EP2646530B1 - Use of the product of reaction of a hydrocarbyl substituted dicarboxylic acid and a nitrogen compound to reduce fuel consumption. - Google Patents

Description

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

oder einem Salz der Stickstoffverbindung I, wobei R¹ und R² unabhängig voneinander Wasserstoff oder einen C₁- bis C₂₀-Hydrocarbylrest bedeuten,
als Additiv in einem Kraftstoff zur Reduktion des Kraftstoffverbrauches beim Betreiben eines fremdgezündeten Verbrennungsmotors mit diesem Kraftstoff oder als Additiv in einem Ottokraftstoff zur Reduktion des Kraftstoffverbrauches beim Betreiben eines selbstzündenden Verbrennungsmotors mit diesem Kraftstoff.The present invention relates to the use as described in claim 1, 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

or a salt of the nitrogen compound I, where 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 to reduce fuel consumption when operating a spark-ignited internal combustion engine with this fuel or as an additive in a gasoline to reduce fuel consumption when operating a self-igniting internal combustion engine with this fuel.

Furthermore, the present invention relates to a fuel composition as described in claim 4, which contains a gasoline fuel, said reaction product and at least one detergent additive.

Furthermore, the present invention relates to an additive concentrate, as described in claim 8, which contains 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 improvers, 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 alkanolamines, 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 solubilizers. 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.

Also in the WO 2007/053787 As a solubilizer for such component mixtures or additive concentrates recommended low molecular weight carboxylic acids and carboxylic acid derivatives, glycol ethers and alkylated phenols are uneconomical due to their high input costs and have no other positive effects except their function as solubilizers. On the contrary, they carry the risk of causing negative effects, such as unwanted oil dilution 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 blends or additive concentrates or in the fuel itself, so that infiltrated water is difficult, or at least very slowly, to be separated again via phase deposition.

So indeed show in the EP-A 1 424 322 and the WO 03/070860 described lubricity improvers based on polyisobutenylsuccinimides with mono- or polyamines or alkanolamines such as butylamine, diethylenetriamine, tetraethylenepentamine or aminoethyleneethanolamine good miscibility with other additive components in corresponding mixtures or concentrates, but have a pronounced tendency to form water-stable emulsions, leading to can carry water and dirt particles in the fuel supply chain and finally get into the engine. Water can cause corrosion, dirt particles can cause damage in fuel pumps, fuel filters and injectors.

In WO 94/29413 is mentioned reacting hydrocarbyl-substituted succinic acid derivatives with compounds containing at least acylatable nitrogen atom. The reaction products can be used as additives to skimmers or fuels.

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 fuel additives and no tendency to emulsify with water. 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 is to be assumed that the fuel saving due to said reaction product is largely due to 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 salt thereof are disclosed in US Pat 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.

From the British patents GB 998 869 and GB 1 020 059 It is known that the reaction product of polyisobutenyl succinic anhydride and aminoguanidine bicarbonate is also useful as a detergent additive in gasoline fuels.

In the European patent application EP 0 310 367 A1 It is described that the reaction product of polyisobutenyl succinic anhydride and aminoguanidine bicarbonate protects copper and copper alloys in diesel engines when contained in 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 but also relates to newly developed internal combustion engines such as the "HCCI" engine, which is self-igniting and is powered by 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 containing 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 sulfo groups can carry as long as the dominant hydrocarbon character of the rest is not distorted by this. 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, 1-propenyl, 2-propenyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, 2-ethylhexyl, neo-octyl, 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 denote 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 only one hydrocarbyl substituent is preferred. 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 der R³ einen Hydrocarbylrest mit 8 bis 250 Kohlenstoffatomen bezeichnet, geeignet. Unter einem Hydrocarbylrest soll auch hier ein Kohlenwasserstoffrest jeglicher Struktur verstanden werden, der jedoch in untergeordneter Menge noch Heteroatome wie Sauerstoff- und/oder Stickstoffatome und/oder Halogenatome enthalten und/oder funktionelle Gruppen wie Hydroxylgruppen, Carboxylgruppen, Carbonsäureestergruppen, Cyanogruppen, Nitrogruppen und/oder Sulfogruppen tragen kann, solange der dominierende Kohlenwasserstoff-Charakter des Restes hierdurch nicht verfälscht wird. Dieser Hydrocarbylrest ist typischerweise ein Alkyl-, Alkenyl-, Cycloalkyl-, Aryl-, Heteroaryl-, Aralkyl- oder Alkylarylrest. Bei längerkettigen Hydrocarbylresten kann er auf einem Olefinpolymerisat basieren, beispielsweise auf einem Polyethylen, Polypropylen oder Polyisobutylen.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.

The hydrocarbyl radical in component (a) or the radical R ³ is a linear or branched C ₈ - to C ₄₀ -alkyl or -alkenyl radical or a polyisobutenyl radical having 24 to 250 carbon atoms.

Linear or branched C ₈ to C ₄₀ alkenyl groups and polyisobutenyl groups are usually generated by a thermal ene reaction between the unsubstituted dicarboxylic acid or anhydride and a long-chain α-olefin to give an olefinic double bond in the α, β position of the hydrocarbyl side chain , 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.

C ₈ - to C ₄₀ -alkenyl radicals, in particular C ₁₀ - to C ₂₄ -alkenyl radicals, are, for example, 1-nonenyl, 1-decenyl, 1-undecenyl, 1-dodecenyl, 1-tridecenyl, 1-tetradecenyl, 1-pentadecenyl, 1-hexadecenyl, 1-octadecenyl, 1-eicosenyl and the corresponding alkenyl radicals from oligoisobutenes such as di-, tri-, tetra- or pentaisobutene or from technical α-olefin mixtures such as C ₂₀ -C ₂₄ -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 1100. 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.

Thus obtained polyisobutenyl succinimides ("PIBSA") generally have a degree of succinylation, i. a molar ratio of succinic anhydride moiety to polyisobutene moieties, from 0.8 to 2.0, especially 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 compound IIIa, and / or compounds containing one or two aminotriazole moieties, for example compound IIIb for the case R ¹ = R ² = H, may be constituents of this mixture :

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 hydrocarbyl-substituted dicarboxylic acid and (b) a nitrogen compound of general formula I and at least one of said 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, petrol fuel compositions of the specification are also according to WO 00/47698 Possible fields of use for the present invention. Next are in the context of the present invention under gasoline fuels also alcoholic gasoline fuels, especially ethanol-containing gasoline fuels, as described for example in the WO 2004/090079 are described, for. B. Flex fuel with an 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 about 96 Vol .-% C ₂ H ₅ OH and about 4 vol .-% H ₂ O is to be understood.

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.

• (Da) Mono- oder Polyaminogruppen mit bis zu 6 Stickstoffatomen, wobei mindestens ein Stickstoffatom basische Eigenschaften hat;
• (Db) Nitrogruppen, gegebenenfalls in Kombination mit Hydroxylgruppen;
• (Dc) Hydroxylgruppen in Kombination mit Mono- oder Polyaminogruppen, wobei mindestens ein Stickstoffatom basische Eigenschaften hat;
• (Dd) Carboxylgruppen oder deren Alkalimetall- oder Erdalkalimetallsalzen;
• (De) Sulfonsäuregruppen oder deren Alkalimetall- oder Erdalkalimetallsalzen;
• (Df) Polyoxy-C₂-C₄-alkylengruppierungen, die durch Hydroxylgruppen, Mono- oder Polyaminogruppen, wobei mindestens ein Stickstoffatom basische Eigenschaften hat, oder durch Carbamatgruppen terminiert sind;
• (Dg) Carbonsäureestergruppen;
• (Dh) aus Bernsteinsäureanhydrid abgeleiteten Gruppierungen mit Hydroxy- und/oder Amino- und/oder Amido- und/oder Imidogruppen; und/oder
• (Di) durch Mannich-Umsetzung von substituierten Phenolen mit Aldehyden und Mono- oder Polyaminen erzeugten Gruppierungen.

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;
• (Dc) 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 which are terminated by hydroxyl groups, mono- or polyamino groups, where 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 groups (Da), (Dc), (Dh) and (Di), come longer-chain alkyl or alkenyl groups, in particular the polypropenyl, polybutenyl and polyisobutenyl having in each case M _n = 300 to 5000, in particular 500 to 2500, especially 700 to 2300, into consideration.

• Mono- oder Polyaminogruppen (Da) enthaltende Additive sind vorzugsweise Polyalkenmono- oder Polyalkenpolyamine auf Basis von Polypropen oder konventionellem (d.h. mit überwiegend mittenständigen Doppelbindungen) Polybuten oder Polyisobuten mit M_n = 300 bis 5000. Geht man bei der Herstellung der Additive von Polybuten oder Polyisobuten mit überwiegend mittenständigen Doppelbindungen (meist in der β- und γ-Position) aus, bietet sich der Herstellweg durch Chlorierung und anschließende Aminierung oder durch Oxidation der Doppelbindung mit Luft oder Ozon zur Carbonyl- oder Carboxylverbindung und anschließende Aminierung unter reduktiven (hydrierenden) Bedingungen an. Zur Aminierung können hier Amine, wie z. B. Ammoniak, Monoamine oder Polyamine, wie Dimethylaminopropylamin, Ethylendiamin, Diethylentriamin, Triethylentetramin oder Tetraethylenpentamin, eingesetzt werden. Entsprechende Additive auf Basis von Polypropen sind insbesondere in der WO-A-94/24231 beschrieben.

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

• Mono- or polyamino (Da) -containing additives are preferably polyalkene mono- or Polyalkenpolyamine based on polypropene or conventional (ie, with predominantly central double bonds) polybutene or polyisobutene with M _n = 300 to 5000. If one goes in 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 the carbonyl or carboxyl compound and subsequent amination under reductive (hydrogenating) conditions , For amination here amines, such as. For example, ammonia, monoamines or polyamines, such as dimethylaminopropylamine, ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine, are used. Corresponding additives based on polypropene are especially in the WO 94/24231 described.

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 WO-A-97/03946 are described.

Further preferred monoamino (Da) -containing additives are the compounds obtainable from polyisobutene epoxides by reaction with amines and subsequent dehydration and reduction of the amino alcohols, as they are in particular DE-A-196 20 262 are described.

Nitro groups (Db), optionally in combination with hydroxyl groups, containing additives are preferably reaction products of polyisobutenes of the average degree of polymerization P = 5 to 100 or 10 to 100 with nitrogen oxides or mixtures of nitrogen oxides and oxygen, as in particular WO-A-96/03367 and WO-A-96/03479 are described. These reaction products are generally mixtures of pure nitropolyisobutenes (eg, α, β-dinitropolyisobutene) and mixed hydroxynitropolyisobutenes (eg, α-nitro-β-hydroxy polyisobutene).

Hydroxyl groups in combination with mono- or polyamino (Dc) -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 EP-A-476485 are described.

Additives carboxyl groups or their alkali metal or alkaline earth metal salts (Dd) are preferably copolymers of _C2-C40 olefins with maleic anhydride having a total molar mass of 500 to 20,000, the carboxyl groups completely or partially to the alkali metal or alkaline earth metal salts and a remaining residue the carboxyl groups are reacted with alcohols or amines. Such additives are in particular from the EP-A-307,815 known. Such additives are primarily for preventing valve seat wear and can, as in the WO-A-87/01126 described, be used with advantage in combination with conventional fuel detergents such as poly (iso) -butene amines or polyetheramines.

Sulfonic acid groups or their alkali metal or alkaline earth metal salts (De) containing additives are preferably alkali metal or alkaline earth metal salts of a Sulfobernsteinsäurealkylesters, as described in particular in EP-A-639 632 is described. 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 (Df) containing additives are preferably polyether or polyetheramines, which by reacting C ₂ -C ₆₀ alkanols, C ₆ -C ₃₀ alkanediols, mono- or di-C ₂ -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 polyetheramines, by subsequent reductive amination with ammonia, Monoamines or polyamines are available. Such products are used in particular EP-A-310 875 . EP-A-356 725 . EP-A-700 985 and U.S. Patent 4,877,416 described. In the case of polyethers, such products also meet carrier oil properties. Typical examples of these are tridecanol or Isotridecanolbutoxylate, Isononylphenolbutoxylate and Polyisobutenolbutoxylate and propoxylates and the corresponding reaction products with ammonia.

Carboxylic ester groups (Dg) containing additives are preferably esters of mono-, di- or tricarboxylic acids with long-chain alkanols or polyols, especially those having a minimum viscosity of 2 mm ² / s at 100 ° C, as in particular 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) additives are preferably corresponding derivatives of alkyl- or alkenyl-substituted succinic anhydride and especially the corresponding derivatives of polyisobutenyl succinic anhydride prepared by reacting 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 here are derivatives with aliphatic polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine. 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 a Acid and an amide, Carbonsäureimide with monoamines, Carbonsäureimide with di- or polyamines, which still have free amine groups in addition to the imide function, or diimides, which are formed by the reaction of di- or polyamines with two succinic acid derivatives. Such fuel additives are particularly in U.S. Patent 4,849,572 described.

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 derived from alkyl, alkenyl or polyisobutenyl succinic anhydride derivatives 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 about 1000.

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 particularly in the EP-A-831 141 described.

The fuel composition of the present invention contains the 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 5000 ppm by weight, more preferably from 20 to 2000 ppm by weight, more preferably from 30 to 1000 ppm by weight, and especially from 40 to 500 ppm by weight, e.g. 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. 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 selected from: polyolefins (polyalphaolefins or polyinteralalefins), (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 polyoxy-C ₂ -C ₄ -alkylene group-containing compounds which are obtained by reacting C ₂ -C ₆₀ -alkanols, C ₆ -C ₃₀ -alkanediols, mono- or di-C ₂ -C ₃₀ alkylamines, C ₁ -C ₃₀ -alkyl-cyclohexanols or C ₁ -C ₃₀ -alkylphenols with 1 to 30 mol of ethylene oxide and / or propylene oxide and / or butylene oxide per hydroxyl group or amino group and, in the case of polyetheramines, by subsequent reductive amination with Ammonia, monoamines or polyamines are available. Such products are used in particular EP-A310 875 . EP-A356 725 . EP-A 700 985 and US-A 4,877,416 described. 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 are described in particular in US Pat DE-A 38 38 918 are described. 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 Isotridecanols, such as. B. di (n- or iso-tridecyl) phthalate.

Further suitable carrier oil systems are, 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 described.

Examples of particularly suitable synthetic carrier oils are alcohol-started polyethers with about 5 to 35, such as. B. about 5 to 30, C ₃ -C ₆ alkylene oxide, 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, where the long-chain alkyl radical is in particular a straight-chain or branched C _β -C ₁₈ -alkyl radical. Preferred examples are tridecanol and nonylphenol.

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

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

Examples of suitable corrosion inhibitors as such coadditives are succinic esters, especially with polyols, fatty acid derivatives, e.g. 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-pentylphenol 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.

Metal deactivators suitable 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 non-polar organic solvents, in particular aromatic and aliphatic hydrocarbons, e.g. Toluene, xylenes, "wide spirit" and the technical solvent mixtures of the names Shellsol® (manufacturer: Royal Dutch / Shell Group), Exxol® (manufacturer: ExxonMobil) and Solvent Naphtha. Furthermore, here, in particular in admixture with said non-polar organic solvents, polar organic solvents, especially alcohols such as tert-butanol, isoamyl alcohol, 2-ethylhexanol and 2-propylheptanol into consideration.

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-type fuel additive which is different from said reaction product. Incidentally, the additive concentrate of the invention may contain the other above-mentioned co-additives.

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 , The at least one detergent additive other than said reaction product is preferably present in the additive concentrate of the invention in an amount of from 1 to 99% by weight, especially 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 bicarbonate was in analogy to Example 1 of US 2009/0282731 A1 Solvesso ™ 150 (manufacturer: ExxonMobil) was used as the diluent.

• 400 Gew.-Teile des erfindungsgemäßen Reaktionsproduktes RP1 (50 gew.-%ig in Solvesso 150)
• 390 Gew.-Teile (Polymergehalt) einer üblichen Detergensadditiv-Komponente (Polyisobutenmonoamin auf Basis eines Polyisobutens mit M_n = 1000)
• 310 Gew.-Teile eines üblichen Trägeröls auf Basis eines alkoholgestarteten Polyethers
• 270 Gew.-Teile Solvent Naphtha als Verdünnungsmittel
• 470 Gew.-Teile 2-Propylheptanol als weiteres Verdünnungsmittel
• 4 Gew.-Teile einer üblichen Dehazer-Komponente (auf Basis eines alkoxylierten Phenol-Formaldehyd-Kondensates)

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 conventional 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 a 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) and RP2 (for comparison) each 390 wt . ppm. 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 gasoline produced by the addition of AK1 at the rate of dosing based on a U.S. commercial baseline fuel used in Example 2 was used to determine fuel economy in a fleet test with three different automobiles according to 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. On average for all cars used this resulted in an average fuel saving of 1.3%

Example 4: Inlet valve cleanliness

Intake valve cleanliness ("IVD") was determined according to CEC F-20-98 in a Mercedes Benz engine M111 with the two gasolines additized with AK1 (according to the invention) or AK2 (for comparison). At a base value of 94 mg per valve for the unadditivated gasoline, the value of 2 mg per valve for the gasoline additized with AK1 (according to the invention) and 6 mg per valve for the Otto fuel additive (for comparison).

Claims (8)

1. The use of the reaction product formed from (a) a hydrocarbyl-substituted dicarboxylic acid whose hydrocarbyl radical is a linear or branched C₈- to C₄₀-alkyl or -alkenyl radical or a polyisobutenyl radical having 24 to 250 carbon atoms, or the anhydride thereof, and (b) a nitrogen compound of the general formula I

   

   or a salt of the nitrogen compound I, where R¹ and R² are each independently hydrogen or a C₁- to C₂₀-hydrocarbyl radical,

   together with a fuel additive having detergent action which is at least one amphiphilic substance having at least one hydrophobic hydrocarbyl radical having a number-average molecular weight (M_n) of 85 to 20 000 and at least one polar moiety,

   as an additive in a fuel for reducing fuel consumption in the operation of a spark-ignited internal combustion engine with this fuel or as an additive in a gasoline fuel for reduction of fuel consumption in the operation of a self-ignition internal combustion engine with this fuel.
2. The use according to claim 1, wherein the hydrocarbyl-substituted dicarboxylic acid of component (a) is based on succinic acid or the anhydride thereof.
3. The use according to claims 1 to 2, wherein the nitrogen compound of component (b) is unsubstituted aminoguanidine hydrogencarbonate.
4. A fuel composition comprising, in a major amount, a gasoline fuel and, in a minor amount, at least one reaction product as defined in claims 1 to 3, formed from (a) a hydrocarbyl-substituted dicarboxylic acid and (b) a nitrogen compound of the general formula I and at least one fuel additive which is different than the reaction product mentioned, has detergent action and is at least one amphiphilic substance having at least one hydrophobic hydrocarbyl radical having a number-average molecular weight (M_n) of 85 to 20 000 and at least one polar moiety.
5. The fuel composition according to claim 4, comprising as the fuel additive which is different than the reaction product mentioned and has detergent action at least one representative selected from:

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

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

   (Dc) hydroxyl groups in combination with mono- or polyamino groups, at least one nitrogen atom having 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-C₂-C₄-alkylene moieties terminated by hydroxyl groups, mono- or polyamino groups, at least one nitrogen atom having basic properties, or by carbamate groups;

   (Dg) carboxylic ester groups;

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

   (Di) moieties obtained by Mannich reaction of substituted phenols with aldehydes and mono- or polyamines.
6. The fuel composition according to claim 4 or 5, additionally comprising, as a further fuel additive in a minor amount, at least one carrier oil.
7. The fuel composition according to claims 4 to 6, additionally comprising, as a further fuel additive in a minor amount, at least one corrosion inhibitor.
8. A fuel additive concentrate comprising at least one reaction product as defined in claims 1 to 3, formed from (a) a hydrocarbyl-substituted dicarboxylic acid or anhydride thereof and (b) a nitrogen compound of the general formula I and at least one fuel additive which is different than the reaction product mentioned, has detergent action and is at least one amphiphilic substance having at least one hydrophobic hydrocarbyl radical having a number-average molecular weight (M_n) of 85 to 20 000 and at least one polar moiety.