KR20140097288A - Quaternized polyetheramines and use thereof as additives in fuels and lubricants - Google Patents

Abstract

The present invention relates to novel quaternized polyetheramines and processes for their preparation. The present invention also relates to the use of these compounds as fuel and lubricant additives. More particularly, the present invention relates to reducing or preventing deposition in a direct injection diesel engine injection system, particularly in a common rail injection system, reducing fuel consumption of a direct injection diesel engine, particularly a diesel engine with a common rail injection system, To the use of these quaternary nitrogen compounds as fuel additives to minimize output losses in diesel engines with injection diesel engines, particularly common rail injection systems. The present invention also relates to these polyetheramines; And an additive package comprising the fuel and lubricant added thereto. The present invention also relates to the use of these quaternary nitrogen compounds as additives for the improvement of the intake system clarity of gasoline engines, especially gasoline engines.

Description

QUATERNIZED POLYETHERAMINES AND USE THEREOF AS ADDITIVES IN FUELS AND LUBRICANTS BACKGROUND OF THE INVENTION < RTI ID = 0.0 > [0001] <

The present invention relates to novel quaternized polyetheramines and processes for their preparation. The present invention also relates to the use of these compounds as fuel and lubricant additives. More particularly, the present invention relates to a method for reducing or preventing deposits in a direct injection diesel engine injection system, particularly in a common rail injection system, reducing fuel consumption of a direct injection diesel engine, particularly a diesel engine with a common rail injection system And to the use of these quaternized nitrogen compounds as fuel additives for minimizing power loss in direct injection diesel engines, especially diesel engines with common rail injection systems. The present invention also relates to these polyetheramines; And an additive package comprising the fuel and the lubricant to which the additive is added. The present invention also relates to the use of these quaternized nitrogen compounds for improving the intake system cleanliness of gasoline engines, particularly gasoline engines.

In a direct injection diesel engine, the fuel is not injected into the pre-chamber or eddy-current chamber as in the case of a conventional (chamber) diesel engine, but instead of being injected and sprayed very finely by a multi-hole injection nozzle, Dispense (spray) (spray). The advantages of direct injection engines are their high performance for diesel engines, and nevertheless low fuel consumption. In addition, these engines achieve very high torque even at low speeds.

Currently, there are basically three methods: a conventional injection pump, a pump-nozzle system (unit-injector system or unit-pump system) and a common rail system are used to directly inject fuel into the combustion chamber of a diesel engine.

In the common rail system, diesel fuel is transported to the high-pressure line, common rail through the pump at pressures up to 2000 bar. On the way from the common rail, the branched line leads to a different injector that injects the fuel directly into the combustion chamber. Sufficient pressure is always applied to the common rail, which allows multiple injections or specific injection configurations. In contrast, in other injection systems, only smaller variations in injection are possible. Spraying from a common rail is basically divided into three groups: (1) pre-injection in which lighter combustion is achieved, such that rough combustion noise ("nailing") is reduced and the engine is running quietly; 2.) a main injection which is particularly responsible for good torque profile, and (3) a post-injection which ensures a particularly low NOx value. In this post-injection, the fuel is generally not combusted, but instead is vaporized by in-cylinder residual heat. The resulting exhaust gas / fuel mixture is transported to an exhaust system where the fuel acts as a reducing agent for nitrogen oxides NOx in the presence of a suitable catalyst.

Variable, cylinder-individual injection in the common rail injection system can positively affect the emission of engine pollutants, for example nitrogen oxides (NOx), carbon monoxide (CO) and particulate matter (soot). This enables, for example, an engine with a common rail injection system to theoretically meet the Euro 4 standard even without the additional particulate filter.

In a modern common rail diesel engine, under certain conditions, when a fuel or bio-diesel containing fuel having metal impurities such as zinc compounds, copper compounds and lead compounds and other metal compounds is used, the deposits are injected onto the injector orifice Which can adversely affect the injection performance of the fuel, thereby impairing the performance of the engine, i. E. Particularly reducing the power, but in some cases also exacerbating combustion. Deposition formation is further enhanced by further growth in the injector component, particularly due to changes in the geometry of the nozzles (narrower conical orifices with rounded outlets). For continuous optimal functioning of the engine and the injector, such deposits in the nozzle orifice should be prevented and reduced by suitable fuel additives.

The injector of the injection system to the fuel capacity as well as the carburetor and intake system of the gasoline engine is contaminated with airborne dust particles, unburned hydrocarbon residues from the combustion chamber, and impurities generated by the crankcase ventilation gas passed through the vaporizer do.

These residues move the air-fuel ratio at idling and in a low partial load range so that the mixture becomes leaner and the combustion becomes less complete so that the unburned or partially burned hydrocarbons in the exhaust gas The ratio becomes larger and the consumption of glycerine is increased.

These disadvantages are known to be prevented by using valves and gasoline engine or fuel additives that maintain the cleanliness of the injection system (see, for example, M. Rossenbeck in Katalysatoren, Tenside, Mineraloadditive [Catalysts, Surfactants, Mineral Oil Additives, eds J. Falbe, U. Hasserodt, p 223, G. Thieme Verlag, Stuttgart 1978).

Depending on the mode of operation, and also on the preferences of use of these detergent additives, differences between the two generations are derived.

While the first generation additive could only prevent formation of deposits in the intake system and could not remove pre-existing deposits, modern second-generation additives were more particularly also used in the relatively hot zone, Both (cleanliness maintenance and cleaning effect) can be performed due to excellent thermal stability. These detergents, which can be produced with a number of chemical classes, such as polyalkenamines, polyether amines, polybutene mannich bases or polybutene succinimides, are generally applied in combination with carrier oils and in some cases It is applied in combination with additional additive components, such as corrosion inhibitors and demulsifiers. The carrier oil performs a solvent or cleaning function in combination with a detergent. Carrier oil is a high melting, viscous, thermally stable liquid that typically covers a hot metal surface and prevents impurities from forming or depositing on the metal surface.

Recent generations of detergent fuel additives often have quaternary nitrogen groups.

For example, WO 2006/135881 discloses the condensation of a hydrocarbyl-substituted acylating agent and an oxygen or nitrogen atom containing compound with a tertiary amino group followed by hydrocarbyl epoxide with a stoichiometric amount of an acid such as, Quaternized ammonium salts prepared by quaternization in combination. These additives are used particularly as diesel fuel additives to reduce power loss.

The use of polyalkene-substituted quaternarized amines such as quaternized quaternized polyisobutene amines, and detergent additives for reducing intake valve deposits, and lubricant additives for internal combustion engines is described in US 2008/0113890.

US 6 331 648 B1 relates to certain quaternary ether amine compounds comprising 1-ethyl-1,3-propylene introduced between an alkoxylate chain and a quaternary nitrogen. While the availability of these compounds as corrosion inhibitors or detergent additives in gasoline and diesel fuels is inferred, there is no evidence of such availability.

EP 182 669 A1 describes halogen- or sulfur-containing alkoxylated quaternary ammonium compounds of the following chemical formulas.

(Wherein R < ₁ > is an alkylene oxide block). For these compounds, a full application series is contemplated, including general use as a fuel and lubricant additive, without substantiating experimental evidence of a particular function. Preferred anions A- are chloride, methyl sulfate and ethyl sulfate.

US 4 564 372, US 4 581 151, US 4 600 409 and WO 1985/000620 relate to quaternization, i. E. Halogenated polyoxyalkyleneamine salts with alkyl halides, wherein the polyoxyalkylene units and amine units are in a variety of Group, e. G. More particularly the amine linker of the type -C (O) -NH-. Although it is envisaged to be used as a dispersant and a corrosion inhibitor in fuel, the specific function has not been proved experimentally.

It is therefore an object of the present invention to provide an improved quaternary fuel additive which is no longer advantageous over the prior art and which can be used more particularly in both diesel fuel and gasoline fuel.

Surprisingly, it has been found that this object is achieved by providing specially added fuels and lubricants as defined in the appended claims. The additives of the present invention are superior in some ways compared to known conventional additives and can be used in both diesel and gasoline fuels. These are notable for the advantageous clean-up and keep-up effects on the injectors of the intake valves and gasoline engines, as well as the various components of the internal combustion engine, such as diesel engine injection nozzles, Or to remove already formed combustion chamber deposits from the internal combustion engine. Additionally they prevent formation of deposits in the fuel filter or remove already formed filter impurities.

1 is a diagram showing the injector cleanliness which can be achieved with the additives of the present invention after a test run with direct injection gasoline engines 1b and 1c as compared to the unadded fuel 1a.
2 is a diagram illustrating a 1-hour engine test cycle according to CEC F-098-08.

A1) Certain embodiments

The present invention relates in particular to the following particular embodiments:

1. Include an effective amount of one or more reaction products comprising quaternized nitrogen compounds or a component fraction thereof containing quaternized nitrogen compounds obtained from the reaction products through a purification, in a major amount of conventional fuel or lubricant Wherein the reaction product is selected from the group consisting of

a. A polyether-substituted amine containing one or more quaternizable tertiary amino groups and

b. And a quaternizing agent which converts at least one tertiary amino group into a quaternary ammonium group, in particular a fuel composition.

2. A fuel composition or lubricant composition according to the first embodiment wherein the polyether substituent comprises monomer units of the formula < RTI ID = 0.0 >

Wherein R ₃ and R ₄ are the same or different and each is H, alkyl, alkylaryl or aryl.

3. In a second embodiment, the polyether-substituted amine has a number average molecular weight in the range of from 500 to 5000, in particular from 800 to 3000 or 900 to 1500. [

4. In any one of the preceding embodiments, the quaternizing agent is an alkylene oxide optionally in combination with an acid; Aliphatic or aromatic mono- or polycarboxylic acid esters such as more particularly mono- or dialkylcarboxylates; Cyclic nonaromatic or aromatic mono- or polycarboxylic acid esters; Dialkyl carbonate; Alkyl sulphate; Alkyl halide; Alkylaryl halides; Especially halogen- and sulfur-free quaternizing agents, such as alkylene oxides in combination with acids, such as carboxylic acids; Aliphatic or aromatic mono- or polycarboxylic acid esters such as more particularly mono- or dialkylcarboxylates; Cyclic nonaromatic or aromatic mono- or polycarboxylic acid esters and dialkyl carbonates; ≪ / RTI > and mixtures thereof.

5. A fuel composition or lubricant composition comprising a major amount of a conventional fuel or lubricant, comprising an effective amount of one or more quaternized nitrogen compounds of formula (Ia) or (Ib)

(Wherein,

R ₁ and R ₂ are the same or different and each is alkyl, alkenyl, hydroxyalkyl, hydroxyalkenyl, aminoalkyl or aminoalkenyl, or R ₁ and R ₂ together are alkylene, oxyalkylene or aminoalkyl ;

R ₃ and R ₄ are the same or different and each is H, alkyl, alkylaryl or aryl;

R ₅ is a radical introduced by quaternization, such as more particularly alkyl, hydroxyalkyl, arylalkyl or hydroxyarylalkyl;

R ₆ is, in each instance, alkyl, alkenyl, optionally mono-or polyunsaturated cycloalkyl or aryl optionally substituted by one or more hydroxyl radicals or alkyl radicals, or interrupted by one or more heteroatoms;

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

n is an integer from 1 to 50;

X ^- is an anion, in particular an anion resulting from the quaternization reaction).

6. In a fifth embodiment, R ₁ and R ₂ are the same or different and each is selected from the group consisting of 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 are C ₂ -C ₆ -alkylene, C ₂ -C ₆ -oxyalkylene or C ₂ -C ₆ -aminoalkylene radical ≪ / RTI >

R ₃ and R ₄ are the same or different and each is H, C ₁ -C ₆ -alkyl or phenyl;

R ₅ is a radical introduced by quaternization, selected from C ₁ -C ₆ -alkyl, hydroxy-C ₁ -C ₆ -alkyl or -CH ₂ CH (OH) aryl;

R ₆ is C ₁ -C ₂₀ - alkyl, for example _{C 10 -C 20 -, C 11} -C 20 - or C ₁₂ -C ₂₀ - alkyl, or aryl or alkyl aryl, wherein alkyl is in particular C ₁ - C ₂₀ ;

A is a straight or branched C ₂ -C ₆ -alkylene radical optionally interrupted by at least one heteroatom such as N, O and S;

n is an integer from 1 to 30;

And X < ^- > is an anion resulting from the quaternization reaction.

7. The fuel composition of any one of the preceding embodiments, wherein the fuel composition is selected from diesel fuel, gasoline fuel, biodiesel fuel, and alkanol-containing gasoline fuel.

8. A quaternized nitrogen compound as defined in any of the preceding embodiments, wherein said quaternized nitrogen compound is selected from those without halogen and sulfur.

9. A process for preparing a quaternized nitrogen compound of the formula < RTI ID = 0.0 > (Ia) <

Wherein R ₁ to R ₅ , A, X and n are each as defined above,

a) alkylating an aminoalkanol of formula (II) with an epoxide of formula (III) to obtain an alkoxylated amine of formula (Ia-1): And

b) quaternizing the thus obtained alkoxy compound of formula (Ia-1) to obtain a reaction product comprising at least one compound of formula (Ia), wherein the quatification is for example a compound of formula (IV) Lt; / RTI > is as defined above, with a compound of formula IVa < RTI ID = 0.0 >

≪ / RTI >

Wherein R ₁ , R ₂ and A are each as defined above,

(Wherein R < ₃ > and R < ₄ > are each as defined above)

(Wherein R ₁ to R ₄ , A and n are each as defined above)

(Wherein R < ₅ > is alkyl or aryl and X is as defined above)

Wherein R _{5 '} is H, alkyl or aryl and the R ₅ radical is a -CH ₂ CH (OH) R _5' group,

10. A process for preparing a quaternized nitrogen compound of formula (Ib)

Wherein R ₁ to R ₆ , X and n are each as defined above,

a) alkoxylating an alcohol of formula V with an epoxide of formula III to give a polyether of formula Ib-1;

b) as so to obtain the poly to the ether to by amination of formula VII amine amine of Formula Ib-2 of the formula Ib-1 obtained, when the amine of formula Ib-2 is R ₁ and / or R ₂ is H Optionally alkylated;

c) quaternizing the product from step b) to obtain a reaction product comprising at least one compound of the formula Ib, wherein the quatification is for example a compound of formula IV, or an acid HX, wherein X is as defined above Lt; RTI ID = 0.0 > (IVa) < / RTI >

≪ / RTI >

(Wherein R < ₆ > is as defined above)

(Wherein R < ₃ > and R < ₄ > are each as defined above)

Wherein R ₃ , R ₄ and R ₆ , A, X and n are each as defined above,

(Wherein R < ₁ > and R < ₂ > are each as defined above)

Wherein R ₁ to R ₄ and R ₆ , A, X and n are each as defined above,

(Wherein R < ₅ > is alkyl or aryl and X is as defined above)

Wherein R _{5 '} is H, alkyl or aryl and the R ₅ radical is a -CH ₂ CH (OH) R _5' group.

11. The ninth or tenth embodiment, the quaternizing agent is an alkylene oxide 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 nonaromatic carboxylic acid esters.

12. Quaternized nitrogen compounds obtainable by the process according to Embodiment 10 or 11, in particular in the halogen- and sulfur-free form.

13. Use of a quaternized nitrogen compound according to embodiment 8 or according to any of embodiments 9 to 11 as a fuel additive or lubricant additive.

14. Use according to the twelfth embodiment as a diesel fuel additive, especially as a low temperature flow improver or anti-wax additive (WASA).

15. Use according to the twelfth embodiment as a gasoline fuel additive for reducing deposits in gasoline engines, such as intake systems of more particularly DISI and PFI (Port Fuel Injector) engines.

16. The twelfth embodiment of the present invention is directed to reducing the fuel consumption of a direct injection diesel engine, particularly a diesel engine with a common rail injection system, or to a direct injection diesel engine, particularly a diesel engine with a common rail injection system And / or an additive to minimize the output loss, or to reduce and / or prevent deposits in the injection system, such as internal diesel injector deposits (IDID), and / or to reduce the amount of deposits in a direct injection diesel engine, Use as an additive to reduce and / or prevent water.

17. A process for the preparation of a quaternary nitrogen compound, as defined in the eighth embodiment, or in combination with one or more quaternized nitrogen compounds prepared according to the ninth or tenth embodiment, in combination with further diesel or gasoline fuel additives, ≪ / RTI >

In certain configurations of the present invention, in some or all of the embodiments, the quaternizing agent is not an aromatic carboxylic acid ester, such as a salicylic acid ester.

In certain embodiments of the present invention, in some or all of the embodiments, the quaternizing agent is selected from the compounds of Formulas 1 and 2 described herein.

In certain embodiments of the present invention, the radicals (nitrogen substituents) introduced by quaternization in some or all of the embodiments are especially alkyl (especially C ₁ -C ₆ -alkyl) or hydroxyarylalkyl 2-hydroxy-2-phenylethyl).

In certain embodiments of the present invention, in some or all of the embodiments, the polyether substituent does not have any aryl or aralkyl group.

In certain embodiments of the present invention, in some or all of the embodiments, the quaternized nitrogen compound is a compound of formula Ia or Ib.

Appropriate test methods in each case for the investigation of the above-cited applications are known to the person skilled in the art or are described in the experimental section according to the plain and general reference.

A2) General definitions

In the context of the present invention, "halogen-free" or "sulfur-free" means that an inorganic or organic halogen or sulfur compound and / or its corresponding ion such as a halide anion and a sulfur-containing anion, . More particularly "halogen-free" or "sulfur-free" includes more particularly the absence of a stoichiometric amount of a halogen or sulfur compound or anion; The stoichiometric amount of the halogen or sulfur compound or anion is, for example, such that the molar ratio of quaternized nitrogen compound to halogen or sulfur compound or ion thereof is less than 1: 0.1, or 1: 0.01 or 1: 0.001, or less than 1: to be. The "halogen-free" or "sulfur-free" more particularly includes also halogens or sulfur compounds and / or their corresponding ions such as halide anions and sulfur containing anions such as more particularly the complete absence of sulphates.

"Carboxylic acid" is more specifically organic carboxylic acids, such as more in particular comprises a monocarboxylic acid of RCOOH type, and in which R is a short-chain hydrocarbyl radical, for example lower alkyl- or C ₁ -C ₄ - Alkylcarboxylic acid.

A "quaternizable" nitrogen or amino group includes in particular primary, secondary and tertiary amino groups.

If there is no counter-statement, the following general definition applies:

"Hydrocarbyl" can be broadly interpreted and refers to a hydrocarbon radical having 1 to 50 carbon atoms, which may optionally contain heteroatoms, such as O, N, NH, S, Cyclic aromatic or nonaromatic and long or short chain, or straight or branched chain hydrocarbyl radical. Hydrocarbyl includes, for example, alkyl, alkenyl, aryl, alkylaryl, cycloalkenyl or cycloalkyl radicals as defined below, and substituted analogs thereof.

"Alkyl" or "lower alkyl" refers to saturated, straight or branched chain hydrocarbyl radicals having 1 to 4, 1 to 6, 1 to 8, 1 to 10, 1 to 14 or 1 to 20 carbon atoms, For example, a methyl group, an ethyl group, a n-propyl group, a 1-methylethyl group, an n-butyl group, a 1-methylpropyl group, Methylbutyl, 2-methylpropyl, 2-methylpentyl, 3-methylpentyl, 1-methylbutyl, Dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethyl Butyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl and 1-ethyl- And also n-heptyl, n-octyl, n-nonyl and n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, and single or multiple branched analogs thereof.

"Hydroxyalkyl" is a mono- or polyhydroxylated, especially monohydroxylated, analog of said alkyl radical, such as a monohydroxylated analog of said linear or branched alkyl radical, for example a linear Those having a hydroxyalkyl group such as a primary (terminal) hydroxyl group such as those having hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, or non-terminal hydroxyl groups Such as 1-hydroxyethyl, 1- or 2-hydroxypropyl, 1- or 2-hydroxybutyl or 1-, 2- or 3-hydroxybutyl.

"Alkenyl" refers to mono- or polyunsaturated, in particular monounsaturated, linear or branched, monovalent, monovalent, Branched hydrocarbyl radicals such as C ₂ -C ₆ -alkenyl such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, Propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3- 1-butenyl, 2-methyl-1-butenyl, 1-methyl-2-butenyl, Butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, Propyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, Methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl- Methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4- Methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, Butenyl, 2,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, Butenyl, 3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl, Ethyl-1-butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl- 2-propenyl, 1-ethyl-2-methyl-1-propenyl and 1-ethyl-2-methyl-2-propenyl.

"Hydroxyalkenyl" means an analog of said alkenyl radical, especially mono- or polyhydroxylated, especially monohydroxylated.

"Aminoalkyl" and "aminoalkenyl" are particularly mono- or polyaminated, especially monoaminated, analogs of the above alkyl and alkenyl radicals, respectively, or analogs of the above hydroxyalkyls in which the OH group is replaced by an amino group.

"Alkenyl" is a carbon number of 1 to 10 individual straight-chain or branched single or multiple hydrocarbylene bridging group, for example _{-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) - C 1} -C 7 selected from-alkyl group or a _{-CH 2 -, - (CH 2} ) 2 -, - (CH 2) 3 -, - (CH 2) 4 -, - (CH ₂ ) a C ₁ -C ₄ -alkylene group or a C ₂ -C ₆ -alkylene group selected from ₂ -CH (CH ₃ ) -, -CH ₂ -CH (CH ₃ ) -CH 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 -,} -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 example _{selected from - (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 - represents an alkylene group - selected from C ₂ -C _4.

The oxyalkylene radical corresponds to the definition of the above-mentioned straight-chain or single or multi-branched alkylene radical having 2 to 10 carbon atoms, wherein the carbon chain is interrupted by 1 or more, especially 1 oxygen heteroatom. Non-limiting examples include -CH ₂ -O-CH ₂ -, - (CH ₂ ) ₂ -O- (CH ₂ ) ₂ -, - (CH ₂ ) ₃ -O- (CH ₂ ) ₃ - ₂ -O- (CH ₂ ) ₂ -, - (CH ₂ ) ₂ -O- (CH ₂ ) ₃ -, -CH ₂ -O- (CH ₂ ) ₃ .

"Aminoalkylene" refers to the above straight-chain or mono- or polyunsaturated alkylene radical having from 2 to 10 carbon atoms, wherein the carbon chain contains one or more, especially one, nitrogen (especially -NH- . Non-limiting examples include -CH ₂ -NH-CH ₂ -, - (CH ₂ ) ₂ -NH- (CH ₂ ) ₂ -, - (CH ₂ ) ₃ -NH- (CH ₂ ) ₃ - _2- NH- (CH ₂ ) ₂ -, - (CH ₂ ) ₂ -NH- (CH ₂ ) ₃ -, -CH ₂ -NH- (CH ₂ ) ₃ .

"Alkenylene" refers to mono- or polyunsaturated, especially monounsaturated, analogues of the above alkylene groups of 2 to 10 carbon atoms, especially C ₂ -C ₇ -alkenylene or C ₂ -C ₄ -alkenylene, CH = CH-, -CH = CH- CH 2 -, - CH 2 -CH = CH-, -CH = CH-CH 2 -CH 2 -, -CH 2 -CH = CH-CH 2 -, -CH 2 a -CH _{2 -CH = CH-, -CH (CH} 3) -CH = CH-, -CH 2 -C (CH 3) = CH-.

"Cycloalkyl" refers to a carbocyclic radical having from 3 to 20 carbon atoms, such as C ₃ -C ₁₂ -cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, Cyclodecyl, cyclodecyl, and cyclododecyl; Preferably cyclopentyl, cyclohexyl, cycloheptyl; And cyclopropylmethyl, cyclopropylethyl, cyclobutylmethyl, cyclobutylethyl, cyclopentylmethyl, cyclopentylethyl, cyclohexylmethyl, or C ₃ -C ₇ -cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclo Hexyl, cycloheptyl, cyclopropylmethyl, cyclopropylethyl, cyclobutylmethyl, cyclopentylethyl, cyclohexylmethyl, wherein the bond to the remainder of the molecule may be through any suitable carbon atom.

"Cycloalkenyl" or "mono- or" polyunsaturated cycloalkyl "is especially a monocyclic mono- or polyunsaturated hydrocarbyl group having from 5 to 8 carbon atoms, preferably from 6 carbon atoms, Cyclopenten-3-yl, cyclohexen-1-yl, cyclohexen-3-yl and cyclohexen-4-yl radicals.

"Aryl" means a monocyclic or bicyclic, optionally substituted aromatic radical having 6 to 20 ring carbon atoms, for example 6 to 10, such as phenyl, biphenyl, naphthyl such as 1- or 2- Naphthyl, tetrahydronaphthyl, fluorenyl, indenyl, and phenanthrenyl. These aryl radicals may optionally bear 1, 2, 3, 4, 5 or 6 identical or different substituents.

"Alkylaryl" means an alkyl-substituted analog of a mono- or polysubstituted, especially mono- or di-substituted, aryl radical at any ring position, wherein aryl is defined analogously as above, g. C ₁ -C ₄ - alkyl means a phenyl-C ₁ -C ₄ alkyl radical which may be present at any ring position.

The "substituent" for the radicals specified herein is selected from a keto group, -COOH, -COO-alkyl, -OH, -SH, -CN, amino, -NO ₂ , alkyl, or an alkenyl group.

Mn (number-average molecular weight) is determined in a conventional manner; More particularly, the values relate to values determined via gel permeation chromatography or mass spectrometry.

A3) Starting compounds (alcohol of formula V and amino alcohol of formula II)

a) an alcohol of formula V:

Wherein R ₆ is an alkyl, alkenyl, optionally mono- or polyunsaturated cycloalkyl, in each case optionally substituted by, for example, one or more hydroxyl radicals or alkyl radicals, or interrupted by one or more heteroatoms, Aryl;

b) amino alkanols of formula II:

(Wherein,

R ₁ and R ₂ are the same or different and each is alkyl, alkenyl, hydroxyalkyl, hydroxyalkenyl, aminoalkyl or aminoalkenyl, or R ₁ and R ₂ together are alkylene, oxyalkylene or aminoalkyl ;

A is a linear or branched alkylene or alkenylene radical optionally interrupted by one or more heteroatoms such as N, O and S.

A4) Quaternizing agent:

The quaternization agents useful in principle include all such suitable compounds. Quaternizing agents are, in particular, alkylene oxides, optionally in combination with acids; Aliphatic or aromatic carboxylic acid esters such as more especially dialkylcarboxylates; Alkanoate; Cyclic nonaromatic or aromatic carboxylic acid esters; Dialkyl carbonate; Alkyl sulphate; Alkyl halide; Alkylaryl halides; And mixtures thereof.

In a specific embodiment, however, at least one quaternizable tertiary nitrogen atom is quaternized with one or more quaternizing agents selected from epoxides, especially hydrocarbyl epoxides of the formula II:

(Wherein the R ^a radicals present are the same or different and are each H or a hydrocarbyl radical). The hydrocarbyl radical may have at least 1 to 14 carbon atoms. Specifically, they are aliphatic or aromatic radicals, such as linear or branched C ₁ -C ₄ -alkyl radicals, or aromatic radicals such as phenyl or C ₁ -C ₄ -alkylphenyl.

Suitable hydrocarbyl epoxides include, for example, aliphatic and aromatic alkylene oxides such as, in particular, C _2-16 -alkylene oxides such as ethylene oxide, propylene oxide, 1,2-butylene oxide, Oxide, 2-methyl-1,2-propene oxide (isobutene oxide), 1,2-pentene oxide, 2,3-pentene oxide, Hexene oxide, 3,4-hexene oxide, 2-methyl-1,2-pentene oxide, 2-ethyl-1,2-butene oxide, 3-hexene oxide, Methyl-1,2-pentene oxide, 1,2-decene oxide, 1,2-dodecene oxide or 4-methyl-1,2-pentene oxide; Tetradecane oxide; Hexadecene oxide; And also aromatic-substituted ethylene oxides such as optionally substituted styrene oxides, especially styrene oxide or 4-methylstyrene oxide.

When epoxides are used as quaternizing agents, they may be used in the presence or absence of free acid, particularly in the presence or absence of free quantitative acid, such as specifically C _1-12 -monocarboxylic acids such as formic acid, acetic acid or propionic acid, or _C12-12 -dicarboxylic acid such as oxalic acid or adipic acid, or a sulfonic acid such as benzenesulfonic acid or toluenesulfonic acid, or an aqueous mineral acid such as sulfuric acid or hydrochloric acid. The quaternized products thus produced are "acid-containing" or "acid-free" in the context of the present invention.

Additional groups of quaternizing agents include alkyl ethers of cycloaromatic or cycloaliphatic mono- or polycarboxylic acids (especially mono- or dicarboxylic acids) or aliphatic polycarboxylic acids (especially dicarboxylic acids).

In a specific embodiment, the quaternization of at least one quaternizable tertiary nitrogen atom is carried out with at least one quaternizing agent selected from the following a) or b):

a) a compound of formula 1:

(Wherein,

R < ₁ > is a lower alkyl radical,

R ₂ is an optionally substituted monocyclic aryl or cycloalkyl radical, wherein the substituents are OH, NH ₂ , NO ₂ , C (O) OR ₃ ; R _1a OC (O) -, wherein R _1a is as defined for R ₁ and R ₃ is H or R ₁ ;

b) a compound of formula 2:

(Wherein,

R < ₁ > and R < _1a > are each independently a lower alkyl radical,

A is hydrocarbylene (such as alkylene or alkenylene).

Particularly suitable quaternizing agents include lower alkyl esters of oxalic acid, such as dimethyl oxalate and diethyl oxalate.

Particularly suitable compounds of formula (1)

R ₁ is a C ₁ -, C ₂ - or C ₃ -alkyl radical,

R ₂ is a substituted phenyl radical wherein the substituent is an ester radical of the formula R _1a OC (O) - or HO- present in the para, meta or ortho position relative to the R ₁ OC (O) - radical on the aromatic ring it means.

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

"4 anion quaternised by reaction result" X ^- is, for example, halide, for example chloride or bromide, the sulfate radical ((SO ₄₎ ^2-), or only basic or polybasic, aliphatic or aromatic carboxylic acid An anionic radical, or an anionic radical ROC (O) O- resulting from the quaternization reaction of the 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 hydroxyl group capable of bonding to the polyether radical and at least one quaternary primary, secondary or tertiary amino group.

Quatemable nitrogen compounds are especially chosen from hydroxyalkyl-substituted primary, secondary, tertiary and quaternary monoamines, and hydroxyalkyl-substituted primary, secondary, tertiary and quaternary diamines.

Suitable "hydroxyalkyl-substituted mono- or polyamines" are those which are provided as substituted in one or more hydroxyalkyl substituted, e.g., 1,2,3,4,5 or 6 hydroxyalkyl.

Examples of "hydroxyalkyl-substituted monoamines" include N-hydroxyalkyl monoamines, N, N-dihydroxyalkyl monoamines, and N, N, N-trihydroxyalkyl monoamines, The hydroxyalkyl groups are the same or different and are also as defined above. Hydroxyalkyl is especially 2-hydroxyethyl, 3-hydroxypropyl or 4-hydroxybutyl.

For example, the following "hydroxyalkyl-substituted polyamines" and particularly "hydroxyalkyl-substituted diamines" refer to (N-hydroxyalkyl) alkylenediamines, N, N-dihydroxyalkyl alkylenediamines Where the hydroxyalkyl groups are the same or different and are also as defined above. Hydroxyalkyl is especially 2-hydroxyethyl, 3-hydroxypropyl or 4-hydroxybutyl; Alkylene is especially ethylene, propylene or butylene.

In particular, mention may be made of the following quaternizable nitrogen compounds:

A6) Preparation of the additive of the present invention:

a) Preparation of polyether-substituted quaternary intermediates (Ia-1 and Ib-1)

a1) proceeding from an amino alcohol of formula II

Aminoalcohols of formula (II) can be alkoxylated in a manner generally known for obtaining the alkoxylated amines of formula (Ia-1).

The alkoxylation performance is generally known to those skilled in the art. Those skilled in the art are aware that reaction conditions, particularly catalyst selection, can affect the molecular weight distribution of alkoxylates.

For alkoxylation, C ₂ -C ₁₆ -alkylene oxides, such as ethylene oxide, propylene oxide or butylene oxide, are used. In each case, it is preferably a 1,2-alkylene oxide.

The alkoxylation can be base-catalyzed alkoxylation. For this purpose, the aminoalcohol (II) may be mixed with an alkali metal hydroxide, preferably potassium hydroxide, or an alkali metal alkoxide, such as sodium methoxide, in a pressure reactor. Water still present in the mixture may be withdrawn through reduced pressure (e.g., 100 mbar) and / or high temperature (30-150 ° C). The alcohol is then present as the corresponding alkoxide. An inert gas (e. G. Nitrogen) is then used for deactivation and the alkylene oxide (s) are added stepwise at a temperature of 60-180 C to maximum pressure. At the end of the reaction, the catalyst can be neutralized by the addition of an acid (e. G., Acetic acid or phosphoric acid) and, if necessary, filtered. The basic catalyst can also be neutralized by the addition of commercially available magnesium silicates which can then be filtered. Optionally, the alkoxylation can be carried out in the presence of a solvent. This may be, for example, toluene, xylene, dimethylformamide or ethylene carbonate.

Alkoxylation of aminoalcohols can also be carried out by other methods, for example, acid-catalyzed alkoxylation. It is also possible, for example, to use double hydroxide clays as described in DE 43 25 237 A1, or to use double metal cyanide catalysts (DMC catalysts). Suitable DMC catalysts are described, for example, in DE 102 43 361 A1, in particular in the paragraphs [0029] to [0041], and in the literature cited therein. For example, it is possible to use a catalyst of the Zn-Co type. To carry out the reaction, the aminoalcohol can be mixed with the catalyst and the mixture can be dehydrated as described above and reacted with an alkylene oxide as described. Catalysts typically not exceeding 1000 ppm, based on the mixture, are used, so that a small amount of catalyst may remain in the product. The amount of catalyst is generally less than 1000 ppm, for example 250 ppm or less.

The alkoxylation can alternatively also be carried out by reacting the compounds of formulas IV and V with cyclic carbonates, such as ethylene carbonate.

a2) proceeding from an alkanol of formula V:

Similarly, it is also possible to alkoxylate the alkanol R ₆ OH in a known manner to obtain the polyether (Ib-1), as described in section a1) above for the aminoalcohol (II). The polyether thus obtained is then reacted with a conventional hydrogenation or amination catalyst such as Ni, Co, Cu, Fe, Pd, Pt, Ru, Rh, Re, Al, Si, Ti, Zr, Nb , A continuous process or a batch process using a catalyst comprising a catalytically active component based on a combination of Mg, Zn, Ag, Au, Os, Ir, Cr, Mo, (Ib-2) via reductive amination with ammonia, a primary amine or a secondary amine (VII). The reaction may be carried out without a solvent, or in the case of a high-viscosity polyether, in the presence of a solvent, preferably in the presence of a branched aliphatic, such as isododecane. The amine component (VII) is generally used in excess, for example, in a 2 to 100-fold excess, preferably in a 10 to 80-fold excess. The reaction is carried out at a pressure of from 10 to 600 bar for a period of from 10 minutes to 10 hours. After cooling, the catalyst is removed by filtration, excess amine component (VII) is evaporated and the reaction water is distilled azeotropically or under a stream of gentle nitrogen.

If the resulting polyether amine (Ib-2) has a primary or secondary amine functionality (R ₁ and / or R ₂ is H) then tertiary amine functionality (R ₁ and R ₂ are not H Lt; RTI ID = 0.0 > polyether < / RTI > Alkylation can generally be carried out in a known manner by reaction with an alkylating agent. All alkylating agents, generally, for example, optionally in combination with acids, include alkylene oxides, dialkyl sulfates, alkylaryl halides, alkyl halides; Aliphatic or aromatic carboxylic acid esters such as more especially dialkylcarboxylates; Alkanoate; Cyclic nonaromatic or aromatic carboxylic acid esters; Dialkyl carbonate; And mixtures thereof. The reaction for obtaining tertiary polyether amines may also be carried out by reductive amination in the presence of a reducing agent by reaction with a carbonyl compound, for example formaldehyde. Suitable reducing agents are hydrogen or formic acid in the presence of a suitable heterogeneous or homogeneous hydrogenation catalyst. The reaction can be carried out without a solvent or in the presence of a solvent. Suitable solvents are, for example, H ₂ O, alkanol, such as methanol or ethanol, or 2-ethylhexanol, aromatic solvents such as toluene, xylene or solvent mixtures of the Solvesso series or aliphatic solvents or mixtures of branched aliphatic solvents. The reaction is carried out at a temperature of 10 ° C to 300 ° C at a pressure of 1 to 600 bar for a period of 10 minutes to 10 hours. The reducing agent is used at least in stoichiometric amounts, preferably in excess amounts, especially in amounts of from 2 to 10 times.

The reaction product (polyetheramine Ib-1 or Ib-2) thus formed can theoretically be purified further or the solvent can be removed. However, in general, this is not absolutely necessary so that the reaction product can be transported to the next synthesis step, quaternization, without further purification.

b) quaternization

b1) Epoxide / acid use

To effect quatification, the reaction product or reaction mixture from step a) above is mixed with one or more epoxide compounds of formula IVa, in particular in the stoichiometric amount necessary to achieve the desired quarternization. The acid may preferably be added in a stoichiometric amount. For example, it is possible to use 0.1 to 2.0 equivalents, or 0.5 to 1.25 equivalents of quaternizing agent per quaternary tertiary nitrogen atom equivalent. More particularly, however, quaternary tertiary amine groups are quenched using approximately equimolar proportions of epoxide. Higher doses are therefore required to quaternize the secondary or primary amine groups. Suitable acids are, in particular, carboxylic acids, such as acetic acid.

Typical working temperatures are in the range of 15 to 160 캜, particularly 20 to 150 or 40 to 140 캜. The reaction time can range from a few minutes or a few hours, for example from about 10 minutes to about 24 hours. The reaction can be carried out at a pressure of about 0.1 to 20 bar, for example 1 to 10 bar. The pressure is generally determined by the vapor pressure of the alkylene oxide used at the particular reaction temperature. More particularly, an inert gas atmosphere such as nitrogen is suitable.

If necessary, the reactants are initially charged for epoxidation in a suitable organic aliphatic or aromatic solvent or mixture thereof, or there is still a sufficient proportion of the solvent derived from reaction step a). Typical examples are, for example, Solvesso series solvents, toluene or xylene. The alkanol is additionally suitable as a co-solvent or solvent mixed with the above-mentioned solvents, for example, methanol, ethanol, propanol, 2-ethylhexanol or 2-propylheptanol.

b2) Use of compound of formula IV

To effect quatification, the reaction product or reaction mixture from step a) above is mixed with at least one alkylating agent of formula (IV) in the stoichiometric amount necessary to achieve the desired quaternization. It is possible to use, for example, 0.1 to 5.0 equivalents or 0.5 to 2.0 equivalents of a quaternizing agent for each equivalent of quaternary tertiary nitrogen atoms. However, more particularly, quaternary tertiary amine groups are quenched using approximate equimolar proportions of alkylating agents. Therefore, higher doses are required to quaternize the secondary or primary amine groups. Particularly suitable quaternizing agents are methyl salicylate, dimethyl oxalate, dimethyl phthalate and dimethyl carbonate.

The reaction can optionally be accelerated by adding a catalytic amount or stoichiometric amount of the acid. Suitable acids are, for example, proton donors such as aliphatic or aromatic carboxylic acids or fatty acids. Additionally, there is suitably a Lewis acid such as boron trifluoride, ZnCl _2, MgCl _2, AlCl _3, or FeCl _3. The acid may be used in an amount of 0.01 to 50% by weight, for example, in an amount of 0.1 to 10% by weight.

In general, the temperature here is in the range of from 151 to 60 캜, particularly from 20 to 150 or 40 to 140 캜. The reaction time can range from a few minutes to several hours, for example from about 10 minutes to about 24 hours. The reaction may be carried out at a pressure of about 0.1 to 20 bar, for example 0.5 to 10 bar. More particularly, the reaction can be carried out at standard pressure. More particularly, an inert gas atmosphere such as nitrogen is suitable.

If necessary, the reactants are initially charged in a suitable aliphatic or aromatic solvent or mixture thereof for quarternization, or there is still a sufficient proportion of the solvent from reaction step a). Typical examples are, for example, Solvesso series solvents, toluene or xylene. The alkanol is additionally suitable as a cosolvent or as a solvent which is a mixture of the above-mentioned solvents, for example, methanol, ethanol, propanol, butanol, 2-ethylhexanol or 2-propylheptanol.

c) Work-up of the reaction mixture

The reaction product thus formed can theoretically be further purified or the solvent removed. This is normal but not absolutely essential, and therefore the reaction product can optionally be used as an additive after further blending with additional ingredients (see below), without further purification. In some cases, the acid used can be removed from the reaction product through filtration, neutralization or extraction. In some cases, excess amounts of alkylating agent may be removed by distillation or filtration.

B) Additional additive components

The fuel to which the quaternary additive of the present invention is added is a gasoline fuel or in particular a medium distillate fuel, especially a diesel fuel.

Fuel may include additional conventional additives to improve efficiency and / or to reduce wear.

In the case of diesel fuel, such additives include, but are not limited to, conventional detergent additives, carrier oils, low temperature flow improvers, lubricity improvers, corrosion inhibitors, demulsifiers, dehazers, defoamers, cetane improvers, Antistatic agents, metallocenes, metal deactivators, dyes and / or solvents.

In the case of gasoline fuels, such additives include, in particular, lubricity improvers (friction modifiers), corrosion inhibitors, demulsifiers, defuzzers, defoamers, combustion improvers, antioxidants or stabilizers, antistatic agents, metallocenes, metal deactivators, Dyes and / or solvents.

A typical example of a suitable auxiliary additive is listed in the following session:

B1) Detergent additive

Typical detergent additives are preferably amphoteric materials having at least one polar moiety selected from (Da) to (DI) and at least one hydrophobic hydrocarbyl radical having a number average molecular weight (Mn) of from 85 to 20 000:

(Da) a monoamino or polyamino group having not more than 6 nitrogen atoms, in which at least one nitrogen atom has a basic characteristic,

(Db) a nitro group, optionally in combination with a hydroxyl group,

(Dc) a hydroxyl group in combination with a monoamino or polyamino group having a basicity of at least one nitrogen atom,

(Dd) carboxyl group or an alkali metal or alkaline earth metal salt thereof,

(De) sulfonic acid group or its alkali metal or alkaline earth metal salt,

(Df) hydroxyl group, a monoamino or polyamino group having at least one nitrogen atom with basic character, or a polyoxy-C ₂ to C ₄ -alkylene moiety terminated by a carbamate group,

(Dg) carboxylic acid ester group,

(Dh) succinic anhydride and having hydroxyl and / or amino and / or amido and / or imido groups, and / or

(Di) moieties obtained by Mannich reaction of substituted phenols with aldehydes and monoamines or polyamines.

The hydrophobic hydrocarbyl radical in the detergent additive, which ensures adequate solubility in the fuel, has a number average molecular weight (Mn) of from 85 to 20,000, preferably from 113 to 10000, more preferably from 300 to 5000, even more preferably from 300 To 3000, even more preferably from 500 to 2500, especially from 700 to 2500, Typical hydrophobic hydrocarbyl radicals, especially those with polar moieties, have a number average molecular weight (Mn) preferably in each case of 300 to 5000, more preferably 300 to 3000, even more preferably 500 to 2500, Even more preferably from 700 to 2500, in particular from 800 to 1500, polypropenyl, polybutenyl and polyisobutenyl radicals.

Examples of the detergent additive group include the following:

The additive (Da) comprising a monoamino or polyamino group is preferably polypropylene or has a high reactivity (i.e., a predominantly double bond) with Mn = 300 to 5000, more preferably 500 to 2500, especially 700 to 2500 ) Or a polyalkenemonamine or polyalkenepolyamine based on polybutene or polyisobutene that is conventional (i.e., has mainly internal double bonds). From a polybutene which may contain up to 20% by weight of n-butene units, from hydroformylation and from ammonia, monoamines or polyamines such as dimethylaminopropylamine, ethylenediamine, diethylenetraamine, triethylenetetraamine or tetra These highly reactive polyisobutene-based additives which can be prepared by reductive amination with ethylene pentaamine are known in particular from EP-A 244 616. When polybutene or polyisobutene having predominantly internal double bonds (generally present in the? And? Positions) is used as the starting material in the preparation of the additive, possible routes of preparation are chlorination and subsequent amination or carbonyl or carboxyl compounds Oxidation of the double bond with air or ozone to produce oxygen and subsequent amination under reductive (hydrogenation) conditions. The amines used for the amination herein may be, for example, ammonia, monoamines or the abovementioned polyamines. Corresponding additives based on polypropenes are described in particular in WO-A-94/24231.

A further specific additive (Da) comprising a monoamino group is a mixture of polyisobutene with an average degree of polymerization P = 5 to 100 and a mixture of nitrogen oxides or nitrogen oxides with oxygen, as described in particular in WO-A 97/03946. Hydrogenation product of the reaction product.

A further specific additive (Da) comprising a monoamino group is obtained by reaction with an amine from a polyisobutene epoxide, as described in DE-A 196 20 262, followed by dehydration and reduction of the amino alcohol Lt; / RTI >

The nitro group-containing additive (Db), optionally in combination with a hydroxyl group, has an average degree of polymerization P = 5-100 or 10-100, as described in particular in WO-A 96/03367 and WO-A 96/03479 Is preferably a reaction product of polyisobutene and a mixture of nitrogen oxide or nitrogen oxide and oxygen. This reaction product is generally prepared by reacting a hydroxy nitropolyisobutene (for example,? -Nitro-? -Hydroxypolyisobutene (for example,?,? - dihydroxypolyisobutene) mixed with pure nitropolyisobutene Tungsten).

The additive (Dc) comprising a hydroxyl group in combination with a monoamino or polyamino group preferably has a terminal double bond, as described in particular in EP-A-476 485, and has Mn = 300 to 5000 A reaction product of a polyisobutene epoxide obtained from polyisobutene with ammonia or a monoamine or polyamine.

The additive (Dd) containing a carboxyl group or an alkali metal or alkaline earth metal salt thereof has a total molar mass of 500 to 20,000, and a part or all of the carboxyl groups are converted into an alkali metal or alkaline earth metal salt, It is preferred that the copolymer is a copolymer of maleic anhydride and a C ₂ to C ₄₀ -olefin, with any of the residues being reacted with an alcohol or an amine. Such additives are described in particular by EP-A 307 815. Such additives act primarily to prevent valve seat wear and may be used in combination with conventional fuel detergents such as poly (iso) butene amines or polyether amines, as described in WO-A 87/01126. Can be advantageously used in combination.

The additive (De) comprising a sulfonic acid group or an alkali metal or alkaline earth metal salt thereof is preferably an alkali metal or alkaline earth metal salt of an alkyl sulfosuccinate, especially as described by EP-A 639 632. Such additives act primarily to prevent valve seat wear and can be advantageously used in combination with conventional fuel detergents such as poly (iso) butene amines or polyether amines.

The additive (Df) comprising a polyoxy-C ₂ -C ₄ -alkylene moiety is preferably a C ₂ - to C ₆₀ -alkanol, a C ₆ - to C ₃₀ -alkanediol, a 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 hydroxyl and / or propylene oxide per amino group And / or a butylene oxide, and in the case of a polyetheramine, a polyether or polyetheramine obtainable by subsequent reductive amination reaction with ammonia, monoamine or polyamine. Such products are described in particular in EP-A 310 875, EP-A 356 725, EP-A 700 985 and US-A 4 877 416. In the case of polyethers, these products also have carrier oil properties. Typical examples of these are the corresponding reaction products with tridecanolbutoxylate, isotridecanolbutoxylate, isononylphenol butoxylate and polyisobutanol butoxylate and propoxylate and also with ammonia.

The additive (Dg) comprising a carboxylic acid ester group is preferably an ester of a mono-, di- or tri-carboxylic acid with a long-chain alkanol or polyol, in particular as described in DE-A 38 38 918, And have a minimum viscosity of 2 mm ² / s at 100 ° C. The mono-, di- or tri-carboxylic acids used may be aliphatic or aromatic acids, and particularly suitable ester alcohols or ester polyols are, for example, long chain representatives having 6 to 24 carbon atoms. Typical examples of esters are adipates, phthalates, isophthalates, terephthalates and trimellitates of isooctanol, isononanol, isodecanol and isotridecanol. Such products also have carrier oil properties.

The additive (Dh) derived from succinic anhydride and comprising hydroxyl and / or amino and / or amido and / or a moiety having especially an imido group is preferably Mn = preferably 300 to 5000, The polyisobutene, which is a typical or highly reactive polyisobutene having a molecular weight of from 300 to 3000, even more preferably from 500 to 2500, even more preferably from 700 to 2500, especially from 800 to 1500, Or the corresponding derivatives of alkyl- or alkenyl-substituted succinic anhydrides, in particular polyisobutenyl succinic anhydrides, which are obtainable by reacting via chlorinated polyisobutene. The moieties having hydroxyl and / or amino and / or amido and / or imido groups are, for example, acid amides of diamines or polyamines having also free amine groups in addition to carboxylic acid groups, acid amides, A succinic acid derivative having an acid and an amide functional group, a carboximide having a monoamine, a carboximide having a diamine or a polyamine having a free amine group in addition to the imide functional group, or a diisocyanate derivative having a di There is Mead. However, already in the presence of moiety D (h), the additional detergent additive in the context of the present invention uses only up to 100% by weight of the compound having a betaine structure. Such fuel additives are general knowledge and are described, for example, in documents (1) and (2). It is preferably the reaction product of an alkyl- or alkenyl-substituted succinic acid or derivative thereof with an amine, more preferably a polyisobutenyl-substituted succinic acid or derivative thereof and an amine. Of particular importance in this context are aliphatic polyamines (polyalkyleneimines) having an imide structure such as, for example, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine and hexaethyleneheptamine ≪ / RTI >

An additive (Di) comprising a moiety obtained by the Mannich reaction of a substituted phenol with an aldehyde and a monoamine or polyamine is prepared by reacting a polyisobutene-substituted phenol with formaldehyde and a monoamine or polyamine such as ethylene diamine, diethylene Triamine, triethylenetetramine, tetraethylenepentamine or dimethylaminopropylamine in the presence of a base. The polyisobutenyl-substituted phenol may be derived from conventional or highly reactive polyisobutene having Mn = 300-5000. Such "polyisobutene mannich base" is described in particular in EP-A 831 141.

One or more of the detergent additives mentioned may be added to the fuel in an amount such that the capacity of these detergent additives is preferably from 50 to 2500 ppm by weight, in particular from 75 to 1500 ppm by weight, in particular from 150 to 1000 ppm by weight.

B2) Carrier oil

Additional used carrier oils may have mineral or synthetic properties. Suitable mineral carrier oils are fractions obtained in the crude oil treatment process, such as brightstocks or base oils having a viscosity, for example a viscosity in the range of 500 to 2000 SN, and also aromatic hydrocarbons, paraffinic hydrocarbons and alkoxyalkanols . Likewise useful are mineral oils which are obtained during refining of mineral oils and which have a boiling range of from about 360 to about < RTI ID = 0.0 > "hydrocrack oil" (contact hydrogenated, Lt; RTI ID = 0.0 > 500 C < / RTI > Also suitable are mixtures of the abovementioned mineral carrier oils.

Examples of suitable synthetic carrier oils include, but are not limited to, polyolefins (polyalphaolefins or polyinteral olefins), (poly) esters, (poly) alkoxylates, polyethers, aliphatic polyether-amines, alkylphenol- Carboxylic acid esters of the polyether amines and long chain alkanols disclosed.

Examples of suitable polyolefins are those based on olefin polymers with Mn = 400 to 1800, in particular polybutene or polyisobutene (hydrogenated or unhydrased).

Examples of suitable polyesters or polyetheramines include C ₂ - to C ₆₀ -alkanols, C ₆ - to C ₃₀ -alkanediol, mono- or di-C _2- to C ₃₀ -alkylamines, C ₁ - to C ₃₀ -alkylcyclohexanol or C ₁ - to C ₃₀ -alkylphenol is reacted 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 polyetheramine, Preferred are the compounds comprising polyoxy-C ₂ - to C ₄ -alkylene moieties obtainable by subsequent reductive amination with ammonia, monoamines or polyamines. Such products are described in particular in EP-A 310 875, EP-A 356 725, EP-A 700 985 and US-A 4,877,416. For example, the polyetheramine used may be a poly-C ₂ - to C ₆ -alkylene oxide amine or a functional derivative thereof. Typical examples thereof include the corresponding reaction products with tridecanolbutoxylate or isotridecanolbutoxylate, isononylphenol butoxylate and also with polyisobutanol butoxylate and propoxylate, also with ammonia.

Examples of carboxylic acid esters of long-chain alkanols are in particular the esters of long-chain alkanols or polyols with mono-, di- or tri-carboxylic acids as described in DE-A 38 38 918. The mono-, di- or tri-carboxylic acid used may be an aliphatic or aromatic acid, and suitable ester alcohols or polyols are, for example, long chain representatives having, for example, from 6 to 24 carbon atoms. Typical typical examples of esters include adipates, phthalates, isophthalates, terephthalates and trimethylates of isooctanol, isononanol, isodecanol and isotridecanol, such as di (n- or i-iso-tri Decyl) phthalate.

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

Particularly suitable synthetic carrier oils are, for example, from about 5 to 35, preferably from about 5 to 30, per molecule of alcohol, selected from, for example, propylene oxide, n-butylene oxide and isobutylene oxide units, , More preferably from 10 to 30, in particular from 15 to 30, C ₃ - to C ₆ -alkylene oxide units. Non-limiting examples of suitable initiator alcohols include long-chain alkanols or phenols substituted by long-chain alkyls, wherein the long-chain alkyl radicals are in particular straight-chain or branched C ₆ - to C ₁₈ -alkyl radicals. Specific examples include tridecanol and nonylphenol. Particularly preferred alcohol-initiated polyethers are the reaction products (polyetherated products) of monovalent aliphatic C ₆ - to C ₁₈ -alcohols with C ₃ - to C ₆ -alkylene oxides. Examples of monovalent aliphatic C ₆ -C ₁₈ -alcohols are hexanol, heptanol, octanol, 2-ethylhexanol, nonyl alcohol, decanol, 3-propylheptanol, undecanol, dodecanol, Tetradecanol, pentadecanol, hexadecanol, octadecanol, and their structures and positional isomers. The alcohol may be used in the form of pure isomers or in the form of a technical grade mixture. A particularly preferred alcohol is tridecanol. Examples of the C ₃ - to C ₆ -alkylene oxides include 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. Particularly preferred among these are C ₃ - to C ₄ -alkylene oxides, i.e., 1,2-propylene oxide and butylene oxide such as 1,2-butylene oxide, 2,3-butylene oxide and isobutylene oxide . In particular, butylene oxide is used.

Further suitable synthetic carrier oils are the alkoxylated alkyl phenols as described in DE-A 10 102 913.

Specific carrier oils include synthetic carrier oils, particularly preferred are the alcohol-initiated polyethers described above.

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

B3) Low temperature fluidity improver

Suitable low temperature flow improvers are in principle all organic compounds capable of improving the flow performance of middle distillate or diesel fuel under low temperature conditions. For the intended purpose, the remedy must have sufficient oil solubility. In particular, the low temperature flow improvers useful for this purpose are low temperature flow improvers (mid oil flow improvers, MDFI) typically used in the case of intermediate fuels of fossil origin, i.e. in the case of conventional mineral diesel fuel. However, it is also possible to use organic compounds which, when used in conventional diesel fuel, have, in part or in principle, the properties of a wax anti-settling additive (WASA). The modifiers may also act partially or mainly as nucleating agents. However, it is also possible to use mixtures of organic compounds which are effective as MDFI and / or effective as WASA and / or effective as nucleating agents.

Low temperature flow improvers are typically selected from (K1) to (K6) below:

(K1) C ₂ - to C ₄₀ - and one or more olefin copolymer of ethylenically unsaturated monomers,

(K2) comb polymers,

(K3) polyoxyalkylene,

(K4) polar nitrogen compound,

(K5) sulfocarboxylic acid or sulfonic acid or derivative thereof, and

(K6) poly (meth) acrylic acid ester.

It is possible to use a mixture of different representatives of one of the specific classes (K1) to (K6) or a mixture of representatives of different classes (K) to (K6).

The C ₂ - to C ₄₀ -olefin monomers suitable for the copolymer of class (K 1) have, for example, from 2 to 20 carbon atoms, in particular from 2 to 10 carbon atoms, and from 1 to 3 carbon- One or two, especially those having one carbon-carbon double bond. In the latter case, the carbon-carbon double bond may be end-aligned or (alpha-olefin) or internally arranged. However, preferred are? -Olefins, more preferably? -Olefins having 2 to 6 carbon atoms, such as propene, 1-butene, 1-pentene, 1-hexene and in particular ethylene.

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

When additional olefins are also polymerized, the olefins are preferably of higher molecular weight than the olefin-based monomers mentioned above. For example, when the olefin-based monomer using ethylene or propenyl, more suitable olefins in particular C ₁₀ - to C4 is ₀ -α- olefin. Additional olefins are, in most cases, only additionally copolymerized when a monomer having a carboxylic acid ester functionality is also used.

Suitable (meth) acrylic esters include, for example, (meth) acrylic acid and C ₁ - to C ₂₀ -alkanols, in particular C ₁ - to C ₁₀ -alkanols, in particular methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, pentanol, hexanol, heptanol, octanol, 2-ethylhexanol, nonanol and decanol, and their structural isomers.

Suitable alkenylcarboxylates include C ₂ - to C ₁₄ -alkylene esters of carboxylic acids with, for example, ₂ to 21 carbon atoms, the hydrocarbyl radicals of which may be linear or branched, such as vinyl And propenyl esters. Of these, vinyl esters are particularly preferable. Of the carboxylic acids having a branched hydrocarbyl radical, particularly preferred are those in which the branch is at the? -Position of the carboxyl group, more preferably those having the? -Carbon atom tertiary, namely the carboxylic acid termed neocarboxylic acid . However, the hydrocarbyl radical of the carboxylic acid is preferably linear.

Examples of suitable alkenylcarboxylates include 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 highly preferred alkenylcarboxylate is vinyl acetate, and the resulting copolymer of the (K1) family is the ethylene vinyl acetate copolymer ("EVA"), which is one of the most commonly used. Very advantageously usable ethylene-vinyl acetate copolymers and their preparation are described in WO 99/29748.

Suitable copolymers of class (Kl) are also those which comprise, in copolymerized form, two or more different alkenyl carboxylates differing in alkenyl functionality and / or carboxylic acid groups. Likewise, copolymers comprising not only alkenyl carboxylate (s) but also one or more olefins and / or one or more (meth) acrylic acid esters in copolymerized form are suitable.

C ₂ - to C ₄₀ - α-olefins, ethylenically unsaturated monocarboxylic acids C ₁ - to C ₂₀ -alkyl esters having 3 to 15 carbon atoms and saturated monocarboxylic acids having 2 to 21 carbon atoms Ternary polymers of C ₂ - to C ₁₄ -alkenyl esters are also suitable as copolymers of class (K1). Ternary copolymers of this type are described in WO 2005/054314. Typical ternary copolymers of this type are formed from ethylene, 2-ethylhexyl acrylate and vinyl acetate.

1 or more or further ethylenically unsaturated monomer (s) is present in the copolymer of class (K1), preferably from 1 to 50% by weight, in particular from 10 to 45% by weight, in particular from 20 to 40% by weight, based on the total copolymer Lt; / RTI > Thus, the main proportion in terms of the weight of the monomer units in the copolymer of class K1 is generally derived from C ₂ to C ₄₀ base olefins.

The copolymer of the class (K1) preferably has a number average molecular weight Mn of 1,000 to 20,000, more preferably 1,000 to 10,000, and particularly 1,000 to 8,000.

A typical comb polymer of component (K2) is prepared by copolymerizing maleic anhydride or fumaric acid with another ethylenically unsaturated monomer, for example an alpha-olefin or unsaturated ester, such as vinyl acetate, and converting the anhydride or acid functionality to carbon Can be obtained by subsequent esterification with an alcohol having a valence of 10 or more. Additional suitable comb polymers include copolymers of alpha-olefins and esterified comonomers, for example, styrene copolymers of styrene and maleic anhydride, or esterified copolymers of styrene and fumaric acid. A suitable comb polymer may also be a poly fumarate or a poly maleate. Homopolymers or copolymers of vinyl ethers are also suitable comonomers. Com polymers suitable as components of class (K2) are described, for example, in WO 2004/035715 and in Comb-Like Polymers. Structure and Properties, N. A. Plate and V. P. Shibaev, J. Poly. Sci. Macromolecular Revs. 8, pages 117 to 253 (1974)]. Mixtures of comb polymers are also suitable.

Suitable polyoxyalkylene as a component of class (K3) are, for example, polyoxyalkylene esters, polyoxyalkylene ethers, mixed polyoxyalkylene esters / ethers and mixtures thereof. Such a polyoxyalkylene compound preferably includes a polyoxyalkylene group having a number average molecular weight of 5,000 or less and at least one linear alkyl group, preferably 2 or more linear alkyl groups, each having 10 to 30 carbon atoms. Such polyoxyalkylene compounds are described, for example, in EP-A 061 895 and also in US 4,491,455. Specific polyoxyalkylene compounds are based on polyethylene glycol and polypropylene glycol having a number average molecular weight of 100 to 5000. In addition, suitable are fatty acids with 10 to 30 carbon atoms, such as stearic acid or polyoxyalkylene monoesters or diesters of behenic acid.

The polar nitrogen compound suitable as a component of class K4 may be ionic or nonionic and is preferably in the form of a tertiary nitrogen atom of the formula > NR ^{7 wherein} R ₇ is a C ₈ - to C ₄₀ -hydrocarbon radical And has at least one substituent, particularly at least two substituents. The nitrogen substituent may also be quatemized, i. E. May be present in a cationic form. Examples of such nitrogen compounds include ammonium salts and / or amides obtainable by reacting at least one amine substituted by at least one hydrocarbyl radical with a carboxylic acid having from 1 to 4 carboxyl groups, or a suitable derivative thereof have. Include alkyl radicals amine is preferably one or more C ₈ - to C _40. Suitable primary amines for preparing the above-mentioned polar nitrogen compounds are, for example, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tetradecylamine and higher-grade linear analogues. Suitable secondary amines for this purpose include, for example, dioctadecylamine and methylbehenylamine. Also suitable for this purpose is a mixture of amines, such as an amine mixture obtainable on an industrial scale, such as, for example, fats and oils, as described in Ullmann's Encyclopedia of Industrial Chemistry, 6th Edition, "Amines, aliphatic & Amine or hydrogenated tollamine. Suitable acids for the reaction include, for example, cyclohexane-1,2-dicarboxylic acid, cyclohexene-1,2-dicarboxylic acid, cyclopentane-1,2-dicarboxylic acid, Dicarboxylic acid, naphthalene dicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, and succinic acid.

Specifically, the component of class (K4) is an oil soluble reaction product of a primary or secondary amine and a poly (C ₂ - to C ₂₀ -carboxylic acid) having at least one tertiary amino group. The poly (C ₂ - to C ₂₀ -carboxylic acid) having at least one tertiary amino group and forming the basis of the reaction product preferably has 3 or more carboxyl groups, especially 3 to 12, in particular 3 to 5 And a carboxyl group. The carboxylic acid unit in the polycarboxylic acid is preferably 2 to 10 carbon atoms, particularly acetic acid unit. The carboxylic acid unit is suitably bonded to the polycarboxylic acid, generally via at least one carbon and / or nitrogen atom. In the case of a plurality of nitrogen atoms, the unit is preferably bonded to a tertiary nitrogen atom bonded through a hydrocarbon chain.

The component of class K4 is preferably an oil soluble reaction product based on a poly ((C ₂ - to C ₂₀ -carboxylic acid) having at least one tertiary amino group and having the formula (IIa) or (IIb)

Wherein the variable A is a straight or branched C ₂ - to C ₆ -alkylene group or a moiety of the formula III:

Here, variable B is a C ₁ - to C ₁₉ -alkylene group. Compounds of general formula (IIa) and (IIb) have particular WASA characteristics.

In addition, the preferred oil solubility reaction products of component (K4), particularly those of general formulas (IIa) and (IIb), are amides, amide-ammonium salts or ammonium salts wherein no more than one carboxylic acid group is converted to an amide group.

Examples of the linear or branched C ₂ - to C ₆ -alkylene group of the variable A include 1,1-ethylene, 1,2-propylene, 1,3-propylene, 1,2-butylene, 1,3-propylene, 1,5-pentylene, 2-methyl-2,4-butylene, 2,2-dimethyl- Propylene, 1,6-hexylene (hexamethylene), especially 1,2-ethylene. The variable A preferably contains 2 to 4, in particular 2 or 3, carbon atoms.

Examples of the C ₁ - to C ₁₉ -alkylene group of the variable B include 1,2-ethylene, 1,3-propylene, 1,4-butylene, hexamethylene, octamethylene, decamethylene, Tetradecamethylene, hexadecamethylene, octadecamethylene, nonadecamethylene, in particular methylene. Variable B preferably comprises 1 to 10, in particular 1 to 4, carbon atoms.

The primary and secondary amines as reaction partners for the polycarboxylic acid to form component (K4) are typically monoamines, especially aliphatic monoamines. These primary and secondary amines may be selected from a plurality of amines having hydrocarbon radicals which may be optionally bonded to one another.

Component parent amines of the oil-soluble reaction product of (K4) is usually a secondary amine, and the two variables R ⁸ are each independently a straight or branched C ₁₀ - to C ₃₀ - alkyl radical, in particular C ₁₄ - to C (R < ⁸ >) _2, which is a ₂₄ -alkyl radical. Such relatively long chain alkyl radicals are preferably straight-chain or only slightly branched. In general, the secondary amines mentioned are derived from naturally occurring fatty acids and their derivatives, for relatively long chain alkyl radicals. The two R < ⁸ > radicals are preferably the same.

The secondary amine mentioned can be bonded to the polycarboxylic acid by an amide structure or in the form of an ammonium salt. It is also possible that only a portion is present as an amide structure and the other portion is present as an ammonium salt. Preferably, there is only a small number of free acid groups. The oil solubility reaction product of component (K4) is preferably all in the form of an amide structure.

Typical examples of such a component (K4) are nitrilotriacetic acid, ethylenediaminetetraacetic acid or propylene-1,2-diamine tetraacetic acid and in each case 0.5 to 1.5 mol per carboxyl group, in particular 0.8 to 1.2 mol per carboxyl group Of dioleoylamine, dipallitine amine, dicoconet fatty amine, distearyl amine, dibehenyl amine or especially dithalaur fatty amine. A particularly preferred component (K4) is the reaction product of 1 mole of ethylenediaminetetraacetic acid with 4 moles of hydrogenated ditallow lower fatty amine.

Additional typical examples of the component (K4) include N, N-dialkylammonium salts of 2-N ', N'-dialkylamidobenzoates, such as 1 mol of phthalic anhydride and 2 mol of ditallow The reaction product of the reaction product (wherein the latter is hydrogenated or unhydrogenated) and 1 mol of alkenyl pyrobislactone and 2 mol of a dialkylamine, such as ditallow and / or tallow fatty amine, wherein , And the latter two are hydrogenated or unhydrogenated).

Additional exemplary structural types for the components of class (K4) include, as described in WO 93/18115, cyclic compounds having tertiary amino groups or condensation of carboxylic acid containing polymers with long chain primary or secondary amines There is water.

Suitable sulfocarboxylic acids, sulfonic acids or their derivatives as low temperature fluidity improvers of class (K5) include, for example, oil soluble carboxamides and ortho-sulfonic acids, as described in EP-A 261 957 Carboxylic acid esters wherein the sulfonic acid functionality is present as a sulfonate having an alkyl-substituted ammonium cation.

Poly (meth) acrylic acid esters suitable as low temperature fluidity improvers of class (K6) include homopolymers or copolymers of acrylic acid and methacrylic acid esters. Preferred are copolymers of two or more different (meth) acrylic acid esters, different for esterified alcohols. The copolymer optionally contains another different olefinically unsaturated monomer in copolymerized form. The weight average molecular weight of the polymer is preferably 50,000 to 500,000. Particularly preferred polymers are copolymers of methacrylic acid and methacrylic acid esters of saturated C ₁₄ and C ₁₅ alcohols, and the acid groups are neutralized with hydrogenated tol amine. Suitable poly (meth) acrylic esters are described, for example, in WO 00/44857.

The low temperature flow improvers or mixtures of different low temperature flow improvers are added to the intermediate oil fuels or the diesel fuel in an amount of preferably from 10 to 5000 ppm by weight, more preferably from 20 to 2000 ppm by weight, even more preferably from 50 to 1000 ppm by weight, 100 to 700 ppm by weight, for example, 200 to 500 ppm by weight.

B4) Lubricant improving agent

Suitable lubricity improvers or friction modifiers are typically based on fatty acids or fatty acid esters. Typical examples are, for example, tol oil fatty acids, such as those described in WO 98/004656, and glyceryl monooleate. The reaction products of natural or synthetic oils, such as triglycerides and alkanolamines, described in US 6 743 266 B2 are also suitable as such lubricity improving agents.

B5) Corrosion inhibitor

Suitable corrosion inhibitors include, for example, succinic acid esters, especially with polyols, fatty acid derivatives such as oleic acid esters, oligomerized fatty acids, substituted ethanolamines, and RC 4801 (Rhein Chemie, Mannheim, Germany) or HiTEC 536 (Ethyl Corporation).

B6)

Suitable anti-oiling agents include, for example, alkali metal or alkaline earth metal salts of alkyl-substituted phenol- and naphthalene-sulfonates, and alkali metal or alkaline earth metal salts of fatty acids and also neutral compounds such as alcohol alkoxylates, For example, condensation products of alcohol ethoxylates, phenol alkoxylates such as tert-butyl phenol ethoxylate or tert-pentyl phenol epoxylate, fatty acids, alkyl phenols, ethylene oxide (EO) and propylene oxide (PO) , For example in the form of BP / PO block copolymers, polyethylene imines or other polysiloxanes.

B7) De Heiser

Suitable dehydizers are, for example, products available under alkoxylated phenol-formaldehyde condensates such as NALCO 7D07 (Nalco) and TOLAD 2683 (Petrolite).

B8) Defoamer

Suitable defoamers include, for example, polyether-modified polysiloxanes such as those available under the trade names TEGOPREN 5851 (Goldschmidt), Q25907 (Dow Corning) and RHODOSIL (Rhone Poulenc).

B9) Cetane improvement agent

Suitable cetane chelating agents include, for example, fatty acid nitrates such as 2-ethylhexyl nitrate and cyclohexyl nitrate and peroxides such as di-tert-butyl peroxide.

B10) Antioxidant

Suitable antioxidants include, for example, substituted phenols such as 2,6-di-tert-butyrenol and 6-di-tert-butyl-3-methylphenol and also phenylenediamines such as N, -sec-butyl-p-phenylenediamine.

B11) Metal deactivating agent

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

B12) Solvent

Suitable solvents include, for example, nonpolar organic solvents such as aromatic and aliphatic hydrocarbons such as toluene, xylene, white spirit and products sold under the trade names SHELLSOL (Royal Dutch / Shell Group) and EXXSOL (ExxonMobil) Organic solvents such as alcohols such as 2-ethylhexanol, decanol and isotridecanol. Such solvents are generally added to the diesel fuel with the above-mentioned additives and auxiliary additives, which are intended to be dissolved or diluted for good handling.

C) Fuel

The additives of the present invention are exceptionally suitable as fuel additives and can in principle be used for all fuels. This in principle leads to all the beneficial effects of the series on the operation of the internal combustion engine by the fuel.

Thus, the present invention also relates to quaternized (quaternized) quaternary ammonium salts of the present invention which are effective as additives for achieving beneficial effects in the operation of internal combustion engines, such as diesel engines, in particular diesel engines with direct injection diesel engines, Provides a fuel having an additive content, in particular a mid-oil fuel. This effective content (capacity) 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, in particular from 30 to 750 ppm by weight, based on the total amount of fuel in each case.

Mid-oil fuels, such as diesel fuel or heating oil, are preferably mineral oil raffinate, typically having a boiling range of 100 to 400 占 폚. These are generally distillates with a 95% point to a temperature of 360 ° C or much higher. They may also be characterized, for example, by a sulfur content of less than or equal to 95% and a sulfur content of less than or equal to 0.005 wt%, or a sulfur content of less than or equal to 0.001 wt% It can be called "ultra low sulfur diesel" or "city diesel". In addition to mineral intermediate oil fuels or diesel fuels obtained by refining, what can be obtained by coal gasification or gas liquefaction ["GTL (gas to liquid)" fuels] or biomass liquefaction ["BTL (biomass to liquid) fuel is also suitable. Also suitable are mixtures of the abovementioned intermediate oil fuels or diesel fuels with renewable fuels such as biodiesel or bioethanol.

The quality of heating oil and diesel fuel can be measured, for example, according to DIN 51603 and EN 590 [also: Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, Volume A 12, p. 617 ff. Reference].

In addition to its use in the above-mentioned intermediate oil fuels of fossil, plant or animal origin, which are substantially hydrocarbon mixtures, the quaternized additives of the present invention can also be used in mixtures of such intermediate oils with biofuel oils (biodiesel) . Such mixtures are also encompassed by the term " intermediate oil fuel "in the context of the present invention. It is commercially available and typically contains a small amount of biofuel, typically from 1 to 30% by weight, in particular from 3 to 10% by weight, based on the total amount of fossil, vegetable or animal origin, .

Biodiesel oils are generally based on fatty esters, preferably alkyl esters of fatty acids derived from substantially vegetable and / or animal oils and / or fats. Alkyl esters are typically understood to mean lower alkyl esters, in particular C ₁ -C ₄ -alkyl esters, which are obtained by reacting glycerides, especially triglycerides, occurring in vegetable and / or animal oils and / or fats with lower alcohols, For example, by transesterification with ethanol or especially methanol ("FAME"). Typical lower alkyl esters based on vegetable and / or animal oils and / or fats found to find use as biofuel oils or their components include, for example, sunflower methyl ester, palm oil methyl ester ("PME &("SME") and especially rapeseed oil methyl ester ("RME").

Mid-oil fuels or diesel fuels are preferably those having a low sulfur content, i.e., those having a sulfur content of less than 0.05 wt%, preferably less than 0.02 wt%, more preferably less than 0.005 wt%, especially less than 0.001 wt%.

Useful gasoline fuels include all commercially available gasoline fuel compositions. One exemplary representative that may be mentioned herein is Eurosuper base fuel according to EN 228, which is customary on the market. In addition, the gasoline fuel composition of the specification according to WO 00/47698 is also usable in the present invention.

The quaternization additive of the present invention is particularly suitable as a fuel additive for fuel compositions, especially diesel fuel, to overcome the problems summarized in the direct injection diesel engine, especially for direct injection diesel engines with a common rail injection system.

Hereinafter, the present invention will be described in detail with reference to the following embodiments. The test methods described herein are not limited to any particular embodiment but are part of the general disclosure of the detailed description and can be used in the context of the present invention in general.

Experiment section:

A. General test methods

1. XUD9 test - Flow restriction measurement

This procedure followed the standard conditions of CEC F-23-1-01.

2. DW10 Test - Measuring Output Loss Due to Injector Deposition in Common Rail Diesel Engines

2.1. DW10-KC - Purification Maintenance Test

The cleanup maintenance test is based on CEC test procedure F-098-08 Issue 5. This is done using the same CEC procedure and the same test setup and engine type (PEUGEOT DW10).

Variations and Singularities:

In the test, a cleaned sprayer was used. 10% super-decotamine (Brussels Material, Intersciences), the cleaning time in the ultrasonic bath was 4 hours.

Test run time:

The test run time was 12 hours without stopper. As shown in Fig. 2, the 1-hour test cycle from CEC F-098-08 was continued 12 times.

Performance measurement:

Initial output P0, KC [kW] was calculated from the torque measured at 4000 / min full load immediately after the start of the test and the engine warmed up. The procedure is described in issue 5 of the test procedure (CEC F-98-08). This was done using the same test setup and the PEUGEOT DW10 engine type.

The final performance (P _end , KC) is measured in the twelfth cycle of 12 steps (see the table of FIG. 2). Here, the working point is also a full load of 4000 / min. P _Final , KC [kW] is calculated from the measured torque.

In the KC test, the output loss is calculated as follows:

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. This procedure is described in issue 5 of the test procedure (CEC F-98-08). This is done using the same test setup and the PEUGEOT DW10 engine type.

The DU-CU test consists of two consecutive individual tests. A first test is provided for deposition (DU), and a second test is for removing deposit (CU). After DU, the output loss is measured. DU After termination of operation, the engine is not operated for more than 8 hours and is cooled to ambient temperature. Next, the CU is started without distillation and injector cleaning using CU fuel. Deposits and power losses are ideally reduced during the CU test procedure.

Variations and Singularities:

The cleaned injector was mounted on the engine before each DU test. The cleaning time in an ultrasonic water bath at 60 ° C with water + 10% Super Deco Amine (Intersciences, Brussels) was 4 hours.

Test run time:

The test execution time is 12 hours for DU and 12 hours for CU. The engine operated at DU and CU tests without stopper.

The one-hour test period from CEC F-098-08, shown in Figure 2, lasted twelve times in each case.

Performance measurement:

Initial output P0, du [kW] is calculated from the torque measured at 4000 / min full load immediately after the start of the test and the engine is warm. This procedure is described in issue 5 of the test procedure.

The final performance (P _final , du) is measured in the twelfth cycle of 12 steps (see table above). Here, the driving point is a full load of 4000 / min. P _Final , du [kW] is calculated from the measured torque.

The output loss at DU is measured as follows:

Purification degree

The initial output P0, cu [kW] is calculated from the torque measured at 4000 / min full load immediately after the test is started and the engine is hot in the CU. The procedure is described in issue 5 of the test procedure.

The final performance (P _final , cu) is measured in the twelfth cycle of 12 steps (see the table of FIG. 2). Here, the driving point is a full load of 4000 / min. P _final , cu [kW] is calculated from the measured torque.

In the CU test, the output loss is calculated as follows (a negative value for the output loss in the CU test means improved performance):

The fuel used is diesel fuel commercially available from Haltermann (RF-06-03). In order to artificially induce formation of deposits in the injector, 1 weight ppm zinc was added to the injector in the form of zinc didodecanoate solution.

3. IDID Test - Measuring Additive Effect on Internal Sprayer Deposits

The formation of deposits in the injector is characterized by the exhaust gas temperature deviation of the cylinders at the cylinder exit at cold start of the EW10 engine.

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

The test was performed as a contamination degree cleanliness test (DU-CU).

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

The DU-CU test consists of two separate tests running continuously. A first test is provided for deposit formation (DU), and a second test is run for deposit removal (CU).

After the DU run, after the remaining time of at least 8 hours, cold start of the engine is performed and idling is followed for 10 minutes.

The CU is then used to start CU without distillation and injector cleaning. After performing the CU for 8 hours, the cold start of the engine is performed after the remaining time of at least 8 hours, followed by idling for 10 minutes. du and CU, the temperature profiles for the individual cylinders are compared and evaluated.

The IDID test implies the formation of internal deposits in the injector. The characteristic used in this test is the exhaust gas temperature of the individual cylinders. In the IDID-less injector system, the exhaust gas temperature of the cylinder rises uniformly. In the presence of the IDID, the temperature of the exhaust gas of the individual cylinders does not rise uniformly but deviates from each other.

The temperature sensor is located beyond the cylinder head outlet in the exhaust manifold. Significant variation in the individual cylinder temperature (e.g., > 20 ° C) implies the presence of internal injector deposits (IDID).

The tests (DU and CU) are performed with an execution time of 8 hours each. The one-hour test cycle from CEC F-098-08 runs eight times in each case. For individual cylinder temperature deviations above 45 ° C at the average for all four cylinders, the test is initially stopped.

B. Preparation Example and Analysis Example:

Reactants used:

N, N-dimethylethanolamine CAS. 108-01-0 BASF Products

1,2-propylene oxide CAS. 75-56-9 BASF Products

1,2-butylene oxide CAS. 106-88-7 BASF Products

Potassium tert-butoxide CAS. 865-47-4 Aldrich products

Dimethyl oxalate CAS. 553-90-2 Aldrich products

Heavy naphtha solvent CAS. 64742-94-5 Exxon Mobile Products

Styrene oxide CAS. 96-09-3 Aldrich Products

2-ethylhexanol CAS. 104-76-7 BASF Products

Lauric acid CAS. 143-07-7 Aldrich Products

Isotridecanol N CAS. 27458-92-0 BASF products

Acetic acid, pure CAS. 64-19-7 Aldrich products

Formic acid, 85% of H ₂ O CAS 64-18-6 Kraft products

Formalin, 36.5% CAS 50-00-0 Aldrich products

The polydispersity (D) was measured by gel permeation chromatography.

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

In a 2 L autoclave, N, N-dimethylethanolamine (76.7 g) was mixed with potassium tert-butoxide (4.1 g). The autoclave was purged with N ₂ three times, an N ₂ feed pressure of about 1.3 bar was established and the temperature was raised to 130 ° C. While 1,2-propylene oxide (750 g) was metered in for 10 hours, the temperature was maintained at 129 ° C-131 ° C. After 6 hours, the mixture was stirred at 130 ℃, and a N ₂ purge, cooled to 60 ℃, emptied the reactor. Excess propylene oxide was removed under reduced pressure on a rotary evaporator. The basic crude product was neutralized using commercially available magnesium silicate and then filtered off. 831 g of the product in the form of an orange oil were thus obtained (TBN 58.1 mg KOH / g; D 1.16).

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

In a 2 L autoclave, N, N-dimethylethanolamine (47.1 g) was mixed with potassium tert-butoxide (5.0 g). The autoclave was purged 3 times with N ₂ , N ₂ feed pressure of about 1.3 bar was established and the temperature was raised to 140 ° C. 1,2-butylene oxide (953 g) was metered in for 9 hours to maintain the temperature at 138-141 占 폚. Was then stirred for 6 hours at 140 ℃ and purged, and cooled to 60 ℃ in N ₂ was emptied and the reactor. Excess butylene oxide was removed under reduced pressure on a rotary evaporator. The basic crude product was neutralized with commercially available magnesium silicate, which was then filtered off. 1000 g of product in the form of a yellow oil were obtained (TBN 28.1 mg KOH / g; D 1.12).

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

The polyetheramine (A) (250 g) of Synthesis Example 1 was mixed with dimethyl oxalate (59 g) and lauric acid (12.5 g) and the reaction mixture was stirred for 4 hours at a temperature of 120 ° C. The excess amount of dimethyl oxalate was then removed at 120 DEG C on a rotary evaporator under reduced pressure (p = 5 mbar). 290 g of product were thus obtained. ¹ H NMR analysis of the quaternized polyetheramine thus obtained confirmed quaternization.

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

The polyetheramine (B) (250 g) of Synthesis Example 2 was mixed with dimethyl oxalate (67.3 g) and lauric acid (6.2 g) and the reaction mixture was stirred at a temperature of 120 ° C for 4.5 hours. The excess amount of dimethyl oxalate was then removed at 120 DEG C on a rotary evaporator under reduced pressure (p = 5 mbar). Thus, 270 g of product was obtained. ¹ H NMR analysis of the quaternized polyetheramine thus obtained confirmed quaternization.

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

The polyetheramine (B) (400 g) of Synthesis Example 2 was dissolved in a heavy naphtha solvent (436 g), mixed with styrene oxide (24.0 g) and acetic acid (12.0 g) Lt; / RTI > After cooling to room temperature, 870 g of product was obtained. ¹ H NMR analysis of the quaternized polyether amine solution in the resulting heavy naphtha solution confirmed quaternization.

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

In a 2 L autoclave, polyetheramine (A) (305 g) of Synthesis Example 1 was dissolved in 2-ethylhexanol (341 g) and mixed with acetic acid (18.3 g). The autoclave was purged with N ₂ three times, an N ₂ feed gas pressure of about 1.3 bar was established and the temperature was raised to 130 ° C. 1,2-propylene oxide (17.7 g) was metered in. Subsequently the stirring was carried out at 130 ℃ for 5 h, and purged with N _2, then emptied the reactor was cooled to 40 ℃. Excess propylene oxide was removed under reduced pressure on a rotary evaporator. This gave 675 g of the product in the form of an orange oil. ¹ H NMR analysis of the quaternized polyether amine solution in the 2-ethylhexanol thus obtained confirmed the quaternization.

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

In a 2 L autoclave, polyetheramine (A) (518 g) of Synthesis Example 1 was dissolved in 2-ethylhexanol (570 g) and mixed with concentrated acetic acid (30 g). The autoclave was purged with N ₂ three times, an N ₂ feed pressure of about 1.3 bar was established and the temperature was raised to 130 ° C. Ethylene oxide (22 g) was metered in. Then it was stirred at 130 ℃ for 5 hours, purged with N _2, and emptied after cooling to 40 ℃ reactor. Thus, 1116 g of an orange oil-like product was obtained. ¹ H NMR analysis of the quaternized polyether amine solution in the 2-ethylhexanol thus obtained confirmed the quaternization.

Synthesis Example 8: Isotridecanol N * 22 BuO: polyether (C)

For example, polyethers were prepared from 1:22 molar proportions of isotridecanol N and 1,2-butylene oxide by DMC catalysis, as described in EP 1591466A, according to known methods.

Synthesis Example 9: Synthesis of NH ₃ : Isotridecanol (Tridecanol N, BASF) aminated with primary polyetheramine * 22 BuO amination (D)

The primary polyetheramines (D) are prepared, for example, by reaction of NH ₃ with the polyether (C) of Synthetic Example 8 in the presence of a suitable hydrogenation catalyst according to known methods, as described in DE 3826608A. Analysis of the polyetheramine (D) thus obtained gave TBN 32.0 mg KOH / g.

Synthesis Example 10: Synthesis of tert-polyetheramine (E)

While cooling with the ice bath was mixed as in Preparation Example 9, the polyether amine (D) to (400 g) of formic acid (65.3 g, 85% of H ₂ O) of. The reaction mixture was then heated to a temperature of 45 ° C and the formaldehyde solution (44.9 g, 36.5% in H ₂ O) was added dropwise at this temperature while the exhausted carbon dioxide was withdrawn from the reaction vessel. The reaction mixture was stirred for 16 hours at a temperature of 80 < 0 > C. The reaction mixture was then cooled to room temperature, mixed with hydrochloric acid (37%; 35.4 g) and stirred at room temperature for 1 hour. H ₂ O (500 ml) was added and a 50% potassium hydroxide solution was added to adjust the pH to about 10. Next, the mixture was repeatedly extracted with tert-butyl methyl ether (total 1200 mL). Washed with saturated aqueous NaCl solution, and the combined organic layer, dried over MgSO ₄ and the solvent removed under reduced pressure. Thus, 403 g of a yellow oil-like product was obtained. ¹ H NMR analysis of the thus obtained tert-polyetheramine confirmed the reductive dimetization.

Synthesis Example 11: Synthesis of NH, quaternized with dimethyl oxalate ₃ (Tridecanol N, BASF) * 22 < / RTI > BuO (VI)

Polyesteramine (E) (172 g) of Synthesis Example 10 was mixed with dimethyl oxalate (55.3 g) and lauric acid (5.2 g), and the reaction mixture was stirred for 4 hours at a temperature of 120 ° C . Subsequently, an excess amount of dimethyl oxalate was removed on a rotary evaporator under reduced pressure (p = 5 mbar) at a temperature of 120 ° C. ¹ H NMR analysis of the obtained quaternized polyether amine confirmed the quaternization.

Synthesis Example 12: Synthesis of styrene oxide / NH ₃ (Tridecanol N, BASF) * 22 < RTI ID = 0.0 > BuO (VII)

Polyetheramine (E) (200 g) of Synthesis Example 10 was dissolved in toluene (222 g), mixed with styrene oxide (14.4 g) and concentrated acetic acid (7.2 g) Lt; / RTI > ¹ H NMR analysis of the obtained solution confirmed the quaternization.

C. Usage example :

In the following examples, additives were used either as pure materials (as synthesized in the above example) or in the form of additive packages.

Use Example 1: Measurement of additive action for formation of deposits in a diesel engine injection nozzle

a) XUD9 test

Fuel Used: RF-06-03 (based on Diesel, Haltermann, Hamburg)

The results are shown in Table 1 below.

XUD9 test Examples Display Capacity according to Preparation Example [mg / kg of active ingredient] Liquidity restriction
0.1 mm Needle stroke [%] #One M1, according to Production 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 below.

DW10 test results additive Volume
[mg / kg] Output loss
KC Output loss
DU Print
DU-CU loss Default 0 5.0% M1, according to Production Example 6, 80 0.61% M2 according to Preparation Example 3, purification degree 75 2.8% 1.7%

Use case 2: Intake air cleanliness (intake pipe injection type gasoline engine)

Method: MB M102 E (CEC F-05-93)

Fuel: E5 according to EN 228

The additive according to Synthesis Example 4

result

Use case 3: cleanliness of injector (direct injection gasoline engine)

Method: BASF in-house method

Engine: 1.6 liter turbo charged 4-cylinder

Test duration: 60 hours

Fuel: Test fuel with 7% by volume oxygen-containing component

additive

A: Additive according to Synthesis Example 4

B: Additive according to Synthesis Example 3

*: FR is a parameter that is detected by engine control, which is related to the duration of fuel injection operation into the combustion chamber. The more deposition marks in the injector nozzle are added, the longer the injection time and the higher the FR. Conversely, if kept in the injector nozzle without deposits, the FR tends to be constant or slightly reduced.

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

Claims (17)

A fuel composition or lubricant composition comprising at least one reaction product comprising a quaternized nitrogen compound in a conventional fuel or lubricant,
a) a polyether-substituted amine comprising one or more tertiary amino groups quaternizable and
b) a quaternizing agent which converts at least one tertiary amino group to a quaternary ammonium group;
Lt; RTI ID = 0.0 > of: < / RTI > The fuel or lubricant composition of claim 1, wherein the polyether substituent comprises a monomer unit of the formula:

(Wherein,
R ₃ and R ₄ are the same or different and each is H, alkyl, alkylaryl or aryl. The fuel or lubricant composition of claim 2, wherein the polyether-substituted amine has a number average molecular weight in the range of 500 to 5000. 4. The process of any one of claims 1 to 3 wherein the quaternizing agent is an alkylene oxide optionally in combination with an acid; Aliphatic or aromatic carboxylic acid esters such as more especially dialkylcarboxylates; Alkanoate; Cyclic nonaromatic or aromatic carboxylic acid esters; Alkyl sulphate; Alkyl halide; Alkylaryl halides; ≪ / RTI > and mixtures thereof. An effective amount of a fuel composition or lubricant composition comprising at least one quaternized nitrogen compound of formula (Ia) or (Ib) in a major amount of conventional fuel or lubricant:

(Wherein,
R ₁ and R ₂ are the same or different and each is alkyl, alkenyl, hydroxyalkyl, hydroxyalkenyl, aminoalkyl or aminoalkenyl, or R ₁ and R ₂ together are alkylene, oxyalkylene or aminoalkyl ;
R ₃ and R ₄ are the same or different and each is H, alkyl, alkylaryl or aryl;
R ₅ is a radical introduced by quaternization, such as more particularly alkyl, hydroxyalkyl, arylalkyl or hydroxyarylalkyl;
R ₆ is in each case, optionally, for example one or more hydroxyl or substituted by a radical or an alkyl radical, or one or more hetero atoms, alkyl, alkenyl interposed, optionally mono-or polyunsaturated cycloalkyl or aryl;
A is a linear or branched alkylene radical optionally interrupted with one or more heteroatoms such as N, O and S;
n is an integer from 1 to 50;
X ^- is an anion, in particular an anion resulting from the quaternization reaction). 6. The method of claim 5,
R ₁ and R ₂ are the same or different and each C ₁ -C ₆ -alkyl, hydroxy -C ₁ -C ₆ -alkyl, hydroxy -C ₁ -C ₆ - alkenyl, or -C ₁ -C ₆ amino Or R ₁ and R ₂ together form a C ₂ -C ₆ -alkylene, a C ₂ -C ₆ -oxyalkylene or a C ₂ -C ₆ -aminoalkylene radical;
R ₃ and R ₄ are the same or different and each is H, C ₁ -C ₆ -alkyl or phenyl;
R ₅ is a radical introduced by quaternization, selected from C ₁ -C ₆ -alkyl, hydroxy-C 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 or branched C ₂ -C ₆ -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. 7. The fuel composition according to any one of claims 1 to 6, wherein the fuel composition is selected from diesel fuel, gasoline fuel, biodiesel fuel and alkanol containing gasoline fuel. A quaternized nitrogen compound as defined in any one of claims 1 to 7. A process for the production of a quaternized nitrogen compound of the formula (Ia)
comprising the steps of: a) alkoxylating an aminoalcohol of formula (II) with an epoxide of formula (III) to obtain an alkoxylated amine of formula (Ia-1): And
b) quaternizing the thus obtained alkoxy compound of formula (Ia-1) to obtain a reaction product comprising at least one compound of formula (Ia), wherein the quatification is for example a compound of formula (IV) With an alkylene oxide of the formula IVa < EMI ID = 4.1 >
≪ / RTI >

Wherein R ₁ to R ₅ , A, X and n are each as defined above,

Wherein R ₁ , R ₂ and A are each as defined above,

(Wherein R < ₃ > and R < ₄ > are each as defined above)

(Wherein R ₁ to R ₄ , A and n are each as defined above)

(Wherein R < ₅ > is alkyl or aryl and X is as defined above)

Wherein R _{5 '} is H, alkyl or aryl and the R ₅ radical is a -CH ₂ CH (OH) R _5' group. A process for the production of a quaternized nitrogen compound of formula (Ib)
a) alkoxylating an alcohol of formula V with an epoxide of formula III to give a polyether of formula Ib-1;
b) aminating the thus obtained polyether of formula (Ib-1) with an amine of formula (VII) to obtain an amine of formula (Ib-2);
c) quarternizing the product of step b) to obtain a reaction product comprising at least one compound of formula (Ib), wherein the quatification is for example a compound of formula IV, or an acid HX, wherein X is as defined above Lt; RTI ID = 0.0 > (IVa) < / RTI >
≪ / RTI >

Wherein R ₁ to R ₆ , X and n are each as defined above,

(Wherein R < ₆ > is as defined above)

(Wherein R < ₃ > and R < ₄ > are each as defined above)

Wherein R ₃ , R ₄ and R ₆ , A, X and n are each as defined above,

(Wherein R < ₁ > and R < ₂ > are each as defined above)

Wherein R ₁ to R ₄ and R ₆ , A, X and n are each as defined above and the amine of the formula Ib-2 is optionally alkylated if R ₁ and / or R ₂ is H,

(Wherein R < ₅ > is alkyl or aryl and X is as defined above)

Wherein R _{5 '} is H, alkyl or aryl and the R ₅ radical is a -CH ₂ CH (OH) R _5' group, 11. A process according to claim 9 or 10 wherein the quaternizing agent is an alkylene oxide 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 nonaromatic carboxylic acid esters. A quaternized nitrogen compound obtainable by the process according to claims 10 or 11. The use of quaternized nitrogen compounds according to claim 8 or as claimed in any of claims 9 to 11 as fuel additives or lubricating additives. 14. Use according to claim 13 as a diesel fuel additive, especially as a low temperature flow improver or as a wax anti-settling additive (WASA) 14. The use of claim 13 as a gasoline fuel additive for reducing or preventing deposits in the intake system of a gasoline engine, especially for reducing or preventing deposits in the injection nozzles of direct injection gasoline engines. 14. The method of claim 13, further comprising reducing the fuel consumption of the direct injection diesel engine, particularly reducing the fuel consumption of the diesel engine with a common rail injection system and / or reducing the fuel consumption of the diesel engine with direct injection diesel engines, Reducing and / or preventing deposits in the injection system, such as more particularly internal diesel injector deposits (IDID), and / or direct injection, as additives for minimizing power losses in the engine, and / Especially as an additive for reducing and / or preventing deposits in a common rail injection system. An additive concentrate comprising at least one quaternized nitrogen compound as defined in claim 8 or prepared according to claim 9 or 10 in combination with an additional diesel or gasoline fuel additive.

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