EP3555244A1

EP3555244A1 - Polymers as additives for fuels

Info

Publication number: EP3555244A1
Application number: EP17807843.2A
Authority: EP
Inventors: Maxim Peretolchin; Ivette Garcia Castro; Aaron FLORES-FIGUEROA
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2016-12-15
Filing date: 2017-11-29
Publication date: 2019-10-23
Anticipated expiration: 2037-11-29
Also published as: US11566196B2; EP3555244B1; US10947467B2; ES2948483T3; PL3555244T3; CN110088253B; CN110088253A; US20210163837A1; MY202420A; US20200056109A1; WO2018108534A1

Abstract

Use of copolymers obtainable by - in a first reaction step (I) - copolymerization of (A) at least one ethylenically unsaturated mono-or dicarboxylic acid or derivatives thereof, preferably a dicarboxylic acid, (B) at least one a-olefin having from at least 12 up to and including 30 carbon atoms, (C) optionally at least one further aliphatic or cycloaliphatic olefin comprising at least 4 carbon atoms which is distinct from (B), and (D) optionally one or more further copolymerizable monomers distinct from the monomers (A), (B) und (C) and selected from the group consisting of (Da) vinyl esters, (Db) vinyl ethers, (Dc) (meth) acrylic esters of alcohols comprising at least 5 carbon atoms, (Dd) allyl alcohols or ethers thereof, (De) N-vinyl compounds selected from the group consisting of vinyl compounds of heterocycles containing at least one nitrogen atom, N-vinyl amides or N-vinyl lactams, (Df) ethylenically unsaturated aromatics, (Dg) α,β-ethylenically unsaturated nitriles, (Dh) (meth)acrylic amides and (Di) allylamines, followed by - in a second reaction step (II) - partial reaction of anhydride or carboxylic acid functionalities present in the copolymers obtained from (I) with at least one compound (E) containing at least one alcohol group and/or at least one amino group and - in a third reaction step (III) -hydrolysis of the anhydride functionalities present in the copolymer obtained from (II) and/or partial saponification of carboxylic ester functionalities present in the copolymer obtained from (II) as a diesel fuel additive.

Description

POLYMERS AS DIESEL FUEL ADDITIVES FOR DIRECT INJECTION DIESEL ENGINES Description

The present invention relates to the use of certain polymers as a diesel fuel additive; Process for the preparation of such additives, and diesel fuels additized therewith; in particular as a detergent additive; Use of these polymers to reduce or prevent deposits in the fuel systems, and more particularly to injection systems of direct injection diesel engines, especially in common rail injection systems, for reducing the fuel consumption of direct injection diesel engines, particularly diesel engines with common rail injection systems, and minimizing power loss (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.

WO 201 1/161 149 A1 discloses quaternized copolymers which are obtainable by copolymerization of ethylenically unsaturated hydrocarbons with monocarboxylic or dicarboxylic acids, subsequent reaction of these compounds with alcohols to give esters or using amines to give amides or imides and subsequent quaternization.

Furthermore, the use of these quaternized copolymers is described as a fuel additive in direct-injection diesel engines. A use of the unquaternized copolymers is not described.

WO 15/1 13681 discloses copolymers having at least one free carboxylic acid side group and their use as fuel additives. Further, the partial reaction of the carboxyl groups of the copolymer with at least one hydroxyl compound, at least one primary or secondary amine or mixtures thereof is generally described, but concrete compounds are absent.

It is known from EP 1541664 A1, EP 1541662 A1, EP 688796 A1 and WO 96/06902 A1 to react copolymers of succinic or succinic anhydride structural units with various amines or alcohols. The products thus obtained are used to reduce the precipitation of paraffins and / or fatty acid ester crystals from middle distillates in the cold. Such precipitations take place at low temperatures and outside the engine.

From US 201 1/0315107 A1 it is known to convert copolymers of α-olefins and maleic anhydride with 3- (N, N-dimethylamino) -propylamine to the imide. The product obtained is quaternized equimolar with propylene oxide and shows an improvement in power losses in direct-injection diesel engines. Uses of the non-quaternized product are not described. 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) pre-injection, which substantially achieves softer combustion, so that hard combustion noise ("nailing") is reduced and engine running appears quiet; (2.) main injection, which is responsible in particular for a good torque curve; and (3) post-injection which provides, in particular, a low NCv value. In this post injection, the fuel is not burned in the rule, but evaporated by residual heat in the cylinder. The resulting exhaust gas / fuel mixture is transported to the exhaust system, where the fuel in the presence of suitable catalysts acts as a reducing agent for the nitrogen oxides NO _x .

Due to the variable, cylinder-specific injection 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 can form under certain conditions, for example when using biodiesel-containing fuels or fuels with metal impurities such as zinc compounds, copper compounds, lead compounds and other metal compounds, the injection behavior of the Negatively affect the performance of the engine, ie in particular reduce the performance, 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 optimum functioning of the engine and injectors, such deposits in the nozzle openings must be prevented or reduced by suitable fuel additives. Deposits cause significant performance problems in the intake systems of modern diesel engines. 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 (IDID)) are also present in certain parts of the injectors, especially the nozzle needle, the control piston, 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 that 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.

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

The task is solved by

the use of copolymers obtainable by

in a first reaction step (I) copolymerization of (A) at least one ethylenically unsaturated mono- or dicarboxylic acid or derivatives thereof, preferably a dicarboxylic acid, at least one α-olefin having from at least 12 up to and including 30 carbon atoms, optionally at least one further, at least 4 Carbon atoms, aliphatic or cycloaliphatic olefin other than (B), and

(D) optionally one or more other copolymerizable monomers other than the monomers (A), (B) and (C) selected from the group consisting of (Da) vinyl esters,

(Db) vinyl ethers,

(De) (meth) acrylic esters of alcohols containing at least 5 carbon atoms, (Dd) allylic alcohols or their ethers, (De) N-vinyl compounds selected from the group consisting of vinyl compounds of heterocycles containing at least one nitrogen atom, N-vinylamides or N-vinyllactams,

(Df) ethylenically unsaturated aromatics

(Dg) α, β-ethylenically unsaturated nitriles,

(That is) (meth) acrylic acid amides and

(Di) allylamines, followed by partial reaction of anhydride or carboxylic acid functionalities contained in the copolymer obtained from (I) in a second reaction step (II) with compound (E) containing at least one alcohol group and / or at least one amino group, and

in a third reaction step (III), hydrolysis of the anhydride functionalities contained in the copolymer obtained from (II) and / or partial saponification of carboxylic acid ester functionalities contained in the copolymer obtained from (II) as diesel fuel additive for minimizing power loss in direct-injection diesel engines, for Reduction of fuel consumption of direct injection diesel engines and / or reduction and / or avoidance of deposits in the fuel system in direct injection diesel engines.

Such copolymers have been shown to be effective in suppressing and / or eliminating the following deposits in diesel and gasoline engines:

Summary of the invention:

These copolymers 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.

Brief Description:

FIG. 1 shows the sequence of a one-hour engine test cycle according to CEC F-098-08. A1) Special embodiments

Specific embodiments of the invention are:

1 . Use of copolymers obtainable by

in a first reaction step (I) copolymerization of

(A) at least one ethylenically unsaturated mono- or dicarboxylic acid or derivatives thereof, preferably a dicarboxylic acid,

(B) at least one α-olefin having from at least 12 up to and including 30 carbon atoms,

(C) optionally at least one further, at least 4 carbon atoms, aliphatic or cycloaliphatic olefin which is other than (B) and

(D) optionally one or more other copolymerizable monomers other than the monomers (A), (B) and (C) selected from the group consisting of

(Da) vinyl esters,

(Db) vinyl ethers,

(De) (meth) acrylic esters of alcohols having at least 5 carbon atoms,

(Dd) allyl alcohols or their ethers,

(De) N-vinyl compounds selected from the group consisting of vinyl compounds of heterocycles containing at least one nitrogen atom, N-

Vinyl amides or N-vinyl lactams,

(Df) ethylenically unsaturated aromatics

(Dg) α, β-ethylenically unsaturated nitriles,

(That is) (meth) acrylic acid amides and

(Di) Allylamines, followed by in a second reaction step (II) partial reaction of the obtained in (I) copolymer containing anhydride or carboxylic acid functionalities with at least one at least one alcohol group and / or at least one amino group-containing compound (E), and in one Third Reaction Step (III) Hydrolysis of the anhydride functionalities contained in the copolymer obtained from (II) and / or partial saponification of carboxylic acid ester functionalities contained in the copolymer obtained from (II) as a diesel fuel additive.

Use according to the embodiment 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 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, in particular 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 the reduction and / or avoidance of 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-containing gasolines. Additive concentrate containing in combination with other diesel or petrol additives or lubricant additives at least one copolymer obtainable by - in a first reaction step (I) copolymerization of

(A) at least one ethylenically unsaturated mono- or dicarboxylic acid or derivatives thereof, preferably a dicarboxylic acid, (B) at least one α-olefin having from at least 12 up to and including 30 carbon atoms,

(Da) vinyl esters,

(Db) vinyl ethers,

(De) (meth) acrylic esters of alcohols having at least 5 carbon atoms,

(Dd) allyl alcohols or their ethers,

(De) N-vinyl compounds selected from the group consisting of vinyl compounds of heterocycles containing at least one nitrogen atom, N-vinylamides or N-vinyllactams,

(Df) ethylenically unsaturated aromatics

(Dg) α, β-ethylenically unsaturated nitriles,

(That is) (meth) acrylic acid amides and

(Di) Allylamines, followed by in a second reaction step (II) partial reaction of the obtained in (I) copolymer containing anhydride or carboxylic acid functionalities with at least one at least one alcohol group and / or at least one amino group-containing compound (E), and in one Third Reaction Step (III) Hydrolysis of the anhydride functionalities contained in the copolymer obtained from (II) and / or partial saponification of carboxylic acid ester functionalities contained in the copolymer obtained from (II). A fuel composition or kerosene composition, especially a diesel fuel composition containing a copolymer obtainable by

in a first reaction step (I) copolymerization of

(B) at least one α-olefin having from at least 12 up to and including 30 carbon atoms, (C) optionally at least one further, at least 4 carbon atoms, aliphatic or cycloaliphatic olefin which is other than (B) and

(Da) vinyl esters,

(Db) vinyl ethers,

(De) (meth) acrylic esters of alcohols having at least 5 carbon atoms,

(Dd) allyl alcohols or their ethers,

Vinyl amides or N-vinyl lactams,

(Df) ethylenically unsaturated aromatics

(Dg) α, β-ethylenically unsaturated nitriles,

(That is) (meth) acrylic acid amides and

(Di) Allylamines, followed by in a second reaction step (II) partial reaction of the obtained in (I) copolymer containing anhydride or carboxylic acid functionalities with at least one at least one alcohol group and / or at least one amino group-containing compound (E), and in one Third Reaction Step (III) Hydrolysis of the anhydride functionalities contained in the copolymer obtained from (II) and / or partial saponification of carboxylic acid ester functionalities contained in the copolymer obtained from (II).

Description of the copolymer

The monomer (A) is at least one, preferably one to three, more preferably one or two and most preferably exactly one ethylenically unsaturated, preferably α, β-ethylenically unsaturated mono- or dicarboxylic acid or derivatives thereof, preferably a dicarboxylic acid or their derivatives, more preferably the anhydride of a dicarboxylic acid, most preferably maleic anhydride.

Derivatives are understood here

the relevant anhydrides in monomeric or polymeric form,

Mono- or dialkyl esters, preferably mono- or di-C 1 -C 4 -alkyl esters, particularly preferably mono- or dimethyl esters or the corresponding mono- or diethyl esters, and mixed esters, preferably mixed esters with different C 1 -C 4 -alkylcomponents, particularly preferably mixed methyl ethyl esters. The derivatives are preferably anhydrides in monomeric form or C1-C4-C4-alkyl esters, more preferably anhydrides in monomeric form. For the purposes of this specification, C 1 -C 4 -alkyl is understood to mean methyl, ethyl, / isopropyl, n-propyl, n-butyl, isobutyl, sec-butyl and fer-butyl, preferably methyl and ethyl, particularly preferably methyl ,

The α, β-ethylenically unsaturated mono- or dicarboxylic acid are those mono- or dicarboxylic acids or derivatives thereof in which the carboxyl group or, in the case of dicarboxylic acids, at least one carboxyl group, preferably both carboxyl groups, are conjugated with the ethylenically unsaturated double bond.

Examples of ethylenically unsaturated mono- or dicarboxylic acid which are not α, β-ethylenically unsaturated are cis-5-norbornene-endo-2,3-dicarboxylic anhydride, exo-3,6-epoxy-1,2,3, 6-tetrahydrophthalic anhydride and cis-4-cyclohexene-1,2-dicarboxylic acid anhydride.

Examples of α, β-ethylenically unsaturated monocarboxylic acids are acrylic acid, methacrylic acid, crotonic acid and ethylacrylic acid, preferably acrylic acid and methacrylic acid, referred to in this document as (meth) acrylic acid, and particularly preferably acrylic acid.

Particularly preferred derivatives of α, β-ethylenically unsaturated monocarboxylic acids are methyl acrylate, ethyl acrylate, n-butyl acrylate and methyl methacrylate.

Examples of dicarboxylic acids are maleic acid, fumaric acid, itaconic acid (2-methylenebutanoic acid), citraconic acid (2-methylmaleic acid), glutaconic acid (pent-2-ene-1, 5-dicarboxylic acid), 2,3-dimethylmaleic acid, 2-methylfumaric acid, 2 , 3-dimethylfumaric acid, methylenemalonic acid and tetrahydrophthalic acid, preferably maleic acid and fumaric acid, and more preferably maleic acid and its derivatives.

In particular, the monomer (A) is maleic anhydride.

The monomer (B) is at least one, preferably one to four, more preferably one to three, most preferably one or two and especially exactly one α-olefin having from at least 12 up to and including 30 carbon atoms. The α-olefins (B) preferably have at least 14, more preferably at least 16, and most preferably at least 18 carbon atoms. Preferably, the alpha-olefins (B) have 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 thereof are 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonodecene, 1-eicosene, 1-doses, 1-tetracoses, 1-hexa cosen, of which 1-octadecene, 1-eicosene, 1-doses and 1-tetracoses, and mixtures thereof are preferred.

Further examples of α-olefin (B) 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 of these are ethene, propene, 1-butene, 2-butene, isobutene, pentene isomers and hexene isomers; preference is given to ethene, propene, 1-butene, 2-butene and isobutene.

Named as α-olefins (B) may be mentioned 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.

In addition to the olefin (B) optionally at least one, preferably one to four, more preferably one to three, most preferably one or two and especially just another, at least 4 carbon atoms, having aliphatic or cycloaliphatic olefin (C), the other than (B) is copolymerized in the copolymer of the invention.

The olefins (C) may be olefins with terminal (o) double bond or those with non-terminal double bond, preferably with a-double bond. Preferably, the olefin (C) is olefins having 4 to less than 12 or more than 30 carbon atoms. When the olefin (C) is an olefin having 12 to 30 carbon atoms, this olefin (C) does not have an α-double bond.

Examples of aliphatic olefins (C) are 1-butene, 2-butene, isobutene, pentene isomers, hexene isomers, heptene isomers, octene isomers, nonene isomers, decene isomers, undecene isomers, and mixtures thereof ,

Examples of cycloaliphatic olefins (C) are cyclopentene, cyclohexene, cyclooctene, cyclodecene, cyclododecene, o or ß-pinene and mixtures thereof, limonene and norbornene.

Further examples of olefins (C) are polymers of propene, 1-butene, 2-butene or isobutene containing more than 30 carbon atoms or olefin mixtures containing such, preferably of isobutene or olefin mixtures containing such, particularly preferably having an average molecular weight M _w in the range of 500 to 5000 g / mol, preferably 650 to 3000, more preferably 800 to 1500 g / mol.

Preferably, the isobutene in polymerized form containing oligomers or polymers have a high content of terminal ethylenic double bonds

(a-double bonds), for example at least 50 mol%, preferably at least 60 mole%, more preferably at least 70 mole%, and most preferably at least 80 mole%.

Both isobutene and isobutene-containing C4 hydrocarbon streams, for example C4 raffinates, in particular "raffinate 1", C4 cuts from isobutane are suitable as isobutene source for the preparation of such isobutene in polymerized form containing oligomers or polymers Dehydrogenation, C4 cuts from steam crackers and fluid catalysed cracking (FCC) crackers provided that they are substantially free of 1,3-butadiene contained therein. A C4 hydrocarbon stream from an FCC refinery unit is also known as a "b / b" stream. Other suitable isobutene-containing C4 hydrocarbon streams are, for example, the product stream of a propylene-isobutane co-oxidation or the product stream from a metathesis unit, which are generally used after customary purification and / or concentration. Suitable C4 hydrocarbon streams typically contain less than 500 ppm, preferably less than 200 ppm, butadiene. The presence of 1-butene and of cis- and trans-2-butene is largely uncritical. Typically, the isobutene concentration in said C4 hydrocarbon streams is in the range of 40 to 60 weight percent. Thus, raffinate 1 usually consists essentially of 30 to 50 wt .-% of isobutene, 10 to 50 wt .-% 1-butene, 10 to 40 wt .-% cis- and trans-2-butene and 2 to 35 wt .-% butanes; In the polymerization process according to the invention, the unsubstituted butenes in the raffinate 1 are generally virtually inert and only the isobutene is polymerized. In a preferred embodiment, the monomer used for the polymerization is a technical C 4 hydrocarbon stream having an isobutene content of 1 to 100% by weight. %, in particular from 1 to

99 wt.%, Especially from 1 to 90 wt.%, Particularly preferably from 30 to 60 wt.%, In particular a raffinate 1 stream, a b / b stream from an FCC refinery unit, a a stream of propylene-isobutane co-oxidation or a product stream from a metathesis unit.

In particular, when using a raffinate 1 stream as isobutene source, the use of water has proved to be the sole or as a further initiator, especially if at temperatures from -20 ° C to + 30 ° C, in particular from 0 ° C to + 20 ° C, polymerized. At temperatures of -20 ° C to + 30 ° C, in particular from 0 ° C to + 20 ° C, however, it is possible to dispense with the use of an initiator when using a raffinate 1 stream as Isobutenquelle. Said isobutene-containing monomer mixture may contain small amounts of contaminants such as water, carboxylic acids or mineral acids, without resulting in critical yield or selectivity losses. It is expedient to avoid an accumulation of these impurities by removing such pollutants from the isobutene-containing monomer mixture, for example by adsorption on solid adsorbents such as activated carbon, molecular sieves or ion exchangers.

Although less preferred, monomer mixtures of isobutene or of the isobutene-containing hydrocarbon mixture can also be reacted with olefinically unsaturated monomers which are copolymerizable with isobutene. If monomer mixtures of isobutene are to be copolymerized with suitable comonomers the monomer mixture preferably at least 5 wt .-%, particularly preferably at least 10 wt .-% and in particular at least 20 wt .-% isobutene, and preferably at most 95 wt .-%, particularly preferably at most 90 wt .-% and in particular at most

80% by weight of comonomers.

In a preferred embodiment, the substance mixture of the olefins (B) and optionally (C) averaged to their substance amounts at least 12 carbon atoms, preferably at least 14, more preferably at least 16 and most preferably at least 17 carbon atoms.

For example, a 2: 3 mixture of docoses and tetradecene has an average value for the carbon atoms of 0.4 ^χ 22 + 0.6 x 14 = 17.2.

The upper limit is less relevant and is usually not more than 60 carbon atoms, preferably not more than 55, more preferably not more than 50, most preferably not more than 45 and especially not more than 40 carbon atoms.

The optional monomer (D) is at least one monomer, preferably one to three, more preferably one or two and most preferably exactly one monomer selected from the group consisting of

(Da) vinyl esters,

(Db) vinyl ethers,

(De) (meth) acrylic esters of alcohols containing at least 5 carbon atoms, (Dd) allylic alcohols or their ethers,

(Df) ethylenically unsaturated aromatics and

(Dg) α, β-ethylenically unsaturated nitriles

(That is) (meth) acrylic acid amides and

(Di) Allylamines.

Examples of vinyl esters (Da) are vinyl esters of C 2 -C 12 -carboxylic acids, preferably vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pentanoate, vinyl hexanoate, vinyl octanoate, vinyl 2-ethylhexanoate, vinyl decanoate, and also vinyl esters of versatic acids 5 to 10 Vinyl esters of 2,2-dimethylpropionic acid (pivalic acid, versatic acid 5), 2,2-dimethylbutyric acid (neohexanoic acid, versatic acid 6), 2,2-dimethylpentanoic acid (neoheptanoic acid, versatic acid 7), 2,2- Dimethylhexanoic acid (neoctanoic acid, versatic acid 8), 2,2-dimethylheptanoic acid (neononanoic acid, versatic acid 9) or 2,2-dimethyloctanoic acid (neodecanoic acid, versatic acid 10).

Examples of vinyl ethers (Db) are vinyl ethers of Cr to C 12 -alkanols, preferably vinyl ethers of methanol, ethanol, / so-propanol, n-propanol, n-butanol, / so-butanol, se / butanol, feri-butanol, n Hexanol, n-heptanol, n-octanol, n-decanol, n-dodecanol (lauryl alcohol) or 2-ethylhexanol. Preferred (meth) acrylic esters (De) are (meth) acrylic esters of C5- to C12-alkanols, preferably of n-pentanol, n-hexanol, n-heptanol, n-octanol, n-decanol, n-dodecanol (lauryl alcohol ), 2-ethylhexanol or 2-propylheptanol. Particular preference is given to acrylic acid pentyl esters, 2-ethylhexyl acrylate, 2-propylheptyl acrylate.

Examples of monomers (Dd) are allyl alcohols and allyl ethers of C 2 - to C 12 -alkanols, preferably allyl ethers of methanol, ethanol, / so-propanol, n-propanol, n-butanol, / so-butanol, sec-butanol, feri-butanol , n-hexanol, n-heptanol, n-octanol, n-decanol, n-dodecanol (lauryl alcohol) or 2-ethylhexanol. Examples of vinyl compounds (De) of heterocycles containing at least one nitrogen atom are N-vinylpyridine, N-vinylimidazole and N-vinylmorpholine.

Preferred compounds (De) are N-vinylamides or N-vinyllactams: examples of N-vinylamides or N-vinyllactams (De) are N-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone and N-vinylcaprolactam.

Examples of ethylenically unsaturated aromatics (Df) are styrene and α-methylstyrene. Examples of α, β-ethylenically unsaturated nitriles (Dg) are acrylonitrile and methacrylonitrile.

Examples of (meth) acrylic acid amides (Dh) are acrylamide and methacrylamide.

Examples of allylamines (di) are allylamine, dialkylallylamine and trialkyl allylammonium halide.

Preferred monomers (D) are (Da), (Db), (De), (De) and / or (Df), particularly preferably (Da), (Db) and / or (De), very particularly preferably (Da) and / or (De) and in particular (De). The incorporation ratio of the monomers (A) and (B) and optionally (C) and optionally (D) in the copolymer obtained from the reaction step (I) is usually as follows:

The molar ratio of (A) / ((B) and (C)) (in total) is generally from 10: 1 to 1:10, preferably 8: 1 to 1: 8, particularly preferably 5: 1 to 1 : 5, most preferably 3: 1 to 1: 3, in particular 2: 1 to 1: 2 and especially 1, 5: 1 to 1: 1, 5. For the particular case of maleic anhydride as monomer (A), the molar incorporation ratio of maleic anhydride to monomers ((B) and (C)) (in total) is about 1: 1. In order to achieve a complete conversion of the α-olefin (B), it may still be useful to use maleic anhydride in a slight excess over the α-olefin, for example, 1, 01-1, 5: 1, preferably 1, 02-1, 4 : 1, particularly preferably 1, 05-1, 3: 1, very particularly preferably 1, 07-1, 2: 1 and especially 1, 1-1, 15: 1.

The molar ratio of the obligate monomer (B) to the monomer (C), as far as it is present, is generally from 1: 0.05 to 10, preferably from 1: 0.1 to 6, particularly preferably from 1: 0, 2 to 4, most preferably from 1: 0.3 to 2.5 and especially 1: 0.5 to 1.5. In a preferred embodiment, in addition to monomer (B), no optional monomer (C) is present.

The proportion of one or more of the monomers (D), if present, based on the amount of the monomers (A), (B) and optionally (C) (in total) is generally from 5 to

200 mol%, preferably 10 to 150 mol%, particularly preferably 15 to 100 mol%, very particularly preferably 20 to 50 mol% and in particular 0 to 25 mol%.

In a preferred embodiment, no optional monomer (D) is present.

In a particularly preferred embodiment, the copolymer consists of the monomers (A) and (B).

In a second reaction step (II), the anhydride or carboxylic ester functionalities contained in the copolymer obtained from (I) are partially reacted with at least one compound (E) containing at least one alcohol group and / or at least one amino group. Preferably, in reaction step (II), anhydride functionalities are reacted and carboxylic acid ester functionalities are left substantially intact. In general, 5 to 75% of the anhydride and carboxylic acid ester functionalities present are reacted with at least one compound (E), preferably 7.5 to 66%, particularly preferably 10 to 50%, very particularly preferably 12.5 to 40% and in particular 15 up to 30%.

Compounds (E) are those which have at least one alcohol group and / or at least one amino group, preferably either at least one alcohol group or at least one amino group.

Examples of alcohols (E1) as compounds (E) are those which have one to six hydroxyl groups, preferably one to four, particularly preferably one to three, very particularly preferably one or two and in particular exactly one hydroxy group.

Examples of amines (E2) as compounds (E) are those which have one to six amino groups, preferably one to four, particularly preferably one to three, very particularly preferably one or two and in particular exactly one amino group.

Also conceivable are amino alcohols (E3) which have at least one hydroxyl group and at least one amino group, preferably exactly one hydroxyl group and at least one amino group, particularly preferably exactly one hydroxy group and exactly one amino group. The amino groups are primary or secondary amino groups, preferably primary amino groups. Tertiary amino groups are not included in compounds (E2) or (E3) since they do not react in reaction step (II).

Examples of monoalcohols are 1 to 20 carbon atoms alkanols and their alkoxylates. Alkanols having 1 to 20 carbon atoms are, for example, methanol, ethanol, isopropanol, n-propanol, n-butanol, / so-butanol, sec-c-butanol, ferric butanol, n-hexanol, n-heptanol, n-octanol , n-decanol, n-dodecanol (lauryl alcohol), 2-ethylhexanol, n-decanol, n-dodecanol, tridecanol, heptadecanol and eicosanol.

Preference is given to fatty alcohols, preferably octyl alcohol (capryl alcohol), nonyl alcohol (pelargonyl alcohol), decyl alcohol (capric alcohol), undecyl alcohol, dodecyl alcohol (lauryl alcohol), tridecyl alcohol, tetradecyl alcohol (myristyl alcohol), pentadecyl alcohol, hexadecyl alcohol (cetyl alcohol, palmityl alcohol). , Heptadecyl alcohol, octadecyl alcohol (stearyl alcohol), oleyl alcohol, elaidyl alcohol, linoleyl alcohol, linolenoyl alcohol, nonadecyl alcohol, eicosyl alcohol (arachyl alcohol) or mixtures thereof.

Preference is given to monoalcohols of the formula (I) wherein

R ^{1 is} a straight-chain or branched C 1 - to C 20 -alkyl- or C 1 - to C 20 -alkenyl radical, preferably a straight-chain or branched C 1 - to C 20 -alkyl radical and

n is 0 (zero) or a positive integer from 1 to 50, preferably 2 to 40 and more preferably 3 to 30, and

each Xi for i = 1 to n may be independently selected from the group consisting of

from -CH ₂ -CH ₂ -O-, -CH ₂ -CH (CH ₃ ) -O-, -CH (CH ₃ ) -CH ₂ -0-, -CH ₂ -C (CH ₃ ) ₂ -O-, - C (CH ₃ ) ₂ -CH ₂ -O-, -CH ₂ -CH (C ₂ H ₅ ) -O-, -CH (C ₂ H ₅ ) -CH ₂ -O- and -CH (CH ₃ ) - CH (CH ₃ ) -O-, preferably selected from the group consisting

from -CH ₂ -CH (CH ₃ ) -O-, -CH (CH ₃ ) -CH ₂ -0-, -CH ₂ -C (CH ₃ ) ₂ -O-, -C (CH ₃ ) ₂ -CH ₂ -0-, -CH ₂ -CH (C ₂ H ₅ ) -O-, -CH (C ₂ H ₅ ) -CH ₂ -O- and -CH (CH ₃ ) -CH (CH ₃ ) -O-, particularly preferably selected from the group

from -CH ₂ -CH (CH ₃ ) -O-, -CH (CH ₃ ) -CH ₂ -0-, -CH ₂ -C (CH ₃ ) ₂ -O-, -C (CH ₃ ) ₂ -CH ₂ -0-, -CH ₂ -CH (C

2H ₅ ) -O- and -CH (C 2 H ₅ ) -CH ₂ -O- and most preferably selected from the group consisting of -CH ₂ -CH (CH ₃ ) -O- and -CH (CH ₃ ) -CH ₂ -0-.

It is preferable that R ¹ is methyl, ethyl, / so-propyl, n-propyl, n-butyl, / so-butyl, sec-butyl, feri-butyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-decyl, 2-propylheptyl, n-dodecyl, tridecyl, n-tetradecyl, n-hexadecyl, heptadecyl, n-octadecyl or n-eicosyl.

R ¹ is particularly preferably 2-ethylhexyl, 2-propylheptyl, stearyl, cetyl, lauryl, C ₃ -isomer mixtures and C 17 isomer mixtures.

In a particularly preferred embodiment, the underlying alcohol R ¹ -OH is a mixture of alcohols having 13 carbon atoms, more preferably one obtainable by hydroformylation of a C 12 -olefin mixture, which in turn is obtainable by oligomerization of an olefin mixture containing predominantly four carbon atoms hydrocarbons. On a statistical average, this olefin mixture has from 1 to 13 carbon atoms, preferably from 1.1 to 12.9, more preferably from 1.2 to 12.8, very particularly preferably from 1.5 to 12.5 and in particular 11, 8 to 12.2. In a most preferred embodiment, this alcohol R ¹ -OH has an average degree of branching, measured as the ISO index, of from 2.8 to 3.7.

In particular, this alcohol R ¹ -OH is obtained by a process as described in WO 00/02978 or WO 00/50543.

In a further particularly preferred embodiment, the underlying alcohol R ¹ -OH is a mixture of alcohols having 17 carbon atoms, particularly preferably one obtainable by hydroformylation of a C 16 -olefin mixture which, in turn, can be obtained by oligomerization of an olefin mixture is that contains predominantly four carbon atoms hydrocarbons.

On a statistical average, this olefin mixture has 15 to 17 carbon atoms, preferably 15.1 to 16.9, particularly preferably 15.2 to 16.8, very particularly preferably 15.5 to 16.5 and in particular 15.8 to 16.2 ,

In a most preferred embodiment, this alcohol R ¹ -OH has an average degree of branching, measured as the ISO index, of from 2.8 to 3.7.

In particular, this alcohol R ¹ -OH is 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 25th , which is hereby incorporated by reference into the present disclosure.

According to this preferred process, the product of the transition metal-catalyzed oligomerization of olefins having 2 to 6 carbon atoms can be a C 17 -alcohol mixture having particularly advantageous performance properties. Initially, a Ci6-olefin mixture is isolated by distillation from the product of the olefin oligomerization and only then subjected to this Ci6-olefin mixture of a hydroformylation. Thus, it is possible to provide a more highly branched C 17 -alcohol mixture having particularly advantageous performance properties.

In a further possible, albeit less preferred embodiment, the alcohols may also carry tertiary amino groups, since these do not react in reaction step (II). Preferred such alcohols are dimethylaminoethanolamine, dimethylaminopropanolamine, diethylaminoethanolamine, diethylaminopropanolamine and hydroxyethylmorpholine.

Examples of diols are ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 1-dimethylethane-1, 2-diol, 2-butyl-2-ethyl-1, 3-propanediol, 2-ethyl-1, 3-propanediol, 2-methyl-1,3-propanediol, neopentyl glycol, hydroxypivalic acid neopentyl glycol ester, 1, 2, 1, 3 or 1, 4-butanediol, 1, 6-hexanediol, 1, 10-decanediol, bis- (4-hydroxycyclohexane) isopropylidene, tetramethylcyclobutanediol, 1, 2, 1, 3 or 1,4-cyclohexanediol, cyclooctanediol, norbornanediol, pinanediol, decalin diol, 2-ethyl-1,3-hexanediol, 2,4-diethyl-octane-1,3-diol, hydroquinone, bisphenol A, bisphenol F, bisphenol B, bisphenol S, 2,2-bis (4-hydroxycyclohexyl) propane, 1, 1, 1, 2, 1, 3 and 1, 4-cyclohexanedimethanol, 1, 2, 1, 3 or 1, 4-cyclohexanediol.

Also conceivable are polyethylene glycol having a molar mass of from 106 to 678 g / mol, poly-1,2-propanediol having a molar mass of from 134 to 888 g / mol, poly-1,3-propanediol having a molar mass of from 134 to 888 g / mol or poly-THF with a molecular weight of 162 to 1098 g / mol. Examples of triols and polyols are trimethylolbutane, trimethylolpropane, trimethylolethane, pentaerythritol, glycerol, ditrimethylolpropane, dipentaerythritol, sorbitol, mannitol, diglycerol, threitol, erythritol, adonite (ribitol), arabitol (lyxite), xylitol, dulcitol (galactitol), maltitol or isomalt ,

Examples of primary or secondary monoamines as amines (E2) are monoamines having from 6 to 200 carbon atoms, which may be monoalkylamines or dialkylamines, preferably monoalkylamines, preferably methylamine, ethylamine, / so-propylamine, n-propylamine, n Butylamine, / so-butylamine, se / butylamine, feri-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-decylamine, n-dodecylamine, 2-ethylhexylamine, stea- rylamine, cetylamine , Laurylamine, dimethylamine, diethylamine, di-n-propylamine, di- / so-propylamine, di-n-butylamine, dihexylamine, dioctylamine, ethylmethylamine, / so-propyl-methylamine, n-butylmethylamine, tert-butylmethylamine, / so-propyl-ethylamine, n-butylethylamine or feri-butyl-ethylamine.

Preferred examples are fatty amines, ie octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine (stearylamine), oleylamine, elaidylamine, linoleylamine, linolenoylamine, nonadecylamine, eicosylamine or mixtures thereof.

In one possible embodiment, the amines may also carry tertiary amino groups, since these do not react in reaction step (II). Preferred such amines are 2-dimethylaminoethylamine, 3-dimethylaminopropylamine and N ', N ", N" -trimethyl diethylenetriamine.

In a preferred embodiment, the amine (E2) is a monoamine of the formula (II)

in the

R ^{2 is} hydrogen or Ci-20-alkyl, preferably hydrogen and

R ^{3 is} Ci2-2oo-alkyl, preferably Ci6-iso-alkyl, particularly preferably C2o-i3o-alkyl, very particularly preferably C3o-ioo-alkyl, which may in each case be linear or branched, mean.

In the amine (II) employed, the radical R ³ in a preferred embodiment is a polyisobutene polymer, and the amines (II) are preferably obtainable by hydroformylation and amination of polyisobutene polymers.

The polyisobutene polymer preferably has a weight-average molecular weight of 550 to 2300 g / mol, particularly preferably 650 to 1500 g / mol, very particularly preferably 850 to 150 g / mol and in particular 950 to 1050 g / mol.

The polyisobutene polymer which can be used for this purpose can be isobutene homopolymers or copolymers which preferably have a content of terminal vinylidene double bonds per polyisobutene chain end of at least 50 mol%. Such polyisobutene polymers have a higher reactivity.

Such homopolymers or copolymers are obtainable by polymerization of isobutene or of an isobutene-containing monomer mixture in the presence of at least one Lewis acid which is suitable as a polymerization catalyst or of a complex comprising at least one Lewis acid and at least one donor and in the presence of at least one initiator as polymerization catalyst. Frequently and preferably boron halides, preferably boron trifluoride, are used as the Lewis acid, but also iron halides, aluminum halides or alkyl aluminum halides.

Isobutene homopolymers are understood within the scope of the present specification to mean those polymers which, based on the polymer, are composed of at least 98 mol%, preferably at least 99 mol%, of isobutene. Accordingly, isobutene copolymers are understood to mean those polymers which contain more than 2 mol% of monomers in copolymerized form which are different from isobutene, for example linear butenes. For the use of isobutene or an isobutene-containing monomer mixture as a monomer to be polymerized is suitable as an isobutene source both pure isobutene and isobutene-containing C4 hydrocarbon streams, such as C ₄ raffinates, especially "raffinate 1", C ₄ cuts isobutane dehydrogenation, C ₄ cuts from steam crackers and FCC (fluid catalysed cracking) crackers, provided that they are largely freed from 1,3-butadiene contained therein. A C ₄ hydrocarbon stream from an FCC refinery unit is also known as a "b / b" stream. Further suitable isobutene-containing C ₄ -hydrocarbon streams are, for example, the product stream of a propylene-isobutane co-oxidation or the product stream from a metathesis unit, which are generally used after customary purification and / or concentration. Suitable C ₄ hydrocarbon streams generally contain less than 500 ppm, preferably less than 200 ppm, butadiene. The presence of 1-butene and of cis- and trans-2-butene is largely uncritical. Typically, the isobutene concentration in said C ₄ hydrocarbon streams is in the range of 40 to

60% by weight. Thus, raffinate 1 usually consists essentially of 30 to 50 wt .-% of isobutene, 10 to 50 wt .-% 1-butene, 10 to 40 wt .-% cis- and trans-2-butene and 2 to 35 wt .-% butanes; In the polymerization process, the unbranched butenes in the raffinate 1 are generally practically inert and only the isobutene is polymerized.

In a preferred embodiment, the monomer used for the polymerization is a technical C 4 hydrocarbon stream having an isobutene content of from 1 to 100% by weight, in particular from 5 to 99% by weight, especially from 20 to 90% by weight. %, more preferably from 30 to 60% by weight, in particular a raffinate 1 stream, a b / b stream from an FCC refinery unit, a product stream from a propylene-isobutane co-oxidation or a product stream from a metathesis unit ,

Also conceivable as amines (E2) are diamines, preferably 1,2-propanediamine, ethylenediamine, 2,2-dimethyl-1,2-ethanediamine, 1,3-propanediamine, 1,2-butanediamine, 1,4-butanediamine, 2 Ethylhexane-1,3-diamine, 2,4-diethyloctane-1,3-diamine, 1,6-hexanediamine, or polyamines, preferably diethylenetriamine, triethylenetetramine, polyethyleneimines and polyethyleneamines.

In a further preferred embodiment, the amine (E2) is an ethylenediamine or its oligomer, preferably it is selected from the group consisting of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and pentaethylenehexamine.

Conceivable as alkanolamines (E3) are monoethanolamine, diethanolamine, monopropanolamine, dipropanolamine, 1,2-propanolamine, 1,3-propanolamine, 1,4-butanolamine, 1,6-hexanolamine and aminoethylethanolamine. Component (E) is preferably monoalcohols, preferably those of the formula (I), monoamines, preferably those of the formula (II), or polyethyleneamines.

Hydrolysis in reaction step (III) is then carried out when an anhydride, preferably the anhydride of a dicarboxylic acid, is used as the derivative of the monomer (A), whereas saponification or hydrolysis can be carried out when an ester is used as the monomer (A).

In a preferred embodiment, the anhydride functionalities contained in the copolymer after reaction step (II) are substantially completely hydrolyzed. However, it is also possible, though less preferred, to hydrolyze at least 50% to less than 100%, for example 66% to 95% or 75% to 90% of the anhydride functionalities contained in the copolymer after reaction step (II).

For hydrolysis, based on the anhydride functionalities contained, the amount of water is added which corresponds to the desired degree of hydrolysis and which heats the copolymer obtained from (I) 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 functions are generally selectively reacted in the copolymer, whereas any carboxylic acid ester functionalities contained in the copolymer do not react or at least only subordinate.

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 obtained from (II) 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 obtained from (II) is then heated in the presence of the added water and the 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 obtained from step (III) 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 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 copolymer obtained from reaction step (III) generally has a weight-average molecular weight Mw of 0.5 to 20 kDa, preferably 0.6 to 15, particularly preferably 0.7 to 7, very particularly preferably 1 to 7 and in particular 1, 5 to 54 kDa (determined by gel permeation chromatography with tetrahydrofuran and polystyrene as standard).

The number average molecular weight Mn is usually from 0.5 to 10 kDa, preferably from 0.6 to 5, particularly preferably from 0.7 to 4, very particularly preferably from 0.8 to 3 and in particular from 1 to 2 kDa (determined by gel permeation chromatography with tetrahydrofuran and polystyrene as standard). The polydispersity is generally from 1 to 10, preferably from 1, 1 to 8, particularly preferably from 1, 2 to 7, very particularly preferably from 1, 3 to 5 and in particular from 1, 5 to 3.

The content of free acid groups in the copolymer after passing through the reaction step (III) is preferably less than 5 mmol / g copolymer, more preferably less than 3, most preferably less than 2 mmol / g copolymer and especially less than 1 mmol / g.

In a preferred embodiment, the copolymers contain a high proportion of adjacent carboxylic acid groups as determined by an adjuacy measurement. For this purpose, a sample of the copolymer is tempered for 30 minutes at a temperature of 290 ° C between two Teflon films and recorded at a bubble-free FTIR spectrum. From the spectra obtained, the IR spectrum of Teflon is subtracted, determines the layer thickness and determines the content of cyclic anhydride. In a preferred embodiment, the adjacency is at least 10%, preferably at least 15%, particularly preferably at least 20%, very particularly preferably at least 25% and in particular at least 30%.

use

The fuel additized with the copolymer 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 copolymers described are used in the form of fuel additive mixtures, together with customary 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 copolymers, demulsifiers, dehazers, defoamers, cetane number improvers, combustion improvers, antioxidants or stabilizers, antistatic agents, Me - tallowene, metal deactivators, dyes and / or solvents. Accordingly, another object of the invention is the use of copolymers obtainable by

in a first reaction step (I) copolymerization of

(B) at least one α-olefin having from at least 12 up to and including 30 carbon atoms, (C) optionally at least one further aliphatic or cycloaliphatic olefin having at least 4 carbon atoms other than (B) and optionally one or more further copolymerizable monomers other than the monomers (A), (B) and (C ) are selected from the group consisting of

(Da) vinyl esters,

(Db) vinyl ethers,

(De) (meth) acrylic acid esters of alcohols containing at least 5 carbon atoms,

(Dd) allyl alcohols or their ethers,

(Df) ethylenically unsaturated aromatics

(Dg) α, β-ethylenically unsaturated nitriles,

(That is) (meth) acrylic acid amides and

(Di) Allylamines, followed by in a second reaction step (II) partial reaction of the obtained in (I) copolymer containing anhydride or carboxylic acid functionalities with at least one at least one alcohol group and / or at least one amino group-containing compound (E), and in one third reaction step (III) hydrolysis of the anhydride functionalities contained in the copolymer obtained from (II) and / or partial saponification of carboxylic acid ester functionalities contained in the copolymer obtained from (II) in additive packages containing at least one additive selected from the group consisting of detergent additives, carrier oils, Cold flow improvers, lubricity improvers, corrosion inhibitors other than the copolymers described, demulsifiers, dehazers, antifoams, cetane number improvers, combustion improvers, antioxidants, stabilizers, antistatic agents, metallocenes, metal deactivators, dyes and the like d solvents to reduce the fuel consumption of direct injection diesel engines, especially diesel engines with common rail injection systems and / or to minimize the power loss in direct injection diesel engines, especially in diesel engines with common rail injection systems.

In the case of gasoline fuels, these are primarily lubricity modifiers (friction modifiers), corrosion inhibitors other than the described copolymers, demulsifiers, dehazers, Antifoaming agents, combustion improvers, antioxidants or stabilizers, antistatic agents, metallocenes, metal deactivators, dyes and / or solvents.

Accordingly, another object of the invention is the use of copolymers obtainable by

in a first reaction step (I) copolymerization of

(Da) vinyl esters,

(Db) vinyl ethers,

(De) (meth) acrylic esters of alcohols having at least 5 carbon atoms,

(Dd) allyl alcohols or their ethers,

(Df) ethylenically unsaturated aromatics

(Dg) α, β-ethylenically unsaturated nitriles,

(That is) (meth) acrylic acid amides and

(Di) Allylamines, followed by in a second reaction step (II) partial reaction of the obtained in (I) copolymer containing anhydride or carboxylic acid functionalities with at least one at least one alcohol group and / or at least one amino group-containing compound (E), and in one Third Reaction Step (III) Hydrolysis of the anhydride functionalities contained in the copolymer obtained from (II) and / or partial saponification of carboxylic acid ester functionalities contained in the copolymer obtained from (II) in additive packages containing at least one additive selected from the group consisting of friction modifiers, corrosion inhibitors other than the copolymers described, demulsifiers, dehazers, antifoams, burn improvers, antioxidants, stabilizers, antistatic agents, metallocenes, metal deactivators, dyes and solvents, for reducing 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 one polar group selected from:

(Da) mono- or polyamino groups having up to 6 nitrogen atoms, wherein at least one nitrogen atom has basic properties; (Db) nitro groups, optionally in combination with hydroxyl groups;

(De) hydroxyl groups in combination with mono- or polyamino groups, wherein at least one nitrogen atom has basic properties; (Dd) carboxyl groups or their alkali metal or alkaline earth metal salts;

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

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

Carbonsäureestergruppen; (Ie) groups derived from succinic anhydride with hydroxyl 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 to 3,000, more preferably from 500 to 2,500 and especially from 700 to 2,500, especially from 800 to 1,500. As a typical hydrophobic hydrocarbon radical, in particular in conjunction with the polar, in particular polypropenyl, polybutenyl and polyisobutenyl radicals having a number average molecular weight M _n of preferably from 300 to 5,000, particularly preferably 300 to 3,000, more preferably 500 to 2,500, even more preferably 700 to 2,500 and in particular 800 to 1, 500 into consideration.

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

Mono- or polyamino (Da) -containing additives are preferably polyalkene mono- or polyalkene polyamines based on polypropene or of highly reactive (ie predominantly terminal double bonds) or conventional (ie predominantly intermediate double bonds) polybutene or polyisobutene having M _n = 300 to 5000 , particularly preferably 500 to 2500 and in particular 700 to 2500. Such additives based on highly reactive polyisobutene, which from the polyisobutene, which may contain up to 20 wt .-% of n-butene units, by hydroformylation and reductive amination with ammonia, monoamines or polyamines, such as dimethylaminopropylamine, ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine, 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-hydroxypolyisobutene).

Hydroxyl groups in combination with mono- or polyamino groups (De) containing additives are in particular reaction products of polyisobutene epoxides, obtainable from vorzugswei- se predominantly terminal double bonds having polyisobutene with M _n = 300 to 5000 with ammonia, mono- or polyamines, as described in particular in EP-A 476 485. 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 primarily used to prevent valve seat wear and, as described in WO-A 87/01 126, can be advantageously used in combination with conventional fuel detergents such as poly (iso) buteneamines or polyetheramines.

Sulfonic acid groups or their alkali metal or alkaline earth metal salts (De) containing additives are preferably alkali metal or alkaline earth metal salts of a Sulfobernsteinsäurealkyl- ester, 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-C 2 -C 4 -alkylene groups (Df) -containing additives are preferably polyethers or polyetheramines, which are prepared by reaction of C 2 - to C 6 -alkanols, C 6 - to C 3 -alkanediols, mono- or C 1 -C -cycloalkylamines, C to C3o-alkylcyclo-hexanols or C to C30-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.

Succinic anhydride-derived groupings containing hydroxyl and / or amino and / or amido and / or imido groups (Dh) containing additives are preferably corresponding derivatives of alkyl- or alkenyl-substituted succinic anhydride and in particular the corresponding derivatives of polyisobutenyl succinic anhydride, which by Reaction of conventional or highly reactive polyisobutene with M _n = preferably 300 to 5000, more preferably 300 to 3000, more preferably 500 to 2500, even more preferably 700 to 2500 and in particular 800 to 1500, with maleic anhydride by thermal means in an ene reaction or are obtainable via the chlorinated polyisobutene. The groups having hydroxyl and / or amino and / or amido and / or imido groups are, for example, carboxylic acid groups, acid amides of monoamines, acid amides of diamines or polyamines which, in addition to the amide function, still have free amine groups, succinic acid derivatives with an acid and an amide function, carboximides with monoamines, carboximides with di- or polyamines which, in addition to the imide function, still have free amine groups, or diimides which are formed by reacting di- or polyamines with two succinic acid derivatives. Such fuel additives are well known and described, for example, in documents (1) and (2). Preference is given to the reaction products of alkyl- or alkenyl-substituted succinic acids or derivatives thereof with amines, and particularly preferably to the reaction products of polyisobutenyl-substituted succinic acids or derivatives thereof with amines. Of particular interest here are reaction products with aliphatic polyamines (polyalkyleneimines), in particular ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine and hexaethyleneheptamine, which have an imide structure. In a preferred embodiment, the compounds according to the invention can be combined with quaternized compounds, as described in WO 2012/004300, there preferably page 5, line 18 to page 33, line 5, particularly preferably of preparation example 1, which hereby expressly by reference in each case part of present disclosure.

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 according to 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, particularly preferably 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 are 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 polyamines generated moieties containing (di) additives are preferably reaction products of polyisobutene-substituted phenols with formaldehyde and mono- or polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine or dimethylaminopropylamine , The polyisobutenyl-substituted phenols may be derived from conventional or highly reactive polyisobutene having M _n = 300 to 5,000. Such "polyisobutene-Mannich bases" are described in particular in EP-A 831 141. One or more of said detergent additives may be added to the fuel in such an amount that the 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 may be mineral or synthetic. Suitable mineral carrier oils are fractions obtained in petroleum processing, such as bright stock or base oils with 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 6 -alkanols, C ₆ - to C 30 -alkanediols, mono- or D 1-C2-bis C 30 -alkylamines, C 1 -C 30 -alkylcyclohexanols or C 1 -C 30 -alkylphenols with 1 to 30 mol of ethylene oxide and / or propylene oxide and / or butylene oxide per hydroxyl group or amino group and, in the case of the polyetheramines, by subsequent reductive amination with ammonia, monoamines or polyamines are available. Such products are described in particular in EP-A 310 875,

EP-A 356 725, EP-A 700 985 and US-A 4,877,416. For example, P0IV-C2 to C6 alkylene oxide amines or functional derivatives thereof may be used as the polyether amines. Typical examples of these are tridecanol or Isotridecanolbutoxylate, isononyl phenol butoxylates and Polyisobutenolbutoxylate and propoxylates and the corresponding reaction products with ammonia.

Examples of carboxylic acid esters of long-chain alkanols are, in particular, esters of mono-, di- or tricarboxylic acids with long-chain alkanols or polyols, as described in particular in DE-A 38 38 918. As mono-, di- or tricarboxylic acids it is possible to use aliphatic or aromatic acids, especially suitable ester alcohols or polyols are long-chain representatives having, for example, 6 to 24 carbon atoms. Typical representatives of the esters are adipates, phthalates, isophthalates, terephthalates and trimellitates of isooctanol, isononanol, isodecanol and of isotridecanol, eg. B. di- (n- or isotridecyl) phthalate. Further suitable carrier oil systems are described, for example, in DE-A 38 26 608, DE-A 41 42 241, DE-A 43 09 074, EP-A 452 328 and EP-A 548 617.

Examples of particularly suitable synthetic carrier oils are alcohol-started polyethers having about 5 to 35, preferably about 5 to 30, particularly preferably 10 to 30 and in particular 15 to 30 C3 to C6 alkylene oxide units, for. For example, propylene oxide, n-butylene oxide and isobutylene oxide units or mixtures thereof, per alcohol molecule. Nonlimiting examples of suitable starter alcohols are long-chain alkanols or long-chain alkyl-substituted phenols, where the long-chain alkyl radical is in particular a straight-chain or branched C 6 - to C 18 -alkyl radical. Specific examples include tridecanol and nonylphenol. Particularly preferred alcohol-started polyethers are the reaction products (polyetherification products) of monohydric C6- to Cis-aliphatic alcohols with C3- to C6-alkylene oxides. Examples of monohydric C6-C8 aliphatic alcohols are hexanol, heptanol, octanol, 2-ethylhexanol, nonyl alcohol, decanol, 3-propylheptanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, octadecanol and their constitution and position isomers. The alcohols can be used both in the form of pure isomers and in the form of technical mixtures. A particularly preferred alcohol is tridecanol. Examples of 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, pentylene oxide and hexylene oxide. Among these, particularly preferred are C ₃ -C ₄ -alkylene oxides, ie, propylene oxide such as 1, 2-propylene oxide and butylene oxide such as 1, 2-butylene oxide, 2,3-butylene oxide and isobutylene oxide. Specifically, butylene oxide is used. Other suitable synthetic carrier oils are alkoxylated alkylphenols, as described in the

DE-A 10 102 913 are described.

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

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

B3) cold flow improver

Suitable cold flow improvers are in principle all organic compounds which are able to improve the flow behavior of middle distillate fuels or diesel fuels in the cold. Conveniently, they must have sufficient oil solubility. In particular, the usually used for middle distillates of fossil origin, ie for conventional mineral diesel fuels, used cold flow improvers ("middle distillate flow improvers", "MDFI") come into consideration. However, it is also possible to use organic compounds which, when used in conventional diesel fuels, have in part or predominantly the properties of a wax anti-settling additive ("WASA"). Also, they can act partly or predominantly as nucleators. However, it is also possible to use mixtures of organic compounds which are active as MDFI and / or which act as WASA and / or as nucleators. 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 a carbon-carbon Dop-pelbindung. In the latter case, the carbon-carbon double bond can be arranged both terminally (α-olefins) and internally. However, preference is given to α-olefins, particularly preferably α-olefins having 2 to 6 carbon atoms, for example propene, 1-butene, 1-pentene, 1-hexene and, above all, ethylene. In the copolymers of class (K1), the at least one further ethylenically unsaturated monomer is preferably selected from carboxylic alkenyl esters, (meth) acrylic esters and further olefins. If further olefins are polymerized in, these are preferably higher molecular weight than the abovementioned C 2 - to C 4 -olefin base monomers. If, for example, ethylene or propene is used as the olefin base monomer, suitable further olefins are, in particular, C 10 - to C 40 -alpha-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), contain 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 C1 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 of the class ( K1) 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 more 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 having at least 10 carbon atoms available. 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 17 to 253 (1974). "" Also suitable are compounds of comb polymers. "" Polyoxyalkylenes suitable as a component of class (K3) are, for example, polyoxyalkylene esters, polyoxyalkylene ethers, mixed polyoxyalkylene ester ethers, and mixtures thereof. "Preferably, these polyoxyalkylene compounds contain at least one , preferably at least two linear alkyl groups each having 10 to 30 carbon atoms and a polyoxyalkylene group having a number average molecular weight of up to 5000. Such polyoxyalkylene compounds are described, for example, in EP-A 061 895 and in US 4 491 455. Special polyoxyalkylene compounds are based on polyethylene glycols and polypropylene glycols having a number average molecular weight of 100 to 5000. Furthermore, 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 Cs to C4o-alkyl radical. Suitable primary amines for the preparation of said polar nitrogen compounds are For example, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tetradecylamine and the higher linear homologues, secondary amines suitable for this purpose are, for example, dioctadecylamine and methylbehenylamine. Also suitable for this purpose are amine mixtures, in particular industrially available amine mixtures such as fatty amines or hydrogenated tallamines, as described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 6th edition, in the chapter "Amines, aliphatic". Suitable acids for the reaction are, for example, cyclohexane-1,2-dicarboxylic acid, cyclohexene-1,2-dicarboxylic acid, cyclopentane-1,2-dicarboxylic acid, naphthalenedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid and succinic acids substituted by long-chain hydrocarbon radicals.

In particular, the component of class (K4) is an oil-soluble reaction product of poly (C 2 - to C 20 -carboxylic acids) containing at least one tertiary amino group 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

HOOC. _DD OOH

B B

HOOC_ .N _ .N_ OOH

B A B

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

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

i

CH ₂ -CH ₂ - 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 amino acid. in which no, one or more carboxylic acid groups are converted into amide groups.

Straight-chain or branched C2 to C6-alkylene groups of the variable A are, for example, 1,1-ethylene, 1,2-propylene, 1,3-propylene, 1,2-butylene, 1,3-butylene, 1,4-butylene, 2-methyl-1,3-propylene, 1,5-pentylene, 2-methyl-1,4-butylene, 2,2-dimethyl-1,3-propylene, 1,6-hexylene (hexamethylene) and especially 1, 2-ethylene. Preferably, the variable A comprises 2 to 4, in particular 2 or 3 carbon atoms. Cr 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 are each independently straight-chain or branched C 10 - to C 30 -alkyl radicals, in particular C14- to C24-alkyl radicals. These longer-chain alkyl radicals are preferably straight-chain or only slightly branched. As a rule, the said secondary amines are derived from naturally occurring fatty acids or their derivatives with respect to their longer-chain alkyl radicals. Preferably, the two radicals R ^{8 are the} same.

The abovementioned secondary amines can be bound to the polycarboxylic acids by means of amide structures or in the form of the ammonium salts, and only one part can be present as amide structures and another part as ammonium salts. Preferably, only a few or no free acid groups are present. Preferably, the oil-soluble reaction products of component (K4) are completely in the form of the amide structures. Typical examples of such components (K4) are reaction products of nitrilotriacetic acid, ethylenediaminetetraacetic acid or propylene-1,2-diaminetetraacetic acid with in each case 0.5 to 1.5 mol per carboxyl group, in particular 0.8 to 1.2 mol per carboxyl group, dioleylamine, dipalmitinamine, dicoco fatty amine, distearylamine, dibehenylamine or especially ditallow fatty amine. A particularly preferred component (K4) is the reaction product of 1 mole of ethylenediaminetetraacetic acid and 4 moles of hydrogenated ditallow fatty amine.

Further typical examples of component (K4) are the N, N-dialkylammonium salts of 2-N ', N'-dialkylamidobenzoates, for example the reaction product of 1 mole of phthalic anhydride and 2 moles of ditallow fatty amine, the latter being hydrogenated or unhydrogenated , and the reaction product of 1 mole of an alkenyl spiro-bis-lactone with 2 moles of a dialkylamine, while 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 a cold flow improver 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 tallamine. Suitable poly (meth) acrylic esters are described, for example, in WO 00/44857. The middle distillate fuel or diesel fuel is the cold flow improver or the mixture of various cold flow improvers in a total amount of preferably 10 to 5000 ppm by weight, more preferably from 20 to 2000 ppm by weight, 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 copolymer

Examples of suitable corrosion inhibitors are succinic esters, especially with polyols, fatty acid derivatives, for example 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 E07PO block copolymers, polyethyleneimines or polysiloxanes.

B7) Dehazer

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

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

B9) Cetane number improver

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

B10) Antioxidants

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

B1 1) Metal deactivators

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

B12) Solvent

Suitable are, for example, nonpolar organic solvents such as aromatic and aliphatic hydrocarbons, for example toluene, xylenes, "white spirit" and products sold under the trade name SHELLSOL (Royal Dutch / Shell Group) and EXXSOL (ExxonMobil), and polar organic solvents, for example Alcohols such as 2-ethylhexanol, decanol and isotridecanol. Such solvents usually 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 relates to fuels, in particular middle latent fuels, with an additive used to achieve advantageous effects in the operation of internal combustion engines, for example diesel engines, in particular direct injection diesel engines, especially 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.

The use according to the invention relates in principle to any fuels, preferably diesel and gasoline fuels.

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 mineral middle distillate fuels or diesel fuels obtainable by refining, those produced 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.).

The use according to the invention in middle distillate fuels of fossil, vegetable or animal origin, which are essentially hydrocarbon mixtures, also relates to mixtures of such middle distillates with biofuel oils (biodiesel). Such mixtures are 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 include, for example, sunflower methyl ester, palm oil methyl ester ("PME"), soybean oil methyl ester ("SME") and in particular rapeseed oil methyl ester. methyl ester ("RME").

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

As gasoline fuels are all commercially available gasoline fuel compositions into consideration. A typical representative here is the market-standard basic fuel of Eurosuper according to EN 228. Furthermore, 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 embodiments.

Examples G PC analysis

Unless stated otherwise, the mass-average Mw and number-average molecular weight Mn of the polymers were measured by gel permeation chromatography (GPC). GPC separation was achieved via two PLge Mixed B columns (Agilent) in tetrahydrofuran at 35 ° C. The calibration was carried out by means of a narrowly distributed polystyrene standard (PSS, Germany) with molecular weight 162-50400 Da. Hexylbenzene was used as a low molecular weight marker. Preparation Examples

General procedure In a reactor with an anchor stirrer, the olefin or the mixture of olefins with or without solvent (as bulk polymerization) was initially charged. The mixture was heated under nitrogen flow with stirring to the indicated temperature. To this was added the specified radical initiator (optionally diluted in the same solvent) and molten maleic anhydride (1 equivalent based on olefin monomer). The reaction mixture was stirred at the same temperature for the specified reaction time and then cooled. Then, water was added (0.9 equivalents based on maleic anhydride, unless indicated otherwise) and stirred at 95 ° C, 10-14 h or under pressure at 110 ° C for 3 h. Synthetic Example 1

In a 6 L metal reactor with anchor stirrer, a mixture of C20-C24 olefins (1743 g, average molecular weight 296 g / mol) and Solvesso® 150 (3420 g, DHC Solvent Chemie GmbH, Speldorf) were submitted. The mixture was heated to 150 ° C. in a stream of nitrogen and with stirring. To this was added within 5 h a mixture of di-tert. Butyl peroxide (23.4 g, Akzo Nobel) and molten maleic anhydride (577.2 g). The reaction mixture was stirred for 1 h at 150 ° C then for 1 h at 1 10 ° C, and cooled to 60 ° C inclusive.

To this was added a solution of polyisobutene amine (M w = 1000 g / mol, 1 148.7 g, BASF SE, Ludwigshafen) in Solvesso® 150 (1639.2 g) and stirred for a further 2 h. Subsequently, 37.1 g of water were added, heated under pressure to 1 10 ° C and stirred for a further 3 hours.

The GPC (in THF) gave an Mn = 1540 g / mol for the copolymer, Mw = 3650 g / mol, which corresponds to a dispersity of 2.4.

Synthesis Example 2

In a 6 L metal reactor with anchor stirrer, a mixture of C20-C24 olefins (1743 g, average molecular weight 296 g / mol) and Solvesso® 150 (3420 g, DHC Solvent Chemie GmbH, Speldorf) were submitted. The mixture was heated to 150 ° C in a stream of nitrogen and with stirring. To this was added within 5 h a di-tert-butyl peroxide (23.4 g, Akzo Nobel) and molten maleic anhydride (577.2 g). The reaction mixture was heated at 150 ° C for 1 h and then reacted at 1 10 ° C for a further hour.

A solution of a propoxylated isomer mixture of C 13 -alkanols, prepared as described in WO 00/02978 (Mn = 1300 g / mol, OH number = 55 mg KOH / g, 1237.3 g, BASF SE, Ludwigshafen) in Solvesso® 150 ( 1768.9 g) was added and stirred at a temperature of 1 10 ° C for a further 2 hours. Subsequently, 37.1 g of water were added at this temperature and stirred under pressure for a further 2 hours. The GPC (in THF) gave an Mn = 1770 g / mol for the copolymer, Mw = 4520 g / mol, which corresponds to a dispersity of 2.6.

applications

Application Example 1: DW10 Na soaps 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 determined as a further test method, in which the exhaust gas temperatures of the cylinders at the cylinder output were determined during the cold start of the DW10 engine. A direct-injection diesel engine with common rail system from the manufacturer Peugeot was used in accordance with test methods CEC F-098-08. The fuel used was a commercial B7 diesel fuel according to EN 590 from Aral. To this was added in each case 1 wt ppm of sodium naphthenate and 20 wt ppm of dodecenylsuccinic acid to artificially induce the formation of deposits.

Similar to the method CEC F-98 -08, the engine power is 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 method was performed without addition of Zn. 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 ("θ5"). 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 a compound according to the invention were added in an amount of 50 mg / kg, unless stated otherwise, and the engine power was determined.

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 obtained: Dirty up -Clean up - Sequence 1: Dirty-up:

Significant deviations in exhaust gas temperatures were observed during the test so that it stopped after 3 hours to avoid engine damage. After dirty up:

θθ Z1: 43 ° C Z2: 28 ° C Z3: 22 ° C Z4: 27 ° C

θ5 Z1: 159 ° C Z2: 69 ° C Z3: 40 ° C Z4: 44 ° C

A: 78 ° C (+ 81 ° C / -34 ° C) Significant deviations from the mean and significant difference between the individual cylinders demonstrate the presence of IDID.

Clean-up: After clean up with 40 ppm additive (based on the solids content) according to Synthesis Example 2 in

Presence of 1 ppm Na + 20 ppm dodecenylsuccinic acid:

θθ Z1: 36 ° C Z2: 37 ° C Z3: 35 ° C Z4: 37 ° C

θ5 Z1: 78 ° C Z2: 73 ° C Z3: 44 ° C Z4: 87 ° C

A: 70.5 ° C (+ 16.5 ° C / -26.5 ° C)

Only slight deviations of the temperature of the exhaust gases between the individual cylinders show the absence of IDID and show the high activity of the product against IDID.

Application example 2: DW10 Na power loss (keep clean)

To investigate the influence of the additives on the power loss caused by metals such as sodium, potassium and others, the I DI D motor test described above was used as a further test method. Instead of a dirty up and clean up sequence, only a keep clean run containing 1 ppm by weight of sodium naphthenate and 40 ppm by weight (based on the solids content) according to Synthesis Example 2 was added.

The power measurement was performed as performed in CEC F-98-08. At the end of a period of 8 hours, a power loss of 0.1% was observed. In the comparative example without addition of the product of Synthesis Example 2, a power loss of 6.0% was observed at the end of a period of 8 hours.

Thus, the compounds of the present invention are effective against deposits caused by metal deposits in direct injection engines.

Application Example 3: DW10 Na soaps IDID test (clean-up)

Another DW10 Na soap IDID test (clean-up) was performed as in Application Example 1.

Dirty up -Clean up - Sequence 1: After dirty up:

θθ Z1: 27 ° C Z2: 26 ° C Z3: 26 ° C Z4: 32C

θ5 Z1: 65 ° C Z2: 53 ° C Z3: 45 ° C Z4: 156 ° C

Δ: 79.75 ° C (+ 76.25 ° C / -34.75 ° C)

High deviations of the exhaust gas temperatures between the individual cylinders prove the presence of IDID.

Clean-up:

After clean up with 40 ppm additive (based on the solids content) according to Synthesis Example 1 in the presence of 1 ppm Na + 20 ppm dodecenylsuccinic acid:

θθ Z1: 35 ° C Z2: 38 ° C Z3: 35 ° C Z4: 36 ° C

θ5 Z1: 85 ° C Z2: 66 ° C Z3: 45 ° C Z4: 82 ° C

Δ: 69.5Χ (+ 15.5 ° C / -24.5 ° C)

Application Example 4: DW10 Na Power loss (keep clean)

Another DW10 Na power loss (keep clean) was carried out as in Application Example 2, but added at 40 ppm by weight (based on the solids content) according to Synthesis Example 1.

The power measurement was performed as performed in CEC F-98-08. At the end of a period of 8 hours, a power loss of 0.6% was observed.

In Comparative Example without addition of the product of Synthetic Example 1, a power loss of 6.0% was observed at the end of a period of 8 hours.

Claims

claims

1 . Use of copolymers obtainable by

in a first reaction step (I) copolymerization of

(Da) vinyl esters,

(Db) vinyl ethers,

(De) (meth) acrylic esters of alcohols having at least 5 carbon atoms,

(Dd) allyl alcohols or their ethers,

(Df) ethylenically unsaturated aromatics

(Dg) α, β-ethylenically unsaturated nitriles,

(That is) (meth) acrylic acid amides and

(Di) Allylamines, followed by in a second reaction step (II) partial reaction of the obtained in (I) copolymer containing anhydride or carboxylic acid functionalities with at least one at least one alcohol group and / or at least one amino group-containing compound (E), and in one Third Reaction Step (III) Hydrolysis of the anhydride functionalities contained in the copolymer obtained from (II) and / or partial saponification of carboxylic acid ester functionalities contained in the copolymer obtained from (II) as a diesel fuel additive to minimize powerloss in direct injection diesel engines, to reduce fuel consumption of direct injection diesel engines, and / or to reduce and / or prevent deposits in the fuel system in direct injection diesel engines.

Use according to claim 1, characterized in that the compound (E) is selected from the group consisting of

monoalcohols

diols

polyols

monoamines

diamines

Polyamines and

Amino alcohols.

Use according to Claim 2, characterized in that the monoalcohol is a compound of the formula (I)

wherein

R ^{1 is} a straight-chain or branched C 1 - to C 20 -alkyl or C 1 - to C 20 -alkenyl radical and

from -CH ₂ -CH (CH ₃ ) -O-, -CH (CH ₃ ) -CH ₂ -0-, -CH ₂ -C (CH ₃ ) ₂ -O-, -C (CH ₃ ) ₂ -CH ₂ -0-, -CH ₂ -CH (C ₂ H ₅₎ -0-, -CH (C2H ₅₎ -CH ₂ -0- and -CH (CH ₃₎ -CH (CH ₃₎ -0-, particularly preferably selected from the group consisting

from -CH ₂ -CH (CH ₃ ) -O-, -CH (CH ₃ ) -CH ₂ -0-, -CH ₂ -C (CH ₃ ) ₂ -O-, -C (CH ₃ ) ₂ -CH ₂ -0-, -CH ₂ -CH (C2H ₅₎ -0- and -CH (C2H ₅₎ -CH2-0-, and most preferably selected from the group consisting of -CH ₂ -CH (CH ₃₎ -0 - and -CH (CH ₃ ) -CH ₂ -0-.

Use according to Claim 2, characterized in that the monoamine is a monoamine containing 6 to 200 carbon atoms.

Use according to claim 4, characterized in that the monoamine has the formula (II)

in the

R ^{2 is} hydrogen or Ci-20-alkyl and

R ³ Ci2-2oo-alkyl, which may be linear or branched mean.

Use according to claim 5, characterized in that the mono- amine is a polyisobuteneamine based on a polyisobutene having a weight-average molecular weight of 550 to 2300 g / mol.

Use according to claim 4, characterized in that it is a monoalkylamine having from 6 to 200 carbon atoms or a dialkylamine.

Use according to claim 2, characterized in that the polyamine is a polyethyleneamine.

Use according to claim 8, characterized in that it is ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and pentaethylenehexamine.

Use according to Claim 2, characterized in that the compound (E2) is 2-dimethylaminoethylamine, 3-dimethylaminopropylamine or N ', N ", N" -trimethyldiethylenetriamine.

Use according to one of the preceding claims, characterized in that deposits in the injection system in direct-injection diesel engines are reduced and / or avoided.

Use according to claim 1 1, characterized in that the deposits are internal diesel injector deposits (IDID).

Use according to claim 1 1, characterized in that the deposits are internal diesel injector deposits (IDID) due to Na, Ca and / or K ions and / or polymeric deposits.

Use according to one of the preceding claims, characterized in that the direct injection diesel engines are diesel engines with common rail injection systems.