WO2012072723A2

WO2012072723A2 - Use of the reaction product of a hydrocarbyl-substituted dicarboxylic acid and a nitrogen compound for reducing fuel consumption

Info

Publication number: WO2012072723A2
Application number: PCT/EP2011/071470
Authority: WO
Inventors: Ludwig Völkel; Marc Walter; Harald BÖHNKE; Hannah Maria KÖNIG; Markus Hansch
Original assignee: Basf Se
Priority date: 2010-12-02
Filing date: 2011-12-01
Publication date: 2012-06-07
Also published as: CA2818837A1; SG190391A1; BR112013012874B1; EP2646530A2; AU2011334961B2; CN103228769A; KR101970939B1; CN103228769B; AU2011334961A1; CA2818837C; EP2646530B1; PL2646530T3; MY166033A; BR112013012874A2; MX2013006022A; WO2012072723A3; SG10201509787PA; KR20130126648A; JP2014501813A; ZA201304841B

Abstract

Use of the reaction product of a hydrocarbyl-substituted dicarboxylic acid or anhydride thereof and a nitrogen compound I or a salt thereof as an additive in a fuel for reducing fuel consumption in internal combustion engines.

Description

Use of the reaction product of a hydrocarbyl-substituted dicarboxylic acid and a nitrogen compound to reduce fuel consumption

description

The present invention relates to the use of the reaction product of (a) a hydrocarbyl-substituted dicarboxylic acid whose hydrocarbyl radical has from 8 to 250 carbon atoms or its anhydride and (b) a nitrogen compound of the general formula I.

ΊΜ H

2

N

(I) or a salt of the nitrogen compound I, wherein R ¹ and R ^{2 are} independently hydrogen or a C ¹ to C 20 hydrocarbyl radical, as an additive in a fuel for reducing fuel consumption when operating a spark-ignited internal combustion engine with said fuel or as an additive in one Petrol to reduce fuel consumption when operating a self-igniting internal combustion engine with this fuel.

Further, the present invention relates to a fuel composition containing a gasoline fuel, said reaction product, and at least one detergent-effect fuel additive.

Furthermore, the present invention relates to an additive concentrate containing the said reaction product and at least one detergent additive with a fuel effect.

It is known that certain substances in the fuel reduce the internal friction in the internal combustion engines, especially in gasoline engines, and thus help save fuel. Such substances are also referred to as lubricity enhancers, friction reducers or friction modifiers. Commercially available lubricity improvers for gasoline fuels are usually condensation products of naturally occurring carboxylic acids such as fatty acids with polyols such as glycerol or with alkanol amines, eg. B. glycerol monooleate.

A disadvantage of the aforementioned lubricity improvers of the prior art is the poor miscibility with other typically used fuel additives, in particular with detergent additives such as polyisobuteneamines and / or carrier oils such as polyalkylene oxides. An important requirement for practice is that the provided component mixtures or additive concentrates are easily pumpable even at lower temperatures, in particular in winter outside temperatures of, for example, down to -20 ° C and remain stable over a longer period stable homogeneous, ie it may not be Phase separation and / or precipitation occur.

Usually, in order to circumvent the described miscibility problems, the component mixtures or additive concentrates are accompanied by relatively large amounts of mixtures of paraffinic or aromatic hydrocarbons with alcohols such as tert-butanol or 2-ethylhexanol as solubilizer. In some cases, however, considerable amounts of these expensive solubilizing agents are necessary to achieve the desired homogeneity, so that this problem solution becomes uneconomical. The low molecular weight carboxylic acids and carboxylic acid derivatives, glycol ethers and alkylated phenols recommended in WO 2007/053787 as solubilizers for such component mixtures or additive concentrates are uneconomical because of their high starting material costs and, apart from their function as solubilizers, have no further positive effects. On the contrary, they carry the risk of causing negative effects, such as unwanted oil thinning and increased formation of combustion chamber deposits.

Furthermore, the cited prior art lubricity improvers often have the tendency to form emulsions with water in the component mixtures or additive concentrates or in the fuel itself, so that infiltrated water can be separated again only with difficulty or at least only very slowly via phase separation.

Thus, although the lubricity improvers based on polyisobutenyl succinimides described in EP-A 1 424 322 and WO 03/070860 with mono- or polyamines or alkanolamines such as butylamine, diethylenetriamine, tetraethylene pentamine or aminoethyleneethanolamine good miscibility with other additive components in corresponding mixtures or concentrates, however, have a pronounced tendency to form stable emulsions with water, which can lead to water and dirt particles in the fuel supply chain being dragged away and ultimately getting into the engine as well. Water can cause corrosion, dirt particles can cause damage in fuel pumps, fuel filters and injectors. The object of the present invention was to provide fuel additives which, on the one hand, bring about effective fuel savings when operating a spark-ignited internal combustion engine and, on the other hand, the described deficiencies of the prior art, that is, in particular the poor miscibility with other fuels. additive and the tendency to form emulsions with water, no longer have. In addition, they should not worsen the high level of intake valve cleanliness achieved by modern fuel additives. Accordingly, the above-defined use of the reaction product of (a) a hydrocarbyl-substituted dicarboxylic acid or derem anhydride and (b) a nitrogen compound of general formula I was found. It can be assumed that the fuel saving due to said reaction product is largely based on its effect as an additive which reduces the internal friction in the internal combustion engines, in particular in gasoline engines. The said reaction product thus functions essentially as a lubricity improver in the context of the present invention.

Reaction products of a hydrocarbyl-substituted dicarboxylic acid or anhydride and an aminoguanidine or a salt thereof are disclosed in US Pat. Nos. US 2009/0282731 A1 and US 2010/0037514 A1 as additives for improving the performance of diesel engines and for cleaning injectors in diesel engines described. It is known from British Patents GB 998 869 and GB 1 020 059 that the reaction product of polyisobutenyl succinic anhydride and aminoguanidine bicarbonate is also useful as a detergent additive in gasoline fuels.

European Patent Application EP 0 310 367 A1 discloses that the reaction product of polyisobutenyl succinic anhydride and aminoguanidine bicarbonate protects copper and copper alloys in diesel engines when it is contained in the engine oil.

Under externally ignited internal combustion engines are preferably gasoline engines, which are usually ignited with spark plugs to understand. In addition to the usual four- and two-stroke gasoline engines include spark-ignition internal combustion engines but also other types of engines, such as the Wankel engine. These are usually engines with commercial gasoline grades, especially gasoline grades according to EN 228, gasoline-alcohol blends such as flex fuel with 75 to 85 vol .-% ethanol, liquid pressure gas ("LPG") or compressed natural gas ("CNG", "natural gas") as fuel.

The use according to the invention of the reaction product of (a) a hydrocarbyl-substituted dicarboxylic acid or anhydride and (b) a nitrogen compound of the general formula I also relates to newly developed internal combustion engines, such as the "HCCI" engine, which is self-igniting and operated with gasoline. The nitrogen compounds of the general formula I for the reaction component (a) are guanidine, substituted guanidines or salts thereof. Possible hydrocarbyl radicals in these compounds contain 1 to 20, in particular 1 to 12, especially 1 to 8 carbon atoms. A hydrocarbyl radical is to be understood here as meaning a hydrocarbon radical of any structure, but which also contains minor amounts of heteroatoms such as oxygen and / or nitrogen atoms and / or halogen atoms and / or functional groups such as hydroxyl groups, carboxyl groups, carboxylic acid ester groups, cyano groups, nitro groups and / or sulpho groups, as long as the dominating hydrocarbon character of the radical is not thereby adulterated. The said hydrocarbyl radical may be saturated or unsaturated in nature; it can be linear or branched; it may contain aromatic and / or heterocyclic substructures.

The nitrogen compound I may have two such hydrocarbyl radicals for R ¹ and R ² or only one such hydrocarbyl radical for R ¹ or R ² , in the latter case the other substituent then being hydrogen. However, both substituents R ¹ and R ² preferably denote hydrogen, ie unsubstituted aminoguanidine is present.

Possible hydrocarbyl radicals for R ¹ and / or R ² are preferably linear or branched alkyl or alkenyl radicals, in particular those having 1 to 8, preferably 1 to 4, carbon atoms, such as methyl, ethyl, vinyl, n-propyl, isopropyl, Propenyl, 2-propenyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, 2-ethylhexyl, neooctyl, nonyl, neononyl, isononyl, decyl, neodecyl, 2-propylheptyl, undecyl, neoundecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl (stearyl), oleyl, linolyl, linolenyl, nonadecyl, eicosyl or their constitutional isomers.

Furthermore, possible hydrocarbyl radicals for R ¹ and / or R ^{2 may} also denote cycloalkyl radicals, for example cyclopentyl, cyclohexyl, 2-, 3- the 4-methylcyclohexyl or cycloheptyl.

Furthermore, possible hydrocarbyl radicals for R ¹ and / or R ^{2 may} also be aryl, alkaryl or arylalkyl radicals, for example phenyl, naphthyl, benzyl, 2-phenylethyl, 3-phenylpropyl, 4-phenylbutyl, tolyl or o-, m- or p-xylyl.

If the nitrogen compounds I are used in the form of one of their salts, this is in particular a halide such as chloride or bromide, carbonate, hydrogen carbonate (bicarbonate), nitrate or orthophosphate. Preferably, a bicarbonate (bicarbonate) is used.

In a preferred embodiment, the nitrogen compound of component (b) is unsubstituted aminoguanidine bicarbonate. The hydrocarbyl-substituted dicarboxylic acid or its anhydride of component (a) typically has a saturated C 2 to C 10 dicarboxylic acid or its anhydride as a backbone. The dicarboxylic acid or its anhydride may carry a plurality, for example two or three, hydrocarbyl substituents, but preference is given to only one hydrocarbyl substituent. The anhydride is usually in cyclic form when anhydride formation is intramolecular. However, open-chain anhydrides formed by intermolecular anhydride formation are also suitable. Examples of such dicarboxylic acids are oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid. Aromatic dicarboxylic acids such as phthalic acid or terephthalic acid are also suitable.

In a preferred embodiment, the hydrocarbyl-substituted dicarboxylic acid used as the reaction component (a) is based on succinic acid or its anhydride. In particular, here is the corresponding Succinanhydrid of formula II

in which R ³ denotes a hydrocarbyl radical having 8 to 250 carbon atoms, suitable. Here too, a hydrocarbyl radical is to be understood to mean a hydrocarbon radical of any structure which, however, contains in a minor amount heteroatoms such as oxygen and / or nitrogen atoms and / or halogen atoms and / or functional groups such as hydroxyl groups, carboxyl groups, carboxylic acid ester groups, cyano groups, nitro groups and / or Can carry sulfo groups, as long as the dominating hydrocarbon character of the rest is not distorted by this. This hydrocarbyl radical is typically an alkyl, alkenyl, cycloalkyl, aryl, heteroaryl, aralkyl or alkylaryl radical. For longer-chain hydrocarbyl radicals, it may be based on an olefin polymer, for example on a polyethylene, polypropylene or polyisobutylene. In a preferred embodiment, the hydrocarbyl radical in component (a) or the radical R ³ is a linear or branched C 1 to C ₄₀ alkyl or alkenyl radical or a polyisobutenyl radical having from 24 to 250 carbon atoms.

Linear or branched Ce- to _C40 alkenyl and polyisobutenyl radicals are customarily cherweise by thermal ene reaction between the unsubstituted dicarboxylic acid or anhydride and alia a long chain α-olefin to obtain an olefinic double bond in α, β-position of the hydrocarbyl Side chain generated. For this purpose, the reactants are usually heated to temperatures of 150 to 250 ° C. Alkenyl radicals can then be hydrogenated to the corresponding saturated alkyl radicals. As Ce to C4o-alkenyl radicals, in particular C10 to C24-alkenyl radicals, there are, for example, 1 -nonyl, 1-decenyl, 1-undecenyl, 1-dodecenyl, 1-tridecenyl, 1-tetradecenyl, 1-pentadecenyl, 1 - Hexadecenyl, 1-octadecenyl, 1-eicosenyl and the corresponding alkenyl radicals from Oligoisobutenen such as di-, tri-, tetra- or Pentaisobuten or from technical α-olefin mixtures such as C2o-C24-α-olefin into consideration.

In the presence of a polyisobutenyl radical, this preferably comprises 24 to 250, in particular 28 to 180, especially 36 to 80 carbon atoms or thus has a number average molecular weight M _n of preferably 330 to 3500, in particular 390 to 2500, especially 500 to 1 100. Such polyisobutenyl radicals are normally prepared from highly reactive polyisobutenes, ie from polyisobutenes with a high proportion, usually at least 60%, in particular at least 70%, especially at least 80%, of terminal vinylidene double bonds. Polyisobutenyl succinimides ("PIBSA") thus obtained generally have a degree of succinylation, ie a molar ratio of succinic anhydride unit to polyisobutene units, of from 0.8 to 2.0, in particular from 1.0 to 1.3. Thus, it is also possible to bind two succinic anhydride units to a polyisobutene chain. The resulting reaction product of (a) the hydrocarbyl-substituted dicarboxylic acid or anhydride and (b) the nitrogen compound I is often a mixture of several compounds of different structure. In particular, imides formed from a primary amino group of I, for example the compound IIIa, and / or compounds containing one or two aminotriazole groups, for example the compound IIIb for the case R ¹ = R ² = H, can be constituents of this mixture , be:

The reaction product according to the invention of (a) the hydrocarbyl-substituted dicarboxylic acid or anhydride and (b) the nitrogen compound I are outstandingly suitable as a fuel additive, which is an effective fuel economy in the Operating a spark-ignited internal combustion engine, in particular a gasoline engine, causes and is well miscible with other fuel additives and has no significant tendency to form emulsions with water. The advantageous properties mentioned are particularly evident in the use in gasoline fuels in the co-use of detergent-additive fuel additives.

Accordingly, the subject of the present invention is also a fuel composition comprising a gasoline in a larger amount and in a smaller amount at least one inventive reaction product of (a) a hydro carbyl-substituted dicarboxylic acid and (b) a nitrogen compound of general formula I and at least one of the mentioned reaction product contains various fuel additive with detergent effect.

The amount of this at least one reaction product according to the invention in the gasoline is usually from 10 to 5000 ppm by weight, more preferably from 20 to 2000 ppm by weight, more preferably from 30 to 1000 ppm by weight and in particular from 40 to 500% by weight. ppm, eg from 50 to 300 ppm by weight.

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. Furthermore, in the context of the present invention under gasoline fuels also alcoholic gasoline fuels, especially ethanol-containing gasoline fuels, as described for example in WO 2004/090079, z. B. Flex fuel with a E- ethanol content of 75 to 85 vol .-% or 85 vol .-% ethanol containing gasoline ("E85"), but also the fuel grade "E100", which is typically azeotropically distilled ethanol and thus from approx 96 Vol .-% C ₂ H ₅ OH and about 4 vol .-% H ₂ 0, to understand.

The reaction product according to the invention of (a) the hydrocarbyl-substituted dicarboxylic acid or anhydride and (b) the nitrogen compound I can be added either to the respective base fuel alone or in the form of fuel additive packages. Such packages are fuel additive concentrates and usually contain in addition to solvents in addition to the at least one different from the reaction product according to the invention detergent additive still a number of other components as co-additives, in particular these are carrier oils, corrosion inhibitors, demulsifiers, dehazers, anti-foaming agents, combustion improvers, antioxidants or Stabilizers, antistatic agents, metallocenes, metal deactivators, solubilizers, markers and / or dyes.

Detergents or detergent additives, hereinafter referred to as component (D), are commonly referred to as fuel deposit inhibitors. Preferably when the detergent additives are amphiphilic substances having at least one hydrophobic hydrocarbon radical having a number average molecular weight (M _n ) of 85 to 20,000, especially from 300 to 5000, especially from 500 to 2500, and at least one polar grouping.

In a preferred embodiment, the fuel composition of the invention comprises as the at least one detergent-effect fuel additive (D) other than the reaction product of the invention at least one member 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 -C 4 -alkylene groups terminated by hydroxyl groups, mono- or polyamino groups, wherein at least one nitrogen atom has basic properties, or by carbamate groups;

(Dg) carboxylic acid ester groups;

(Ie) derived from succinic anhydride moieties having hydroxy and / or amino and / or amido and / or imido groups; and or

(Di) by Mannich reaction of substituted phenols with aldehydes and mono- or polyamines generated groupings. The hydrophobic hydrocarbon radical in the above detergent additives, which provides sufficient solubility in the fuel composition, has a number average molecular weight (M _n ) of from 85 to 20,000, especially from 300 to 5,000, especially from 500 to 2,500. As a typical hydrophobic hydrocarbon radical , in particular in connection with the polar groupings (Da), (De), (Dh) and (Di), come longer-chain alkyl or alkenyl groups, in particular the polypropenyl, polybutenyl and polyisobutenyl radical each having M _n = 300 to 5000, especially 500 to 2500, especially 700 to 2300, into consideration. As examples of the above groups of detergent additives, the following are mentioned:

Mono- or polyamino (Da) -containing additives are preferably polyalkylene mono- or polyalkene polyamines based on polypropene or conventional (ie with predominantly intermediate double bonds) polybutene or polyisobutene with M _n = 300 to 5000. If polybutene is used in the preparation of the additives or polyisobutylene with predominantly intermediate double bonds (usually in the β and γ positions), the preparation route is afforded by chlorination and subsequent amination or by oxidation of the double bond with air or ozone to the carbonyl or carboxyl compound and subsequent amination under reductive ( hydrogenating) conditions. For amination here amines, such as. As ammonia, mono amines or polyamines, such as dimethylaminopropylamine, ethylenediamine, Diethylent amine, triethylenetetramine or tetraethylenepentamine, are used. Corresponding additives based on polypropene are described in particular in WO-A-94/24231.

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

Further preferred monoamino (Da) -containing additives are the compounds obtainable from polyisobutenepoxides 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-A-96/03367 and

WO-A-96/03479 are described. As a rule, these reaction products are mixtures of pure nitropolyisobutenes (for example α, β-dinitropolyisobutene) and mixed hydroxynitropolyisobutenes (for example α-nitro-β-hydroxy polyisobutene).

Hydroxyl groups in combination with mono- or polyamino groups (De) containing additives are in particular reaction products of polyisobutene epoxides obtainable from preferably predominantly terminal double bonds having polyisobutene with M _n = 300 to 5000, with ammonia, mono- or polyamines, as described in particular in EP-A -476 485 are described. Carboxyl groups or their alkali metal or alkaline earth metal salts (Dd) -containing additives are preferably copolymers of C 2 -C 4 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 remainder 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-87/01126, can be advantageously used in combination with conventional fuel detergents such as poly (iso) butenamines or polyetheramines.

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

Polyoxy-C2-C4-alkylene (Df) containing additives are preferably lyether or polyetheramines, which by reaction of C2-C6o-alkanols, C6-C30- alkanediols, mono- or di-C2-C3o-alkylamines, Ci-C3o 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. Such products are described in particular in EP-A-310 875, EP-A-356 725, EP-A-700 985 and US-A-4 877 416. In the case of polyethers, such products also meet carrier oil properties. Typical examples of these are tridecanol or Isotridecanolbutoxylate, Isononylphenolbutoxylate and Polyisobute- nolbutoxylate 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 fulfill carrier oil properties.

Succinic anhydride-derived groupings containing hydroxyl and / or amino and / or amido and / or imido (Dh) containing additives are preferably corresponding derivatives of alkyl- or alkenyl-substituted succinic anhydride and especially the corresponding derivatives of polyisobutenyl succinic anhydride, which by Reaction of conventional or highly reactive polyisobutene with M _n = 300 to 5000 with maleic anhydride by thermal means or via the chlorinated polyisobutene are available. Of particular interest are with aliphatic polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine. The groupings having hydroxyl and / or amino and / or amido and / or imido groups are, for example, carboxylic acid groups, acid amides of monoamines, acid amides of 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 more particularly described in US-A-4,849,572.

The detergent additives from the group (Dh) are preferably the reaction products of alkyl- or alkenyl-substituted succinic anhydrides, in particular of polyisobutenylsuccinic anhydrides ("PIBSA"), with amines and / or alcohols. These are thus derivatives derived from alkyl, alkenyl or polyisobutenyl succinic anhydride with amino and / or amido and / or imido and / or hydroxyl groups. It goes without saying that these reaction products are obtainable not only when substituted succinic anhydride is used, but also when substituted succinic acid or suitable acid derivatives such as succinic acid halides or esters are used.

Preferably, the additized fuel comprises at least one detergent based on a polyisobutenyl-substituted succinimide. Of particular interest are the imides with aliphatic polyamines. Particularly preferred polyamines are ethylenediamine, diethylenetriamine, triethylenetetramine, pentaethylenehexamine and especially tetraethylenepentamine. The polyisobutenyl radical has a number-average molecular weight M _n of preferably 500 to 5000, particularly preferably 500 to 2000 and in particular of about 1000. Additives produced by Mannich reaction of substituted phenols with aldehydes and mono- or polyamines-produced groupings (Di) 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.

The fuel composition of the present invention contains at least one detergent-type fuel additive other than the reaction product of the present invention, which is normally selected from the above groups (Da) to (Di) in an amount of usually 10 to 5,000 ppm by weight, especially preferably. from 20 to 2000 ppm by weight, more preferably from 30 to 1000 ppm by weight and in particular from 40 to 500 ppm by weight, for. B. from 50 to 250 ppm by weight.

Preferably, said detergent additives (D) are used in combination with at least one carrier oil. In a preferred embodiment, in addition to the at least one reaction product according to the invention and the at least one detergent additive other than the reaction product according to the invention, the fuel composition according to the invention contains at least one carrier oil in a smaller amount as a further fuel additive.

Suitable mineral carrier oils are fractions obtained in petroleum processing, such as bright stock or base oils with viscosities such as from class SN 500-2000; but also aromatic hydrocarbons, paraffinic hydrocarbons and alkoxyalkanols. Also useful is a fraction known as "hydrocrack oil" and derived from the refining of mineral oil (vacuum distillate cut having a boiling range of about 360 to 500 ° C, available from high pressure, catalytically hydrogenated and isomerized and dewaxed natural mineral oil). Also suitable are mixtures of the abovementioned mineral carrier oils. Examples of suitable synthetic carrier oils are selected from: polyolefins (polyalphaolefins or polyinternalolefins), (poly) esters, (poly) alkoxylates, polyethers, aliphatic polyetheramines, alkylphenol-initiated polyethers, alkylphenol-initiated polyetheramines and carboxylic acid esters of long-chain alkanols. Examples of suitable polyolefins are olefin polymers having M _n = 400 to 1800, especially based on polybutene or polyisobutene (hydrogenated or non-hydrogenated).

Examples of suitable polyethers or polyetheramines are preferably compounds containing polyoxy-C 2 -C 4 -alkylene groups, which are prepared by reacting C 2 -C 10 -alkanols, C 6 -C 30 -alkanediols, mono- or di-C 2 -C 30 -alkylamines, C 1 -C 30 -alkyl - Cyclohexanolen or Ci-C3o-Alkylphenolen 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 polyether amines, by subsequent reductive amination with ammonia, mono amines 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, as polyetheramines, poly-C 2 -C 6 -alkylene oxide amines or functional derivatives thereof can be used. Typical examples of these are tridecanol or Isotridecanolbutoxylate, Isononylphenolbutoxylate and Polyisobutenolbutoxylate and propoxylates and the corresponding reaction products with ammonia.

Examples of carboxylic acid esters of long-chain alkanols are in particular esters of mono-, di- or tricarboxylic acids with long-chain alkanols or polyols, as described in particular in DE-A 38 38 918. As mono-, di- or tricarboxylic acids Aliphatic or aromatic acids can be used as ester alcohols or polyols are especially long-chain representatives with, 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 isotricanecanol, such as, for example, B. di (n- or iso-tridecyl) 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 0 452 328 and EP-A 0 548 617. Examples of particularly suitable synthetic carrier oils are alcohol-started polyethers with about 5 to 35, such as. B. about 5 to 30, C3-C6 alkylene oxide units, such as. B. selected from propylene oxide, n-butylene oxide and i-butylene oxide units, or mixtures thereof. Nonlimiting examples of suitable starter alcohols are long-chain alkanols or long-chain alkyl-substituted phenols, the long-chain alkyl radical in particular being a straight-chain or branched Cβ-Cie-alkyl radical. Preferred examples are tridecanol and nonylphenol.

Further suitable synthetic carrier oils are alkoxylated alkylphenols, as described in DE-A 101 02 913.

Preferred carrier oils are synthetic carrier oils, with polyethers being particularly preferred.

If a carrier oil is used, it is added to the additive fuel according to the invention 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 ,

In a preferred embodiment, in addition to the at least one reaction product according to the invention, the at least one detergent additive and optionally the at least one carrier oil in a smaller amount as further fuel additive contains at least one corrosion inhibitor.

Corrosion inhibitors which are suitable as such coadditives are, for example, succinic esters, especially with polyols, fatty acid derivatives, for example oleic acid esters, oligomerized fatty acids and substituted ethanolamines. Demulsifiers suitable as further coadditives are, for example, the alkali and alkaline earth metal salts of alkyl-substituted phenol and naphthalene sulfonates and the alkali and alkaline earth metal salts of fatty acid, furthermore alcohol alkoxylates, for example alcohol ethoxylates, phenol alkoxylates, for example tert-butylphenol ethoxylates or tert-pentyl phenol ethoxylates, fatty acid, alkylphenols, condensation products of ethylene oxide and propylene oxide, for example ethylene oxide-propylene oxide block copolymers, polyethyleneimines and polysiloxanes. Dehazers suitable as further coadditives are, for example, alkoxylated phenol-formaldehyde condensates.

Antifoams which are suitable as further coadditives are, for example, polyether-modified polysiloxanes.

As further co-additives suitable antioxidants are, for example, substituted phenols, e.g. 2,6-di-tert-butylphenol and 2,6-di-tert-butyl-3-methylphenol, as well as phenylenediamines, e.g. N, N'-di-sec-butyl-p-phenylenediamine. Suitable metal deactivators as further co-additives include, for example, salicylic acid derivatives, e.g. N, N'-disalicylidene-1,2-propanediamine.

Suitable solvents are, in particular also for fuel additive packages, for example nonpolar organic solvents, in particular aromatic and aliphatic hydrocarbons, e.g. Toluene, xylenes, "white spirit" and the technical solvent mixtures of the names Shellsol® (manufacturer: Royal Dutch / Shell Group), Exxol® (manufacturer: ExxonMobil) and Solvent Naphtha. Also suitable here, in particular in admixture with the abovementioned nonpolar organic solvents, are polar organic solvents, especially alcohols, such as tert-butanol, isoamyl alcohol, 2-ethylhexanol and 2-propylheptanol.

If the said co-additives and / or solvents are used in gasoline, they are used in the amounts customary for this purpose. The present invention also provides an additive concentrate which comprises at least one reaction product according to the invention of (a) a hydrocarbyl-substituted dicarboxylic acid or anhydride and (b) a nitrogen compound of the general formula I and at least one detergent-specific fuel additive which is different from said reaction product. Incidentally, the additive concentrate according to the invention may contain the other aforementioned coadditives.

The reaction product according to the invention is preferably present in the additive concentrate according to the invention in an amount of from 1 to 99% by weight, more preferably from 15 to 95% by weight and in particular from 30 to 90% by weight, based in each case on the total weight of the concentrate , in front. The at least one detergent additive other than said reaction product is preferably present in the additive concentrate according to the invention in an amount of from 1 to 99% by weight. more preferably from 5 to 85 wt .-% and in particular from 10 to 70 wt .-%, each based on the total weight of the concentrate, before.

The following examples are intended to illustrate the present invention without limiting it.

Example 1: mixing behavior

The reaction product ("RP1") of a polyisobutenyl succinic anhydride, produced by thermal ene reaction (200 ° C) of maleic anhydride with a polyisobutene of number average molecular weight M _n of 1000 and a content of terminal vinylidene double bonds of 85%, and aminoguanidine Hydrogen carbonate was prepared in analogy to Example 1 of US 2009/0282731 A1, using as diluent Solvesso ™ 150 (manufacturer: ExxonMobil) was used.

From the thus prepared reaction product ("RP1"), an additive concentrate ("AK1") was prepared by simply admixing the components listed below:

400 parts by weight of the reaction product RP1 according to the invention (50% strength by weight in Solvesso 150)

• 390 parts by weight (polymer content) of a customary detergent additive component (polyisobutene monoamine based on a polyisobutene with M _n = 1000) »310 parts by weight of a conventional carrier oil based on an alcohol-started polyether

• 270 parts by weight of solvent naphtha as diluent. 470 parts by weight of 2-propylheptanol as further diluent

4 parts by weight of a conventional Dehazer component (based on an alkoxylated phenol-formaldehyde condensate) The components mentioned could be easily mixed together to form a clear liquid whose consistency remained stable for several days.

For comparison, the additive concentrate "AK2" was prepared, which differed from AK1 only in that the reaction product RP1 according to the invention by the same amount of active ingredient of a conventional lubricity improver of the prior art ("RP2"), namely the imide of polyisobutenyl succinic anhydride (based on a polyisobutene with M _n = 1000) and tetraethylenepentamine. - After this Mixing RP2 was a cloudy liquid, from which precipitated a few days after a rainfall.

Example 2: Emulsion behavior

A typical commercially available Eurosuper base fuel according to EN 228 was added as a gasoline each with the additive concentrate AK1 (according to the invention) and AK2 (for comparison) in such an amount that the dosage of lubricity enhancer RP1 (according to the invention) or RP2 (for comparison) respectively 390 ppm by weight. According to the phase separation test ASTM D 1094, water was added to the systems and the phase separation behavior was evaluated. After 5 minutes, AK1 gave two clear and sharply separated phases (phase separation according to ASTM D 1094: 1), whereas after 5 minutes with AK 2 an emulsion resulted in the water phase and a cloudy fuel phase (phase separation according to ASTM D 1094: 4). ,

Example 3: Fuel Economy

A dosing rate based on a U.S. Patent No. 4,769,774, by addition of AK1 at the dosage rate mentioned in Example 2. petrol produced on the market for basic fuel was used to determine fuel economy in a fleet test with three different automobiles in accordance with U.S. Pat. Environmental Protection Agency Test Protocol, C.F.R. Title 40, Part 600, Subpart B, used. For each car, the fuel consumption was first determined with unadditiertem fuel and then with the same fuel, but now containing the additive concentrate AK1 in the dosage indicated in Example 2, determined. On average over all automobiles used this resulted in an average fuel saving of 1.3%

Example 4: Intake Valve Cleanliness Intake valve cleanliness ("IVD") was determined according to CEC F-20-98 in a Mercedes Benz engine M 1 1 1 with the two gasolines additized with AK1 (according to the invention) or AK2 (for comparison) , With a basic value of 94 mg per valve for the unadditivated petrol, the value of 2 mg per valve for the petrol fuel additized with AK1 (according to the invention) would be 6 mg per valve for the petrol fuel additized with AK2 (for comparison).

Claims

PF71 156 2012/072723 PCT / EP2011 / 071470 17 Claims

1 . Use of the reaction product of (a) a hydrocarbyl-substituted dicarboxylic acid whose hydrocarbyl radical has 8 to 250 carbon atoms, or its anhydride and (b) a nitrogen compound of the general formula I

ΊΜ H

^" FT

(I) or a salt of the nitrogen compound I, wherein R ¹ and R ^2, independently of one another, denote hydrogen or a C 1 - to C 20 hydrocarbyl radical, as an additive in a fuel for reducing fuel consumption when operating a spark-ignited internal combustion engine with said fuel or as Additive in a gasoline fuel to reduce fuel consumption when operating a self-igniting internal combustion engine with this fuel.

2. Use according to claim 1, wherein the hydrocarbyl-substituted dicarboxylic acid of component (a) is based on succinic acid or its anhydride.

3. Use according to claim 1 or 2, wherein the hydrocarbyl substituent in the component (a) is a linear or branched Ce- to C ₄ o-alkyl or alkenyl radical or a polyisobutenyl radical having 24 to 250 carbon atoms.

4. Use according to claims 1 to 3, wherein the nitrogen compound of component (b) is unsubstituted aminoguanidine bicarbonate.

5. A fuel composition comprising in a larger amount a gasoline and in a smaller amount at least one reaction product of (a) a hydrocarbyl-substituted dicarboxylic acid and (b) a nitrogen compound of the general formula I according to claims 1 to 4 and at least one of said Reaction product various fuel additive with detergent effect.

6. A fuel composition according to claim 5, comprising at least one member selected from: a detergent-effect fuel additive other than said reaction product selected from:

(Da) mono- or polyamino groups having up to 6 nitrogen atoms, wherein at least one nitrogen atom has basic properties; PF71156

2012/072723 PCT / EP2011 / 071470

18

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

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

(Dg) carboxylic acid ester groups;

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

7. A fuel composition according to claim 5 or 6, comprising in addition in a smaller amount than further fuel additive at least one carrier oil.

8. A fuel composition according to claims 5 to 7, comprising in addition in a smaller amount than further fuel additive at least one corrosion inhibitor.

9. additive concentrate containing at least one reaction product of (a) one

hydrocarbyl-substituted dicarboxylic acid or anhydride and (b) a nitrogen compound of general formula I according to claims 1 to 4 and at least one detergent additive other than said reaction product.