated by impurities caused by dust particles from the air, unburned hydrocarbon residues from the combustion chamber and the crankcase ventilation gases directed into the gasifier.

These residues shift the air-fuel ratio at idle and in the lower part-load range, making the mixture leaner, incomplete combustion and, in turn, increasing the proportion of unburned or partially combusted hydrocarbons in the exhaust gas and increasing gasoline consumption.

It is known that to avoid these disadvantages, fuel additives are used for keeping valves and carburetors or injection systems of gasoline engines clean (cf., for example: M. Rossenbeck in Catalysts, Surfactants, Mineral Oil Additives, ed. J. Falbe, U. Hasserodt, p. 223, G. Thieme Verlag, Stuttgart 1978 ).

Depending on the mode of action but also on the preferred site of action of such detergent additives, a distinction is made today between two generations.

The first additive generation could only prevent the formation of deposits in the intake system, but not remove existing deposits again, whereas the modern second-generation additives can do both (keepclean and clean-up effect), especially because of their outstanding Thermostability at higher temperature zones, namely at the inlet valves. Such detergents, which can originate from a large number of chemical substance classes, such as, for example, polyalkeneamines, polyetheramines, polybutene-Mannich bases or polybutene succinimides, are generally used in combination with carrier oils and in some cases further additive components, for example corrosion inhibitors and demulsifiers. The carrier oils perform a solvent or wash function in combination with the detergents. Carrier oils are usually high-boiling, viscous, thermostable liquids which coat the hot metal surface and thereby prevent the formation or deposition of impurities on the metal surface.

Detergent-effect fuel additives of the younger generation often have quaternized nitrogen groups.

So describes the example WO 2006/135881 quaternized ammonium salts prepared by condensation of a hydrocarbyl-substituted acylating agent and an 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. These additives are used especially as diesel fuel additives to reduce power loss.

Polyalkene substituted quaternized amines, such as, in particular, quaternized polyisobuteneamines, and their use as detergent additives to reduce inlet valve deposits and as lubricant additives for internal combustion engines are disclosed in U.S.P. US 2008/0113890 described.

The US 6 331 648 B1 relates to specific quaternary etheramine compounds which incorporate a 1-ethyl-1,3-propylene unit between the alkoxylate chain and quaternary nitrogen. The use of these compounds as anticorrosion or detergent additives in gasoline and diesel fuels is speculated, but without demonstrating their usefulness.

The EP 182 669 A1 describes halogenated or sulfur-containing alkoxylated quaternary ammonium compounds of the general structure

[RO (R ₁ ) _x CH ₂ CH (R ₂ ) HNR ₃ R ₄ R ₆ ] ⁺ A ^-

wherein R _{1 represents} an alkylene oxide block. For these compounds, a whole range of applications are postulated, including generally as fuel and lubricant additives, but without actually demonstrating specific functions experimentally. Preferred anions A- are chloride, methylsulfate and ethylsulfate.

The U.S. 4,564,372 . US 4,581,151 . US 4,600,409 and the WO 1985/000620 refer to alkyl halides quaternized, ie halogenated, polyoxyalkyleneamine salts in which polyoxyalkylene unit and amine unit via different linker groups, in particular amine linker of the type -C (O) -NH-. Use as dispersants and corrosion inhibitors in fuels is postulated, but without actually demonstrating specific functions experimentally.

It is therefore an object to provide improved quaternized fuel additives, which no longer have the disadvantages of the prior art mentioned and in particular are simultaneously used in diesel fuels and gasoline.

Brief description of the invention:

It has now surprisingly been found that the above object can be achieved by providing specially additized fuels and lubricants as defined in the appended claims. The additives to be used according to the invention are superior in several respects to the known additives according to the prior art and can be used simultaneously in diesel and gasoline fuels. They are characterized by their advantageous cleaning and keeping clean effect on various components of internal combustion engines, such as diesel engine injectors but also on intake valves and injectors of gasoline engines, and prevent the formation of combustion chamber deposits or eliminate ready formed combustion chamber deposits of internal combustion engines. In addition, they prevent the formation of deposits in fuel filters or eliminate already formed filter contaminants.

Brief Description:

• FIG. 1 shows the injector cleanliness achievable by the use according to the invention of the claimed quaternized compounds after a test operation with a direct-injection gasoline engine (1b and 1c) in comparison to operation with non-additive fuel (1a).
• FIG. 2 shows the sequence of a one-hour motor test cycle according to CEC F-098-08.

Detailed description of the invention: A1) Special embodiments and aspects

1. a. eines Polyether-substituierten Amins, enthaltend wenigstens eine tertiäre, quaternisierbare Aminogruppe mit
2. b. einem Quaternisierungsmittel, das die wenigstens eine tertiäre Aminogruppe in eine quaternäre Ammoniumgruppe überführt,

als Ottokraftstoffadditiv zur Verringerung bzw. Vermeidung von Ablagerungen im Einlasssystem eines Ottomotors oder als Dieselkraftstoffadditiv zur Verringerung des Kraftstoffverbrauches von direkteinspritzenden Dieselmotoren und/oder zur Minimierung des Leistungsverlustes (powerloss) in direkteinspritzenden Dieselmotoren oder als Additiv zur Verringerung und/oder Vermeidung von Ablagerungen in den Einspritzsystemen, und/oder zur Verringerung und/oder Vermeidung der Internal Diesel Injector Deposits (IDID), und/oder zur Verringerung und/oder Vermeidung von Ablagerungen in den Einspritzdüsen in direkteinspritzenden Dieselmotoren, wobei
die quaternisierte Stickstoffverbindung ausgewählt ist unter Verbindungen der allgemeinen Formel Ia oder Ib,

worin

• R₁ und R₂ gleich oder verschieden sind und für C₁-C₆-Alkyl, Hydroxy-C₁-C₆-alkyl, Hydroxy-C₁-C₆-alkenyl, oder Amino-C₁-C₆-alkyl stehen, oder R₁ und R₂ zusammen eine C₂-C₆-Alkylen-, C₂-C₆-Oxyalkylen- oder C₂-C₆-Aminoalkylen-Rest bilden;
• R₃ und R₄ gleich oder verschieden sind und für H, C₁-C₆-Alkyl oder Phenyl stehen;
• R₅ für einen durch Quaternisierung eingeführten Rest, ausgewählt unter C₁-C₆-Alkyl, Hydroxy-C₁-C₆-alkyl oder -CH₂CH(OH)Aryl steht;
• R₆ für C₁-C₂₀-Alkyl oder Aryl oder Alkylaryl steht;
• A für einen geradkettigen oder verzweigten C₂-C₆-Alkylenrest steht, der gegebenenfalls durch ein oder mehrere Heteroatome, wie N, O und S, unterbrochen ist;
• n für einen ganzzahligen Wert von 1 bis 30 und
• X- für ein aus der Quaternisierungsreaktion resultierendes Anion steht;
• wobei das Quaternisierungsmittel ausgewählt ist unter
  1. (i) einem Epoxid der allgemeinen Formel II
     
     wobei die darin enthaltenen R^a Reste gleich oder verschieden sind und für H oder für einen Hydrocarbylrest stehen,
  2. (ii) einem Salicylat, ausgewählt unter, wie Methylsalicylat, Ethylsalicylat, n- und i-Propylsalicylat, und n-, i- oder tert-Butylsalicylat;
  3. (iii) einem Oxalat, ausgewählt unter Dimethyloxalat und Diethyloxalat; und
  4. (iv) Dimethylcarbonat.

The scope of the invention is defined by the claims. The present invention thus relates, in a first embodiment, to the use of a reaction product comprising a quaternized nitrogen compound, the reaction product being obtainable by reaction

1. a. a polyether-substituted amine containing at least one tertiary, quaternizable amino group
2. b. a quaternizing agent which converts the at least one tertiary amino group into a quaternary ammonium group,

as a gasoline additive to reduce or prevent deposits in the intake system of a gasoline engine or as a diesel fuel additive to reduce the fuel consumption of direct injection diesel engines and / or to minimize the power loss in direct injection diesel engines or as an additive for reducing and / or preventing deposits in the injection systems and / or for reducing and / or avoiding Internal Diesel Injector Deposits (IDID), and / or for reducing and / or preventing deposits in the injectors in direct injection diesel engines, wherein
the quaternized nitrogen compound is selected from compounds of general formula Ia or Ib,

wherein

• R ₁ and R _{2 are the} same or different and are C ₁ -C ₆ -alkyl, hydroxy-C ₁ -C ₆ -alkyl, hydroxy-C ₁ -C ₆ -alkenyl, or amino-C ₁ -C ₆ -alkyl or R ₁ and R ₂ together form a C ₂ -C ₆ alkylene, C ₂ -C ₆ oxyalkylene or C ₂ -C ₆ aminoalkylene radical;
• R ₃ and R _{4 are the} same or different and are H, C ₁ -C ₆ alkyl or phenyl;
• R _{5 is} a quaternized radical selected from C ₁ -C ₆ alkyl, hydroxyC ₁ -C ₆ alkyl or -CH ₂ CH (OH) aryl;
• R _{6 is} C ₁ -C ₂₀ alkyl or aryl or alkylaryl;
• A is a straight-chain or branched C ₂ -C ₆ -alkylene radical which is optionally interrupted by one or more heteroatoms, such as N, O and S;
• n for an integer value of 1 to 30 and
• X- represents an anion resulting from the quaternization reaction;
• wherein the quaternizing agent is selected from
  1. (i) an epoxide of general formula II
     
     wherein the R ^a radicals contained therein are identical or different and represent H or a hydrocarbyl radical,
  2. (ii) a salicylate selected from such as methyl salicylate, ethyl salicylate, n- and i-propyl salicylate, and n-, i- or tert-butyl salicylate;
  3. (iii) an oxalate selected from dimethyloxalate and diethyl oxalate; and
  4. (iv) dimethyl carbonate.

In a second embodiment, the present invention relates to the use of Embodiment 1, wherein the polyether-substituted amine has a number average molecular weight in the range of 500 to 5,000.

In a third embodiment, the present invention relates to the use of any of the preceding embodiments, wherein the fuel is selected from diesel fuels, gasoline fuels, biodiesel fuels and alkanol-containing gasoline fuels.

In a fourth embodiment, the present invention relates to the use of any one of the first to third embodiments as a gasoline additive for reducing or preventing deposits in the intake system of a gasoline engine, to reduce or avoid deposits in injection nozzles of direct injection gasoline engines.

In a fifth embodiment, the present invention relates to the use of any one of the first to third embodiments as an additive for reducing the fuel consumption of direct injection diesel engines, for reducing the fuel consumption of diesel engines with common rail injection systems, and / or for minimizing the power loss In direct injection diesel engines, to minimize powerloss in diesel engines with common rail injection systems or as an additive to reduce and / or prevent deposits in the injection systems, to reduce and / or avoid internal diesel injector deposits (IDIDs) and / or reduce them and / or preventing deposits in the injectors in direct injection diesel engines to reduce and / or prevent deposits in common rail injection systems.

1. 1. Kraftstoff- oder Schmierstoffzusammensetung, insbesondere Kraftstoffzusammensetzung, enthaltend in einer Hauptmenge eines üblichen Kraft- oder Schmierstoffs 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
   1. a. eines Polyether-substituierten Amins, enthaltend wenigstens eine tertiäre, quaternisierbare Aminogruppe mit
   2. b. einem Quaternisierungsmittel, das die wenigstens eine tertiäre Aminogruppe in eine quaternäre Ammoniumgruppe überführt.
2. 2. Kraftstoff- oder Schmierstoffzusammensetzung nach Aspekt 1, worin der Polyether-Substituent Monomereinheiten der allgemeinen Formel Ic
   
           -[-CH(R₃)-CH(R₄)-O-]-     (Ic)
   
   umfasst, worin
   R₃ und R₄ gleich oder verschieden sind und für H, Alkyl, Alkylaryl oder Aryl stehen.
3. 3. Kraftstoff- oder Schmierstoffzusammensetzung nach Aspekt 2, wobei das Polyether-substituierte Amin ein zahlenmittleres Molekulargewicht im Bereich von 500 bis 5000, insbesondere 800 bis 3000 oder 900 bis 1500 aufweist.
4. 4. Kraftstoff- oder Schmierstoffzusammensetzung nach einem der vorhergehenden Aspekte, wobei das Quaternisierungsmittel ausgewählt ist unter Alkylenoxiden ggf in Kombination mit Säure; aliphatische oder aromatische Mono- oder Polycarbonsäureestern, wie insbesondere Mono- oder Dialkylcarbonsäureestern; cyclischen nichtaromatischen oder aromatischen Mono- oder Polycarbonsäureestern; Dialkylcarbonaten; Alkylsulfaten; Alkylhalogeniden; Alkylarylhalogeniden; insbesondere halogen- und schwefelfreien Quaternisierungsmitteln, wie Alkylenoxiden in Kombination mit Säure, wie z.B. einer Carbonsäure; aliphatische oder aromatische Mono- oder Polycarbonsäureestern, wie insbesondere Mono- oder Dialkylcarbonsäureestern; cyclischen nichtaromatischen oder aromatischen Mono- oder Polycarbonsäureestern und Dialkylcarbonaten; und Mischungen davon.
5. 5. Kraftstoff- oder Schmierstoffzusammensetzung, enthaltend in einer Hauptmenge eines üblichen Kraft- oder Schmierstoffs eine wirksame Menge wenigstens einer quaternisierten Stickstoffverbindung der allgemeinen Formel Ia oder Ib,
   
   
   worin
   • R₁ und R₂ gleich oder verschieden sind und für Alkyl, Alkenyl, Hydroxyalkyl, Hydroxyalkenyl, Aminoalkyl oder Aminoalkenyl stehen, oder R₁ und R₂ zusammen für Alkylen, Oxyalkylen oder Aminoalkylen stehen;
   • R₃ und R₄ gleich oder verschieden sind und für H, Alkyl, Alkylaryl oder Aryl stehen;
   • R5 für einen durch Quaternisierung eingeführten Rest, wie insbesondere Alkyl, Hydroxyalkyl, Arylalkyl oder Hydroxyarylalkyl steht;
   • R₆ für Alkyl, Alkenyl, ggf ein oder mehrfach ungesättigtes Cycloalkyl, Aryl, jeweils gegebenenfalls substituiert, wie z.B. mit wenigstens einem Hydroxylrest oder Alkylrest, oder unterbrochen durch wenigstens ein Heteroatom, steht;
   • A für einen geradkettigen oder verzweigten Alkylenrest steht, der gegebenenfalls durch ein oder mehrere Heteroatome, wie N, O und S, unterbrochen ist;
   • n für einen ganzzahligen Wert von 1 bis 50 steht und
   • X- für ein Anion, insbesondere ein aus der Quaternisierungsreaktion resultierendes Anion, steht.
6. 6. Kraftstoff- oder Schmierstoffzusammensetzung nach Aspekt 5, worin
   R₁ und R₂ gleich oder verschieden sind und für C₁-C₆-Alkyl, Hydroxy-C₁-C₆-alkyl, Hydroxy-C₁-C₆-alkenyl, oder Amino-C₁-C₆-alkyl stehen, oder R₁ und R₂ zusammen eine C₂-C₆-Alkylen-, C₂-C₆-Oxyalkylen- oder C₂-C₆-Aminoalkylen-Rest bilden;
   R₃ und R₄ gleich oder verschieden sind und für H, C₁-C₆-Alkyl oder Phenyl stehen;
   R₅ für einen durch Quaternisierung eingeführter Rest, ausgewählt unter C₁-C₆-Alkyl, Hydroxy-C₁-C₆-alkyl oder -CH₂CH (OH)Aryl steht;
   R₆ für C₁-C₂₀-Alkyl, wie z.B. C₁₀-C₂₀-, C₁₁-C₂₀- oder C₁₂-C₂₀-Alkyl oder Aryl oder Alkylaryl, wobei Alkyl insbesondere für C₁-C₂₀- bedeutet, steht;
   A für einen geradkettigen oder verzweigten C₂-C₆-Alkylenrest steht, der gegebenenfalls durch ein oder mehrere Heteroatome, wie N, O und S, unterbrochen ist;
   n für einen ganzzahligen Wert von 1 bis 30 und
   X- für ein aus der Quaternisierungsreaktion resultierendes Anion steht.
7. 7. Kraftstoffstoffzusammensetzung nach einem der vorhergehenden Aspekte, ausgewählt unter Dieselkraftstoffen, Ottokraftstoffen, Biodieselkraftstoffen und Alkanol-haltigen Ottokraftstoffen.
8. 8. Quaternisierte Stickstoffverbindung gemäß der Definition in einer der vorhergehenden Aspekte, insbesondere ausgewählt unter solchen, die halogen- und schwefelfrei sind.
9. 9. Verfahren zur Herstellung quaternisierter Stickstoffverbindungen der allgemeinen Formel Ia,
   
   worin
   R₁ bis R₅, A, X und n die oben angegebenen Bedeutungen besitzen
   wobei man
   • a. ein Aminoalkanol der allgemeinen Formel II
     
             (R₁)(R₂)N-A-OH     (II)
     
     worin
     • R₁, R₂ und A die oben angegebenen Bedeutungen besitzen,
     • mit einem Epoxid der allgemeinen Formel III
     
     worin
     R₃ und R₄ die oben angegebenen Bedeutungen besitzen,
     alkoxyliert, wobei man ein alkoxyliertes Amin der Formel
     
     erhält, worin R₁ bis R₄, A und n die oben angegebenen Bedeutungen besitzen und
   • b) die so erhaltene Alkoxylverbindung der Formel la-1 quaternisiert, wobei man ein Reaktionsprodukt, umfassend wenigstens eine Verbindung der allgemeinen Formel la erhält, wobei die Quaternisierung beispielsweise mit einer Verbindung der allgemeinen Formel IV erfolgt
     
             R₅-X     (IV)
     
     worin
     R₅ für Alkyl oder Aryl steht und X die oben angegebene Bedeutung besitzt, oder mit einem Alkylenoxid der Formel
     
     in Kombination mit einer Säure HX quaternisiert, worin X die oben angegebene Bedeutung besitzt, wobei R_5' für H, Alkyl oder Aryl steht und der Rest R₅ für eine Gruppe -CH₂CH(OH)R_5' steht.
10. 10. Verfahren zur Herstellung quaternisierter Stickstoffverbindungen der allgemeinen Formel Ib,
    
    worin R₁ bis R₆, X und n die oben angegebenen Bedeutungen besitzen
    wobei man
    1. a) einen Alkohol der allgemeinen Formel V
       
               R₆-OH     (V)
       
       worin
       R₆ die oben angegebenen Bedeutungen besitzt, mit einem Epoxid der allgemeinen Formel III
       
       worin
       R₃ und R₄ die oben angegebenen Bedeutungen besitzen, alkoxyliert, wobei man einen Polyether der Formel Ib-1 ;
       
       erhält; worin R₃, R₄ und R₆, A, X und n die oben angegebenen Bedeutungen besitzen
    2. b) anschließend den so erhaltenen Polyether der Formel Ib-1 mit einem Amin der allgemeinen Formel
       
               NH(R₁)(R₂)     (VII)
       
       worin R₁ und R₂ die oben angegebenen Bedeutungen besitzen,
       aminiert, wobei man ein Amin der Formel Ib-2 erhält
       
       worin R₁ bis R₄ und R₆, A, X und n die oben angegebenen Bedeutungen besitzen, das Amin der Formel (lb-2) gegebenenfalls alkyliert, falls R₁ und/oder R₂ für H stehen und anschließend
    3. c) das Produkt aus Stufe b) quaternisiert, wobei man ein Reaktionsprodukt, umfassend wenigstens eine Verbindung der allgemeinen Formel Ib erhält, wobei die Quaternisierung beispielsweise mit einer Verbindung der allgemeinen Formel IV erfolgt
       
               R₅-X     (IV)
       
       worin
       R₅ für Alkyl oder Aryl steht und X die oben angegebene Bedeutung besitzt, oder mit einem Alkylenoxid der Formel
       
       in Kombination mit einer Säure HX quaternisiert, worin X die oben angegebene Bedeutung besitzt, wobei R_5' für H, Alkyl oder Aryl steht und der Rest R₅ für eine Gruppe -CH₂CH(OH)R_5' steht.
11. 11. Verfahren nach Aspekt 9 oder 10, wobei das Quaternisierungsmittel ausgewählt ist unter: Alkylenoxiden, ggf. in Kombination mit einer Säure; Alkylcarbonaten, wie Dialkylcarbonaten; Alkylsulfaten, wie Dialkylsulfaten; Alkylphosphaten, Dialkylphosphaten, Halogeniden, wie Alkyl- oder Arylhalogeniden; aliphatischen und aromatischen Carbonsäureestern, wie Alkanoaten, Dicarbonsäureestern; sowie cyclischen aromatischen oder nichtaromatischen Carbonsäureestern.
12. 12. Quaternisierte Stickstoffverbindung erhältlich nach einem Verfahren nach Aspekt 10 oder 11, insbesondere in halogen- und schwefelfreier Form.
13. 13. Verwendung einer quaternisierten Stickstoffverbindung nach Aspekt 8 oder hergestellt nach einem der Aspekte 9 bis 11 als Kraftstoffadditiv oder Schmierstoffadditiv.
14. 14. Verwendung nach Aspekt 12 als Dieselkraftstoffadditiv, insbesondere als Kaltfließverbesserer, als Wachs-Anti-Settling Additiv (WASA).
15. 15. Verwendung nach Aspekt 12 als Ottokraftstoffadditiv zur Verringerung von Ablagerungen im Einlasssystem eines Ottomotors, wie insbesondere DISI und PFI(Port Fuel Injector) -Motoren
16. 16. Verwendung nach Aspekt 12 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 oder als Additiv zur Verringerung und/ oder Vermeidung von Ablagerungen in den Einspritzsystemen, wie insbesondere der Internal Diesel Injector Deposits (IDID) und / oder zur Verringerung und/ oder Vermeidung von Ablagerungen in den Einspritzdüsen 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 8 oder hergestellt nach einem der Aspekte 9 oder 10.

The further disclosure relates in particular to the following aspects. To the extent that these aspects are the subject of the invention, the aspects constitute specific embodiments of the invention.

1. A fuel or lubricant composition, in particular a fuel composition, comprising, in a majority of a conventional fuel or lubricant, an effective amount of at least one quaternized nitrogen compound-containing reaction product, or a quaternized nitrogen compound-containing partial fraction thereof obtained from the reaction product, wherein the reaction product is available through implementation
   1. a. a polyether-substituted amine containing at least one tertiary, quaternizable amino group
   2. b. a quaternizing agent which converts the at least one tertiary amino group into a quaternary ammonium group.
2. 2. A fuel or lubricant composition according to aspect 1, wherein the polyether substituent monomer units of the general formula Ic
   
   - [- CH (R ₃ ) -CH (R ₄ ) -O -] - (Ic)
   
   which comprises
   R ₃ and R _{4 are the} same or different and are H, alkyl, alkylaryl or aryl.
3. 3. A fuel or lubricant composition according to aspect 2, wherein the polyether-substituted amine has a number average molecular weight in the range of 500 to 5000, in particular 800 to 3000 or 900 to 1500.
4. 4. A fuel or lubricant composition according to any one of the preceding aspects, wherein the quaternizing agent is selected from alkylene oxides, optionally in combination with acid; aliphatic or aromatic mono- or polycarboxylic acid esters, in particular mono- or dialkylcarboxylic acid esters; cyclic non-aromatic or aromatic mono- or polycarboxylic acid esters; dialkyl; alkyl sulfates; alkyl halides; alkylaryl halides; in particular halogen and sulfur-free quaternizing agents, such as alkylene oxides in combination with acid, such as a carboxylic acid; aliphatic or aromatic mono- or polycarboxylic acid esters, in particular mono- or dialkylcarboxylic acid esters; cyclic non-aromatic or aromatic mono- or polycarboxylic acid esters and dialkyl carbonates; and mixtures thereof.
5. 5. A fuel or lubricant composition comprising, in a majority of a conventional fuel or lubricant, an effective amount of at least one quaternized nitrogen compound of general formula Ia or Ib,
   
   
   wherein
   • R ₁ and R _{2 are the} same or different and are alkyl, alkenyl, hydroxyalkyl, hydroxyalkenyl, aminoalkyl or aminoalkenyl, or R ₁ and R ₂ together represent alkylene, oxyalkylene or aminoalkylene;
   • R ₃ and R _{4 are the} same or different and are H, alkyl, alkylaryl or aryl;
   • R5 is a radical introduced by quaternization, in particular alkyl, hydroxyalkyl, arylalkyl or hydroxyarylalkyl;
   • R _{6 is} alkyl, alkenyl, optionally mono- or polyunsaturated cycloalkyl, aryl, in each case optionally substituted, for example with at least one hydroxyl radical or alkyl radical, or interrupted by at least one heteroatom;
   • A is a straight-chain or branched alkylene radical which is optionally interrupted by one or more heteroatoms, such as N, O and S;
   • n stands for an integer value of 1 to 50 and
   • X- represents an anion, in particular an anion resulting from the quaternization reaction.
6. 6. A fuel or lubricant composition according to aspect 5, wherein
   R ₁ and R _{2 are the} same or different and are C ₁ -C ₆ -alkyl, hydroxy-C ₁ -C ₆ -alkyl, hydroxy-C ₁ -C ₆ -alkenyl, or amino-C ₁ -C ₆ -alkyl or R ₁ and R ₂ together form a C ₂ -C ₆ alkylene, C ₂ -C ₆ oxyalkylene or C ₂ -C ₆ aminoalkylene radical;
   R ₃ and R _{4 are the} same or different and are H, C ₁ -C ₆ alkyl or phenyl;
   R _{5 is} a quaternized radical selected from C ₁ -C ₆ alkyl, hydroxyC ₁ -C ₆ alkyl or -CH ₂ CH (OH) aryl;
   R _{6 is} C ₁ -C ₂₀ -alkyl, such as C ₁₀ -C ₂₀ -, C ₁₁ -C ₂₀ - or C ₁₂ -C ₂₀ -alkyl or aryl or alkylaryl, where alkyl is in particular C ₁ -C ₂₀ - , stands;
   A is a straight-chain or branched C ₂ -C ₆ -alkylene radical which is optionally interrupted by one or more heteroatoms, such as N, O and S;
   n for an integer value of 1 to 30 and
   X- represents an anion resulting from the quaternization reaction.
7. 7. Fuel composition according to one of the preceding aspects, selected from diesel fuels, gasoline fuels, biodiesel fuels and alkanol-containing gasoline.
8. 8. Quaternized nitrogen compound as defined in any one of the preceding aspects, in particular selected from those which are halogen and sulfur-free.
9. 9. A process for preparing quaternized nitrogen compounds of general formula Ia,
   
   wherein
   R ₁ to R ₅ , A, X and n have the meanings given above
   where you are
   • a. an aminoalkanol of the general formula II
     
     (R ₁ ) (R ₂ ) NA-OH (II)
     
     wherein
     • R ₁ , R ₂ and A have the meanings given above,
     • with an epoxide of the general formula III
     
     wherein
     R ₃ and R _{4 have} the meanings given above,
     alkoxylated to give an alkoxylated amine of the formula
     
     wherein R ₁ to R ₄ , A and n have the meanings given above, and
   • b) the resulting alkoxyl compound of the formula Ia-1 is quaternized to obtain a reaction product comprising at least one compound of the general formula Ia, the quaternization being effected, for example, with a compound of the general formula IV
     
     R ₅ -X (IV)
     
     wherein
     R _{5 is} alkyl or aryl and X has the meaning given above, or with an alkylene oxide of the formula
     
     quaternized in combination with an acid HX, wherein X has the meaning indicated above, wherein R _{5 'is} H, alkyl or aryl and the radical R _{5 is} a group -CH ₂ CH (OH) R _5' .
10. 10. A process for the preparation of quaternized nitrogen compounds of general formula Ib,
    
    wherein R ₁ to R ₆ , X and n have the meanings given above
    where you are
    1. a) an alcohol of the general formula V
       
       R ₆ -OH (V)
       
       wherein
       R _{6 has} the meanings given above, with an epoxide of the general formula III
       
       wherein
       R ₃ and R _{4 have} the meanings given above, alkoxylated to give a polyether of formula Ib-1;
       
       obtained; wherein R ₃ , R ₄ and R ₆ , A, X and n have the meanings given above
    2. b) then the polyether of the formula Ib-1 thus obtained with an amine of the general formula
       
       NH (R ₁ ) (R ₂ ) (VII)
       
       wherein R ₁ and R _{2 have} the meanings given above,
       aminated to obtain an amine of the formula Ib-2
       
       wherein R ₁ to R ₄ and R ₆ , A, X and n have the meanings given above, the amine of formula (lb-2) optionally alkylated, if R ₁ and / or R _{2 is} H and then
    3. c) the product from step b) quaternized to obtain a reaction product comprising at least one compound of general formula Ib, wherein the quaternization is carried out for example with a compound of general formula IV
       
       R ₅ -X (IV)
       
       wherein
       R _{5 is} alkyl or aryl and X has the meaning given above, or with an alkylene oxide of the formula
       
       quaternized in combination with an acid HX, wherein X has the meaning indicated above, wherein R _{5 'is} H, alkyl or aryl and the radical R _{5 is} a group -CH ₂ CH (OH) R _5' .
11. 11. The method according to aspect 9 or 10, wherein the quaternizing agent is selected from: alkylene oxides, optionally in combination with an acid; Alkyl carbonates, such as dialkyl carbonates; Alkyl sulfates, such as dialkyl sulfates; Alkyl phosphates, dialkyl phosphates, halides such as alkyl or aryl halides; aliphatic and aromatic carboxylic acid esters, such as alkanoates, dicarboxylic acid esters; and cyclic aromatic or non-aromatic carboxylic acid esters.
12. 12. Quaternized nitrogen compound obtainable by a process according to aspect 10 or 11, in particular in halogen and sulfur-free form.
13. 13. Use of a quaternized nitrogen compound according to aspect 8 or prepared according to any one of aspects 9 to 11 as a fuel additive or lubricant additive.
14. 14. Use according to aspect 12 as a diesel fuel additive, in particular as a cold flow improver, as a wax anti-settling additive (WASA).
15. 15. Use according to aspect 12 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 aspect 12 as an additive for reducing the fuel consumption of direct injection diesel engines, in particular of diesel engines with common rail injection systems, and / or for minimizing the power loss in direct injection diesel engines, especially in diesel engines with common rail injection systems or as an additive for reducing and / or preventing deposits in the injection systems, such as in particular the Internal Diesel Injector Deposits (IDID) and / or for reducing and / or preventing deposits in the injectors in direct injection diesel engines, especially in common rail injection systems. ,
17. 17. An additive concentrate comprising, in combination with further diesel or petrol additives, in particular diesel fuel additives, at least one quaternized nitrogen compound as defined in embodiment 8 or prepared according to one of aspects 9 or 10.

In a particular embodiment, in some or all of the above embodiments, the quaternizing agent is an aromatic carboxylic acid ester, such as e.g. Salicylates.

In a specific embodiment, in some or all of the above embodiments or aspects, the quaternizing agent is selected from compounds of the formulas (1) or (2) described herein.

In a specific embodiment, in some or all of the above embodiments or aspects of the quaternized radical (nitrogen substituent) is in particular alkyl (especially C ₁ -C ₆ alkyl), or hydroxyarylalkyl (such as 2-hydroxy-2-phenyl ethyl).

In a specific embodiment, in some or all of the above embodiments or aspects, the polyether substituent does not have aryl or aralkyl groups.

In a specific embodiment, in some or all of the above embodiments or aspects, the quaternized nitrogen compound is a compound of formula (Ia) or (Ib).

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

A2) General definitions

"Halogen-free" or "sulfur-free" in the context of the present invention and further disclosure means the absence of inorganic or organic halogen-containing or sulfur-containing compounds and / or their corresponding ions, such as halide anion and sulfur-containing anions, in particular sulfates. "Halogen-free" or "sulfur-free" includes in particular the absence of stoichiometric amounts of halogen-containing or sulfur-containing compounds or anions. Substoichiometric amounts of halogen-containing or sulfur-containing compounds or anions are present, for example, in molar ratios of less than 1: 0.1, or less than 1. 0.01 or 1: 0.001, or 1: 0.0001 of quaternized nitrogen compound to halogen-containing or sulfur-containing compound or ions thereof. "Halogen-free" or "sulfur-free" includes in particular the complete absence of halogen-containing or sulfur-containing compounds and / or of their corresponding ions, such as halide anion and sulfur-containing anions, in particular sulfates.

"Carboxylic acids" include, in particular, organic carboxylic acids, such as, in particular, monocarboxylic acids of the RCOOH type, in which R represents a short-chain hydrocarbyl radical, such as, for example, a lower alkyl or C ₁ -C ₄ -alkylcarboxylic acid.

"Quaternizable" nitrogen groups or amino groups include in particular primary, secondary and tertiary amino groups.

Unless otherwise indicated, the following general meanings apply:
"Hydrocarbyl" is to be interpreted broadly and includes both cyclic aromatic or non-aromatic, as well as long-chain or short-chain, straight or branched hydrocarbon radicals having 1 to 50 carbon atoms, which may additionally contain heteroatoms, such as O, N, NH, S, in their chain or Can contain ring. Hydrocarbyl includes, for example, the alkyl, alkenyl, aryl, alkylaryl, cycloalkenyl or cycloalkyl radicals and their substituted analogs as defined below.

"Alkyl" or "lower alkyl" in particular represents saturated, straight-chain or branched hydrocarbon radicals having 1 to 4, 1 to 6, 1 to 8, 1 to 10, 1 to 14 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, n-dodecyl, n-tetradecyl, n-hexadecyl, and the mono- or poly-branched analogs thereof.

"Hydroxyalkyl" is in particular the mono- or polysubstituted, in particular monohydroxylated analogs of the above alkyl radicals, for example the monohydroxylated analogs of the above straight-chain or branched alkyl radicals, for example the linear hydroxyalkyl groups, for example those having a primary (terminal) hydroxyl group, such as hydroxymethyl, 2 -Hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, or those with non-terminal Hydroxyl groups such as 1-hydroxyethyl, 1- or 2-hydroxypropyl, 1- or 2-hydroxybutyl or 1-, 2- or 3-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.

"Hydroxyalkenyl" is in particular the mono- or polysubstituted, in particular simply hydroxylated, analogs of the above alkenyl radicals

"Aminoalkyl" and "aminoalkenyl" are in particular the mono- or polysubstituted, in particular simply aminated, analogs of the above alkyl or alkenyl radicals, or analogs of the above hydroxyalkyl, where the OH group has been replaced by an amino group.

"Alkylene" represents 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 ) 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 ) ₄ -, - (CH ₂ ) ₂ -CH (CH ₃ ) -, -CH ₂ -CH (CH ₃ ) -CH ₂ -
or for C ₂ -C ₆ -alkylene groups, such as
-CH ₂ -CH (CH ₃ ) -, -CH (CH ₃ ) -CH ₂ -, -CH (CH ₃ ) -CH (CH ₃ ) -, -C (CH ₃ ) ₂ -CH ₂ -, -CH ₂ -C (CH ₃ ) ₂ -, -C (CH ₃ ) ₂ -CH (CH ₃ ) -, -CH (CH ₃ ) -C (CH ₃ ) ₂ -, -CH ₂ -CH (Et) -, -CH (CH ₂ CH ₃ ) -CH ₂ -, -CH (CH ₂ CH ₃ ) -CH (CH ₂ CH ₃ ) -, -C (CH ₂ CH ₃ ) ₂ -CH ₂ -, -CH ₂ -C (CH ₂ CH ₃ ) ₂ -, -CH ₂ -CH (n-propyl) -, -CH (n-propyl) -CH ₂ -, -CH (n-propyl) -CH (CH ₃ ) -, -CH ₂ -CH (n-butyl) -, -CH (n-butyl) -CH ₂ -, -CH (CH ₃ ) -CH (CH ₂ CH ₃ ) -, -CH (CH ₃ ) -CH (n-propyl ) -, -CH (CH ₂ CH ₃ ) -CH (CH ₃ ) -, -CH (CH ₃ ) -CH (CH ₂ CH ₃ ) -, or for C ₂ -C ₄ -alkylene groups, such as selected among - (CH ₂ ) ₂ -, -CH ₂ -CH (CH ₃ ) -, -CH (CH ₃ ) -CH ₂ -, -CH (CH ₃ ) -CH (CH ₃ ) -, -C (CH ₃ ) ₂ -CH ₂ -, -CH ₂ -C (CH ₃ ) ₂ -, -CH ₂ -CH (CH ₂ CH ₃ ) -, -CH (CH ₂ CH ₃ ) -CH ₂ -,

"Oxyalkylene radicals correspond to the definition of the above straight-chain or mono- or polysubstituted alkylene radicals having 2 to 10 carbon atoms, the coal chain being interrupted by an oxygen heteroatom 1 or more times, in particular 1 times. CH ₂ -O-CH ₂ -, - (CH ₂ ) ₂ -O- (CH ₂ ) ₂ -, - (CH ₂ ) ₃ -O- (CH ₂ ) ₃ -, or -CH ₂ -O- (CH ₂ ) ₂ -, - (CH ₂ ) ₂ -O- (CH ₂ ) ₃ -, -CH ₂ -O- (CH ₂ ) ₃

"Aminoalkylene" correspond to the definition of the above straight-chain or mono- or polysubstituted alkylene radicals having 2 to 10 carbon atoms, wherein the coal chain is interrupted by a nitrogen group (especially -NH group) 1 or more times, in particular 1-fold. Non-limiting examples are: -CH ₂ -NH-CH ₂ -, - (CH ₂ ) ₂ -NH- (CH ₂ ) ₂ -, - (CH ₂ ) ₃ -NH- (CH ₂ ) ₃ -, or -CH ₂ -NH- (CH ₂ ) ₂ -, - (CH ₂ ) ₂ -NH- (CH ₂ ) ₃ -, - CH ₂ -NH- (CH ₂ ) ₃ .

"Alkenylene" is the mono- or polysubstituted, especially monounsaturated, analogs of the above alkylene groups having 2 to 10 carbon atoms, in particular C ₂ -C ₇ -alkenylenes 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" denotes 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" or mono- or polyunsaturated cycloalkyl "in particular represents monocyclic, mono- or polyunsaturated hydrocarbon groups having 5 to 8, preferably up to 6 carbon ring members, such as the monounsaturated radicals cyclopenten-1-yl, cyclopenten-3-yl, cyclohexene -1-yl, cyclohexen-3-yl and cyclohexen-4-yl;

"Aryl" represents mono- or polynuclear, preferably mono- or binuclear, optionally substituted aromatic radicals having from 6 to 20, such as e.g. From 6 to 10 ring carbon atoms, e.g. 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.

"Alkylaryl" stands for the in any position of the ring one or more times, in particular 1- or 2-fold, alkyl-substituted analogs of the above aryl radicals, where aryl likewise has the meanings indicated above, such as, for example, C ₁ -C ₄ -alkyl-phenyl in which the C ₁ -C ₄ -alkyl radicals can be in any desired ring position.

"Substituents" for radicals specified herein are especially selected from keto groups, -COOH, -COO-alkyl, -OH, -SH, -CN, amino, -NO ₂ , alkyl, or alkenyl groups.

Mn (number average molecular weight) is determined in a conventional manner; in particular, the data refer to values determined by gel permeation chromatography or mass spectrometry.

A3) starter compounds (alcohols of the formula V and amino alcohols of the formula II)

1. a) alcohols of the general formula V
   
   R ₆ -OH (V)
   
   wherein R _{6 is} alkyl, alkenyl, optionally mono- or polyunsaturated cycloalkyl, aryl, in each case optionally substituted, for example with at least one hydroxyl radical or alkyl radical, or interrupted by at least one heteroatom;
2. b) aminoalkanols of the general formula II
   
   (R ₁ ) (R ₂ ) NA-OH (II)
   
   wherein
   • R ₁ and R _{2 are the} same or different and are alkyl, alkenyl, hydroxyalkyl, hydroxyalkenyl, aminoalkyl or aminoalkenyl, or R ₁ and R ₂ together represent alkylene, oxyalkylene or aminoalkylene; and
   • A is a straight-chain or branched alkylene or alkenylene radical which is optionally interrupted by one or more heteroatoms, such as N, O and S.

In embodiments of the invention R ₁ , R ₂ and R _{6 are} as defined in the above first embodiment and according to claim 1.

A4) Quaternizing agent:

Suitable quaternizing agents are, in principle, all compounds suitable as such. The quaternizing agent is in particular selected from alkylene oxides, if appropriate in combination with acid; aliphatic or aromatic carboxylic acid esters, in particular dialkyl carboxylates; alkanoates; cyclic non-aromatic or aromatic carboxylic acid esters; dialkyl; alkyl sulfates; alkyl halides; alkylaryl halides; and mixtures thereof.

1. (i) einem Epoxid der allgemeinen Formel II
   
   wobei die darin enthaltenen R^a Reste gleich oder verschieden sind und für H oder für einen Hydrocarbylrest stehen,
2. (ii) einem Salicylat, ausgewählt unter, wie Methylsalicylat, Ethylsalicylat, n- und i-Propylsalicylat, und n-, i- oder tert-Butylsalicylat;
3. (iii) einem Oxalat, ausgewählt unter Dimethyloxalat und Diethyloxalat; und
4. (iv) Dimethylcarbonat.

According to the invention, the quaternizing agent is selected from those mentioned in the first embodiment or in claim 1, namely under

1. (i) an epoxide of general formula II
   
   wherein the R ^a radicals contained therein are identical or different and represent H or a hydrocarbyl radical,
2. (ii) a salicylate selected from such as methyl salicylate, ethyl salicylate, n- and i-propyl salicylate, and n-, i- or tert-butyl salicylate;
3. (iii) an oxalate selected from dimethyloxalate and diethyl oxalate; and
4. (iv) dimethyl carbonate.

wobei die darin enthaltenen R^a Reste gleich oder verschieden sind und für H oder für einen Hydrocarbylrest stehen. Dabei kann der Hydrocarbylrest wenigstens 1 bis 14 Kohlenstoffatome aufweisen. Insbesondere sind dies aliphatische oder aromatische Reste, wie z.B. lineare oder verzweigte C₁-C₁₄-Alkylreste oder aromatische Reste, wie Phenyl oder C₁-C₄-Alkylphenyl.In a particular embodiment of the invention, however, the quaternization of the at least one quaternizable tertiary nitrogen atom takes place with at least one quaternizing agent selected from epoxides, in particular hydrocarbyl epoxides

wherein the R ^a radicals contained therein are identical or different and represent H or a hydrocarbyl radical. In this case, the hydrocarbyl radical may have at least 1 to 14 carbon atoms. In particular, these are aliphatic or aromatic radicals, such as linear or branched C ₁ -C ₁₄ -alkyl radicals or aromatic radicals, such as phenyl or C ₁ -C ₄ -alkylphenyl.

Examples of suitable hydrocarbyl epoxides are aliphatic and aromatic alkylene oxides, in particular C _2-16 -alkylene oxides, such as ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 2-methyl-1,2-propene oxide (isobutene oxide). , 1,2-pentene oxide, 2,3-pentene oxide, 2-methyl-1,2-butene oxide, 3-methyl-1,2-butene oxide, 1,2-hexene oxide, 2,3-hexene oxide, 3,4-hexene oxide , 2-methyl-1,2-pentene oxide, 2-ethyl-1,2-butene oxide, 3-methyl-1,2-pentene oxide, 1,2-decene oxide, 1,2-dodecene oxide or 4-methyl-1,2 -pentenoxid; Tetradecanoxid; hexadecene; and also aromatic-substituted ethylene oxides, such as optionally substituted styrene oxide, in particular styrene oxide or 4-methyl-styrene oxide.

In the case of using epoxides as quaternizing these are in the presence or absence of free acids, especially in the presence or absence of free protic acids, such as especially with C _1-12 monocarboxylic acids, such as formic acid, acetic acid or propionic acid or C _2-12 Dicarboxylic acids such as oxalic acid or adipic acid; or in the presence or absence of sulfonic acids, such as benzenesulfonic acid or toluenesulfonic acid or aqueous mineral acids, such as sulfuric acid or hydrochloric acid. The quaternization product thus produced is thus either "acidic" or "acid-free" within the meaning of the present invention and further disclosure.

As a further group of quaternizing agents, particular mention may be made of alkyl esters of a cycloaromatic or cycloaliphatic mono- or polycarboxylic acid (in particular a mono- or dicarboxylic acid) or of an aliphatic polycarboxylic acid (in particular dicarboxylic acid).

1. a) Verbindungen der allgemeinen Formel 1
   
           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 another aspect disclosed herein, the quaternization of the at least one quaternizable tertiary nitrogen atom is carried out with at least one quaternizing agent of the following generic formulas a) or b):

1. a) compounds of the 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, 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 quaternizing agents according to the invention are the lower alkyl esters of oxalic acid, such as dimethyl oxalate and diethyl oxalate.

In another aspect disclosed herein, the quaternizing agent is selected from 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 according to the invention 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.

An "anion resulting from the quaternization reaction" X- is, for example, a halide such as a chloride or bromide, a sulfate radical ((SO ₄ ) ^2- ), or the anionic radical of a mono- or polyhydric, aliphatic or aromatic carboxylic acid, or anionic radical ROC (O) O- resulting from the quaternization reaction of a dialkyl carbonate.

A5) Quaternizable nitrogen compounds (of formula II):

The quaternizable nitrogen compound is selected from hydroxyalkyl-substituted mono- or polyamines having at least one quaternizable, primary, secondary or tertiary amino group and at least one hydroxyl group which is linkable with a polyether radical.

In particular, the quaternizable nitrogen compound is selected from hydroxyalkyl-substituted primary, secondary, tertiary or quaternary monoamines and hydroxyalkyl-substituted primary, secondary, tertiary or quaternary diamines.

Examples of suitable "hydroxyalkyl-substituted mono- or polyamines" are those containing at least one, e.g. 1, 2, 3, 4, 5 or 6, hydroxyalkyl substituents are equipped.

As examples of "hydroxyalkyl-substituted monoamines" may be mentioned: N-hydroxyalkyl-monoamines, N, N-dihydroxyalkyl-monoamines and N, N, N-trihydroxyalkylmonoamines, 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.

3-Hydroxy-1-propylamin

Diethanolamin

Diisopropanolamin

N-(2-Hydroxyethyl)ethylendiamin

Alkohole mit tertiärem Amin Triethanolamin, (2,2^I,2^II-Nitrilotriethanol)

1-(3-Hydroxypropyl)imidazol

Tris(hydroxymethyl)amin

3-Dimethylamino-1-propanol

3-Diethylamino-1-propanol

2-Dimethylamino-1-ethanol

4-Diethylamino-1-butanol

The following quaternizable nitrogen compounds may be mentioned in particular: SURNAME FORMULA Alcohols with primary and secondary amine ethanolamine

3-hydroxy-1-propylamine

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 the additives: a) Preparation of the Polyether-Substituted Quaternizable Intermediates (Ia-1 and Ib-1) a1) starting from amino alcohols of the formula II:

The amino alcohols of the general formula II can be alkoxylated in a manner known in principle, giving alkoxylated amines of the general formula Ia-1.

The carrying out of alkoxylations is known in principle to the person skilled in the art. It is also known to the person skilled in the art that the reaction conditions, in particular the choice of catalyst, can influence the molecular weight distribution of the alkoxylates.

For the alkoxylation, C ₂ -C ₁₆ -alkylene oxides are used, for example ethylene oxide, propylene oxide or butylene oxide. Preference is given in each case to the 1,2-alkylene oxides.

The alkoxylation may be a base-catalyzed alkoxylation. For this purpose, the amino alcohols (II) can be mixed in a pressure reactor with alkali metal hydroxides, preferably potassium hydroxide or with alkali metal such as sodium methylate. By reducing the pressure (for example <100 mbar) and / or increasing the temperature (30 to 150 ° C), water still present in the mixture can be withdrawn. The alcohol is then present as the corresponding alkoxide. It is then inertized with inert gas (eg nitrogen) and the (the) alkylene oxide (s) at temperatures of 60 to 180 ° C up to a pressure of max. 10 bar added gradually. At the end of the reaction, the catalyst can be replaced by the addition of acid (eg Acetic or phosphoric acid) neutralized and can be filtered off if necessary. However, the basic catalyst can also be neutralized by adding commercial Mg silicates, which are then filtered off. Optionally, the alkoxylation can also be carried out in the presence of a solvent. This may be, for example, toluene, xylene, dimethylformamide or ethylene carbonate.

However, the alkoxylation of the amino alcohols can also be carried out by other methods, for example by acid-catalyzed alkoxylation. Furthermore, for example, Doppelhydroxidtone as in DE 43 25 237 A1 or double metal cyanide (DMC) catalysts can be used. Suitable DMC catalysts are for example in the DE 102 43 361 A1 , in particular sections [0029] to [0041] and the literature cited therein. For example, Zn-Co type catalysts can be used. To carry out the reaction, the aminoalcohol can be admixed with the catalyst, the mixture can be dehydrated as described above and reacted with the alkylene oxides as described. It is usually not more than 1000 ppm catalyst used with respect to the mixture, and the catalyst can remain in the product due to this small amount. The amount of catalyst can typically be less than 1000 ppm, for example 250 ppm and less.

The alkoxylation can alternatively be carried out by reaction of the compounds (IV) and (V) with cyclic carbonates such as ethylene carbonate.

a2) starting from alkanols of the formula V:

As described under the previous section a1) for amino alcohols (II), analogously, alkanols R ₆ OH can also be alkoxylated in a manner known in principle to give polyethers (Ib-1). The polyethers thus obtained can then by reductive amination with ammonia, primary amines or secondary amines (VII) by conventional methods in continuous or batch processes using conventional hydrogenation or amination catalysts such as those, the catalytically active ingredients based on the elements Ni , Co, Cu, Fe, Pd, Pt, Ru, Rh, Re, Al, Si, Ti, Zr, Nb, Mg, Zn, Ag, Au, Os, Ir, Cr, Mo ,, W or combinations of these elements with each other contained, in conventional amounts to the corresponding polyetheramines (Ib-2). The reaction can be carried out without solvent or at high polyether viscosities in the presence of a solvent, preferably in the presence of branched aliphatics such as isododecane. The amine component (VII) is generally used in excess, for example in 2 to 100-fold excess, preferably 10 to 80-fold excess used. The reaction is carried out at pressures of 10 to 600 bar over a period of 10 minutes to 10 hours. After cooling, the catalyst is separated by filtration, excess amine component (VII) is evaporated off and the reaction water is distilled off azeotropically or under a gentle stream of nitrogen.

If the resulting polyetheramine (Ib-2) have primary or secondary amine functionalities (R ₁ and / or R ₂ is H), this can subsequently be converted into a polyether amine having a tertiary amine function (R ₁ and R ₂ not equal to H). The alkylation can be carried out in a manner known in principle by reaction with alkylating agents. In principle, all alkylating agents such as, for example, alkyl halides, alkylaryl halides, dialkyl sulfates, alkylene oxides, if appropriate in combination with acid, are suitable; aliphatic or aromatic carboxylic acid esters, in particular dialkylcarboxylates; alkanoates; cyclic non-aromatic or aromatic carboxylic esters; dialkyl; and mixtures thereof. The reactions to the tertiary polyetheramine can also take place by reductive amination by reaction with a carbonyl compound such as formaldehyde in the presence of a reducing agent. Suitable reducing agents are formic acid or hydrogen in the presence of a suitable heterogeneous or homogeneous hydrogenation catalyst. The reactions can be carried out without solvent or in the presence of solvents. Suitable solvents are for example H ₂ O, alkanols such as methanol or ethanol, or 2-ethylhexanol, aromatic solvents such as toluene, xylene or solvent mixtures of the Solvesso series, or aliphatic solvents, in particular mixtures of branched aliphatic solvents. The reactions are carried out at temperatures of 10 ° C to 300 ° C at pressures of 1 to 600 bar over a period of 10 minutes to 10 hours. The reducing agent is used at least stoichiometrically, preferably in excess, in particular in a 2- to 10-fold excess.

The reaction product thus formed (polyetheramine Ib-1 or Ib-2) 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 b1) with epoxide / acid

To carry out the quaternization, the reaction product or reaction mixture from stage a) above is mixed with at least one epoxide compound of the above formula (IVa), in particular in the required stoichiometric amounts, in order to achieve the desired quaternization. The acid is preferably also added in stoichiometric amounts. Per equivalent of quaternizable tertiary nitrogen atom can be e.g. Use 0.1 to 2.0 equivalents, or 0.5 to 1.25 equivalents, of quaternizing agent. In particular, however, approximately equimolar amounts of the epoxide are used to quaternize a tertiary amine group. Correspondingly, higher amounts are required to quaternize a secondary or primary amine group. Suitable acids are especially carboxylic acids such as acetic acid.

In this case, one typically works at temperatures in the range of 15 to 160 ° C, in particular from 20 to 150 or 40 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 bar pressure. The pressure is usually determined by the vapor pressure of the alkylene oxide used at the respective reaction temperature. In particular, an inert gas atmosphere, such as e.g. Nitrogen, appropriate.

If necessary, the reactants may be presented in a suitable organic aliphatic or aromatic solvent or a mixture thereof for epoxidation, or there may still be a sufficient amount of solvent from reaction step a). Typical examples include Solvesso series solvents, toluene or xylene. Furthermore, alkanols are used as solvents or as a co-solvent in admixture with the aforementioned solvents, such as methanol, ethanol, propanol, 2-ethylhexanol or 2-propylheptanol.

b2) With compounds of the formula IV

To carry out the quaternization, the reaction product or reaction mixture from stage a) above is mixed with at least one alkylating agent of the formula (IV), 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 5.0 equivalents, or 0.5 to 2.0 equivalents, of quaternizing agent. In particular, however, approximately equimolar proportions of the alkylating agent are used to quaternize a tertiary amine group. Correspondingly, higher amounts are required to quaternize a secondary or primary amine group. Particularly suitable quaternizing agents are methyl salicylate, dimethyl oxalate, dimethyl phthalate and dimethyl carbonate.

Optionally, the reaction can be accelerated by adding catalytic or stoichiometric amounts of an acid. Suitable acids are, for example, proton donors, such as aliphatic or aromatic carboxylic acids or fatty acids. Furthermore, Lewis acids, such as boron trifluoride, ZnCl ₂ , MgCl ₂ , AlCl ₃ or FeCl ₃ , are suitable. The acid can be used in amounts of from 0.01 to 50% by weight, for example in the range from 0.1 to 10% by weight.

In this case, one typically works at temperatures in the range of 15 to 160 ° C, in particular from 20 to 150 or 40 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 can be at about 0.1 to 20 bar, such as. 0.5 to 10 bar pressure, done. In particular, the reaction can be carried out at atmospheric pressure. In particular, an inert gas atmosphere, such as e.g. Nitrogen, appropriate.

If necessary, the reactants may be presented in a suitable organic aliphatic or aromatic solvent or a mixture thereof for quaternization, or it may still be a sufficient proportion of solvent from reaction step a). Typical examples include Solvesso series solvents, toluene or xylene. Furthermore, alkanols are suitable as solvents or as cosolvents in a mixture with the abovementioned solvents, such as, for example, methanol, ethanol, propanol, butanol, 2-ethylhexanol or 2-propylheptanol.

c) work-up of the reaction mixture

The final 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 used without further purification as an additive, if appropriate after mixing with further additive components (see below). Optionally, the acid used can be removed by filtration, neutralization or extraction from the reaction product. Optionally, an excess of alkylating agent may be removed by distillation or by filtration.

B) Further additive components

The fuel to be 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 which are terminated by hydroxyl groups, mono- or polyamino groups, where at least one nitrogen atom has basic properties, or by carbamate groups;
• (Dg) carboxylic acid ester groups;
• (Ie) derived from succinic anhydride moieties having hydroxy and / or amino and / or amido and / or imido groups; and or
• (Di) by Mannich reaction of substituted phenols with aldehydes and mono- or polyamines generated groupings.

The hydrophobic hydrocarbon residue in the above detergent additives which provides 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 1,500. As a typical hydrophobic hydrocarbon radical, in particular in connection with the polar groups are in particular polypropenyl, polybutenyl and polyisobutenyl radicals having a number average molecular weight M _n from preferably in each case 300 to 5,000, particularly preferably 300 to 3,000, more preferably 500 to 2,500, even more preferably 700 to 2,500 and in particular 800 to 1,500 into consideration.

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

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

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

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

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

Carboxyl groups or their alkali metal or alkaline earth metal salts (Dd) containing additives are preferably copolymers of C ₂ - to C ₄₀ olefins with maleic anhydride having a total molecular weight of 500 to 20,000, 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 used to prevent valve seat wear and can be used to advantage in combination with conventional fuel detergents such as poly (iso) butenamines or polyetheramines.

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

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

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

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

One or more of said detergent additives may be added to the fuel in such an amount that the 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, as polyetheramines poly-C ₂ - to C ₆ alkylene oxide or functional derivatives thereof. 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 able to improve the flow behavior of middle distillate fuels or diesel fuels in the cold. Conveniently, they must have sufficient oil solubility. In particular, the usually used for middle distillates of fossil origin, ie for conventional mineral diesel fuels, used cold flow improvers ("middle distillate flow improvers", "MDFI") come into consideration. However, it is also possible to use organic compounds which, when used in conventional diesel fuels, have in part or predominantly the properties of a wax anti-settling additive ("WASA"). Also, they can act partly or predominantly as nucleators. However, it is also possible to use mixtures of organic compounds which are active as MDFI and / or which act as WASA and / or as nucleators.

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

Typically, the cold flow improver is selected from:

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

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

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

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

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

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

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

Examples of suitable carboxylic alkenyl esters are vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl neopentanoate, vinyl hexanoate, vinyl neononanoate, vinyl neodecanoate and the corresponding propenyl esters, with vinyl esters being preferred. A particularly preferred carboxylic acid alkenyl ester is vinyl acetate; typical resulting copolymers of group (K1) are the most commonly used ethylene-vinyl acetate copolymers ("EVA"). Particularly advantageous ethylene-vinyl acetate copolymers and their preparation are in the WO 99/29748 described.

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

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

The at least one or 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. Further suitable comb polymers are copolymers of α-olefins and esterified comonomers, for example esterified copolymers of styrene and maleic anhydride or esterified copolymers of styrene and fumaric acid. Suitable comb polymers may also be polyfumarates or polymaleinates. In addition, homopolymers and copolymers of vinyl ethers are suitable comb polymers. As a component of class (K2) suitable comb polymers are, for example, those which are described in the WO 2004/035715 and in " Comb-like polymers. Structure and Properties ", NA Plate and VP Shibaev, J. Poly. Sci. Macromolecular Revs., 8, pp. 117-253 (1974 Also mixtures of comb polymers are suitable.

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

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

In particular, the component of class (K4) is an oil-soluble reaction product of at least one tertiary amino group-containing poly (C ₂ - to C ₂₀ -carboxylic acids) with primary or secondary amines. The poly (C ₂ - to C ₂₀ -carboxylic acids) which have at least one tertiary amino group and are based on this reaction product preferably contain at least 3 carboxyl groups, in particular 3 to 12, especially 3 to 5 carboxyl groups. The carboxylic acid units in the polycarboxylic acids preferably have 2 to 10 carbon atoms, in particular they are acetic acid units. The carboxylic acid units are suitably to the Polycarboxylic linked, 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.

in denen die Variable A eine geradkettige oder verzweigte C₂- bis C₆-Alkylengruppe oder die Gruppierung der Formel III

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.Preferably, the component of class (K4) is an oil-soluble reaction product based on at least one tertiary amino group-containing poly (C ₂ - to C ₂₀ -carboxylic acids) of the general formula IIa or IIb

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

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

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

Straight-chain or branched C ₂ -C ₆ -alkylene groups of the variable A are, for example, 1,1-ethylene, 1,2-propylene, 1,3-propylene, 1,2-butylene, 1,3-butylene, 1,4- Butylene, 2-methyl-1,3-propylene, 1,5-pentylene, 2-methyl-1,4-butylene, 2,2-dimethyl-1,3-propylene, 1,6-hexylene (hexamethylene) and especially 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 Moles per carboxyl group, dioleylamine, dipalmitinamine, dicoco fatty amine, distearylamine, dibehenylamine or especially ditallow fatty amine. A particularly preferred component (K4) is the reaction product of 1 mole of ethylenediaminetetraacetic acid and 4 moles of hydrogenated ditallow fatty amine.

Other 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 e.g. Salicylic acid derivatives such as N, N'-disalicylidene-1,2-propanediamine.

B12) Solvent

Suitable are, for example, 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), and 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 should solve or dilute for better handling, in the diesel fuel.

C) fuels

The additive to be used according to the invention is outstandingly suitable as a fuel additive and, in principle, can be used in any fuel. It has a number of beneficial effects on the operation of internal combustion engines with fuels.

The present disclosure therefore also fuels, in particular middle distillate fuels, with an effective content as an additive to achieve advantageous 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 on the quaternized additive to be used according to the invention. This effective content (metering rate) is generally from 10 to 5000 ppm by weight, preferably from 20 to 1500 ppm by weight, in particular from 25 to 1000 ppm by weight, especially from 30 to 750 ppm by weight, each based on the total amount of fuel.

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

The qualities of 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 .).

The quaternized additive to be used according to the invention, in addition to its use in the abovementioned middle distillate fuels of fossil, vegetable or animal origin, which are essentially hydrocarbon mixtures, can also be used in mixtures of such middle distillates with biofuel oils (biodiesel). For the purposes of the present invention and further disclosure, 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 from 1 to 30% by weight, 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 to be used according to the invention is particularly suitable as a fuel additive in fuel compositions, in particular in diesel fuels, to overcome the problems described above in direct-injection diesel engines, especially in those with common-rail injection systems.

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

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

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

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

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

Change and special features:

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

Test run times:

The test period was 12h without shutdown periods. The in FIG. 2 The one-hour test cycle from CEC F-098-08 was traversed 12 times.

Power determination:

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

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

The power loss in the KC test is calculated as follows: $$\mathbf{Power\; loss}.\mathbf{KC}\left[\%\right]=\left(1-\frac{\mathit{Pend}.\mathit{KC}}{P0.\mathit{KC}}\right)*100$$

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

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

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

Change and special features:

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

Test run times:

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

The in FIG. 2 The one-hour test cycle from CEC F-098-08 was traversed 12 times in each case.

Power determination:

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

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

The power loss in the DU is calculated as follows $$\mathbf{Power\; loss}.\mathbf{you}\left[\%\right]=\left(1-\frac{\mathit{Pend}.\mathit{you}}{P0.\mathit{you}}\right)*100$$

Clean up

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

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

The power loss in the CU test is calculated as follows (negative powerloss count in the cu test means performance gain) $$\mathbf{Power\; loss}.\left(\mathbf{YOU},\mathbf{CU}\right)\left[\%\right]=\left(\frac{\mathit{Pend}.\mathit{you}-\mathit{pend}.\mathit{cu}}{P0.\mathit{you}}\right)*100$$

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

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

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

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

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

DU-CU is based on the CEC Test Procedure F-098-08 Issue 5.
The DU - CU test consists of two separate tests that are run one behind the other. The first test is for deposit formation (DU), the second for deposit removal (CU).

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

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

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

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

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

B. Manufacturing and Analysis Examples: Reactants used:

N, N-dimethyl CAS. 108-01-0 Company BASF 1,2-propylene oxide CAS. 75-56-9 Company BASF 1,2-butylene oxide CAS. 106-88-7 Company BASF Potassium tert -butylate CAS. 865-47-4 Company Aldrich dimethyl CAS. 553-90-2 Company Aldrich Solvent Naphtha Heavy CAS. 64742-94-5 Exxon Mobil company styrene CAS. 96-09-3 Company Aldrich 2-ethylhexanol CAS. 104-76-7 Company BASF lauric acid CAS. 143-07-7 Company Aldrich Isotridecanol N CAS. 27458-92-0 Company BASF Acetic acid, pure CAS. 64-19-7 Company Aldrich Formic acid, 85% in H ₂ O CAS 64-18-6 Company Kraft Formalin, 36.5% CAS 50-00-0 Company Aldrich

Polydispersities D were determined by gel permeation chromatography.

Synthetic Example 1: N, N-dimethylethanolamine * 15 PO (A)

In a 2 liter autoclave, N, N-dimethylethanolamine (76.7 g) is added with potassium tert -butylate (4.1 g). It is purged three times with N ₂ , a pre-pressure of about 1.3 bar N ₂ adjusted and the temperature increased to 130 ° C. 1,2-propylene oxide (750 g) is metered in over a period of 10 hours so that the temperature remains between 129 ° C-131 ° C. The mixture is then stirred for 6 h at 130 ° C, rinsed with N ₂ , cooled to 60 ° C and the reactor emptied. Excess propylene oxide is removed on a rotary evaporator in vacuo. The basic crude product is neutralized using commercially available Mg silicates, which are then filtered off. 831 g of the product are obtained in the form of an orange oil (TBN 58.1 mg KOH / g; D 1.16).

Synthetic Example 2: N, N-dimethylethanolamine * 25 BuO (B)

In a 2 liter autoclave, N, N-dimethylethanolamine (47.1 g) is added with potassium tert -butylate (5.0 g). It is purged three times with N ₂ , a pre-pressure of about 1.3 bar N ₂ adjusted and the temperature increased to 140 ° C. 1,2-Butylene oxide (953 g) is added over a period of 9 h so that the temperature remains between 138 ° C-141 ° C. The mixture is then stirred for 6 h at 140 ° C, rinsed with N ₂ , cooled to 60 ° C and the reactor emptied. Excess butylene oxide is removed on a rotary evaporator in vacuo. The basic crude product is neutralized using commercially available Mg silicates, which are then filtered off. 1000 g of the product are obtained in the form of a yellow oil (TBN 28.1 mg KOH / g; D 1.12).

Synthesis Example 3: N, N-Dimethylethanolamine * 15 PO quaternized with dimethyl oxalate (I)

Polyetheramine (A) (250 g) from Synthesis Example 1 was treated with dimethyloxalate (59 g) and lauric acid (12.5 g) and the reaction mixture was stirred for 4 h at a temperature of 120 ° C. Subsequently, excess dimethyl oxalate on a rotary evaporator removed in vacuo (p = 5 mbar) at a temperature of 120 ° C. This gives 290 g of the product. ¹ H-NMR analysis of the resulting quaternized polyetheramine shows the quaternization.

Synthesis Example 4: N, N-Dimethylethanolamine * 25 BuO quaternized with dimethyl oxalate (II)

Polyetheramine (B) (250 g) from Synthesis Example 2 is added with dimethyl oxalate (67.3 g) and lauric acid (6.2 g), and the reaction mixture is stirred for 4.5 hours at a temperature of 120 ° C. Subsequently, excess dimethyl oxalate is removed on a rotary evaporator under reduced pressure (p = 5 mbar) at a temperature of 120 ° C. 270 g of the product are obtained. ¹ H-NMR analysis of the resulting quaternized polyetheramine shows the quaternization.

Synthesis Example 5: N, N-Dimethylethanolamine * 25 BuO quaternized with styrene oxide / acetic acid (III)

Polyetheramine (B) (400 g) from Synthesis Example 2 is dissolved in Solvent Naphtha Heavy (436 g), added with styrene oxide (24.0 g) and acetic acid (12.0 g) and then at 80 ° C for 8 h touched. After cooling to room temperature, 870 g of the product are obtained. ¹ H NMR analysis of the quaternized polyetheramine solution thus obtained in Solvent Naphtha Heavy shows the quaternization.

Synthesis Example 6: N, N-Dimethylethanolamine * 15 PO quaternized with propylene oxide / acetic acid (IV)

In a 2 liter autoclave, polyetheramine (A) (305 g) from Synthesis Example 1 is dissolved in 2-ethylhexanol (341 g) and acetic acid (18.3 g) is added. It is purged three times with N ₂ , a pre-pressure of about 1.3 bar N ₂ adjusted and the temperature increased to 130 ° C. 1,2-propylene oxide (17.7 g) is added. The mixture is then stirred for 5 h at 130 ° C, rinsed with N ₂ , cooled to 40 ° C and the reactor emptied. Excess propylene oxide is removed on a rotary evaporator in vacuo. You get 675 g of the product in the form of an orange oil. ¹ H-NMR analysis of the resulting solution of the quaternized polyetheramine in 2-ethylhexanol shows the quaternization.

Synthesis Example 7: N, N-Dimethylethanolamine * 15 PO quaternized with ethylene oxide / acetic acid (V)

In a 2 liter autoclave, polyetheramine (A) (518 g) from Synthesis Example 1 is dissolved in 2-ethylhexanol (570 g) and treated with conc. Acetic acid (30 g) was added. It is purged three times with N ₂ , a pre-pressure of about 1.3 bar N ₂ adjusted and the temperature increased to 130 ° C. Ethylene oxide (22 g) is added. The mixture is then stirred for 5 h at 130 ° C, rinsed with N ₂ , cooled to 40 ° C and the reactor emptied. This gives 1116 g of the product in the form of an orange oil. ¹ H-NMR analysis of the resulting solution of the quaternized polyetheramine in 2-ethylhexanol shows the quaternization.

Synthetic Example 8: Isotridecanol N * 22 BuO: Polyether (C)

The preparation of the polyether of isotridecanol N and 1,2-butylene oxide in a molar ratio of 1:22 is carried out by known methods by DMC catalysis, as described, for example in EP1591466A ,

Synthetic Example 9: Isotridecanol (Tridecanol N, BASF) * 22 BuO aminated with NH ₃ : prim. Polyetheramine (D)

The production of the prim. Polyetheramine (D) by reacting the polyether (C) from Synthesis Example 8 with NH ₃ in the presence of a suitable hydrogenation catalyst by known methods, such as described in DE3826608A , Analysis of the polyetheramine (D) thus obtained gives TBN 32.0 mg KOH / g.

Synthesis Example 10: Tert. Polyetheramine (E)

The polyetheramine (D) (400 g) from Synthesis Example 9 is mixed with ice-bath cooling with formic acid (65.3 g, 85% in H ₂ O). The reaction mixture is then heated to a temperature of 45 ° C and formaldehyde solution (44.9 g, 36.5% in H ₂ O) is added dropwise at this temperature, the liberated carbon dioxide is derived from the reaction vessel. The reaction mixture is stirred for 16 h at a temperature of 80 ° C. The reaction mixture is then cooled to room temperature, admixed with hydrochloric acid (37%, 35.4 g) and stirred at room temperature for 1 h. H ₂ O (500 ml) is added and the aqueous phase is adjusted to a pH of about 10 by addition of 50% potassium hydroxide solution. The mixture is then extracted several times with tert -butyl methyl ether (total 1200 ml). The combined organic phases are washed with sat. washed aqueous NaCl solution, dried over MgSO ₄ and the solvent is removed in vacuo. 403 g of the product are obtained in the form of a yellow oil. ¹ H-NMR analysis of the thus obtained tert. Polyetheramine shows the reductive dimethylation.

Synthetic Example 11: Isotridecanol (Tridecanol N, BASF) * 22 BuO aminated with NH ₃ , red. dimethylated, quaternized with dimethyl oxalate (VI)

Tert. Polyetheramine (E) (172 g) from Synthesis Example 10 is added with dimethyl oxalate (55.3 g) and lauric acid (5.2 g), and the reaction mixture is stirred for 4 hours at a temperature of 120 ° C. Subsequently, excess dimethyl oxalate is removed on a rotary evaporator under reduced pressure (p = 5 mbar) at a temperature of 120 ° C. ¹ H-NMR analysis of the resulting quaternized polyetheramine shows the quaternization.

Synthetic Example 12: Isotridecanol (Tridecanol N, BASF) * 22 BuO aminated with NH ₃ , dimethylated, quaternized styrene oxide / acetic acid (VII)

Tert. Polyetheramine (E) (200 g) from Synthesis Example 10 is dissolved in toluene (222 g) with styrene oxide (14.4 g) and conc. Acetic acid (7.2 g) was added and then stirred for 7 h at a temperature of 80 ° C. ¹ H-NMR analysis of the solution thus obtained shows the quaternization.

C. Application examples:

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

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

Fuel used: RF-06-03 (Referenzdiesel, Haltermann Products, Hamburg) The results are summarized in Table 1. Table 1: XUD9 tests Ex. designation Dosage acc. Production example [mg active substance / kg] Flow restriction 0.1 mm needle stroke [%] #1 M1, according to Preparation Example 4 30 20.9 # 2 M2, according to Preparation Example 3 30 44.5

b) DW10 test

The test results are shown in Table 2. Table 2: Results of the DW10 test additive Dose [mg / kg] Powerloss KC Powerloss DU Powerloss DU-CU basic value 0 5.0% M1, according to Preparation Example 6, Keep-Clean 80 0.61% M2, according to Preparation Example 3, Clean-up 75 08.02% 1.7%

Application Example 2: Intake valve cleanliness (intake manifold injection of Otto engine)

• Method: MB M102 E (CEC F-05-93)
• Fuel: E5 according to EN 228
• Additive according to Synthesis Example 4

Results :

Inlet valve deposit after end of test (mg / V) Basic value (without additive) 112 With 116 mg / kg additive 86

Example of use 3: Injector cleanliness (Direct injection of petrol engine)

1. A : Additiv gemäß Synthesebeispiel 4
2. B : Additiv gemäß Synthesebeispiel 3

FR-Wert* Testbeginn FR-Wert* Testende Aussehen Injektor Testende Grundwert (ohne Additiv) 0,95 1,00 Siehe Fig. 1a Mit 116 mg/kg Additiv A 0,96 0,94 Siehe Fig. 1b Mit 116 mg/kg Additiv B 0,96 0,93 Siehe Fig. 1c * : Der FR-Wert ist ein durch die Motorsteuerung erfasster Parameter, der mit der Dauer des Einspritzvorgangs des Kraftstoffes in den Brennraum korreliert. Je ausgeprägter die Bildung von Ablagerungen in den Injektordüsen, desto länger die Einspritzdauer bzw. höher der FR-Wert. Umgekehrt bleibt der FR-Wert konstant bzw. nimmt tendenziell leicht ab, wenn die Injektordüsen frei von Ablagerungen bleiben.
Method: BASF house method
Engine: Charged four-cylinder with 1.6 liter displacement
Test duration: 60 hours
Fuel: test fuel with 7 vol.% Oxygenated components
Additives:

1. A: additive according to Synthesis Example 4
2. B: additive according to Synthesis Example 3

FR value * Start of test FR value * End of test Appearance injector test end Basic value (without additive) 0.95 1.00 Please refer Fig. 1a With 116 mg / kg additive A 0.96 0.94 Please refer Fig. 1b With 116 mg / kg additive B 0.96 0.93 Please refer Fig. 1c *: The FR value is a parameter detected by the engine control, which correlates with the duration of fuel injection into the combustion chamber. The more pronounced the formation of deposits in the injector nozzles, the longer the injection time or higher the FR value. Conversely, the FR value remains constant or tends to decrease slightly as the injector nozzles remain debris free.

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

Claims (5)

1. The use of a reaction product comprising a quaternized nitrogen compound, said reaction product being obtainable by reaction

   a) of a polyether-substituted amine comprising at least one tertiary quaternizable amino group with

   b) a quaternizing agent which converts the at least one tertiary amino group to a quaternary ammonium group

   as a gasoline fuel additive for reducing or preventing deposits in the intake system of a gasoline engine or as a diesel fuel additive for reducing fuel consumption of direct injection diesel engines and/or for minimizing power loss in direct injection diesel engines or as an additive for reducing and/or preventing deposits in the injection systems, and/or for reducing and/or preventing internal diesel injector deposits (IDID), and/or for reducing and/or preventing deposits in the injection nozzles in direct diesel engines, said quaternized nitrogen compound being selected from compounds of the general formula Ia or Ib

   

   

   in which

   R₁ and R₂ are the same or different and are each C₁-C₆-alkyl, hydroxy-C₁-C₆-alkyl, hydroxy-C₁-C₆-alkenyl, or amino-C₁-C₆-alkyl, or R₁ and R₂ together form a C₂-C₆-alkylene, C₂-C₆-oxyalkylene or C₂-C₆-aminoalkylene radical;

   R₃ and R₄ are the same or different and are each H, C₁-C₆-alkyl or phenyl;

   R₅ is a radical introduced by quaternization, selected from C₁-C₆-alkyl, hydroxy-C₁-C₆-alkyl or-CH₂CH(OH) aryl;

   R₆ is C₁-C₂₀-alkyl or aryl or alkylaryl;

   A is a straight-chain or branched C₂-C₆-alkylene radical optionally interrupted by one or more heteroatoms such as N, O and S;

   n is an integer from 1 to 30 and

   X^- is an anion resulting from the quaternization reaction;

   where the quaternizing agent is selected from

   (i) an epoxide of the general formula II

   

   where the R^a radicals present therein are the same or different and are H or a hydrocarbyl radical,

   (ii) a salicylate selected from such as methyl salicylate, ethyl salicylate, n- and i-propyl salicylate, and n-, i- or tert-butyl salicylate;

   (iii) an oxalate selected from dimethyl oxalate and diethyl oxalate; and

   (iv) dimethyl carbonate.
2. The use according to claim 1, wherein the polyether-substituted amine has a number-average molecular weight in the range from 500 to 5000.
3. The use according to either of the preceding claims, wherein the fuel is selected from diesel fuels, gasoline fuels, biodiesel fuels and alkanol-containing gasoline fuels.
4. The use according to any of claims 1 to 3 as a gasoline fuel additive for reducing or preventing deposits in the intake system of a gasoline engine, for reducing or preventing deposits in injection nozzles of direct injection gasoline engines.
5. The use according to any of claims 1 to 3 as an additive for reducing fuel consumption of direct injection diesel engines, for reducing the fuel consumption of diesel engines with common rail injection systems, and/or for minimizing power loss in direct injection diesel engines, for minimizing power loss in diesel engines with common rail injection systems, or as an additive for reducing and/or preventing deposits in the injection systems, for reducing and/or preventing internal diesel injector deposits (IDID), and/or for reducing and/or preventing deposits in the injection nozzles in direct injection diesel engines, for reducing and/or preventing deposits in common rail injection systems.

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