WO2013064689A1

WO2013064689A1 - Quaternized polyetheramines and use thereof as additives in fuels and lubricants

Info

Publication number: WO2013064689A1
Application number: PCT/EP2012/071844
Authority: WO
Inventors: Markus Hansch; Harald BÖHNKE; Ludwig Völkel; Marc Walter; Wolfgang Grabarse
Original assignee: Basf Se
Priority date: 2011-11-04
Filing date: 2012-11-05
Publication date: 2013-05-10
Also published as: CN104024385B; CN104024385A; KR20140097288A; BR112014010671A2; ES2726102T3; PL2773729T3; CA2854421C; EP2773729B1; EP2773729A1; CA2854421A1; TR201905501T4; KR102033606B1; MX2014005325A; HUE044181T2; AU2012331073A1; AU2012331073B2; EP2589647A1

Abstract

The present invention relates to innovative quaternized polyetheramines and to the preparation thereof. The present invention further relates to the use of these compounds as a fuel and lubricant additive. More particularly the invention relates to the use of these quaternized nitrogen compounds as a fuel additive for reducing or preventing deposits in the injection systems of direct injection diesel engines, especially in common rail injection systems, for reducing the fuel consumption of direct injection diesel engines, especially of diesel engines with common rail injection systems, and for minimizing power loss in direct injection diesel engines, especially in diesel engines with common rail injection systems. The invention also provides additive packages comprising these polyetheramines, and fuels and lubricants additized therewith. The invention further relates to the use of these quaternized nitrogen compounds as an additive for gasoline fuels, especially for improving the intake system cleanliness of gasoline engines.

Description

Quaternized polyetheramines and their use as additives in fuels and lubricants

The present invention relates to novel quaternized polyetheramines and their preparation, Furthermore, the present invention relates to the use of these compounds as a fuel and lubricant additive. More particularly, the invention relates to the use of these quaternized nitrogen compounds as a fuel additive to reduce or prevent deposits in the injection systems of direct injection diesel engines, particularly in common rail injection systems, to reduce fuel consumption of direct injection diesel engines, particularly diesel engines with common rail injection systems. and to minimize the power loss in direct injection diesel engines, especially in diesel engines with common rail injection systems. The invention also relates to additive packages containing these polyetheramines; as well as with it additized fuels and lubricants. Furthermore, the invention relates to the use of these quaternized nitrogen compounds as an additive for gasoline fuels, in particular for improving the intake system cleanliness of gasoline engines.

State of the art:

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

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

Due to the variable, cylinder-specific injection, the pollutant emissions of the engine, eg the emission of nitrogen oxides (NO _x ), carbon monoxide (CO) and particulate matter (soot), can be positively influenced in the common-rail injection system. This allows, for example, that equipped with common-rail injection systems engines of Euro 4 standard can theoretically meet without additional particulate filter. In modern common-rail diesel engines deposits can form under certain conditions, for example when using biodiesel-containing fuels or fuels with metal impurities such as zinc compounds, copper compounds, lead compounds and other metal compounds, the injection behavior of the Negatively affect the performance of the engine, ie in particular reduce the power, but in part also deteriorate the combustion. The formation of deposits is further enhanced by structural developments of the injectors, in particular by the change in the geometry of the nozzles (narrower, conical openings with rounded outlet). For a permanently optimal functioning of the engine and injectors, such deposits in the nozzle orifices must be prevented or reduced by suitable fuel additives.

Carburetors and intake systems of gasoline engines, as well as injectors Fuel metering systems are contaminated by impurities caused by dust particles from the air, unburned hydrocarbon residues from the combustion chamber and the crankcase ventilation gases directed into the gasifier. These residues shift the air-fuel ratio at idle and in the lower part-load range, making the mixture leaner, incomplete combustion and, in turn, increasing the proportion of unburned or partially combusted hydrocarbons in the exhaust gas and increasing gasoline consumption. It is known that to avoid these disadvantages, fuel additives are used for keeping valves and carburetors or injection systems of gasoline engines clean (cf., for example: M. Rossenbeck in Catalysts, Surfactants, Mineral Oil Additives, Ed. J. Falbe, U. Hasserodt, S. 223, G. Thieme Verlag, Stuttgart 1978). Depending on the mode of action but also on the preferred site of action of such detergent additives, a distinction is made today between two generations.

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

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

Thus, e.g. WO 2006/135881 quaternized ammonium salts, prepared by condensation of a hydrocarbyl-substituted acylating agent and an oxygen- or nitrogen-containing compound having a tertiary amino group, followed by quaternization by means of hydrocarbyl epoxide in combination with stoichiometric amounts of an acid, in particular acetic acid. These additives are used especially as diesel fuel additives to reduce power loss. Polyalkene-substituted quaternized amines, such as in particular quaternized polyisobuteneamines, and their use as detergent additives to reduce inlet valve deposits and as lubricant additives for internal combustion engines are described in US 2008/01 13890. No. 6,331,648 B1 relates to specific quaternary etheramine compounds which contain a 1-ethyl-1,3-propylene unit incorporated between the alkoxylate chain and quaternary nitrogen. The use of these compounds as corrosion inhibitors or detergent additives in gasoline and diesel fuels is speculated, but without demonstrating their usefulness.

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

[RO (R i) x CH ₂ CH (R ₂ ) HNR ₃ R 4 R 6] ⁺ A- wherein R i represents an alkylene oxide block. For these compounds, a whole range of applications are postulated, including generally as fuel and lubricant additives, but without actually demonstrating specific functions experimentally. Preferred anions A- are chloride, methylsulfate and ethylsulfate. US 4 564 372, US 4 581 151, US 4 600 409 and WO 1985/000620 relate to alkyl halides quaternized, ie halogen-containing, polyoxyalkyleneamine salts in which polyoxyalkylene unit and amine moiety via different linker groups, in particular amine linkers of Type - C (0) -NH-. Use as dispersants and corrosion inhibitors in fuels is postulated, but without actually demonstrating specific functions experimentally.

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

Brief description of the invention:

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

DESCRIPTION OF THE FIGURES FIG. 1 shows the injector cleanliness achievable with additives according to the invention after a test operation with a direct-injection gasoline engine (1 b and 1 c) in comparison to operation with non-additized fuel (1 a).

FIG. 2 shows the sequence of a one-hour engine test cycle according to CEC F-098-08. Detailed description of the invention:

A1) Special Embodiments The present invention relates in particular to the following specific embodiments:

1 . A fuel or lubricant composition, in particular a fuel composition, comprising, in a majority of a conventional fuel or lubricant, an effective amount of at least one quaternized nitrogen compound-containing reaction product, or a quaternized nitrogen compound-containing partial fraction thereof obtained from the reaction product, wherein the reaction product is available through implementation

a. a polyether-substituted amine containing at least one tertiary, quaternizable amino group

b. a quaternizing agent which converts the at least one tertiary amino group into a quaternary ammonium group.

2. A fuel or lubricant composition according to claim 1, wherein the polyether substituent monomer units of the general formula Ic

- [- CH (R ₃ ) -CH (R ₄ ) -O -] - (Ic), wherein

R 3 and R ₄ are identical or different and are H, alkyl, alkylaryl or aryl.

3. A fuel or lubricant composition according to embodiment 2, wherein the polyether-substituted amine has a number average molecular weight in the range of 500 to 5000, in particular 800 to 3000 or 900 to 1500.

4. A fuel or lubricant composition according to any one of the preceding embodiments, wherein the quaternizing agent is selected from among Alky- lenoxiden optionally in combination with acid; aliphatic or aromatic mono- or polycarboxylic acid esters, in particular mono- or dialkylcarboxylic acid esters; cyclic non-aromatic or aromatic mono- or polycarboxylic acid esters; dialkyl; alkyl sulfates; alkyl halides; Alkylaryl halides; in particular halogen and sulfur-free quaternizing agents, such as alkylene oxides in combination with acid, such as a carboxylic acid; aliphatic or aromatic mono- or polycarboxylic acid esters, in particular mono- or dialkylcarboxylic acid esters; cyclic non-aromatic or aromatic mono- or polycarboxylic acid esters and dialkyl carbonates; and mixtures thereof.

A fuel or lubricant composition comprising, in a majority of a conventional fuel or lubricant, an effective amount of at least one quaternized nitrogen compound of general formula Ia or Ib,

(RsX) X ^ N -A-O-f-CHiRgJ-CHiR ^ -O-Jn-H (la)

X ^"

Re-O-CHiR _g J-CHiR ^ -O-Jn-CHiR _g J-CHiR ^ -N ^ Ji ^ XR _g ) (Ib)

X ^" in which

R 1 and R 2 are identical or different and represent alkyl, alkenyl, hydroxyalkyl, hydroxyalkynyl, aminoalkyl or aminoalkenyl, or R 1 and R 2 together represent alkylene, oxyalkylene or aminoalkylene;

R 3 and R ₄ are identical or different and are H, alkyl, alkylaryl, or aryl;

R5 is a radical introduced by quaternization, in particular alkyl, hydroxyalkyl, arylalkyl or hydroxyarylalkyl;

R 6 is alkyl, alkenyl, optionally mono- or polyunsaturated cycloalkyl, aryl, in each case optionally substituted, for example with at least one hydroxyl radical or alkyl radical, or interrupted by at least one heteroatom; A is a straight-chain or branched alkylene radical which is optionally interrupted by one or more heteroatoms, such as N, O and S; n stands for an integer value of 1 to 50 and

X- represents an anion, in particular an anion resulting from the quaternization reaction.

A fuel or lubricant composition according to embodiment 5, wherein R 1 and R 2 are identical or different and are C 1 -C 6 -alkyl, hydroxy-C 1 -C 6 -alkyl, hydroxy-C 1 -C 6 -alkenyl, or amino-C 1 -C 6 -alkyl, or R1 and R2 together form a C2-C6-alkylene, C2-C6-oxyalkylene or C2-C6-aminoalkylene radical;

R 3 and R ₄ are identical or different and represent H, Ci-C6 alkyl or phenyl;

R5 is a quaternized radical 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, e.g. C10-C20, Cn-C2o or Ci2-C2o-alkyl or aryl or alkylaryl, wherein alkyl is in particular C1-C20- stands;

A is a straight-chain or branched C 2 -C 6 -alkylene radical which is optionally interrupted by one or more heteroatoms, such as N, O and S; n for an integer value of 1 to 30 and

X- represents an anion resulting from the quaternization reaction.

Fuel composition according to one of the preceding embodiments, selected from diesel fuels, gasoline fuels, biodiesel fuels and alkanol-containing gasolines.

Quaternized nitrogen compound as defined in one of the preceding embodiments, in particular selected from halogen-free and sulfur-free.

Process for the preparation of quaternized nitrogen compounds of the general formula Ia,

X

wherein i to R5, A, X and n have the meanings given above wherein a. an aminoalkanol of the general formula II

(R,) (R ₂ ) NA-OH (II) wherein

Ri, R2 and A have the meanings given above, with an epoxide of the general formula I I I

O

/ \

(R ₃ ) HC CH (R ₄ ) wherein

Rs and R _{4 have} the meanings given above,

alkoxylated to give an alkoxylated amine of the formula

(R ₁ ) (R ₂ ) NA n † cH (R ₃ ) -CH (R ₄ ) -O, where R 1 to R ₄ , A and n have the abovementioned meanings, and b) the alkoxyl compound of the formula Quaternized to obtain a reaction product comprising at least one compound of general formula Ia, the quaternization being carried out, for example, with a compound of general formula IV

R ₅ -X (IV) wherein

R _{5 is} alkyl or aryl and X has the meaning given above, or with an alkylene oxide of the formula

CH (R _5. ) Is quaternized in combination with an acid HX in which X has the abovementioned meaning, where Rs 'is H, alkyl or aryl and the radical R _{5 is} a group -CH ₂ CH (OH) R ₅ ' stands. Process for the preparation of quaternized nitrogen compounds of general formula Ib,

Rg-O4 -CHiR2 -CHiR2 -O- ^ CHiR2 -CHiR2 -Ni ^ i ^ XR _g ) (Ib)

X ^" wherein Ri to R6, X and n have the meanings given above wherein

a) an alcohol of the general formula VR ₆ -OH (V) wherein

R6 has the meanings given above, with an epoxide of the general formula III

O

/ (III)

(R ₃ ) HC CH (R ₄ ) wherein

R ₃ and R _{4 have} the meanings given above, alkoxylated, to give a polyether of the formula Ib-1; R ₆ -O-CH (R ₃ ) -CH (R ₄ ) -O-CH (R ₃ ) -CH (R ₄ ) OH (Ib-1); in which R ₃ , R ₄ and FS, A, X and n have the abovementioned meanings b) subsequently the polyether of the formula Ib-1 thus obtained with an amine of the general formula

in which R1 and R2 have the meanings given above,

aminated to obtain an amine of the formula Ib-2

R ^ - O- [ "CH ₍₃₎ CH ₍₄₎ -0-j ^ - ₁ CH ₍₃₎ CH ₍₄₎ ^_ N ₍₁₎ ₍₂₎ (lb-2)

in which R 1 to R ₄ and R ₆ , A, X and n have the abovementioned meanings, the alkyl of the formula (Ib-2) is optionally alkylated, if R 1 and / or R 2 are H and then c) the product from stage b) quaternized to obtain a reaction product comprising at least one compound of general formula Ib, wherein the quaternization is carried out for example with a compound of general formula IV

R ₅ -X (IV) wherein

O

/ (IVa)

H ₂ C CH (R _5. ) quaternized in combination with an acid HX, wherein X has the meaning indicated above, wherein R5 'is H, alkyl or aryl and the radical R _{5 is} a group -CH ₂ CH (OH) R ₅ '. A process according to embodiment 9 or 10, wherein the quaternizing agent is selected from: alkylene oxides, optionally in combination with an acid; Alkyl carbonates, such as dialkyl carbonates; Alkyl sulfates, such as dialkyl sulfates; Alkyl phosphates, dialkyl phosphates, halides, such as alkyl or aryl halides; aliphatic and aromatic carboxylic acid esters, such as alkanoates, dicarboxylic acid esters; and cyclic aromatic or non-aromatic carboxylic acid esters. Quaternized nitrogen compound obtainable by a process according to embodiment 10 or 11, in particular in halogen- and sulfur-free form. Use of a quaternized nitrogen compound according to embodiment 8 or prepared according to any of embodiments 9 to 11 as a fuel additive or lubricant additive.

Use according to embodiment 12 as a diesel fuel additive, in particular as a cold flow improver, as a wax anti-settling additive (WASA).

Use according to embodiment 12 as a gasoline additive for reducing deposits in the intake system of a gasoline engine, in particular DISI and PFI (Port Fuel Injector) engines

Use according to embodiment 12 as an additive for reducing the fuel consumption of direct injection diesel engines, in particular diesel engines with common rail injection systems, and / or for minimizing the power loss in direct injection diesel engines, especially in diesel engines with common rail injection systems or as an additive for reducing and / or preventing deposits in the injection systems, such as in particular the Internal Diesel Injector Deposits (I DID) and / or for reducing and / or preventing deposits in the Injectors in direct injection diesel engines, especially in common rail injection systems.

17. Additive concentrate, containing in combination with further diesel or Otto fuel additives, in particular diesel fuel additives, at least one quaternized nitrogen compound as defined in embodiment 8 or prepared according to one of embodiments 9 or 10.

In a specific embodiment of the invention, in some or all of the above embodiments, the quaternizing agent is not an aromatic carboxylic acid ester, such as e.g. Salicylates.

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

In a specific embodiment of the invention, in some or all of the above embodiments, the quaternized (nitrogen) substituent is especially alkyl (especially C1-C6 alkyl), or hydroxyarylalkyl (such as 2-hydroxy-2-phenylethyl).

In a specific embodiment of the invention, in some or all of the above embodiments, the polyether substituent has no aryl or aralkyl groups. In a specific embodiment of the invention, in some or all of the above embodiments, the quaternized nitrogen compound is a compound of formula (Ia) or (Ib).

Suitable test methods for checking the above-described applications are known to the person skilled in the art or are described in the following experimental part, to which reference is expressly made in general terms.

A2) General definitions In the context of the present invention, "halogen-free" or "sulfur-free" means the absence of inorganic or organic halogen-containing or sulfur-containing compounds and / or their corresponding ions, such as halide anion and sulfur-containing anions, in particular sulfates. "Halogen-free" or "sulfur-free" in particular includes the absence of stoichiometric amounts of halogen-containing or sulfur-containing compounds or anions. Substoichiometric amounts of halogen-containing or sulfur-containing compounds or anions are present, for example, in molar ratios of less than 1: 0.1, or less 1 . 0.01 or 1: 0.001, or 1: 0.0001 of quaternized nitrogen compound to halogen-containing or sulfur-containing compound or ions thereof before. "Halogen-free" or "sulfur-free" includes in particular the complete absence of halogen-containing or sulfur-containing compounds and / or their corresponding ions, such as halide anion and sulfur-containing anions, in particular sulfates. "Carboxylic acids" include, in particular, organic carboxylic acids, in particular monocarboxylic acids of the RCOOH type, in which R represents a short-chain hydrocarbyl radical, for example a lower alkyl or C 1 -C 4 -alkylcarboxylic acid.

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

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

"Alkyl" or "lower alkyl" in particular represents saturated, straight-chain or branched hydrocarbon radicals having 1 to 4, 1 to 6, 1 to 8, 1 to 10, 1 to 14 or 1 to 20 carbon atoms, such as. Methyl, ethyl, n -propyl, 1-methylethyl, n-butyl, 1 - Methyl-propyl, 2-methylpropyl, 1,1-dimethylethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1, 1 - Dimethylpropyl, 1, 2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2,2-dimethylbutyl, 2 , 3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1, 1, 2-trimethylpropyl, 1, 2,2-trimethylpropyl, 1-ethyl-1-methylpropyl and 1-ethyl-2-methylpropyl ; and n-heptyl, n-octyl, n-nonyl and n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, and the mono- or poly-branched analogs thereof.

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

"Alkenyl" is mono- or polysubstituted, in particular monounsaturated, straight-chain or branched hydrocarbon radicals having 2 to 4, 2 to 6, 2 to 8 2 to 10 or 2 or to 20 carbon atoms and a double bond in any position, for example C2-C6 alkenyl such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1 Methyl 2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl -1 -butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3 -butenyl, 1,1-dimethyl-2-propenyl, 1, 2-dimethyl-1-propenyl, 1, 2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1 -Hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pentenyl , 1-methyl-2-pentenyl, 2-methyl-2 pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1 Methyl 4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl,

1: 1 - dimethyl-2-butenyl, 1, 1-dimethyl-3-butenyl, 1, 2-dimethyl-1-butenyl,

1, 2-dimethyl-2-butenyl, 1, 2-dimethyl-3-butenyl, 1, 3-dimethyl-1-butenyl,

1, 3-dimethyl-2-butenyl, 1, 3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl,

3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1 - butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1, 1, 2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl 1-propenyl and 1-ethyl-2-methyl-2-propenyl.

"Hydroxyalkenyl" in particular for the mono- or polysubstituted, in particular simply hydroxylated analogs of the above AI kenylreste

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

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

-CH ₂ -CH (CH ₃ ) -, -CH (CH ₃ ) -CH ₂ -, -CH (CH ₃ ) -CH (CH ₃ ) -, -C (CH ₃ ) ₂ -CH ₂ -, -CH ₂ -C (CH ₃ ) ₂ -, -C (CH ₃ ) ₂ -CH (CH ₃ ) -, -CH (CH ₃ ) -C (CH ₃ ) ₂ -, -CH ₂ -CH (Et) -, -CH (CH ₂ CH ₃ ) -CH ₂ -,

-CH (CH ₂ CH ₃ ) -CH (CH ₂ CH ₃ ) -, -C (CH ₂ CH ₃ ) ₂ -CH ₂ -, -CH ₂ -C (CH ₂ CH ₃ ) ₂ -,

-CH ₂ -CH (n-propyl) -, -CH (n-propyl) -CH ₂ -, -CH (n-propyl) -CH (CH ₃ ) -, -CH ₂ -CH (n-butyl) - , -CH (n-butyl) -CH ₂ -, -CH (CH ₃ ) -CH (CH ₂ CH ₃ ) -, -CH (CH ₃ ) -CH (n-propyl) -, -CH (CH ₂ CH ₃ ) - CH (CH ₃ ) -, -CH (CH ₃ ) -CH (CH ₂ CH ₃ ) -, or for C ₂ -C ₄ -alkylene groups, such as selected among - (CH ₂ ) ₂ -, -CH ₂ -CH (CH ₃ ) -, -CH (CH ₃ ) -CH ₂ -, -CH (CH ₃ ) -CH (CH ₃ ) -, -C (CH ₃ ) ₂ - CH ₂ -, -CH ₂ - C (CH ₃ ) ₂ -, -CH ₂ -CH (CH ₂ CH ₃ ) -, -CH (CH ₂ CH ₃ ) -CH ₂ -.

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

"Alkenylene" refers to the mono- or polysubstituted, in particular mono-unsaturated analogs of the above alkylene groups having 2 to 10 carbon atoms, in particular C ₂ - C ₇ -Alkenylene or C ₂ -C ₄ alkenylene, such as -CH = CH-, -CH = CH-CH ₂ -, - CH ₂ -CH = CH-, -CH = CH-CH ₂ -CH ₂ -, -CH ₂ -CH = CH-CH ₂ -, -CH ₂ -CH ₂ -CH = CH -, -CH (CH ₃₎ -CH = CH-, -CH ₂ -C (CH ₃₎ = CH- -. "cycloalkyl" means carbocyclic radicals of 3 to 20 carbon atoms, such as C ₃ -C ₂ cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; preference is given to cyclopentyl, cyclohexyl, cycloheptyl and also cyclopropylmethyl, cyclopropylethyl, cyclobutylmethyl, cyclobutylethyl, cyclopentylmethyl, cyclopentylethyl, cyclohexylmethyl or C ₃ -C ₇ -cycloalkyl, such as cyclopropyl, cyclobutyl, Cyclopentyl, cyclohexyl, cycloheptyl, cyclopropyl-methyl, cyclopropyl-ethyl, cyclobutyl-methyl, cyclopentyl-ethyl, cyclohexyl-methyl, wherein the attachment to the rest of the molecule via any suitable carbon atom can take place. "Cycloalkenyl" or mono- or polyunsaturated cycloalkyl "in particular represents monocyclic, mono- or polyunsaturated hydrocarbon groups having 5 to 8, preferably up to 6 carbon ring members, such as the monounsaturated radicals cyclopenten-1-yl, cyclopenten-3-yl, cyclohexene -1 -yl, cyclohexen-3-yl and cyclohexyl-4-yl;

"Aryl" denotes mononuclear or polynuclear, preferably mononuclear or dinuclear, optionally substituted aromatic radicals having 6 to 20, for example 6 to 10, ring carbon atoms, for example phenyl, biphenyl, naphthyl, such as 1- or 2-naphthyl, tetracyclic hydronaphthyl, fluorenyl, indenyl and phenanthrenyl These aryl radicals may optionally carry 1, 2, 3, 4, 5 or 6 identical or different substituents. "Alkylaryl" stands for the in any position of the ring one or more times, in particular 1- or 2-fold, alkyl-substituted analogs of the above aryl radicals, wherein aryl also has the abovementioned meanings, such as CrC ₄ alkyl-phenyl, wherein the C 1 -C ₄ -alkyl radicals can be in any desired ring position.

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

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

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

Re-OH (V) wherein R6 is alkyl, alkenyl, optionally mono- or polyunsaturated cycloalkyl, aryl, each optionally substituted, e.g. with at least one hydroxyl radical or alkyl radical, or interrupted by at least one heteroatom; b) aminoalkanols of the general formula I I

(R,) (R ₂ ) NA-OH (II) wherein

R 1 and R 2 are identical or different and are alkyl, alkenyl, hydroxyalkyl, hydroxyalkenyl, aminoalkyl or aminoalkenyl, or R 1 and R 2 together represent alkylene, oxyalkylene or aminoalkylene; and A is a straight-chain or branched alkylene or alkenylene radical which is optionally interrupted by one or more heteroatoms, such as N, O and S;

A4) Quaternizing agent:

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

In a particular embodiment, however, the quaternization of the at least one quaternizable tertiary nitrogen atom takes place with at least one quaternizing agent selected from epoxides, in particular hydrocarbyl epoxides.

wherein the R ^a radicals contained therein are identical or different and represent H or a hydrocarbyl radical. In this case, the hydrocarbyl radical may have at least 1 to 14 carbon atoms. In particular, these are aliphatic or aromatic radicals, such as, for example, linear or branched C 1 -C 6 -alkyl radicals or aromatic radicals, such as phenyl or C 1 -C 4 -alkylphenyl. Suitable hydrocarbyl epoxides are, for example, aliphatic and aromatic alkylene oxides, in particular C 2-6 -alkylene oxides, such as ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 2-methyl-1,2-propene oxide (isobutene oxide ), 1,2-pentenoxide, 2,3-pentenoxide, 2-methyl-1,2-butene oxide, 3-methyl-1,2-butene oxide, 1,2-hexene oxide, 2,3-hexene oxide, 3,4- Hexene oxide, 2-methyl-1,2-pentenoxide, 2-ethyl-1,2-butene oxide, 3-methyl-1,2-pentene oxide, 1,2-decene oxide, 1,2-dodecene oxide or 4-methyl-1, 2-pentene; Tetra-decane oxide; hexadecene; and also aromatic-substituted ethylene oxides, such as optionally substituted styrene oxide, in particular styrene oxide or 4-methyl-styrene oxide. In the case of the use of epoxides as quaternizing these are in the presence or absence of free acids, especially in the presence or absence of free protic acids, such as especially with C-12 monocarboxylic acids, such as formic acid, acetic acid or propionic acid or C2-i2-dicarboxylic acids such as oxalic acid or adipic acid; or in the presence or absence of sulfonic acids, such as benzenesulfonic acid or toluenesulfonic acid or aqueous mineral acids, such as sulfuric acid or hydrochloric acid. The quaternization product thus produced is thus either "acidic" or "acid-free" within the meaning of the present invention.

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

In a particular embodiment, however, the quaternization of the at least one quaternizable tertiary nitrogen atom is carried out with at least one quaternizing agent selected from a) compounds of general formula 1

wherein

Ri is a lower alkyl radical and

R ₂ is an optionally substituted mononuclear aryl or cycloalkyl radical, the substituent being selected from OH, NH ₂ , NO ₂ , C (O) OR ₃ ; RiaOC (O) -, wherein Ri _{a has} the meanings given above for R 1, and R 3 is H or R 1; or

b) Compounds of the general formula 2 RiOC (0) -AC (0) ORia (2) where

Ri and Ria independently represent a lower alkyl radical and

A represents hydrocarbylene (such as alkylene or alkenylene).

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

Particularly suitable compounds of formula 1, wherein

Ri is a d, C2 or C3 alkyl radical and

R 2 is a substituted phenyl radical, where the substituent for HO or an ester radical of the formula R i _a OC (O) - which is in the para, meta or in particular ortho position to the radical R i OC (O) - on the aromatic ring ,

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

An "anion resulting from the quaternization reaction" X- is, for example, a halide such as a chloride or bromide, a sulfate radical ((SO4) ^{2 "} ), or the anionic radical of a mono- or polyhydric, aliphatic or aromatic carboxylic acid, or the anionic one Rest ROC (0) 0- resulting from the quaternization of a dialkyl carbonate.

A5) Quaternizable nitrogen compounds (of formula II):

The quaternizable nitrogen compound is selected from hydroxyalkyl substituted mono- or polyamines having at least one quaternizable, primary, secondary or tertiary amino group and at least one hydroxyl group attachable to a polyether radical. In particular, the quaternizable nitrogen compound is selected from hydroxyalkyl-substituted primary, secondary, tertiary or quaternary monoamines and hydroxyalkyl-substituted primary, secondary, tertiary or quaternary diamines.

Examples of suitable "hydroxyalkyl-substituted mono- or polyamines" are those which are endowed with at least one, such as 1, 2, 3, 4, 5 or 6, hydroxyalkyl substituents Ala may be examples of "hydroxyalkyl-substituted monoamines" N-hydroxyalkyl-monoamines, Ν, Ν-dihydroxyalkyl-monoamines and Ν, Ν, Ν-trihydroxyalkyl-monoamines, wherein the hydroxyalkyl groups are the same or different and are also as defined above. Hydroxyalkyl stands in particular for 2-hydroxyethyl, 3-hydroxypropyl or 4-hydroxybutyl.

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

The following quaternizable nitrogen compounds may be mentioned in particular:

NAME FORMULA

Alcohols with primary and secondary amine

H ₉ I \ L

Ethanolamine ² ^ - "^ OH

3-hydroxy-1-propylamine

H

diethanolamine

^ OH

A6) Preparation of additives according to the invention: a) Preparation of the Polyether-Substituted Quaternizable Intermediates (Ia-1 and Ib-1) a1) Starting from aminoalcohols of the formula II:

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

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

For the alkoxylation C2-C6-alkylene oxides are used, for example ethylene oxide, propylene oxide, or butylene oxide. Preference is given in each case to the 1, 2-alkylene oxides.

The alkoxylation may be a base-catalyzed alkoxylation. For this purpose, the amino alcohols (II) can be mixed in a pressure reactor with alkali metal hydroxides, preferably potassium hydroxide or with alkali metal alkoxides such as sodium thylate. By reducing the pressure (for example <100 mbar) and / or increasing the temperature (30 to 150 ° C), water still present in the mixture can be withdrawn. The alcohol is then present as the corresponding alkoxide. It is then inertized with inert gas (eg nitrogen) and the (the) alkylene oxide (s) at temperatures of 60 to 180 ° C up to a pressure of max. 10 bar added gradually. At the end of the reaction, the catalyst can be neutralized by addition of acid (eg acetic acid or phosphoric acid) and can be filtered off if necessary. However, the basic catalyst can also be neutralized by adding commercial Mg silicates, which are then filtered off. Optionally, the alkoxylation can also be carried out in the presence of a solvent. This may be, for example, toluene, xylene, dimethylformamide or ethylene carbonate. However, the alkoxylation of the amino alcohols can also be carried out by other methods, for example by acid-catalyzed alkoxylation. Furthermore, for example Doppelhydroxidtone as described in DE 43 25 237 A1 can be used, or it can double metal cyanide catalysts (DMC catalysts) can be used. Suitable DMC catalysts are disclosed, for example, in DE 102 43 361 A1, in particular sections [0029] to [0041], and the literature cited therein. For example, Zn-Co type catalysts can be used. To carry out the reaction, the aminoalcohol can be admixed with the catalyst, the mixture can be dehydrated as described above and reacted with the alkylene oxides as described. It is usually not more than 1000 ppm catalyst used with respect to the mixture, and the catalyst can remain in the product due to this small amount. The amount of catalyst can typically be less than 1000 ppm, for example 250 ppm and less. The alkoxylation can alternatively be carried out by reaction of the compounds (IV) and (V) with cyclic carbonates such as ethylene carbonate. a2) Starting from alkanols of the formula V: As described under the previous section a1) for amino alcohols (II), alkanols ReOH can also be alkoxylated analogously to polyethers (Ib-1) in a manner known in principle. The polyethers thus obtained can then by reductive amination with ammonia, primary amines or secondary amines (VI I) by conventional methods in continuous or batch processes using customary hydrogenation or amination catalysts such as those based on catalytically active ingredients the elements Ni, Co, Cu, Fe, Pd, Pt, Ru, Rh, Re, Al, Si, Ti, Zr, Nb, Mg, Zn, Ag, Au, Os, Ir, Cr, Mo ,, W or combinations of these elements with one another, are reacted in conventional amounts to the corresponding polyetheramines (Ib-2). The reaction can be carried out without solvent or at high polyether viscosities in the presence of a solvent, preferably in the presence of branched aliphatics such as isododecane. The amine component (VII) is generally used in excess, for example in 2 to 100-fold excess, preferably 10 to 80-fold excess used. The reaction is carried out at pressures of 10 to 600 bar over a period of 10 Minutes to 10 hours. After cooling, the catalyst is separated by filtration, excess amine component (VII) is evaporated off and the reaction water is distilled off azeotropically or under a gentle stream of nitrogen. If the resulting polyetheramine (Ib-2) have primary or secondary amine functionality (R 1 and / or R 2 is H), this can subsequently be converted into a polyether amine having a tertiary amine function (R 1 and R 2 not equal to H). The alkylation can be carried out in a manner known in principle by reaction with alkylating agents. In principle, all alkylating agents such as, for example, alkyl halides, alkylaryl halides, dialkyl sulfates, alkylene oxides, if appropriate in combination with acid, are suitable; aliphatic or aromatic carboxylic acid esters, in particular dialkylcarboxylates; alkanoates; cyclic non-aromatic or aromatic carboxylic esters; Dialkyl carbonates; and mixtures thereof. The reactions to the tertiary polyetheramine can also take place by reductive amination by reaction with a carbonyl compound such as formaldehyde in the presence of a reducing agent. Suitable reducing agents are formic acid or hydrogen in the presence of a suitable heterogeneous or homogeneous hydrogenation catalyst. The reactions can be carried out without solvent or in the presence of solvents. Suitable solvents are, for example, H 2 O, alkanols, such as methanol or ethanol, or 2-ethylhexanol, aromatic solvents, such as toluene, xylene or solvent mixtures of the Solvesso series, or aliphatic solvents, in particular mixtures of branched aliphatic solvents. The reactions are carried out at temperatures of 10 ° C to 300 ° C at pressures of 1 to 600 bar over a period of 10 minutes to 10 hours. The reducing agent is used at least stoichiometrically, preferably in excess, in particular in 2- to 10-fold excess.

The reaction product thus formed (polyetheramine Ib-1 or Ib-2) can theoretically be further purified or the solvent removed. Usually, however, this is not absolutely necessary, so that the reaction product can be converted into the next synthesis step, the quaternization, without further purification. b) Quaternization b1) with epoxide / acid

To carry out the quaternization, the reaction product or reaction mixture from stage a) above is mixed with at least one epoxide compound of the above formula (IVa), in particular in the required stoichiometric amounts, in order to achieve the desired quaternization. The acid is preferably also added in stoichiometric amounts. Per equivalent of quaternizable tertiary nitrogen atom can be e.g. Use 0.1 to 2.0 equivalents, or 0.5 to 1, 25 equivalents of quaternizing agent. In particular, however, approximately equimolar amounts of the epoxide are used to quaternize a tertiary amine group. Correspondingly, higher amounts are required to quaternize a secondary or primary amine group. Suitable acids are especially carboxylic acids such as acetic acid. In this case, one typically works at temperatures in the range of 15 to 160 ° C, in particular from 20 to 150 or 40 to 140 ° C. The reaction time may be in the range of a few minutes or a few hours, e.g. about 10 minutes to about 24 hours. The reaction may be carried out at about 0.1 to 20 bar, e.g. 1 to 10 bar pressure. The pressure is usually determined by the vapor pressure of the alkylene oxide used at the respective reaction temperature. In particular, an inert gas atmosphere, such as e.g. Nitrogen, appropriate.

If necessary, the reactants may be presented in a suitable organic aliphatic or aromatic solvent or a mixture thereof for epoxidation, or there may still be a sufficient proportion of solvent from reaction step a). Typical examples are e.g. Solvesso series solvent, toluene or xylene. Furthermore, alkanols are suitable as solvents or as cosolvents in a mixture with the abovementioned solvents, such as, for example, methanol, ethanol, propanol, 2-ethylhexanol or 2-propylheptanol. b2) With compounds of the formula IV

To carry out the quaternization, the reaction product or reaction mixture from the above stage a) is admixed with at least one alkylating agent of the formula (IV), especially in the stoichiometric amounts required to achieve the desired quaternization. For example, 0, 1 to 5.0 equivalents, or 0.5 to 2.0 equivalents of quaternizing agent can be used per equivalent of quaternizable tertiary nitrogen atom. In particular, however, approximately equimolar amounts of the alkylating agent are used to quaternize a tertiary amine group. Correspondingly, higher amounts are required to quaternize a secondary or primary amine group. Particularly suitable quaternizing agents are methyl salicylate, dimethyl oxalate, dimethyl phthalate and dimethyl carbonate.

The reaction may optionally be accelerated by the addition of catalytic or stoichiometric amounts of an acid. Suitable acids are, for example, proton donors, such as aliphatic or aromatic carboxylic acids or fatty acids. Furthermore, Lewis acids, such as boron trifluoride, ZnC, MgC, AlC or FeC, are suitable. The acid can be used in amounts of 0.01 to 50% by weight, for example in the range 0, 1 to 10% by weight.

In this case, one typically works at temperatures in the range of 15 to 160 ° C, in particular from 20 to 150 or 40 to 140 ° C. The reaction time can be in the range of a few minutes or a few hours, such as about 10 minutes to about 24 hours. The reaction can be carried out at about 0.1 to 20 bar, such as 0.5 to 10 bar pressure. In particular, the reaction can be carried out at atmospheric pressure. In particular, an inert gas atmosphere, such as nitrogen, is useful. If necessary, the reactants may be presented in a suitable organic aliphatic or aromatic solvent or mixture thereof for quaternization, or there may still be a sufficient amount of solvent from reaction step a). Typical examples are, for example, solvents of the Solvesso series, toluene or xylene. Furthermore, alkanols are suitable as solvents or as cosolvents in a mixture with the abovementioned solvents, such as, for example, methanol, ethanol, propanol, butanol, 2-ethylhexanol or 2-propylheptanol. c) work-up of the reaction mixture The final reaction product thus formed can theoretically be further purified or the solvent removed. Usually, however, this is not absolutely necessary, so that the reaction product can be used without further purification as an additive, if appropriate after mixing with further additive components (see below). Optionally, the acid used can be removed by filtration, neutralization or extraction from the reaction product. Optionally, an excess of alkylating agent may be removed by distillation or by filtration. B) Further additive components

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

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

In the case of diesel fuels, these are primarily conventional detergent additives, carrier oils, cold flow improvers, lubricity improvers, corrosion inhibitors, demulsifiers, dehazers, antifoams, cetane number improvers, combustion improvers, antioxidants or stabilizers, antistatic agents, metallocene, metal deactivators, Dyes and / or solvents. In the case of gasoline fuels, these are mainly friction modifiers, corrosion inhibitors, demulsifiers, dehazers, antifoams, combustion improvers, antioxidants or stabilizers, antistatic agents, metallocenes, metal deactivators, dyes and / or solvents. Typical examples of suitable co-additives are listed in the following section:

B1) detergent additives The usual detergent additives are preferably amphiphilic substances which have at least one hydrophobic hydrocarbon radical with a number-average molecular weight (M _n ) of from 85 to 20 000 and at least one polar group selected from:

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

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

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

(Dd) carboxyl groups or their alkali metal or alkaline earth metal salts;

(De) sulfonic acid groups or their alkali metal or alkaline earth metal salts;

(Df) polyoxy-C 2 to C 4 -alkylene groups terminated by hydroxyl groups, mono or polyamino groups, wherein at least one nitrogen atom has basic properties, or terminated by carbamate groups;

(Dg) carboxylic acid ester groups; succinic anhydride-derived moieties having hydroxy and / or amino and / or amido and / or imido groups; and / or by Mannich reaction of substituted phenols with aldehydes and mono- or polyamines generated groups.

The hydrophobic hydrocarbon radical in the above detergent additives which provides sufficient solubility in the fuel has a number average molecular weight (M _n ) of 85 to 20,000, preferably 1 13 to 10,000, more preferably 300 to 5,000, more preferably 300 to 3,000, more preferably from 500 to 2,500, and especially from 700 to 2,500, especially from 800 to 1,500. As a typical hydrophobic hydrocarbon radical, in particular in connection with the polar groupings, in particular polypropenyl, polybutenyl and polyisobutenyl radicals having a number average molecular weight M _n of preferably from 300 to 5,000, more preferably from 300 to 3,000, more preferably from 500 to 2,500 are even more preferred 700 to 2,500 and especially 800 to 1, 500.

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

Other special monoamine (Da) containing additives are the hydrogenation products of the reaction products of polyisobutenes having an average degree of polymerization P = 5 to 100 with nitrogen oxides or mixtures of nitrogen oxides and oxygen, as described in particular in WO-A 97/03946. Other particular monoamino (Da) containing additives are the polyisobutene epoxides by reaction with amines and subsequent dehydration and reduction of the amino alcohols available compounds, as described in particular in DE-A 196 20 262.

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

Hydroxyl groups in combination with mono- or polyamino (De) containing additives are in particular reaction products of polyisobutene epoxides obtainable from preferably predominantly terminal double bonds having poly isobutene with M _n = 300 to 5000 with ammonia, mono- or polyamines, as described in particular in EP -A 476 485 are described. Carboxyl groups or their alkali metal or alkaline earth metal salts (Dd) containing additives are preferably copolymers of C2 to C4o-olefins with maleic anhydride having a total molecular weight of 500 to 20,000, the carboxyl groups wholly or partially to the alkali metal or alkaline earth metal salts and a remainder of the Carboxyl groups are reacted with alcohols or amines. Such additives are known in particular from EP-A 307 815. Such additives are primarily used to prevent valve seat wear and, as described in WO-A 87/01 126, can be advantageously used in combination with conventional fuel detergents such as poly (iso) buteneamines or polyetheramines. Sulfonic acid groups or their alkali metal or alkaline earth metal salts (De) containing additives are preferably alkali metal or alkaline earth metal salts of a Sulfobern- steinsäurealkylesters, as described in particular in EP-A 639 632. Such additives are mainly used to prevent valve seat wear and can be used with advantage in combination with conventional fuel detergents such as poly (iso) butenines or polyetheramines.

Polyoxy-C2-C4-alkylene (Df) containing additives are preferably lyether or polyetheramines, which by reaction of C2 to C6o-alkanols, C6 to C3o-alkanediols, mono- or D1-C2 to C3o-alkylamines, C 1 -C 30 -alkylcyclohexanols or C 1 -C 30 -alkylphenols with 1 to 30 mol of ethylene oxide and / or propylene oxide and / or butylene oxide per hydroxyl group or amino group and, in the case of polyetheramines, by subsequent reductive amination with ammonia, monoamines or polyamines are available. Such products are described in particular in EP-A 310 875, EP-A 356 725, EP-A 700 985 and US-A 4,877,416. In the case of polyethers, such products also meet carrier oil properties. Typical examples of these are tridecanol or Isotridecanolbutoxylate, isononylphenol butoxylates and Polyisobutenolbutoxylate and propoxylates and the corresponding reaction products with ammonia.

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

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

By Mannich reaction of substituted phenols with aldehydes and mono- or polyamines generated moieties containing (di) additives are preferably reaction products of polyisobutene-substituted phenols with formaldehyde and mono- or polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine or dimethylaminopropylamine , The polyisobutenyl-substituted phenols may be derived from conventional or highly reactive polyisobutene having M _n = 300 to 5,000. Such "polyisobutene-Mannich bases" are described in particular in EP-A 831 141. One or more of said detergent additives may be added to the fuel in such an amount that the dosage rate of these detergent additives is preferably from 25 to 2500 ppm by weight, in particular from 75 to 1500 ppm by weight, especially from 150 to 1000% by weight . ppm. B2) carrier oils

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

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

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

Examples of suitable polyethers or polyetheramines are preferably compounds containing polyoxy-C ₂ - to C ₄ -alkylene groups which are prepared by reacting C ₂ - to C ₆ -alkanols, C ₆ - to C ₃ -oxanediols, mono- or C 1 - to C 20 -alkylamines, C 1 -C 30 -alkylcyclohexanols or C 1 -C 30 -alkylphenols with 1 to 30 mol of ethylenoxide and / or propylene oxide and / or butylene oxide per hydroxyl group or amino group and, in the case of the polyetheramines, by subsequent reductive amination with ammonia, monoamines or polyamines are available. 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, P0IV-C2 to C6 alkylene oxide amines or functional derivatives thereof may be used as the polyether amines. Typical examples of these are tridecanol or Isotridecanolbutoxylate, Isononylphenolbutoxylate and Polyisobutenolbutoxylate and propoxylates and the corresponding reaction products with ammonia. Examples of carboxylic acid esters of long-chain alkanols are in particular esters of mono-, di- or tricarboxylic acids with long-chain alkanols or polyols, as described in particular in DE-A 38 38 918. As mono-, di- or tricarboxylic acids it is possible to use aliphatic or aromatic acids, especially suitable ester alcohols or polyols are long-chain representatives having, for example, 6 to 24 carbon atoms. Typical representatives of the esters are adipates, phthalates, isophthalates, terephthalates and trimellitates of isooctanol, isononanol, isodecanol and of isotridecanol, eg. B. di- (n- or isotridecyl) phthalate. 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-A 548 617.

Examples of particularly suitable synthetic carrier oils are alcohol-started polyethers having from about 5 to 35, preferably about 5 to 30, particularly preferably 10 to 30 and in particular 15 to 30 C3 to C6 alkylene oxide units, for. For example, propylene oxide, n-butylene oxide and isobutylene oxide units or mixtures thereof, per alcohol molecule. Nonlimiting examples of suitable starter alcohols are long-chain alkanols or long-chain alkyl-substituted phenols, where the long-chain alkyl radical is, in particular, a straight-chain or branched C 6 - to C 18 -alkyl radical. Specific examples include tridecanol and nonylphenol. Particularly preferred alcohol-started polyethers are the reaction products (polyetherification products) of monohydric C6- to Cis-aliphatic alcohols with C3- to C6-alkylene oxides. Examples of monohydric C6-C18 aliphatic alcohols are hexanol, heptanol, octanol, 2-ethylhexanol, nonyl alcohol, decanol, 3-propylheptanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, octadecanol and their constitution and positional isomers. The alcohols can be used both in the form of pure isomers and in the form of technical mixtures. A particularly preferred alcohol is tridecanol. Examples of C 3 - to C 6 -alkylene oxides are propylene oxide, such as 1, 2-propylene oxide, butylene oxide, such as 1, 2-butylene oxide, 2,3-butylene oxide, isobutylene oxide or tetrahydrofuran, pentylene oxide and hexylene oxide. Among these, particularly preferred are C ₃ -C ₄ -alkylene oxides, ie, propylene oxide such as 1, 2-propylene oxide and butylene oxide such as 1, 2-butylene oxide, 2,3-butylene oxide and isobutylene oxide. Specifically, butylene oxide is used. Further suitable synthetic carrier oils are alkoxylated alkylphenols, as described in DE-A 10 102 913.

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

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

B3) cold flow improver

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

Typically, the cold flow improver is selected from:

(K1) copolymers of a C2- to C4o-olefin with at least one further ethylenically unsaturated monomer;

(K2) comb polymers;

(K3) polyoxyalkylenes;

(K4) polar nitrogen compounds;

(K5) sulfocarboxylic acids or sulfonic acids or their derivatives; and

(K6) poly (meth) acrylic acid esters. Mixtures of different representatives from one of the respective classes (K1) to (K6) as well as mixtures of representatives from different classes (K1) to (K6) can be used. Suitable C2 to C4o-olefin monomers for the copolymers of class (K1) are for example those having 2 to 20, in particular 2 to 10 carbon atoms and having 1 to 3, preferably 1 or 2, in particular having a carbon-carbon double bond. In the latter case, the carbon-carbon double bond can be arranged both terminally (a-olefins) and internally. However, preference is given to α-olefins, more preferably α-olefins having 2 to 6 carbon atoms, for example propene, 1-butene, 1-pentene, 1-hexene and, above all, ethylene.

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

If further olefins are polymerized in, these are preferably higher molecular weight than the abovementioned C 2 - to C 4 -olefin base monomers. If, for example, ethylene or propene is used as the olefin base monomer, suitable further olefins are, in particular, C 10 -C ₄ -olefins. Other olefins are polymerized in most cases only when monomers with carboxylic acid ester functions are used.

Suitable (meth) acrylic esters are, for example, esters of (meth) acrylic acid with Cr to C 2 alkanols, in particular C 1 to C 1 alkanols, especially with methanol, ethanol, propanol, isopropanol, n-butanol, sec-butanol, isobutanol, tert Butanol, pentanol, hexanol, heptanol, octanol, 2-ethylhexanol, nonanol and decanol and structural isomers thereof. Suitable carboxylic alkenyl esters are, for example, C 2 - to C 6 -alkenyl esters, for example the vinyl and propenyl esters, of carboxylic acids having 2 to 21 carbon atoms, whose hydrocarbon radical may be linear or branched. Preferred among these are the vinyl esters. Among the carboxylic acids with a branched hydrocarbon radical, preference is given to those whose branching is in the α-position to the carboxyl group, wherein the α-carbon atom is particularly preferably tertiary, ie the carboxylic acid is a so-called neocarboxylic acid. Preferably, however, the hydrocarbon radical of the carboxylic acid is linear. Examples of suitable carboxylic alkenyl esters are vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl neopentanoate, vinyl hexanoate, vinyl neononanoate, vinyl neodecanoate and the corresponding propenyl esters, the vinyl esters being preferred. A particularly preferred carboxylic acid alkenyl ester is vinyl acetate; typical resulting copolymers of group (K1) are the most commonly used ethylene-vinyl acetate copolymers ("EVA"). Particularly advantageous ethylene-vinyl acetate copolymers and their preparation are described in WO 99/29748.

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

Terpolymers of a C2 to C ₄ oa olefin, a C to C2o alkyl ester of an ethylenically unsaturated monocarboxylic acid having 3 to 15 carbon atoms and a C 2 to C ₄ alkenyl ester of a saturated monocarboxylic acid having 2 to 21 carbon atoms as copolymers of the class (K1). Such terpolymers are described in WO 2005/054314. A typical such terpolymer is composed of ethylene, 2-ethylhexyl acrylate and vinyl acetate.

The at least one or the other ethylenically unsaturated monomers are present in the copolymers of class (K1) in an amount of preferably from 1 to 50% by weight, in particular from 10 to 45% by weight and especially from 20 to 40% by weight. %, based on the total copolymer, copolymerized. The majority by weight of the monomer units in the copolymers of class (K1) thus usually comes from the C2 to C ₄ o-based olefins. The copolymers of class (K1) preferably have a number-average molecular weight Mn of from 1000 to 20,000, particularly preferably from 1000 to 10,000 and in particular from 1000 to 8000. Typical comb polymers of component (K2) are, for example, by the copolymerization of maleic anhydride or fumaric acid with another ethylenically unsaturated monomer, for example with an α-olefin or an unsaturated ester, such as vinyl acetate, and subsequent esterification of the anhydride or acid function with an alcohol available with at least 10 carbon atoms. Other suitable comb polymers are copolymers of α-olefins and esterified comonomers, for example esterified copolymers of styrene and maleic anhydride or esterified copolymers of styrene and fumaric acid. Suitable comb polymers may also be polyfumarates or polymaleinates. In addition, homopolymers and copolymers of vinyl ethers are suitable comb polymers. Comb polymers suitable as a component of class (K2) are, for example, those described in WO 2004/035715 and in "Comb-Like Polymers, Structure and Properties", NA Plate and VP Shibaev, J. Poly. Be. Macromolecular Revs. Also, mixtures of comb polymers are suitable Polyoxyalkylenes suitable as a component of class (K3) are, for example, oxyalkylene esters, polyoxyalkylene ethers, mixed polyoxyalkylene ester ethers and mixtures thereof , preferably at least two linear alkyl groups each having 10 to 30 carbon atoms and a polyoxyalkylene group having a number average molecular weight of up to 5000. Such polyoxyalkylene compounds are described for example in EP-A 061 895 and in US 4 491 455. Particular polyoxyalkylene compounds are based on polyethylene glycols and Polypropylene glycols having a number average molecular weight of 100 to 5000. Further, polyoxyalkylene mono- and diesters of fatty acids having 10 to 30 carbon atoms such as stearic acid or behenic acid are suitable.

Polar nitrogen compounds suitable as a component of class (K4) may be both of ionic and nonionic nature and preferably have at least one, in particular at least two, substituents in the form of a tertiary nitrogen radical. atom of the general formula> NR ⁷ , in which R ^{7 is} a Cs to C4o hydrocarbon radical. The nitrogen substituents may also be quaternized, that is in cationic form. Examples of such nitrogen compounds are ammonium salts and / or amides obtainable by reacting at least one amine substituted with at least one hydrocarbyl radical with a carboxylic acid having 1 to 4 carboxyl groups or with a suitable derivative thereof. Preferably, the amines contain at least one linear Cs to C4o-alkyl radical. Examples of suitable primary amines for the preparation of said polar nitrogen compounds are octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tetradecylamine and the higher linear homologues, suitable secondary amines for this purpose are, for example, dioctadecylamine and methylbehenylamine. Also suitable for this purpose are amine mixtures, in particular industrially available amine mixtures such as fatty amines or hydrogenated tallamines, as described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 6th edition, in the chapter "Amines, aliphatic". Suitable acids for the reaction are, for example, cyclohexane-1,2-dicarboxylic acid, cyclohexene-1,2-dicarboxylic acid, cyclopentane-1,2-dicarboxylic acid, naphthalenedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid and succinic acids substituted by long-chain hydrocarbon radicals. In particular, the component of class (K4) is an oil-soluble reaction product of at least one tertiary amino group-containing poly (C 2 - to C 20 -carboxylic acids) with primary or secondary amines. The poly (C 2 - to C 20 -carboxylic acids) which have at least one tertiary amino group and are based on this reaction product preferably contain at least 3 carboxyl groups, in particular 3 to 12, especially 3 to 5, carboxyl groups. The carboxylic acid units in the polycarboxylic acids preferably have 2 to 10 carbon atoms, in particular they are acetic acid units. The carboxylic acid units are suitably linked to the polycarboxylic acids, usually via one or more carbon and / or nitrogen atoms. Preferably, they are attached to tertiary nitrogen atoms, which are connected in the case of several nitrogen atoms via hydrocarbon chains.

The component of class (K4) is preferably an oil-soluble reaction product based on poly (C 2 - to C 20 -carboxylic acids) of general formula IIa or IIb having at least one tertiary amino group HOOC. _DD OOH

B B

HOOC_ .N _ .N COOH

B A B (IIa)

HOOC " ^B " N " ^B " COOH

i

^{B ^} COOH (IIb) in which the variable A is a straight-chain or branched C 2 - to C 6 -alkylene group or the grouping of the formula III

HOOC ' ^{B 1} N ^{' CH 2 'CH 2'}

1

CH2-CH2- and the variable B denotes a C to Cig-alkylene group. The compounds of the general formula IIa and IIb have in particular the properties of a WASA.

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

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

Cr to Ci9-alkylene groups of the variables B are before, for example, 1, 2-ethylene, 1, 3-propylene, 1, 4-butylene, hexamethylene, octamethylene, decamethylene, dodecamethylene, tetradecamethylene, hexadecamethylene, octadecamethylene, Nonadecamethylen and especially methylene. Preferably, the variable B comprises 1 to 10, in particular 1 to 4, carbon atoms.

The primary and secondary amines as reaction partners for the polycarboxylic acids to form the component (K4) are usually monoamines, in particular aliphatic monoamines. These primary and secondary amines may be selected from a variety of amines bearing hydrocarbon radicals, optionally linked together. Most of these amines which are the oil-soluble reaction products of component (K4) are secondary amines and have the general formula HN (R ⁸ ) 2 in which the two variables R ⁸ independently of one another each represent straight-chain or branched C 10 - to C 30 -alkyl radicals, in particular Cu - to C24-alkyl radicals mean. These longer-chain alkyl radicals are preferably straight-chain or only slightly branched. As a rule, the abovementioned secondary amines are derived with regard to their longer-chain alkyl radicals from naturally occurring fatty acid or from its derivatives. Preferably, the two radicals R ^{8 are the} same.

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

Typical examples of such components (K4) are reaction products of nitrilotriacetic acid, ethylenediaminetetraacetic acid or propylene-1,2-diaminetetraacetic acid with in each case 0.5 to 1.5 mol per carboxyl group, in particular 0.8 to 1.2 mol per carboxyl group, dioleylamine, dipalmitinamine, dicoco fatty amine, distearylamine, dibehenylamine or especially ditallow fatty amine. A particularly preferred component (K4) is the reaction product of 1 mole of ethylenediaminetetraacetic acid and 4 moles of hydrogenated ditallow fatty amine. Other typical examples of the component (K4) include the N, N-dialkylammonium salts of 2-N ', Ν'-dialkylamidobenzoates, for example the reaction product of 1 mole of phthalic anhydride and 2 moles of Ditaigfettamin, the latter may be hydrogenated or unhydrogenated , and the reaction product of 1 mole of a Alkenylspirobislac- tons with 2 moles of a dialkylamine, for example, Ditaigfettamin and / or tallow fatty amine, the latter two may be hydrogenated or unhydrogenated, called.

Further typical structural types for the component of the class (K4) are cyclic compounds having tertiary amino groups or condensates of long-chain primary or secondary amines with carboxylic acid-containing polymers, as described in WO 93/181 15.

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

As cold flow improvers of the component of the class (K6) suitable poly (meth) acrylic esters are both homo- and copolymers of acrylic and methacrylic esters. Preferred are copolymers of at least two mutually different (meth) acrylic acid esters, which differ with respect to the fused alcohol. Optionally, the copolymer contains a further, different of which olefinically unsaturated monomer copolymerized. The weight-average molecular weight of the polymer is preferably 50,000 to 500,000. A particularly preferred polymer is a copolymer of methacrylic acid and methacrylic acid esters of saturated C14 and Cis alcohols wherein the acid groups are neutralized with hydrogenated tallamine. Suitable poly (meth) acrylic esters are described, for example, in WO 00/44857.

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

B4) Lubricity improver

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

B5) Corrosion inhibitors Suitable corrosion inhibitors are e.g. Succinic esters, especially with polyols, fatty acid derivatives, e.g. Oleic acid esters, oligomerized fatty acids, substituted ethanolamines and products sold under the trade name RC 4801 (Rhein Chemie Mannheim, Germany) or HiTEC 536 (Ethyl Corporation). B6) Demulsifiers

Suitable demulsifiers are e.g. the alkali or alkaline earth salts of alkyl-substituted phenol and naphthalene sulfonates and the alkali or alkaline earth salts of fatty acids, as well as neutral compounds such as alcohol alkoxylates, e.g. Alcohol ethoxylates, phenol alkoxylates, e.g. tert-butylphenol ethoxylate or tert-pentylphenol ethoxylate, fatty acids, alkylphenols, condensation products of ethylene oxide (EO) and propylene oxide (PO), e.g. also in the form of EO / PO block copolymers, polyethyleneimines or polysiloxanes. B7) Dehazer

Suitable dehazers are, for example, alkoxylated phenol-formaldehyde condensates, such as, for example, the products NALCO 7D07 (Nalco) and TOLAD 2683 (Petrolite) available under the trade name. B8) antifoam

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

B9) Cetane number improvers Suitable cetane number improvers are e.g. aliphatic nitrates such as 2-ethylhexyl nitrate and cyclohexyl nitrate and peroxides such as di-tert-butyl peroxide.

B10) Antioxidants Suitable antioxidants are e.g. substituted phenols such as 2,6-di-tert-butylphenol and 6-di-tert-butyl-3-methylphenol and phenylenediamines such as N, N'-di-sec-butyl-p-phenylenediamine.

B1 1) Metal deactivators

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

B12) Solvent

Suitable are, for example, nonpolar organic solvents such as aromatic and aliphatic hydrocarbons, for example toluene, xylenes, "white spirit" and products marketed under the trade name SHELLSOL (Royal Dutch / Shell Group) and EXXSOL (Exxon Mobil), and polar organic solvents, For example, alcohols such as 2-ethylhexanol, decanol and isotridecanol. Such solvents usually enter the diesel fuel together with the abovementioned additives and coadditives, which they are intended to dissolve or dilute for better handling. C) fuels The additive of the invention is outstandingly suitable as a fuel additive and can be used in principle in any fuels. It has a number of beneficial effects on the operation of internal combustion engines with fuels.

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

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

The qualities of fuel oils and diesel fuels are specified in greater detail in, for example, DI N 51603 and EN 590 (cf., also, Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Volume A12, page 617 ff.). In addition to its use in the abovementioned middle distillate fuels of fossil, vegetable or animal origin, which are essentially hydrocarbon mixtures, the quaternized additive according to the invention can also be used in mixtures of such middle distillates with biofuel oils (biodiesel). For the purposes of the present invention, such mixtures are also encompassed by the term "middle distillate fuel". They are commercially available and usually contain the biofuel oils in minor amounts, typically in amounts of 1 to 30 wt .-%, in particular from 3 to 10 wt .-%, based on the total amount of middle distillate of fossil, vegetable or animal origin and biofuel.

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

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

As gasoline fuels are all commercially available gasoline fuel compositions into consideration. A typical representative here is the market-standard basic fuel of Eurosuper according to EN 228. Furthermore, gasoline compositions of the specification according to WO 00/47698 are also possible fields of use for the present invention. The quaternized additive according to the invention is particularly suitable as a fuel additive in fuel compositions, especially in diesel fuels, to overcome the initially described problems in direct injection diesel engines, especially in those with common rail injection systems.

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

Experimental part:

A. General testing methods

1. XUD9 Test - Determination of Flow Restriction

The procedure is carried out according to the standard regulations according to CEC F-23-1 -01. 2. DWI O test - Determination of power loss due to injector deposits in the common rail diesel engine

2.1. DW10-KC - Keep Clean Test

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

Change and special features:

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

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

Power determination:

The initial power P0, KC [kW] is calculated from the measured torque at 4000 rpm full load directly after the test start and warm-up of the engine. The procedure is described in issue 5 of the test procedure (CEC F-98-08). The same test setup and the PEUGEOT DW10 motor type are used. The final power (Pend, KC) is determined in the 12th cycle in stage 12, (see table, Figure 2). Again, the operating point is 4000 / min full load. Pend, KC [kW] is calculated from the measured torque.

The power loss in the KC test is calculated as follows:

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

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

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

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

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

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

Power determination:

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

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

The power loss in the DU is calculated as follows

Clean up

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

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

The power loss in the CU test is calculated as follows (negative number in the power loss in the cu test means performance increase)

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

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

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

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

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

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

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

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

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

The IDID test indicates internal deposit formation in the injector. The characteristic used in this test is the exhaust gas temperature of the individual cylinders. For an injector system Without IDID, the exhaust gas temperatures of the cylinders increase evenly. If the IDID is available, the exhaust gas temperatures of the individual cylinders do not increase uniformly and deviate from one another. The temperature sensors are located behind the cylinder head outlet in the exhaust manifold. Significant deviations of the individual cylinder temperatures (eg> 20 ° C) indicate the presence of internal injector deposits (IDID).

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

B. Manufacturing and Analysis Examples:

Reactants used:

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

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

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

Potassium butoxide-butylate CAS. 865-47-4 Company Aldrich

Dimethyloxalate CAS. 553-90-2 Company Aldrich

Solvent Naphtha Heavy CAS. 64742-94-5 Company Exxon Mobil

Styrene oxide CAS. 96-09-3 Company Aldrich

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

Lauric acid CAS. 143-07-7 Company Aldrich

Isotridecanol N CAS. 27458-92-0 Company BASF

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

Formic acid, 85% in H2O CAS 64-18-6 company Kraft

Formalin, 36.5% CAS 50-00-0 Aldrich

Polydispersities D were determined by gel permeation chromatography. Synthetic Example 1: N, N-dimethylethanolamine * 15 PO (A) In an autoclave, N, N-dimethylethanolamine (76.7 g) is treated with potassium ferric butylate (4.1 g). It is rinsed three times with N2, a pre-pressure of approximately 1.3 bar N2 is set and the temperature is raised to 130.degree. 1, 2-Propylene oxide (750 g) is metered in over a period of 10 h so that the temperature remains between 129 ° C-131 ° C. The mixture is then 6 h at 130 ° C stirred, rinsed with N 2, cooled to 60 ° C and the reactor emptied. Excess propylene oxide is removed on a rotary evaporator in vacuo. The basic crude product is neutralized using commercially available Mg silicates, which are then filtered off. 831 g of the product are obtained in the form of an orange oil (TBN 58, 1 mg KOH / g; D 1, 16).

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

In an autoclave, N, N-dimethylethanolamine (47.1 g) is added with potassium feri-butylate (5.0 g). It is rinsed three times with N2, a pre-pressure of approximately 1.3 bar N2 is set and the temperature is increased to 140.degree. 1, 2-butylene oxide (953 g) is metered over a period of 9 h so that the temperature remains between 138 ° C-141 ° C. The mixture is then stirred for 6 h at 140 ° C, rinsed with N2, cooled to 60 ° C and the reactor emptied. Excess butylene oxide is removed on a rotary evaporator in vacuo. The basic crude product is neutralized using commercially available Mg silicates, which are then filtered off. 1000 g of the product are obtained in the form of a yellow oil (TBN 28, 1 mg KOH / g, D 1, 12).

Synthesis Example 3: N, N-Dimethylethanolamine * 15 PO quaternized with dimethyl oxalate (I) Polyetheramine (A) (250 g) from Synthesis Example 1 is treated with dimethyl oxalate (59 g) and lauric acid (12.5 g) and the reaction mixture is treated for 4 Stirred at a temperature of 120 ° C. Subsequently, excess dimethyl oxalate is removed on a rotary evaporator under reduced pressure (p = 5 mbar) at a temperature of 120 ° C. This gives 290 g of the product. ¹ H NMR analysis of the resulting quaternized polyetheramine shows the quaternization.

Synthesis Example 4: N, N-Dimethylethanolamine * 25 BuO quaternized with dimethyl oxalate (II) Polyetheramine (B) (250 g) from Synthesis Example 2 is added with dimethyl oxalate (67.3 g) and lauric acid (6.2 g), and the reaction mixture is stirred for 4.5 hours at a temperature of 120 ° C. Subsequently, excess dimethyl oxalate is removed on a rotary evaporator under reduced pressure (p = 5 mbar) at a temperature of 120 ° C. 270 g of the product are obtained. ¹ H NMR analysis of the resulting quaternized polyetheramine shows the quaternization.

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

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

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

Polyetheramine (A) (305 g) from Synthesis Example 1 is dissolved in 2-ethylhexanol (341 g) in a 21-liter autoclave, and acetic acid (18.3 g) is added. It is rinsed three times with N2, a pre-pressure of about 1 .3 bar N2 set and the temperature increased to 130 ° C. 1, 2-propylene oxide (17.7 g) is metered. The mixture is then stirred for 5 h at 130 ° C, rinsed with N2, cooled to 40 ° C and the reactor emptied. Excess propylene oxide is removed on a rotary evaporator in vacuo. This gives 675 g of the product in the form of an orange oil. ¹ H-NMR analysis of the resulting solution of the quaternized polyetheramine in 2-ethylhexanol shows the quaternization. Synthesis Example 7: N, N-Dimethylethanolamine * 15 PO quaternized with ethylene oxide / acetic acid (V)

In a 21-liter autoclave, polyetheramine (A) (518 g) from Synthesis Example 1 is dissolved in 2-ethylhexanol (570 g) and treated with conc. Acetic acid (30 g) was added. It will be three times flushed with N2, a pre-pressure of about 1 .3 bar N2 set and the temperature increased to 130 ° C. Ethylene oxide (22 g) is added. The mixture is then stirred for 5 h at 130 ° C, rinsed with N2, cooled to 40 ° C and the reactor emptied. This gives 1 1 16 g of the product in the form of an orange oil. ¹ H-NMR analysis of the resulting solution of the quaternized polyetheramine in 2-ethylhexanol shows the quaternization.

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

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

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

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

Synthesis Example 10: Tert. Polyetheramine (E)

The polyetheramine (D) (400 g) from Synthesis Example 9 is treated under ice bath cooling with formic acid (65.3 g, 85% in H2O). The reaction mixture is then heated to a temperature of 45 ° C and formaldehyde solution (44.9 g, 36.5% in H 2 O) is added dropwise at this temperature, wherein the liberated carbon dioxide is discharged from the reaction vessel. The reaction mixture is stirred for 16 h at a temperature of 80 ° C. The reaction mixture is then cooled to room temperature, admixed with hydrochloric acid (37%, 35.4 g) and stirred at room temperature for 1 h. H2O (500 ml) is added and the aqueous phase is adjusted to a pH of about 10 by addition of 50% potassium hydroxide solution. Then the mixture is extracted several times with ferric butyl methyl ether (total 1200 ml). The combined organic phases are washed with sat. washed aqueous NaCl solution, dried over MgSC and the solvent is removed in vacuo. You get 403 g of the product in the form of a yellow oil. ¹ H-NMR analysis of the thus obtained tert. Polyetheramine shows the reductive dimethylation.

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

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

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

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

C. Application examples:

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

Application Example 1: Determination of the Additive Effect on the Formation of Deposits in Diesel Engine Injectors a) XUD9 Tests

Fuel used: RF-06-03 (Referenzdiesel, Haltermann Products, Hamburg) The results are summarized in Table 1. Table 1: XUD9 tests

b) DWI O Test The test results are shown in Table 2.

Table 2: Results of the DW10 test

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

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

Fuel: E5 according to EN 228

Additive according to Synthesis Example 4

Results :

Inlet valve deposit after end of test (mg / V)

Basic value (without additive) 1 12

With 1 16 mg / kg additive 86 Example of use 3: Injector cleanliness

(Direct injection of petrol engine)

Method: BASF house method

Engine: Charged four-cylinder with 1, 6 liter capacity

Test duration: 60 hours

Fuel: test fuel with 7 vol.% Oxygenated components

Additives:

A: additive according to Synthesis Example 4

B: additive according to Synthesis Example 3

*: The FR value is a parameter detected by the engine control, which correlates with the duration of fuel injection into the combustion chamber. The more pronounced the formation of deposits in the injector nozzles, the longer the injection duration or higher the FR value. Conversely, the FR value remains constant or tends to decrease slightly as the injector nozzles remain debris free.

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

Claims

claims

1 . A fuel or lubricant composition comprising, in a conventional fuel or lubricant, at least one reaction product comprising a quaternized nitrogen compound, the reaction product being obtainable by

implementation

a) a polyether-substituted amine containing at least one tertiary, quaternizable amino group

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

2. A fuel or lubricant composition according to claim 1, wherein the polyether substituent comprises monomer units of general formula Ic - [- CH (R ₃ ) -CH (R ₄ ) -O -] - (Ic) wherein

R 3 and R ₄ are identical or different and are H, alkyl, alkylaryl or aryl.

3. 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 5,000. 4. A fuel or lubricant composition according to any one of the preceding claims, wherein the quaternizing agent is selected from alkylene oxides, optionally in combination with acid; aliphatic or aromatic carboxylic acid esters, in particular dialkyl carboxylates; alkanoates; cyclic non-aromatic or aromatic carboxylic acid esters; alkyl sulfates; Alkyl halides; alkylaryl halides; and mixtures thereof.

5. A fuel or lubricant composition comprising, in a majority of a conventional fuel or lubricant, an effective amount of at least one quaternized nitrogen compound of general formula Ia or Ib,

X ^"

X ^" in which

R 3 and R ₄ are identical or different and are H, alkyl, alkylaryl, or aryl;

R6 is alkyl, alkenyl, optionally mono- or polyunsaturated cycloalkyl, aryl, each optionally substituted, e.g. with at least one hydroxyl radical or alkyl radical, or interrupted by at least one heteroatom;

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

n stands for an integer value of 1 to 50 and

A fuel or lubricant composition according to claim 5, wherein

R 1 and R 2 are identical or different and are C 1 -C 6 -alkyl, hydroxy-C 1 -C 6 -alkyl, hydroxy-C 1 -C 6 -alkenyl, or amino-C 1 -C 6 -alkyl, or R 1 and R 2 together form a C 2 -C 6 Alkylene, C2-C6-oxyalkylene or C2-C6-aminoalkylene radical;

R 6 is C 1 -C 20 -alkyl or aryl or alkylaryl; A is a straight-chain or branched C 2 -C 6 -alkylene radical which is optionally interrupted by one or more heteroatoms, such as N, O and S; n for an integer value of 1 to 30 and

X- represents an anion resulting from the quaternization reaction.

Fuel composition according to one of the preceding claims, selected from diesel fuels, gasoline fuels, biodiesel fuels and alkanol-containing gasolines.

Quaternized nitrogen compound as defined in any one of the preceding claims.

X

wherein

Ri to R5, A, X and n have the abovementioned meanings wherein a) an aminoalkanol of the general formula II

(R.XFyN where

Ri, R2 and A have the meanings given above, with an epoxide of the general formula III O

/ \

(R ₃ ) HC CH (R ₄ ) wherein

Rβ and R _{4 have} the meanings given above,

alkoxylated to give an alkoxylated amine of the formula

R ₅ -X (IV) wherein

O

/ (IVa)

Quaternized H ₂ C CH (R _5. ) In combination with an acid HX in which X has the abovementioned meaning, where Rs' is H, alkyl or aryl and the radical R _{5 is} a group -CH ₂ CH (OH) R ₅ 'is. 10. A process for the preparation of quaternized nitrogen compounds of general formula Ib,

X in which Ri to R6, X and n have the abovementioned meanings

a) an alcohol of the general formula V

Re-OH (V) wherein

R6 has the meanings given above, with an epoxide of the general formula III

O

/ (III)

(R ₃ ) HC CH (R ₄ ) wherein

R ₃ and R _{4 have} the meanings given above, alkoxylated, to give a polyether of the formula Ib-1;

R ₆ -O-CH (R ₃ ) -CH (R ₄ ) -O-CH (R ₃ ) -CH (R ₄ ) OH (Ib-1); wherein R3, _R4 and R6, A, X and n have the meanings given above b) then the polyether of the formula lb-1 thus obtained with an amine of general formula

in which R1 and R2 have the meanings given above,

aminated to obtain an amine of the formula Ib-2

R 1 - O- ["CH (R ₃ ) -CH (R ₄ ) -O-j ₁ -1CH (R ₃ ) -CH (R ₄ ) ^_N (R ₁ ) (R ₂ ) (lb-2) in which R 1 to R ₄ and R ₆ , A, X and n have the abovementioned meanings, the alkyl of the formula (Ib-2) is optionally alkylated, if R 1 and / or R 2 are H and then c) the product from stage b) quaternized to obtain a reaction product comprising at least one compound of general formula Ib, wherein the quaternization is carried out for example with a compound of general formula IV

R ₅ -X (IV) wherein

O

/ (IVa)

H ₂ C CH (R _5. ) Quaternized in combination with an acid HX, wherein X has the meaning indicated above, wherein R ₅ 'is H, alkyl or aryl and the radical R _{5 is} a

Group -CH ₂ CH (OH) R ₅ '.

1 1. A method according to claim 9 or 10, wherein the quaternizing agent is selected from: alkylene oxides, optionally in combination with an acid; Alkylcarbonates, such as dialkyl carbonates; Alkyl sulfates, such as dialkyl sulfates; alkyl phosphates,

Dialkyl phosphates, halides such as alkyl or aryl halides; aliphatic and aromatic carboxylic acid esters, such as alkanoates, dicarboxylic acid esters; and cyclic aromatic or non-aromatic carboxylic acid esters. 12. Quaternized nitrogen compound obtainable by a process according to claim 10 or 11.

13. Use of a quaternized nitrogen compound according to claim 8 or prepared according to any one of claims 9 to 1 1 as a fuel additive or lubricant additive.

14. Use according to claim 13 as a diesel fuel additive, in particular as a cold flow improver or as a wax anti-settling additive (WASA).

15. Use according to claim 13 as a gasoline additive for reducing or

Avoiding deposits in the intake system of a gasoline engine, in particular for reducing or avoiding deposits in injection nozzles of direct-injection gasoline engines.

16. Use according to claim 13 as an additive for reducing the fuel consumption of direct injection diesel engines, in particular for reducing the fuel consumption of diesel engines with common rail injection systems, and / or for minimizing the power loss in direct injection diesel engines, especially in diesel engines with Com- Mon-Rail injection systems or as an additive for reducing and / or preventing deposits in the injection systems, such as in particular the Internal Diesel Injector Deposits (IDID) and / or for reducing and / or preventing deposits in the injectors in direct-injection diesel engines, in particular common rail injection systems.

17. An additive concentrate, containing in combination with other diesel or petrol additives, at least one quaternized nitrogen compound as defined in claim 8 or prepared according to any one of claims 9 or 10.