WO2018007486A1

WO2018007486A1 - Polymers as additives for fuels and lubricants

Info

Publication number: WO2018007486A1
Application number: PCT/EP2017/066865
Authority: WO
Inventors: Ivette Garcia Castro; Maxim Peretolchin; Jochen Mezger; Aaron FLORES-FIGUEROA
Original assignee: Basf Se
Priority date: 2016-07-07
Filing date: 2017-07-06
Publication date: 2018-01-11

Abstract

The invention relates to the use of specific polymers as fuel or lubricant additives; to methods for producing said additives, and to fuels and lubricants comprising said additives; and in particular as a detergent additive; to the use of said polymers for reducing or preventing deposits in the fuel systems and particularly in the injection systems of direct-injection diesel engines, in particular in common rail injection systems, for reducing the fuel consumption of direct-injection diesel engines, in particular of diesel engines having common rail injection systems, and for minimizing the power loss in direct-injection diesel engines, in particular in diesel engines having common rail injection systems. The invention further relates to their use as additives for spark-ignition fuels, in particular for the operation of DISI engines.

Description

Polymers as additives for power and lubricants

The present invention relates to the use of certain polymers as a fuel or lubricant additive; Process for the preparation of such additives, and additives and fuels additized therewith; in particular as a detergent additive; Use of these polymers to reduce or prevent deposits in the fuel systems and in particular injection systems of direct injection diesel engines, especially in common rail injection systems, to reduce the fuel consumption of direct injection diesel engines, especially diesel engines with common rail injection systems, and to minimize the Power loss in direct injection diesel engines, especially in diesel engines with common rail injection systems; and as an additive for gasoline fuels, in particular for the operation of DISI engines.

Background of the invention:

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

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

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

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

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

Deposits in the injection systems of modern diesel engines cause significant perfor- mance problems. It is widely recognized that such deposits in the spray channels can lead to a reduction of the fuel flow and thus to power losses. Deposits on the injector tip, on the other hand, impair the optimum formation of fuel spray and thus cause a deterioration in combustion and, as a result, higher emissions and increased fuel consumption. In contrast to these conventional "outward" deposition phenomena, "internal" deposits (collectively referred to as internal diesel injector deposits (I DI D)) also present in certain parts of the injectors, such as the nozzle needle, the spool, the valve piston, the valve seat , on the drive unit and on the guides of these components increasingly performance problems. Conventional additives show insufficient activity against these IDIDs. The term "injection system" is understood to mean the part of the fuel system in motor vehicles from the fuel pump through the injector outlet. In this case, the term "fuel system" is understood to mean the components of motor vehicles that are in contact with the respective fuel, preferably the area from the tank up to and including the injector outlet.

It is an embodiment of the present invention that the compounds of the invention against deposits not only act in the injection system, but also in the rest of the fuel system, in particular against deposits in fuel filters and pumps. US Pat. No. 4,248,719 describes quaternized ammonium salts which are prepared by reacting an alkenyl succinimide with a monocarboxylic acid ester and are used as dispersants in lubricating oils to prevent sludge formation. In particular, the reaction of polyisobutylsuccinic anhydride (PIBSA) with Ν, Ν-dimethylaminopropylamine (DMAPA) and quaternization with methyl salicylate is described, for example. However, an application in fuels, in particular diesel fuels, is not proposed therein. The use of PIBSA with low bis-malalination <20% is not described therein.

US Pat. No. 4,171,959 describes quaternized ammonium salts of hydrocarbyl-substituted succinimides which are suitable as detergent additives for gasoline fuel compositions. For quaternization, alkyl halides are preferably used. Also mentioned are organic C 2 -C 8 hydrocarbyl carboxylates and

Sulfonates. Thus, the quaternized ammonium salts provided by the teachings have as counterion either a halide or a C 2 -C 8 hydrocarbyl carboxylate or a C 2 -C 8 hydrocarbyl sulfonate group. The use of PIBSA with low bis-malalination <20% is also not described therein.

From EP-A-2 033 945 cold flow improvers are known which are prepared by quaternization of special tertiary monoamines which carry at least one Ce-C4o-alkyl radical with a C1-C4 alkyl ester of special carboxylic acids. Examples of such carboxylic acid esters are dimethyloxalate, dimethyl maleate, dimethyl phthalate and dimethyl fumarate. Applications other than to improve the CFPP value of middle distillates are not documented in EP-A-2 033 945. WO 2006/135881 describes quaternized ammonium salts prepared by condensation of a hydrocarbyl-substituted acylating agent and an oxygen or nitrogen tertiary amino group-containing compound, followed by quaternization by means of hydrocarbyl epoxide in combination with stoichiometric amounts of an acid such as in particular acetic acid. Further quaternizing agents claimed in WO 2006/135881 are dialkyl sulfates, benzyl halides and hydrocarbyl-substituted carbonates, with dimethyl sulfate, benzyl chloride and dimethyl carbonate being investigated experimentally.

WO 201 1/146289 discloses nitrogen-free additives of a substituted hydrocarbon having at least two carboxyl groups in free or anhydride form for improving detergency in fuel systems. As an example, hydrocarbyl substituted succinic anhydrides and hydrolyzed forms thereof are disclosed, inter alia.

WO 2012/130824 describes copolymers of ethylenically α, β-unsaturated dicarboxylic acids or derivatives thereof and ethylenically unsaturated carboxylic acid esters in which the ethylenic double bond is not in conjugation with the carboxyl-carbon atom.

The copolymers are used to improve the cold flow properties of middle distillate fuels. An effect of these copolymers to reduce or reduce deposits is not mentioned.

The present invention has for its object to provide a new class of polymer-based additives for use in modern diesel and gasoline fuels.

Summary of the invention:

Surprisingly, the above problem could be solved by polymers composed of (i) 10 to 90 mol% of repeating units of structure W1

in which the variables R ¹ and R ² independently of one another denote hydrogen, C 1 - to C ₄ -alkyl, carboxyl-COOH or carboxyl ester

Grouping of the formula -COOR ⁹ , wherein R ^{9 is} a C6 to C30 hydrocarbyl radical and wherein one of the variables R ¹ or R ^{2 is} hydrogen or

C 1 to C ₄ alkyl and the other represents a carboxyl-COOH or carboxyl ester group of formula -COOR ⁹ , and in the variables R ³ and R ^4, independently of one another, denote hydrogen, C 1 -C 4 -alkyl, carboxyl-COOH or carboxyl ester groupings of the formula -COOR ⁹ , where R ^{9 is} a C 6 - to C 30 -hydrocarbyl radical, where carboxyl groups also in the form of their alkali metal, Erdalkalimetalloder or ammonium salts, wherein one of the variables R ³ or R ^{4 is} hydrogen or C 1 to C ₄ alkyl and the other a carboxyl ester group of the formula -COOR ⁹ and / or a carboxyl group, which may also be in the form of its alkali metal, alkaline earth metal or ammonium salt,

or one of the radicals R ¹ and R ² and one of the radicals R ³ and R ^{4 may} together form a grouping -CO-O-CO-,

and (ii) 90 to 10 mole% repeat units of structure W2

in which the variable R ^{5 is} the radical of a carboxylic acid ester of the formula

-A-CO-OR ⁰ , where the variable A is a C 1 to C 20 alkylene group and the

Variable R ¹⁰ denotes a hydrogen or a C 1 to C 30 hydrocarbyl radical, or the grouping of the formula -COOR ^{10 represents} a carboxyl group which may also be present in the form of its alkali metal, alkaline earth metal or ammonium salt and in which the variables R ⁶ , R ⁷ and R ^{8 are} independently hydrogen or C 1 to C ⁶ alkyl, and

(iii) 0 to 80 mole% repeat units of the structure W3 - [- H ₂ C-CHR ^a -] - (W 3) in which the variable R ^{a is} a C 10 to C 28 hydrocarbyl radical, wherein the sum of repeat units W1, W2 and W3 is 100 mol%. The polymers according to the present invention are copolymers.

The polymers can be obtained by any desired method, preferably by polyaddition or polycondensation, preferably by polyaddition. The polyaddition can preferably be free-radical or ionic, preferably free-radical. These polymers are characterized in particular by the fact that they act against a variety of deposits that affect the performance of modern diesel engines. The compounds according to the invention have an effect, for example, against loss of power, both caused by zinc input and also due to sodium introduction into the diesel fuel. In this case, deposits in the spray channels and the injector tip are essentially eliminated or avoided. On the other hand, however, the compounds according to the invention also act against internal diesel injector deposits (IDID), caused by Na, Ca and / or K ions (so-called Na, Ca or K soaps IDID) and / or polymers deposits. Na, Ca or K soaps IDIDs are deposits that contain the respective metal ions with any counterions. In contrast, the polymeric deposits are free of metal ions and due to high molecular weight and in the fuel little or insoluble organic material.

DESCRIPTION OF THE FIGURES FIG. 1 shows the sequence of a one-hour engine test cycle according to CEC F-098-08.

Detailed Description of the Invention: A1) Specific Embodiments

Specific embodiments of the invention are:

1. Use of the polymers described in this document as a fuel or lubricant additive, in particular diesel fuel additive.

2. Use according to the embodiment 1 as an additive for reducing the fuel consumption of direct-injection diesel engines, in particular of diesel engines with common-rail injection systems. Use according to one of the embodiments as an additive for minimizing the power loss in direct injection diesel engines, in particular in diesel engines with common rail injection systems.

Use according to one of the embodiments as an additive for minimizing the power loss due to K, Zn, Ca and / or Na ions (so-called K, Zn, Ca or Na powerloss).

Use according to one of the embodiments 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 one of the embodiments as a diesel fuel additive for reducing and / or avoiding deposits in the fuel systems, in particular injection systems, such as in particular the Internal Diesel Injector Deposits (IDID) and / or valve sticking in direct injection diesel engines, especially in common rail injection systems.

Use according to one of the embodiments as a diesel fuel additive for reducing and / or avoiding internal diesel injector deposits (IDID) caused by Na, Ca and / or K ions (so-called Na, Ca or K soaps IDID).

Use according to one of the embodiments as a diesel fuel additive for reducing and / or avoiding internal diesel injector deposits (IDID) due to polymer deposits.

Use according to one of the preceding embodiments, wherein the fuel is selected from diesel fuels, biodiesel fuels, gasoline fuels and alkanol, in particular ethanol-containing gasoline fuels. Additive concentrate containing in combination with other diesel or petrol additives or lubricant additives at least one of the polymers described in this document. 1 1. A fuel composition, lubricant composition or kerosene composition, in particular a diesel fuel composition, containing at least one of the polymers described in this document. Description of the polymer

The polymers of the invention are composed of

(i) 10 to 90 mole% repeat units of structure W1

Grouping of the formula -COOR ⁹ , wherein R ^{9 is} a C6 to C30 hydrocarbyl radical and wherein one of the variables R ¹ or R ^{2 is} hydrogen or Cr to C ₄ alkyl and the other is a carboxyl-COOH or carboxyl ester group of the Formula -COOR ⁹ , and in the variable R ³ and R ^{4 are} independently hydrogen, Cr to C ₄ alkyl, carboxyl-COOH or carboxyl ester groups of the formula -COOR ⁹ , wherein R ^{9 is} a C6 to C3o Hydrocarbyl is, wherein carboxyl groups may also be present in the form of their alkali metal, Erdalkalimetalloder or ammonium salts, wherein one of the variables R ³ or R ^{4 is} hydrogen or C to C ₄ alkyl and the other a carboxyl ester group of the formula -COOR ⁹ and / or a carboxyl group which is also present in

Form of their alkali metal, alkaline earth metal or ammonium salt,

or one of the radicals R ¹ and R ² and one of the radicals R ³ and R ⁴ together a

Grouping -CO-O-CO- [we would have detected unhydrolysed maleic anhydride units],

and

90 to 10 mol% of repeating units of structure W2

in which the variable R ^{5 is} the radical of a carboxylic acid ester of the formula -A-CO-OR ⁰ , where the variable A is a C 1 - to C 20 -alkylene group and the

Variable R ¹⁰ denotes a hydrogen or a C 1 to C 30 hydrocarbyl radical, or the grouping of the formula -COOR ^{10 represents} a carboxyl group which may also be present in the form of its alkali metal, alkaline earth metal or ammonium salt and in which the variables R ⁶ , R ⁷ and R ^{8 are} independently hydrogen or C to Ce-alkyl, and

(iii) 0 to 80 mole% repeat units of structure W3

- [- H ₂ C-CHR ^a -] - (W 3) in which the variable R ^{a is} a C 10 to C 28 hydrocarbyl radical, the sum of the repeat units W 1, W 2 and W 3 giving 100 mol%.

In the context of the present invention, the following definitions apply to generically defined radicals:

Hydrocarbyl radicals are radicals of linear or branched hydrocarbon chains, which may also contain minor amounts of heteroatoms such as oxygen, nitrogen or halogen atoms, for example chlorine, and / or non-protic functional groups such as carboxyl ester groups, cyano groups or nitro groups, without the predominantly hydrophobic hydrocarbon character of these radicals substantially, and usually no carbon-carbon double or triple bonds and also no other unsaturations, which could interfere formation of copolymers of (i) and (ii) have. However, preference is given as the C 1 -C 30 -hydrocarbyl radicals to pure cycloalkyl radicals which may also carry alkyl side chains, and / or in particular to straight-chain or branched alkyl radicals having in each case the same total number of carbon atoms.

Examples of such d- to C ₄ - or d- to Cs- or d- to C30- or C6- to C30- or C10- to C28- or Cs- to C16- or C10- to Ci _4- alkyl or -cycloalkyl radicals are methyl, ethyl, n- Propyl, isopropyl, n -butyl, 2-butyl, isobutyl, tert -butyl, 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, 1-ethyl 2-methylpropyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, iso-nonyl, n-decyl, 2-propylheptyl, n-undecyl, n-dodecyl, n-tri-decyl, iso-tridecyl , n-tetradecyl, n-hexadecyl, n-octadecyl, n-eicosyl, n-heneicosyl, n -docosyl, n-tricosyl, n-tetracosyl, n-pentacosyl, and n-hexacosyl and as corresponding cycloalkyl radicals which also carry alkyl side chains may be cyclopentyl, 2- or 3-methylcyclopentyl, 2,3-, 2,4- or 2,5-dimethylcyclopentyl, cyclohexyl, 2-, 3- or 4-methylcyclohexyl, 2,3-, 2,4-, 2 . 5-, 2,6-, 3,4-, 3,5- or 3,6-dimethylcyclohexyl, cycloheptyl, 2-, 3- or 4-methylcycloheptyl, cyclooctyl, 2-, 3-, 4- or 5 -Methylcyclooctyl. Reasonable cycloalkyl radicals usually carry at least 4 carbon atoms in the ring.

Suitable C 1 to C 20 or linear C ₄ to C 12 and preferably C ₆ to C 10 alkylene groups for the variable A are, in principle, all divalent linear or branched saturated aliphatic hydrocarbon radicals, but preference is given to polyalkylene groups of the formula - (CH ₂ ) _m -, in which m is a number from 1 to 20, in particular 2 to 16, especially 4 to 12, very particularly preferably 6 to 10, for example 7, 8 or 9. In the case of branched alkylene groups, in addition to the α, ω-linking hydrocarbon bodies, nonlinear bridge members such as 1,1-ethylene, 1,1-propylene, 2,2-propylene, 1,2-propylene, 2-methyl-1, 4-butylene, 3-methyl-1, 5-pentylene or 2-ethyl-1, 6-hexylene. Preferred radicals A are methylene, 1,2-ethylene, 1,2-propylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene, 1,6-hexylene, 1,7-heptylene, 1, 8-octylene, 1, 9-nonylene and 1, 10-decylene.

The novel copolymer can in principle be random, block-like or alternating. An alternate construction is preferred. In particular, it is an alternating structure of structural units W1 and a structural unit selected from the group consisting of W2 and W3. Accordingly, the copolymer according to the invention is preferably from 25 to 75 mol%, in particular from 45 to 55 mol%, especially from 49 to 51 mol% of repeating units of structure W1 and from 75 to 25 mol%, in particular from 55 to 45 mol%, Above all, 51 to 49 mol% of repeat units of the structure W2 built.

In the event that structural units W3 are present, the copolymer according to the invention is preferably from 25 to 75 mol%, in particular from 45 to 55 mol%, especially from 49 to 51 mol% of repeat units of structure W1 and from 75 to 25 mol%, in particular 55 to 45 mol%, in particular 51 to 49 mol% of repeat units of structure W2 and W3 (in total). In this case, the molar distribution of the structural units W2 and W3 can vary, for example, from 10: 1 to 1:10, preferably from 7: 1 to 1: 7, particularly preferably from 5: 1 to 1: 5, very particularly preferably from 4: 1 to 1: 4, in particular from 3: 1 to 1: 3 and especially from 2: 1 to 1: 2. In a particular embodiment, the ratio of the structural units W2 and W3 is 1: 1.

In a preferred embodiment, the variables in repeat unit W1 have the following meanings:

R ^{1 is} hydrogen,

R ² is a carboxylic ester group of the formula -COOR ⁹ wherein R ⁹ is a Cs to Ci6-, more particularly a C10 to Cu-hydrocarbyl group,

R ³ is hydrogen,

R ^{4 is} a carboxyl ester grouping of the formula -COOR ⁹ , where R ^{9 is} a C 8 to C 16, in particular a C 10 to C 30 hydrocarbyl radical, and / or a carboxyl group, which is also present in the form of its alkali metal, alkaline earth metal or ammonium salt may be present. In a further preferred embodiment, the variables in the repeat unit W1 have the following meanings:

R ^{1 is} hydrogen, R ^{3 is} hydrogen,

R ² and R ⁴ together form a grouping -CO-O-CO-.

In a further preferred embodiment, the variables in the repetition unit W2 have the following meanings:

R ^{5 is} the radical of a carboxylic ester of the formula -A-CO-OR ¹⁰ , where A denotes a linear C ₄ - to C 12 -alkylene group and R ¹⁰ denotes a C 1 - to C ₄ -alkyl radical, R ⁶ , R ⁷ and R ⁸ denotes hydrogen

Preferred radicals R ^a are n-dodecyl, n-tri-decyl, isotridecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, n-eicosyl, n-heneicosyl, n-docosyl, n-tricosyl, n-tetracosyl , n-pentacosyl, and n-hexacosyl.

If carboxyl groups are present in the repeat unit W1 in the form of their alkali metal, alkaline earth metal or ammonium salts, the lithium, sodium, potassium meant magnesium, magnesium or calcium salts. In the case of ammonium salts, the ammonium cation on the nitrogen may, for example, carry up to 4 identical or different alkyl substituents, such as methyl, ethyl, n-propyl or n-butyl.

The copolymer of the invention can be advantageously prepared by known and conventional radical polymerization techniques. Therefore, the subject of the present invention is a copolymer which by free radical copolymerization of

(i) 10 to 90 mol%, preferably 25 to 75 mol%, in particular 45 to 55 mol%,

especially 49 to 51 mol% of monomer units of structure M1

in which the variables R ¹¹ , R ¹² , R ¹³ and R ¹⁴ independently of one another hydrogen,

C 1 to C ₄ alkyl, carboxyl groups, carboxyl ester groups of the formula

-COOR ¹⁵ wherein R ^{15 is} a C 1 to C ₄ alkyl radical or carboxyl halide moieties of the formula -COX wherein X is fluoro, chloro, bromo or iodo, with the proviso that M1 is vicinal such carboxyl groups and / or carboxyl ester groups in the cis position or in cis position in the cis position in the cis position or in the cis position, these may also be in the form of their cyclic anhydride

(ii) 90 to 10 mol%, preferably 75 to 25 mol%, in particular 55 to 45 mol%, especially 51 to 49 mol% of monomer units of structure M2

in which the variable R ^{5 is} the radical of a carboxylic acid ester of the formula -A-CO-OR ¹⁰ , where the variable A is a C 1 - to C 20 -alkylene group, in particular a linear C ₄ - to C 12 -alkylene group, and the variable R ¹⁰ denotes hydrogen or a C 1 to C 30 hydrocarbyl radical, in particular a C 1 to C 5 hydrocarbyl radical, especially a C 1 to C ₄ alkyl radical, or

the grouping of the formula -COOR ^{10 represents} a carboxyl group which is also present in May be present in the form of their alkali metal, alkaline earth metal or ammonium salt and in which the variables R ⁶ , R ⁷ and R ⁸ independently of one another represent hydrogen

or Cr to Cs-alkyl,

0 to 80 mol%, preferably 10 to 50 mol%, in particular 15 to 40 mol%, especially 20 to 30 mol% monomer units of the structure M3

H ₂ C = CHR ^a (M3) in which the variable R ^{a is} a C 10 to C 28 hydrocarbyl radical where the sum of the monomer units M1, M2 and M3 gives 100 mol%, and subsequent, partial or complete polymer-analogous reaction of the formed Product having at least 0.1 to 2, preferably 0.2 to 1, 7, particularly preferably 0.3 to 1, 5, very particularly preferably 0.4 to 1, 3 and in particular 0.5 to 1.3 moles of a C6 - Until C30 hydrocarbyl alcohol per mole of monomer M1 used is available.

The present invention also provides a process for the preparation of the copolymer according to the invention which is characterized in that (i) 10 to 90 mol%, preferably 25 to 75 mol%, in particular 45 to 55 mol%,

especially 49 to 51 mol% of monomer units of structure M1

C 1 to C 4 alkyl, carboxyl groups, carboxyl ester groups of the formula

-COOR ¹⁵ wherein R ^{15 is} a C ₄ to C ₄ alkyl radical or carboxyl halide moieties of the formula -COX wherein X is fluoro, chloro, bromo or iodo, with the proviso that M1 is vicinal Containing carboxyl groups and / or carboxyl ester groups in the cis position or in the cis position, wherein these may also be present in the form of their cyclic anhydride in vicisally permanent carboxyl groups, and

(ü) 90 to 10 mol%, preferably 75 to 25 mol%, in particular 55 to 45 mol%, before 51 to 49 mol% of monomer units of structure M2

-A-CO-OR ⁰ is a linear C ₄ - to Ci2 alkylene group, and the variable R ¹⁰ is hydrogen or Cr to C3o hydrocarbyl group, in particular a d- to Cs hydrocarbyl group, especially a d- to C ₄ - Alkyl radical, called, or

the grouping of the formula -COOR ^{10 represents} a carboxyl group which may also be in the form of its alkali metal, alkaline earth metal or ammonium salt and in which the variables R ⁶ , R ⁷ and R ⁸ independently of one another represent hydrogen

or Cr to Cs-alkyl, (iii) 0 to 80 mol%, preferably 10 to 50 mol%, in particular 15 to 40 mol%,

especially 20 to 30 mol% monomer units of the structure M3

H ₂ C = CHR ^a (M3) in which the variable R ^{a is} a C 10 to C 28 hydrocarbyl radical, the sum of the monomer units M1, M2 and M3 being 100 mol%, copolymerized with each other in a free-radically copolymer and then the product formed, in part or completely polymer-analogous with at least 0.1 to 2, preferably 0.2 to 1, 7, particularly preferably 0.3 to 1.5, very particularly preferably 0.4 to 1, 3 and in particular 0.5 to 1.3 mol of a C6 to C3o-hydrocarbyl alcohol per mole of monomer M1 reacted.

The monomer components (i) are ethylenically α, β-unsaturated dicarboxylic acids or derivatives thereof, such as esters, cyclic anhydrides or carboxylic acid halides, such as carbonyl chlorides. In a preferred embodiment, the copolymerization of M1 and M2, which expediently uses free-radically decomposing Initiators is performed, maleic acid, maleic anhydride, maleic mono- or

dimethyl ester, maleic acid mono- or diethyl ester, fumaric acid, fumaric acid mono- or dimethyl ester or fumaric acid mono- or

diethyl ester as M1 monomer units. Other suitable monomer units M1 include, for example, 2-methylmaleic acid, 2-methylmaleic anhydride, 2,3-dimethylmaleic acid, 2,3-dimethylmaleic anhydride, 2-methylfumaric acid, 2,3-dimethylfumaric acid and also mono- and dimethyl- and mono- and Diethyl esters of these dicarboxylic acids.

The monomer components (ii) are ethylenically unsaturated carboxylic acid esters in which the ethylenic double bond is not in conjugation with the carboxyl carbon atom. Preferably, such monomer units M2 are used in which the variables R ⁶ , R ⁷ and R ^{8 are} hydrogen are, the variable R ¹⁰ is hydrogen or d- to C ₄ - alkyl, in particular methyl, ethyl, n-propyl or n-butyl, referred to and the variable a is a linear C ₄ - to Ci2 alkylene group, in particular a linear C6 - Cio-alkylene group, especially a linear C7, C & - or Cg-alkylene group, is.

It is also conceivable that the grouping of the formula -COOR ^{10 represents} a carboxyl group, which may also be in the form of its alkali metal, alkaline earth metal or ammonium salt. Examples of monomer units M2 are:

But-3-enoic acid methyl, ethyl, n-propyl and n-butyl ester,

Pent-3-enoic acid methyl, ethyl, n-propyl and n-butyl esters,

Pent-4-enoic acid methyl, ethyl, n-propyl and n-butyl esters,

Hex-3-enoic acid methyl, ethyl, n-propyl and n-butyl esters,

Hex-4-enoic acid methyl, ethyl, n-propyl and n-butyl esters,

Hex-5-enoic acid methyl, ethyl, n-propyl and n-butyl ester,

Hept-3-enoic acid methyl, ethyl, n-propyl and n-butyl ester,

Hept-4-enoic acid methyl, ethyl, n-propyl and n-butyl ester,

Hept-5-enoic acid methyl, ethyl, n-propyl and n-butyl ester,

Hept-6-enoic acid methyl, ethyl, n-propyl and n-butyl ester,

Oct-3-enoic acid methyl, ethyl, n-propyl and n-butyl esters,

Oct-4-enoic acid methyl, ethyl, n-propyl and n-butyl esters,

Oct-5-enoic acid methyl, ethyl, n-propyl and n-butyl esters,

Oct-6-enoic acid methyl, ethyl, n-propyl and n-butyl esters,

Oct-7-enoic acid methyl, ethyl, n-propyl and n-butyl esters, i-enoic acid methyl, ethyl, n-propyl and n-butyl esters, Νοη-4-enoic acid methyl, ethyl, n-propyl and n-butyl esters, Νοη-5-enoic acid-methyl, ethyl, n-propyl and n-butyl esters, Νοη-6-enoic acid-methyl, ethyl , n-propyl and n-butyl esters, o-7-enoic acid methyl, ethyl, n-propyl and n-butyl esters, o-o-8-enoic acid methyl, ethyl, n-propyl and n-butyl esters,

Methyl 3-decyl, ethyl, n-propyl and n-butyl esters, methyl decyl 4-decanoate, ethyl, n-propyl and n-butyl esters, methyl decyl 5-decatonic acid, ethyl -, n-propyl and n-butyl ester, dec-6-enoic acid methyl, ethyl, n-propyl and n-butyl ester, dec-7-enoic acid methyl, ethyl, n-propyl and n-butyl ester, Methyl 8-decanoic acid, ethyl, n-propyl and n-butyl esters, methyl deca- 9, 9-ethynoic, ethyl, n-propyl and n-butyl esters, undec-3-enoic acid methyl, ethyl , n-propyl and n-butyl esters, undec-4-enoic acid methyl, ethyl, n-propyl and n-butyl esters, undec-5-enoic acid methyl, ethyl, n-propyl and n-butyl esters, Undec-6-enoic acid methyl, ethyl, n-propyl and n-butyl ester, undec-7-enoic acid methyl, ethyl, n-propyl and n-butyl ester, undec-8-enoic acid methyl, ethyl , n-propyl and n-butyl ester, undec-9-enoic acid methyl, ethyl, n-propyl and n-butyl ester, undec-10-enoic acid methyl, ethyl, n-propyl and n-butyl ester,

Dodec-3-enoic acid methyl, ethyl, n-propyl and n-butyl ester, dodec-4-enoic acid methyl, ethyl, n-propyl and n-butyl ester, dodec-5-enoic acid methyl, ethyl , n-propyl and n-butyl esters, dodec-6-enoic acid methyl, ethyl, n-propyl and n-butyl esters, dodec-7-enoic acid methyl, ethyl, n-propyl and n-butyl esters, Dodec-8-enoic acid methyl, ethyl, n-propyl and n-butyl ester, dodec-9-enoic acid methyl, ethyl, n-propyl and n-butyl ester, dodec-10-enoic acid methyl, ethyl , n-propyl and n-butyl ester, dodec-1-1-acid-methyl, ethyl, n-propyl and n-butyl ester,

Tri-dec-3-enoic acid methyl, ethyl, n-propyl and n-butyl ester, tri-dec-4-enoic acid methyl, ethyl, n-propyl and n-butyl ester, tri dec-5-enoic acid methyl , ethyl, n-propyl and n-butyl esters, tri-dec-6-enoic acid methyl, ethyl, n-propyl and n-butyl esters, tri-dec-7-enoic acid methyl, ethyl, n-propyl and n-butyl ester, tri-dec-8-enoic acid methyl, ethyl, n-propyl and n-butyl ester, tri-dec-9-enoic acid methyl, ethyl, n-propyl and n-butyl ester, tri-decanoic acid. 10-enoic acid methyl, ethyl, n-propyl and n-butyl esters, tri-dec-1-1-acid-methyl, ethyl, n-propyl and n-butyl esters, Tridec-12-enoic acid methyl, ethyl, n-propyl and n-butyl ester,

Tetradec-3-enoic acid methyl, ethyl, n-propyl and n-butyl esters,

Tetradec-4-enoic acid methyl, ethyl, n-propyl and n-butyl esters,

Tetradec-5-enoic acid methyl, ethyl, n-propyl and n-butyl esters,

Tetradec-6-enoic acid-methyl, ethyl, n-propyl and n-butyl esters,

Tetradec-7-enoic acid-methyl, ethyl, n-propyl and n-butyl esters,

Tetradec-8-enoic acid-methyl, ethyl, n-propyl and n-butyl esters,

Tetradec-9-enoic acid-methyl, ethyl, n-propyl and n-butyl esters,

Tetradec-10-enoic acid-methyl, ethyl, n-propyl and n-butyl esters,

Tetradec-1 1-enoic acid methyl, ethyl, n-propyl and n-butyl ester,

Tetradec-12-enoic acid-methyl, ethyl, n-propyl and n-butyl esters,

Tetradec-13-enoic acid methyl, ethyl, n-propyl and n-butyl esters, pentadec-3-enoic acid methyl, ethyl, n-propyl and n-butyl esters,

Pentadec-4-enoic acid methyl, ethyl, n-propyl and n-butyl esters,

Pentadec-5-enoic acid methyl, ethyl, n-propyl and n-butyl esters,

Pentadec-6-enoic acid methyl, ethyl, n-propyl and n-butyl esters,

Pentadec-7-enoic acid methyl, ethyl, n-propyl and n-butyl ester,

Pentadec-8-enoic acid methyl, ethyl, n-propyl and n-butyl ester,

Pentadec-9-enoic acid methyl, ethyl, n-propyl and n-butyl ester,

Pentadec-10-enoic acid methyl, ethyl, n-propyl and n-butyl esters,

Pentadec-1-1-acid-methyl, ethyl, n-propyl and n-butyl ester,

Pentadec-12-enoic acid-methyl, ethyl, n-propyl and n-butyl esters,

Pentadec-13-enoic acid methyl, ethyl, n-propyl and n-butyl esters,

Pentadec-14-enoic acid methyl, ethyl, n-propyl and n-butyl esters

Among them, the respective ω-alkenoic acid methyl, ethyl, n-propyl and n-butyl esters are preferred.

These methyl, ethyl, n-propyl and n-butyl esters can then be converted, for example by hydrolysis or saponification, into the free acid or into the form of its alkali metal, alkaline earth or ammonium salt. The ethylenic double bond in all the above-mentioned monomer components M2 ice or trans-configured.

The monomer component (iii) is at least one, preferably one to four, particularly preferably one to three, very particularly preferably one or two and in particular exactly one α-olefin having from at least 12 up to and including 30 carbon atoms. The o olefins (iii) preferably have at least 14, more preferably at least 16 and most preferably at least 18 carbon atoms. The α-olefins (iii) are preferably up to and including 28, more preferably up to and including 26, and most preferably up to and including 24 carbon atoms.

The α-olefins may preferably be linear or branched, preferably linear, 1-alkenes.

Examples of these are 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonodecene, 1-eicosene, 1-docoses, 1-tetracoses, 1-hexacoses of which 1-octadecene, 1-eicosene, 1-docoses and 1-tetracoses, as well as their mixtures, are preferred.

Further examples of α-olefins (iii) are those olefins which are oligomers or polymers of C ₂ to C 12 olefins, preferably C ₃ to C 10 olefins, more preferably C ₄ to C ₆ olefins. Examples thereof are ethene, propene, 1-butene, 2-butene, isobutene, pentene isomers and hexene isomers, preferred are ethene, propene, 1-butene, 2-butene and isobutene.

Specifically mentioned as α-olefins (iii) are oligomers and polymers of propene, 1-butene, 2-butene, isobutene, and mixtures thereof, especially oligomers and polymers of propene or isobutene or of mixtures of 1-butene and 2-butene. Among the oligomers, the trimers, tetramers, pentamers and hexamers and mixtures thereof are preferred.

It is possible to polymerize the two monomer components (i) and (ii) and optionally (iii) in the first preparation stage in bulk, in suspension or preferably in solution. For each monomer component (i) and (ii) and optionally (iii), it is possible in each case to use a single monomer species or a mixture of a plurality of such monomer species. The polymerization reaction is usually carried out under atmospheric pressure and under an inert gas such as nitrogen, but it can also operate at elevated pressures, for example in an autoclave. The polymerization temperatures are generally from 50 to 250 ° C, especially at 90 to 210 ° C, especially at 120 to 180 ° C, typically at 140 to 160 ° C. Suitable polymerization reactors are, in principle, all customary continuously or discontinuously operated apparatus such as, for example, stirred tank, stirred tank cascade, tube reactor or loop reactor.

Usually, the polymerization is initiated by radically decomposing initiators, suitable for this purpose are air or oxygen or organic peroxides and / or hydroperoxides and organic azo compounds. Suitable organic peroxides or hydroperoxides are, for example, diisopropylbenzene hydroperoxide, cumene hydroperoxide, methyl isobutyl ketone peroxide, di-tert-butyl peroxide and tert-butyl perisononate. As the organic azo compound, for example, azobisisobutyronitrile ("Al BN") is suitable. Furthermore, suitable regulators such as aliphatic see aldehydes or ketones or hydrogen can also be used in the polymerization. If solvents or suspending agents are used in the polymerization, the usual high-boiling inert liquids such as aromatic hydrocarbons, for. As toluene, xylenes or corresponding technical hydrocarbon mixtures such as Solvesso® or solvent naphtha, into consideration.

Suitable C6- to C30-hydrocarbyl alcohols for the polymer-analogous reaction of the polymerization product prepared as described above in the second preparation stage are alcohols which carry the abovementioned hydrocarbyl radicals, in particular alkyl or cycloalkyl radicals. Branched or, in particular, linear primary C 6 to C 16 hydrocarbyl alcohols, in particular branched or in particular linear primary C 10 to C 14 hydrocarbyl alcohols, are preferred here. Typical examples of such hydrocarbyl alcohols are 2-ethylhexanol, n-octanol, n-nonanol, n-decanol, 2-propylheptanol, n-undecanol, n-dodecanol, n-tridecanol, isotridecanol and iso-heptadecanols. It is also possible to use technical mixtures of such medium-chain aliphatic alcohols.

In a preferred embodiment, iso-heptadecanols are used, obtained by a process as described in WO 2009/124979 A1, there especially page 5, line 4 to page 16, line 29, and the examples of page 19, line 19 to page 21, Line 25, which is hereby incorporated by reference.

The reaction of the polymerization with Ce to C3o-hydrocarbyl alcohol or with a mixture of such alcohols is generally carried out by heating at atmospheric pressure and typically under an inert gas such as nitrogen to temperatures in the range of 50 to 200 ° C, in particular from 90 to 180 ° C, especially from 120 to 170 ° C, typically from 140 to 160 ° C. In this case, one can use acids or bases as esterification catalysts. When the esterification is complete or has reached the desired level of conversion, it works as usual. If the carboxyl group to be esterified exist as esters of lower alcohols, ie as C ₄ to C ₄ -alkyl esters, transesterification takes place in which the lower alcohol is displaced from the less volatile C 6 to C 30 -hydrocarbyl alcohol in the molecule. In addition to the transesterification reactions on the carboxyl functions in M1, transesterification reactions on the carboxyl function in M2 can also take place here. If the carboxyl functions are present in M1 as free carboxylic acids, as anhydrides or as carboxyl halides, transesterification on the carboxyl function in M2 is largely avoided. In order to esterify or transesterify the polymerization product, it is usual to use as much C 6 to C 30 hydrocarbyl alcohol as to convert one or both of the carboxyl functions derived from M 1 into long-chain esters. However, it is also possible to control the amount of C6- to C30-hydrocarbyl alcohol such that this degree of esterification or transesterification at the carboxyl functions at the repeat unit W1 is between 1 and 2. If the carboxyl ester function on the repeat unit W2 is or should also be transesterified to a long-chain ester, more than 2 moles of C6 to C30 hydrocarbyl alcohol per mole of M1 necessary, for example, up to 3 moles per mole of M1, when M1 and M2 are copolymerized in an equimolar ratio.

In an alternative embodiment, the anhydride or carboxylic ester functionalities contained in the copolymer obtained can be partially or completely hydrolyzed and / or saponified.

Preferably, 10 to 100% of the anhydride or carboxylic acid ester functionalities present are hydrolyzed and / or saponified, preferably at least 20%, more preferably at least 30%, even more preferably at least 50% and especially at least 75% and especially at least 85%.

For a hydrolysis, based on the anhydride functionalities contained, the amount of water is added which corresponds to the desired degree of hydrolysis and the resulting copolymer is heated in the presence of the added water. As a rule, a temperature of preferably 20 to 150 ° C. is sufficient for this, preferably 60 to 100 ° C. If necessary, the reaction can be carried out under pressure to prevent the escape of water. Under these reaction conditions, the anhydride functionalities are usually selectively reacted in the copolymer, whereas any carboxylic acid ester functionalities present in the copolymer do not react or at least react only in a subordinate manner.

For saponification, the copolymer is reacted with an amount of a strong base in the presence of water, which corresponds to the desired degree of saponification. Preferred strong bases are hydroxides, oxides, carbonates or bicarbonates of alkali metals or alkaline earth metals.

The copolymer is then heated in the presence of the added water and the strong base. In general, a temperature of preferably 20 to 130 ° C is sufficient, preferably 50 to 1 10 ° C. If necessary, the reaction can be carried out under pressure.

It is also possible to hydrolyze the carboxylic acid ester functionalities with water in the presence of an acid. Preferred acids are mineral, carbon, sulfone or phosphorus-containing acids having a pKa of not more than 5, more preferably not more than 4.

Examples are acetic acid, formic acid, oxalic acid, salicylic acid, substituted succinic acids, aromatic or unsubstituted benzenesulfonic acids, sulfuric acid, nitric acid, hydrochloric acid or phosphoric acid. The use of acidic ion exchanger resins is also conceivable. The copolymer is then heated in the presence of the added water and acid. As a rule, a temperature of preferably 40 to 200 ° C. is sufficient for this, preferably 80 to 150 ° C. If necessary, the reaction can be carried out under pressure. If the copolymers thus obtained still contain residues of acid anions, it may be preferable to remove these acid anions from the copolymer with the aid of an ion exchanger and to exchange them for preference for hydroxide ions or carboxylate ions, more preferably hydroxide ions. This is particularly the case when the acid anions contained in the copolymer are halides, sulfur-containing or nitrogen-containing.

The precursor of the copolymer according to the invention which has not yet reacted with the C 6 - to C 30 -hydrocarbyl alcohol and results from the free-radical copolymerization of the monomer units M1 and M2 preferably has a number-average molecular weight (M _n ) in the range from 500 to 10,000, in particular from 1000 to 5,000 , or alternatively a weight-average molecular weight (M _w ) of 750 to 50,000, in particular from 1500 to 25,000, (all data in g / mol, in each case determined by gel permeation chromatography).

Based on the number of repeating units of the structure W1 and W2 and optionally W3, the copolymer according to the invention preferably contains a total of 4 to 80, in particular 8 to 40, of these repeating units, wherein in the preferred embodiment of the alternating structure of the copolymer the number of W1 and W2 and optional W3 are the same or approximately the same.

use

The fuel additized with the polymer 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.

Frequently, the polymers described are used in the form of fuel additive mixtures, together with conventional additives: In the case of diesel fuels, these are primarily conventional detergent additives, carrier oils, cold flow improvers, lubricity improvers, corrosion inhibitors other than the described polymers, demulsifiers, dehazers , Antifoaming agents, cetane improvers, combustion improvers, antioxidants or stabilizers, antistatic agents, metallocenes, metal deactivators, dyes and / or solvents. Accordingly, another object of the invention is the use of polymers composed of

(i) 10 to 90 mole% repeat units of structure W1

C 1 to C ₄ -alkyl and the other a carboxyl-COOH or carboxyl ester grouping of the formula -COOR ⁹ , and in the variables R ³ and R ⁴ independently of one another hydrogen, C 1 to C ₄ -alkyl, carboxyl-COOH or carboxylester- Groupings of the formula -COOR ⁹ , wherein R ^{9 is} a C 6 - to C 30 -hydrocarbyl radical, where carboxyl groups may also be present in the form of their alkali metal, alkaline earth metal or ammonium salts, where one of the variables R ³ or R ^{4 is} hydrogen or C to C ₄ -alkyl and the other a carboxyl ester group of the formula -COOR ⁹ and / or a carboxyl group, which may also be in the form of its alkali metal, alkaline earth metal or ammonium salt, means

Can form a grouping -CO-O-CO-,

and

90 to 10 mol% of repeating units of structure W2

-A-CO-OR ⁰ , wherein the variable A is a C to C 20 -alkylene group and the Variable R ¹⁰ denotes hydrogen or a C 1 -C 30 -hydrocarbyl radical, or the grouping of the formula -COOR ^{10 represents} a carboxyl group which may also be in the form of its alkali metal, alkaline earth metal or ammonium salt and in which the variables R ⁶ , R ⁷ and R ^{8 are} independently hydrogen or

C to Ce-alkyl, and

(iii) 0 to 80 mole% repeat units of structure W3

- [- H ₂ C-CHR ^a -] - (W 3) in which the variable R ^{a is} a C 10 to C 28 hydrocarbyl radical, the sum of repeat units W 1, W 2 and W 3 giving 100 mol%, in additive packages containing at least one additive selected from the group consisting of detergent additives, carrier oils, cold flow improvers, lubricity improvers, other corrosion inhibitors than the polymers described, demulsifiers, dehazers, defoamers, cetane improvers, combustion improvers, antioxidants, stabilizers, antistatic agents, metallocenes, metal deactivators, Dyes and solvents, for reducing the fuel consumption of direct-injection diesel engines, in particular of diesel engines with common-rail injection systems and / or for minimizing the loss of power (powerloss) in direct-injection diesel engines, especially in diesel engines with common-rail injection systems.

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

Accordingly, another object of the invention is the use of polymers, built from

(i) 10 to 90 mole% repeat units of structure W1

(W1) in which the variables R ¹ and R ² independently of one another denote hydrogen, C ^{1 to} C ⁴ -alkyl, carboxyl-COOH or carboxyl ester

C 1 to C ₄ -alkyl and the other a carboxyl-COOH or carboxyl ester grouping of the formula -COOR ⁹ , and in the variables R ³ and R ⁴ independently of one another hydrogen, C 1 to C ₄ -alkyl, carboxyl-COOH or carboxylester- Groupings of the formula -COOR ⁹ , wherein R ^{9 is} a C 6 - to C 30 -hydrocarbyl radical, where carboxyl groups may also be present in the form of their alkali metal, alkaline earth metal or ammonium salts, where one of the variables R ³ or R ^{4 is} hydrogen or C to C ₄ alkyl and the other a carboxyl ester group of the formula -COOR ⁹ and / or a carboxyl group which also in

Form of their alkali metal, alkaline earth metal or ammonium salt,

and

90 to 10 mol% of repeating units of structure W2

-A-CO-OR ⁰ , wherein the variable A is a C to C 20 -alkylene group and the

Variable R ¹⁰ denotes hydrogen or a C 3 to C 30 hydrocarbyl radical, or the grouping of the formula -COOR ^{10 represents} a carboxyl group which may also be present in the form of its alkali metal, alkaline earth metal or ammonium salt and in which the variables R ⁶ , R ⁷ and R ^{8 is} independently hydrogen or

C to Ce-alkyl, and - [- H ₂ C-CHR ^a -] - (W 3) in which the variable R ^{a is} a C 10 to C 28 hydrocarbyl radical, the sum of repeat units W 1, W 2 and W 3 giving 100 mol%, in additive packages containing at least one additive selected from the group consisting of friction modifiers, corrosion inhibitors other than the polymers described, demulsifiers, dehazers, antifoaming agents, combustion improvers, antioxidants, stabilizers, antistatic agents, metallocenes, metal deactivators, dyes and solvents to reduce deposits in the intake system of a gasoline engine, in particular DISI and PFI (Port Fuel Injector) engines.

Typical examples of suitable coadditives 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 having a number average molecular weight (M _n ) of from 85 to 20,000 and at least have a polar moiety selected from: (da) mono- or polyamino groups having up to 6 nitrogen atoms, at least one nitrogen atom having 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; (Dh) derived from succinic anhydride groups with hydroxy and / or

Amino and / or amido and / or imido groups; and or

(Di) by Mannich reaction of substituted phenols with aldehydes and mono- or polyamines generated groupings.

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

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

Mono- or polyamino (Da) -containing additives are preferably polyalkene mono- or polyalkene polyamines based on polypropene or of highly reactive (ie predominantly terminal double bonds) or conventional (ie predominantly intermediate double bonds) polybutene or polyisobutene with M _n = 300 to 5000, especially preferably 500 to 2500 and especially 700 to 2500. Such additives based on highly reactive polyisobutene, which from the polyisobutene, which may contain up to 20 wt .-% n-butene units, by hydroformylation and reductive amination with ammonia, monoamines or polyamines, such as dimethylaminopropylamine, ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine, are known in particular from EP-A 244 616. 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. 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 particular monoamino (Da) containing additives are the hydrogenation of the reaction products of polyisobutenes having an average degree of polymerization P = 5 to 100 with nitrogen oxides or mixtures of nitrogen oxides and oxygen, as described in particular in WO-A 97/03946. Further special monoamino (Da) -containing additives are the compounds obtained from polyisobutene epoxides by reaction with amines and subsequent dehydration and reduction of the amino alcohols, 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-hydroxy polyisobutene).

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 polyisobutene with M _n = 300 to 5000 with ammonia, mono- or polyamines, as 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, their carboxyl groups wholly or partly to the alkali metal or alkaline earth metal salts and a remaining Rest of the carboxyl groups are reacted with alcohols or amines. Such additives are known in particular from EP-A 307 815. Such additives are mainly 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) -butene amines or polyetheramines.

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

Polyoxy-C2-C4-alkylene (Df) containing additives are preferably polyether or polyetheramines which by reaction of C2 to C6o-alkanols, C6 to C30 alkanediols, mono- or D1-C2 to C3o-alkylamines, Cr to C3o-alkylcyclo-hexanols or C1- to C3o-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 fulfill carrier oil properties. Typical examples thereof are tridecanol or isotridecanol butoxylates, isononylphenol butoxylates and also polyisobutenol butoxylates and propoxylates, and the corresponding reaction products with ammonia.

Carboxyl 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 meet carrier oil properties. Derivatives derived from succinic anhydride with hydroxyl and / or amino and / or amido and / or imido (Dh) containing additives are preferably corresponding derivatives of alkyl- or alkenyl-substituted succinic anhydride and in particular the corresponding derivatives of polyisobutenyl succinic anhydride, which by reaction of conventional or highly reactive polyisobutene having M _n = preferably 300 to 5000, more preferably 300 to 3000, more preferably 500 to 2500, even more preferably 700 to 2500 and especially 800 to 1500, with maleic anhydride by thermal means in an ene reaction or via the chlorinated polyisobutene are available. The groups having hydroxyl and / or amino and / or amido and / or imido groups are, for example, carboxylic acid groups, acid amides of monoamines, acid amides of di- or polyamines which, in addition to the amide function, also have free amine groups,

Succinic acid derivatives having 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. Such fuel additives are generally 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.

In a preferred embodiment, the compounds according to the invention can be combined with quaternized compounds as described in WO 2012/004300, preferably on page 5, line 18 to page 33, line 5, particularly preferably of preparation example 1, which is hereby expressly incorporated herein by reference.

In a further preferred embodiment, the compounds according to the invention can be combined with quaternized compounds as described in unpublished International Application with the file reference PCT / EP2014 / 061834 and the filing date 6 June 2014, there preferably page 5, line 21 to page 47, line 34, more preferably Preparation Examples 1 to 17. In a further preferred embodiment, the compounds of the invention can be combined with quaternized compounds, as described in WO 1 1/95819 A1, there preferably page 4, line 5 to page 13, line 26, especially preferred preparation example 2.

In a further preferred embodiment, the compounds according to the invention can be combined with quaternized compounds as described in WO 1 1/1 10860 A1, there preferably page 4, line 7 to page 16, line 26, particularly preferably the preparation examples 8, 9, 1 1 and 13.

In a further preferred embodiment, the compounds according to the invention can be combined with quaternized compounds as described in WO 06/135881 A2, there preferably page 5, line 14 to page 12, line 14, particularly preferably examples 1 to 4.

In a further preferred embodiment, the compounds according to the invention can be combined with quaternized compounds as described in WO 10/132259 A1, there preferably page 3, line 29 to page 10, line 21, particularly preferably example 3.

In a further preferred embodiment, the compounds according to the invention can be combined with quaternized compounds as described in WO 08/060888 A2, there preferably page 6, line 15 to page 14, line 29, particularly preferably examples 1 to 4.

In a further preferred embodiment, the compounds according to the invention can be combined with quaternized compounds as described in GB 2496514 A, there preferably paragraphs [00012] to [00039], particularly preferably examples 1 to 3. In a further preferred embodiment, the compounds according to the invention can be combined with quaternized compounds as described in WO 2013 070503 A1, there preferably paragraphs [0001 1] to [00039], particularly preferably Examples 1 to 5. By Mannich reaction of substituted phenols with Aldehydes and mono- or polyamine-produced groupings (Di) -containing 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 metering rate of these detergent additives is preferably from 25 to 2500 ppm by weight, in particular from 75 to 1500 ppm by weight, especially from 150 to 1000% by weight . ppm.

B2) Carrier oils Co-used carrier oils can be of mineral or synthetic nature. Suitable mineral carrier oils are fractions obtained in petroleum processing, such as bright stock or base oils having viscosities such as from class SN 500 to 2000, but also aromatic hydrocarbons, paraffinic hydrocarbons and alkoxyalkanols. It is also useful as a "hydrocrack oil" known and obtained in the refining of mineral oil fraction (Vakuumdestillatschnitt with a boiling range of about 360 to 500 ° C, available from high pressure catalytically hydrogenated and isomerized and dewaxed natural mineral oil). Also suitable are mixtures of the abovementioned mineral carrier oils.

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

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

Examples of suitable polyethers or polyetheramines are preferably compounds containing polyoxy-C ₂ - to C ₄ -alkylene groups which are prepared by reacting C ₂ - to C 60 -alkanols, C ₆ - to C 30 -alkanediols, mono- or C 1 -C -cycloalkylamines, C 1 -C 30 -alkylcyclohexanols or C 3 -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 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 thereof are tridecanol or isotridecanol butoxylates, isononylphenol butoxylates and also polyisobutenol butoxylates 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 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 Ce to Cie-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 aliphatic C6-C18-alcohols are hexanol, heptanol, octanol, 2-ethyl-hexanol, nonyl alcohol, decanol, 3-propylheptanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol and their constitutional 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 C3 to C6 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, pentylenoxid and hexylene oxide. Particularly preferred among these are C3 to C4 alkylene oxides, i. 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. Further suitable synthetic carrier oils are alkoxylated iso-heptadecanol, as described in unpublished European application with the file reference 15198684.1 and the filing date 15 December 2015. Particular carrier oils are synthetic carrier oils, the alcohol-initiated polyethers described above being particularly preferred.

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

B3) cold flow improver

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

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 C 2 - to C 4 -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 one carbon-carbon atom. Dop-pelbindung. In the latter case, the carbon-carbon double bond can be both terminal (α-olefins) as can also be arranged internally. However, preference is given to α-olefins, particularly preferably 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, be added as olefin

Base monomer ethylene or propene, are suitable as further olefins, in particular C10 to C4o-α-olefins. Other olefins are polymerized in most cases only when monomers with carboxylic acid ester functions are used. Suitable (meth) acrylic acid esters are, for example, esters of (meth) acrylic acid with C 2 to C 20 alkanols, in particular C 1 to C 10 alkanols, especially with methanol, ethanol, propanol, isopropanol, n-butanol, sec-butanol, isobutanol, tert Butanol, pentanol, hexanol, heptanol, octanol, 2-ethylhexanol, nonanol and decanol and structural isomers thereof. Suitable carboxylic alkenyl esters are, for example, C2 to C-u-alkenyl esters, e.g. the vinyl and propenyl esters of carboxylic acids having from 2 to 21 carbon atoms, the hydrocarbon radical of which may be linear or branched. Preferred among these are the vinyl esters. Among the carboxylic acids having a branched hydrocarbon radical, preference is given to those whose branching is in the α-position relative to the carboxyl group, the α-carbon atom being particularly preferably tertiary, ie. H. the carboxylic acid is a so-called neocarboxylic acid. Preferably, however, the hydrocarbon radical of the carboxylic acid is linear.

Examples of suitable alkenyl carboxylic acid 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.

Suitable copolymers of class (K1) are also those which contain two or more mutually 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), comprise at least one olefin and / or at least one (meth) acrylic acid ester in copolymerized form. Terpolymers of a C2 to C4o-α-olefin, a C to C2o-alkyl ester of an ethylenically unsaturated monocarboxylic acid having 3 to 15 carbon atoms and a C2 to C14 alkenyl ester of a saturated monocarboxylic acid having 2 to 21 carbon atoms are also known as copolymers. polymers of class (K1) are suitable. 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 C4o-based olefins.

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

Typical comb polymers of component (K2) are, for example, by the copolymerization of maleic anhydride or fumaric acid with another ethylenically unsaturated monomer, for example with an α-olefin or an unsaturated ester such as vinyl acetate, and subsequent esterification of the anhydride or acid function with an alcohol available with at least 10 carbon atoms. Other suitable comb polymers are copolymers of 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 component of class (K2) are, for example, those described in WO 2004/035715 and in "Comb-Like Polymers, Structure and Properties", N.A. Plate and V.P. Shibaev, J. Poly. Be. Macromolecular Revs. 8, pages 1 17 to 253 (1974). "Mixtures of comb polymers are also suitable.

Polyoxyalkylenes suitable as a component of class (K3) are, for example, polyalkylene esters, polyoxyalkylene ethers, mixed polyoxyalkylene ester ethers and mixtures thereof. These polyoxyalkylene compounds preferably contain at least one, preferably at least two, linear alkyl groups each having from 10 to 30 carbon atoms and a polyoxyalkylene group having a number average molecular weight of up to 5,000. Such polyoxyalkylene compounds are described, for example, in EP-A 061 895 and in US Pat. No. 4,491,455 described. Particular polyoxyalkylene compounds are based on polyethylene glycols and polypropylene glycols having a number average molecular weight of 100 to 5000. Further, polyoxyalkylene mono- and diesters of fatty acids having 10 to 30 carbon atoms such as stearic acid or behenic acid are suitable. Polar nitrogen compounds suitable as a component of class (K4) may be of both ionic and nonionic nature, and preferably have at least one, especially at least two, tertiary nitrogen substituent of the general formula> NR ⁷ , wherein R ^{7 is} Cs to C 40 Hydrocarbon residue stands. The nitrogen substituents may also be quaternized, ie 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 Ce 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 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 the class (K4) is preferably an oil-soluble reaction product based on poly (C 2 - to C 20 -carboxylic acids) having the general formula IIa or IIb and having at least one tertiary amino group

HOOCk_ _, COOH

B B

i i

HOOC_.N.COOH

BAB (IIa)

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

and the variable B denotes a C 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 (hexa-1-propylene), methylene) and in particular 1, 2-ethylene. Preferably, the variable A comprises 2 to 4, in particular 2 or 3 carbon atoms.

C to Ci9 alkylene groups of the variable B are, for example, 1, 2-ethylene, 1, 3-propylene, 1, 4-butylene, hexamethylene, octamethylene, decamethylene, dodecamethylene, Tetradecamethyl- en, 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 C 14 - 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 acids or from their derivatives. Preferably, the two radicals R ^{8 are the} same. The abovementioned secondary amines can be bound to the polycarboxylic acids by means of amide structures or in the form of the ammonium salts, and only a part can be bound as amide structures and another part is present 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.

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

Further typical structural types for the component of the class (K4) are cyclic compounds with tertiary amino groups or condensates of long-chain primary or secondary amines with carboxylic acid-containing polymers, as described in 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 carboxamides and carboxylic acid esters of ortho-sulfobenzoic acid in which the sulfonic acid function is present as sulfonate with alkyl-substituted ammonium cations, as described in EP-A 261 957 are described.

As cold flow improvers of the component of the class (K6) suitable poly (meth) acrylic acid esters are both homo- and copolymers of acrylic and methacrylic acid esters. Preferred are copolymers of at least two mutually different (meth) acrylic acid esters, which differ with respect to the fused alcohol. Optionally, the copolymer contains a further, different of which olefinically unsaturated monomer copolymerized. The weight-average molecular weight of the polymer is preferably 50,000 to 500,000. A particularly preferred polymer is a copolymer of methacrylic acid and methacrylic acid esters of saturated C14 and Cis alcohols wherein the acid groups are neutralized with hydrogenated talla- min. 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, more preferably from 50 to 1000 Ppm by weight and in particular from 100 to 700 ppm by weight, for example from 200 to 500 ppm by weight, added.

B4) Lubricity improver

Suitable lubricity improvers (or friction modifiers) are usually based on fatty acids or fatty acid esters. Typical examples are tall oil fatty acid, 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) Other corrosion inhibitors than the described polymer 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), Irgora® L12 (BASF SE) 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-butylphenolethoxylate or tert-pentylphenolethoxylate, fatty acids, alkylphenols, condensation products of ethylene oxide (EO) and propylene oxide (PO), e.g. also in the form of EO / PO block copolymers, polyethyleneimines or polysiloxanes.

B7) Dehazer

Suitable dehazers are e.g. alkoxylated phenol-formaldehyde condensates such as the NALCO 7D07 (Nalco) and TOLAD 2683 (Petrolite) products available under the tradename. B8) antifoam

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

B9) Cetane number improver Suitable cetane number improvers are, for example, 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 ones are e.g. nonpolar organic solvents such as aromatic and aliphatic hydrocarbons, for example, toluene, xylenes, white spirit, and products sold under the trade name SHELLSOL (Royal Dutch / Shell Group) and EXXSOL (ExxonMobil), as well as polar organic solvents, for example, alcohols such as 2-ethylhexanol, decanol and isotridecanol. Such solvents usually enter the diesel fuel together with the abovementioned additives and co-additives, which they are intended to dissolve or dilute for better handling.

C) fuels

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

The present invention therefore also fuels, in particular middle distillate fuels, with an additive as an additive to achieve advantageous effects in the operation of internal combustion engines, such as diesel engines, especially direct-injection diesel engines, especially of diesel engines with common-rail injection systems, effective content of the quaternized additive according to the invention. This effective content (metering rate) is generally from 10 to 5000 ppm by weight, preferably from 20 to 1500 ppm by weight, in particular from 25 to 1000 ppm by weight, especially from 30 to 750 ppm by weight, each based on the total amount of fuel. Middle distillate fuels, such as diesel fuels or fuel oils, are preferably petroleum raffinates, which usually have a boiling range of from 100 to 400.degree. These are mostly distillates with a 95% point up to 360 ° C or even beyond. However, these may also be so-called "Ultra Low Sulfur Diesel" or "City Diesel", characterized by a 95% point of, for example, a maximum of 345 ° C and a maximum sulfur content of 0.005 wt .-% or by a 95% point of for example, 285 ° C and a maximum sulfur content of 0.001 wt .-%. In addition to the mineral middle distillate fuels or diesel fuels obtainable by refining, those which are obtained by coal gasification or gas liquefaction [GTL] or by biomass liquefaction [BTL], Fuels] 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, DIN 51603 and EN 590 (cf., also, Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Volume A12, page 617 et seq.).

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

Biofuel oils are generally based on fatty acid esters, preferably substantially on alkyl esters of fatty acids derived from vegetable and / or animal oils and / or fats. Alkyl esters are usually lower alkyl esters, 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 seed oils. methyl ester, palm oil methyl ester ("PME"), soybean oil methyl ester ("SME") and in particular rapeseed oil methyl ester ("RME").

Particularly preferably, the middle distillate fuels or diesel fuels are those with a low sulfur content, that is to say with a sulfur content of less than

0.05% by weight, preferably less than 0.02% by weight, in particular 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.

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

A. General testing methods

1. DW10 test - Determination of Leistungsveriusts by injector deposits in the common rail diesel engine

The tests are 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.

Changes and special features are described in the following application examples. 2. IDID test - Determination of the additive effect against internal injector deposits

The formation of deposits inside the injector was characterized by the deviations of the exhaust temperatures of the cylinders at the cylinder outlet during the 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 dodecenylsuccinic acid used was obtained by hydrolysis of dodecenylsuccinic anhydride, isomeric mixture from Aldrich, CAS no. 26544-38-7.

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

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

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

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

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

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

The temperature sensors are located behind the cylinder head 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 CEC F-098-08 (see FIG. 1) is passed through 8 times in each case. In the case of deviations of the individual cylinder temperatures from greater than 45 ° C to the mean value of all 4 cylinders, the test is terminated prematurely.

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

B. Synthesis Examples

Example 1 :

85.8 g of C20-C24 olefin mixture were mixed together with 100.7 g Solvesso® 150 as a template in a 1 liter pilot agitator. The mixture was rendered inert with N ₂ and heated to 145 ° C. Then, maleic anhydride (56.8 g) (melted at 80 ° C.), methyl undecenoate (57.4 g) and a solution of ditert were added in parallel. butylperoxide (3 g) in Solvesso® 150 (17 g) separately added to the reaction mixture over a total of 3 hours. Thereafter, the reaction mixture was postpolymerized for one hour. The solution contained 59.3% polymer (solids content, measured after drying in a drying oven over 2 hours at 100 ° C. Theory: 62.5%).

Hydrolysis of Example 1: 101, 18 g of Example 1 were mixed with 10.3 g of water in a 250 ml one-necked flask. The reaction mixture was stirred at about 92 ° C for 3 hours. Thereafter, the excess water was distilled off under vacuum. Polymer content: 60.6%. (measured after drying in a drying oven for 2 hours at 100 ° C). Acid value: 89.6 mg KOH / g product. Appearance: yellow, clear, gel-like.

C. Application examples

Application example 1: DW10 Na soap IDID test (clean-up) To investigate the influence of additives on the performance of direct-injection diesel engines, the I DI D engine test was used as a further test method in which the exhaust gas temperatures of the cylinders at the cylinder exit during the cold start of the DW10- Motor were correct. A direct-injection diesel engine with common rail system from the manufacturer Peugeot according to test method CEC F-098-08 was used. The fuel used was a commercial B7 diesel fuel according to EN 590 from Aral. To this was added in each case 1 ppm by weight of sodium naphthenate and 20 ppm by weight of dodecenylsuccinic acid to artificially induce the formation of deposits.

Similar to the method CEC F-98 -08, the engine power was measured during the test. The test consisted of two parts:

I. Dirty-up:

The test was carried out without the addition of compounds according to this invention. The test was shortened to 8 hours, the CEC F-98 -08 process was carried out without the addition of Zn but with the addition of sodium naphthenate and dodecenylsuccinic acid. If significant deviations from exhaust gas temperatures were observed, the test was stopped before reaching the 8 hour mark to avoid engine damage. After the dirty up run, the engine was allowed to cool and then started again and idle for 5 minutes. During these 5 minutes the engine was warmed up. The exhaust temperature of each cylinder was recorded. The smaller the differences between the detected exhaust gas temperatures, the lower the amount of IDID formed. The exhaust gas temperatures of the 4 cylinders ("Z1" to "Z4") at the cylinder outlets were measured after 0 minutes ("θθ") and after 5 minutes ("5"). The results of the exhaust gas temperature measurements with average values ("Δ") and the largest deviations from Δ down ("-") and above ("+") for the two test runs are summarized in the following overview.

II. Clean-up:

The test was shortened to 8 hours, the CEC F-98 -08 method was performed without addition of Zn. However, in each case 1 ppm by weight of sodium naphthenate and 20 ppm by weight of dodecenylsuccinic acid and 50 mg / kg of a compound according to the invention were added.

After the clean up, the engine was cooled and restarted. The exhaust temperature of each cylinder was recorded. The smaller the differences between the detected exhaust gas temperatures, the lower the amount of IDID formed.

The exhaust gas temperatures of the 4 cylinders ("Z1" to "Z4") at the cylinder outlets were measured after 0 minutes ("θθ") and after 5 minutes ("θ5"). The results of the exhaust gas temperature measurements with average values ("Δ") and the largest deviations from Δ down ("-") and above ("+") are summarized in the following overview.

The following results were determined: Dirty up -Clean up - Sequence 1:

After dirty up:

θθ Z1: 23 ° C Z2: 22 ° C Z3: 22 ° C Z4: 21 ° C

θ5 Z1: 35 ° C Z2: 44 ° C Z3: 75 ° C Z4: 101 ° C

Δ: 63.75 ° C (+ 37.25 ° C / -28.75 ° C)

Significant deviations from the mean and significant difference between the individual cylinders demonstrate the presence of IDID.

Clean-up:

After clean up with 50 ppm of additive from Example 1 in the presence of 1 ppm of Na + 20 ppm of dodecenylsuccinic acid:

θθ Z1: 21 ° C Z2: 21 ° C Z3: 20 ° C Z4: 20 ° C

θ5 Z1: 63 ° C Z2: 69 ° C Z3: 65 ° C Z4: 69 ° C

A: 66.5 ° C (+ 2.5 ° C / -3.5 ° C)

The deviation from the mean value of the temperature of the exhaust gases is low, which speaks for the removal of IDID.

Thus, the compounds according to the present invention are very efficient for prevention / removal in direct injection engines, as seen on the Peugeot DW10 engine in a test similar to CEC F-98-08, but with 1 wt ppm Na in the form of sodium naph - Thenat and 20 wt ppm dodecenylsuccinic acid.

Application example 2: DW10 Na power loss test (clean up)

To investigate the effect of the compounds of the present invention on power loss caused by metal compounds other than zinc, such as sodium, potassium and other compounds, the above experimental set-up of the I DI D motor test was used. During the dirty up and the clean up period, the performance of the engine was measured, as in the CEC F-98-08 Test Specification. Test Additive Performance Performance Change in performance before test, after in test,%

kW test, kW

Dirty up, 8 hours, 1 ppm Na + 20 ppm 92 87.3 -5.1

Processes such as dodecenylsuccinic acid

described above

Clean up, 8 hours, 1 ppm Na + 20 ppm 86.8 90.2 +3.9

Processes such as dodecenylsuccinic acid

described above and 50 ppm of active ingredient from Example 1

(Hydrolysed)

The compounds according to the present invention are effective against deposits caused by metal compounds other than zinc, as demonstrated by the above Na power loss test.

Claims

claims

1. Use of polymers, composed of

(i) 10 to 90 mole% repeat units of structure W1

in which the variables R ¹ and R ² independently of one another are hydrogen, C ¹ - to C ₄ -alkyl,

Carboxyl-COOH or Carboxylester-

Groupings of the formula -COOR ⁹ where R ^{9 is} a C ₆ to C 30 hydrocarbyl radical and wherein one of the variables R ¹ or R ^{2 is} hydrogen or C to C ₄ alkyl and the other is a carboxyl-COOH or carboxyl ester grouping

of the formula -COOR ⁹ , and in the variables R ³ and R ^{4 are} independently hydrogen, Cr to C ₄ alkyl, carboxyl-COOH or carboxyl ester groups of the formula -COOR ⁹ , wherein R ^{9 is} a C6 bis C3o-hydrocarbyl radical, where carboxyl groups may also be present in the form of their alkali metal, alkaline earth metal or ammonium salts, where one of the variables R ³ or R ^{4 is} hydrogen or C to C ₄ alkyl and the other a carboxyl ester group of the formula -COOR ⁹ and / or a carboxyl group, which may also be in the form of its alkali metal, alkaline earth metal or ammonium salt, means

and

(ii) 90 to 10 mole% repeat units of structure W2

in which the variable R ^{5 is} the radical of a carboxylic acid ester of the formula -A-CO-OR ¹⁰ , wherein the variable A is a C 1 to C 20 alkylene group and the variable R ¹⁰ denotes a hydrogen or a C 1 to C 30 hydrocarbyl radical, or

the grouping of the formula -COOR ^{10 represents} a carboxyl group which may also be in the form of its alkali metal, alkaline earth metal or ammonium salt and in which the variables R ⁶ , R ⁷ and R ⁸ independently of one another represent hydrogen or C ¹ -C ⁶ -alkyl, and

(iii) 0 to 80 mol% repeating units of the structure W3 - [- h C-CHRH- (W3) in which the variable R ^a represents a C10 to C28-hydrocarbyl group, wherein the sum of the repeating units W1, W2 and W3 100 mol% results, as a fuel or lubricant additive, in particular diesel fuel additive.

Use according to claim 1 as an additive for reducing the fuel consumption of direct injection diesel engines, in particular diesel engines with common rail injection systems.

Use according to claim 1 as an additive for minimizing the power loss in direct-injection diesel engines, in particular in diesel engines with common-rail injection systems.

Use according to claim 3 as an additive for minimizing power loss due to K, Zn, Ca and / or Na ions (so-called K, Zn, Ca or Na powerloss).

Use according to claim 1 as a gasoline additive for reducing deposits in the intake system of a gasoline engine, in particular DISI and PFI (Port Fuel Injector) engines.

Use according to any one of claims 1 to 3 as a diesel fuel additive for reducing and / or avoiding deposits in the fuel systems, in particular injection systems, such as in particular the Internal Diesel Injector Deposits (IDID) and / or valve sticking in direct injection diesel engines, especially in common Rail injection systems.

Use according to claim 6 as a diesel fuel additive for reducing and / or avoiding internal diesel injector deposits (IDID) caused by Na, Ca and / or K ions (so-called Na, Ca or K soaps IDID).

Use according to claim 6 as a diesel fuel additive for reducing and / or avoiding the internal diesel injector deposits (IDID) due to polymeric deposits.

Use according to one of the preceding claims, wherein the fuel is selected from diesel fuels, biodiesel fuels, gasoline fuels and alkanol, in particular ethanol-containing gasoline.

Use according to one of the preceding claims, characterized in that the variables in the repeating unit W1 have the following meanings:

R ^{1 is} hydrogen,

R ³ is hydrogen,

R ² and R ⁴ together form a grouping -CO-O-CO-.

Use according to any one of the preceding claims, characterized in that 25 to 75 mol% of a repeating unit W3 are present, in which R ^{a is} selected from the group consisting of n-dodecyl, n-tri-decyl, iso-tridecyl, n- Tetradecyl, n-hexadecyl, n-octadecyl, n-eicosyl, n-heneicosyl, n -docosyl, n-tricosyl, n-tetracosyl, n -pentacosyl, and n-hexacosyl.

Additive concentrate containing in combination with other diesel or petrol additives or lubricant additives at least one of the polymers as described in claim 1, 10 or 11.

A fuel composition, lubricant composition or kerosene composition, in particular a diesel fuel composition, comprising at least one of the polymers as described in claim 1, 10 or 11.