KR101970939B1 - Use of the reaction product of a hydrocarbyl-substituted dicarboxlic acid and a nitrogen compound for reducing fuel consumption - Google Patents

Abstract

Use of a reaction product of a hydrocarbyl-substituted dicarboxylic acid or anhydride thereof and a nitrogen compound of formula (I) or a salt thereof as a fuel additive to reduce fuel consumption in an internal combustion engine:

Description

USE OF THE REACTION PRODUCTS OF HYDROCARBILL-SUBSTITUTED DICARBOXLIC ACID AND A NITROGEN COMPOUND FOR REDUCING FUEL CONSUMPTION FOR HYDROCARBILL-SUBSTITUTED DICARBOXYLIC ACID AND NITROGEN COMPOUND FOR TREATING FUEL CONSUMPTION

The present invention relates to a process for the preparation of a hydrocarbyl-substituted dicarboxylic acid or its anhydride, which comprises (a) hydrocarbyl-substituted dicarboxylic acids having from 8 to 250 carbon atoms in their hydrocarbyl radicals or anhydrides thereof, and (b) Additives in fuels to reduce fuel consumption during operation of spark-ignition internal combustion engines using corresponding fuels of reaction products, or as additives in gasoline fuels to reduce fuel consumption during operation of a natural-ignition internal combustion engine using the fuels Lt; / RTI >

Wherein R ¹ and R ² are each independently hydrogen or a C ₁ - to C ₂₀ -hydrocarbyl radical.

The present invention further relates to a fuel composition containing gasoline fuel, the aforementioned reaction product and at least one fuel additive having a surfactant action.

The present invention further relates to an additive concentrate containing the aforementioned reaction product and at least one fuel additive having a surfactant action.

Special materials in fuel are known to reduce internal friction in internal combustion engines, particularly gasoline engines, thereby helping to save fuel. Such materials are also referred to as lubricity enhancers, friction modifiers, or friction modifiers. Lubricity enhancing agents marketed for gasoline fuels are generally condensation products of naturally occurring carboxylic acids, such as condensation products of fatty acids with polyols, such as glycerol, or alkanolamines thereof, such as glyceryl monooleate.

Disadvantages of the lubricity improvers of the prior art mentioned above are poor compatibility with other commonly used fuel additives, especially surfactants such as polyisobutene amine and / or carrier oils such as polyalkylene oxides. An important prerequisite in practice is that the component mixture or additive concentrate to be provided can be easily pumped even at relatively low temperatures, in particular at winter outdoor temperatures, for example down to -20 占 폚, and remain homogeneously stable over a long period of time , That is, phase separation and / or sediment should not appear.

In general, the miscibility problems described have been avoided by adding paraffinic or aromatic hydrocarbons as solubilizing agents and a mixture of alcohols such as tert-butanol or 2-ethylhexanol in relatively large amounts to the component mixture or additive concentrate. However, in some cases, a significant amount of such expensive solubilizing agents are required to achieve the desired homogeneity, and thus the solution is confronted with the problem of being uneconomical.

The low molecular weight carboxylic acid and carboxylic acid derivatives, glycol ethers and alkylated phenols recommended in WO 2007/053787 as such solubilizers for such component mixtures or additive concentrates are also economically disadvantageous due to their high feedstock cost , And they do not have any positive effect when they separate their functions as solubilizers. In addition, they are at risk of causing side effects such as, for example, unwanted oil dilution and increased combustion chamber deposition.

In addition, the lubricity enhancing agents of the prior art mentioned above often have a tendency to form emulsions in water or in fuel concentrates or in the fuel itself, such that the penetrated water is difficult or too Slowly removed again.

For example, polyisobutenylsuccinimide and mono- or polyamines or alkanolamines such as butylamine, diethylenetriamine, tetraethylenepentamine or diethylenepentamine, described in EP-A 1 424 322 and WO 03/070860, The lubricity enhancer based on aminoethylenethanolamine exhibits excellent compatibility with further additive components in the corresponding mixture or concentrate, but has a distinct tendency to form a stable emulsion with water, , And ultimately, it is possible to enter the engine. Water can cause corrosion; Particles can lead to damage to fuel pumps, fuel filters, and injectors.

The object of the invention is firstly to provide fuel savings which are effective in the operation of a spark-ignition internal combustion engine, and secondly to the disadvantages described in the prior art, namely more particularly to poor compatibility with other fuel additives, To provide a fuel additive that no longer has the tendency to form. In addition, the present invention does not deteriorate the high level intake valve clean performance achieved by modern fuel additives.

Thus, we have found the use of a reaction product prepared from (a) a hydrocarbyl-substituted dicarboxylic acid or anhydride thereof and (b) a nitrogen compound of formula (I) as defined earlier. It can be inferred that the reason for the fuel savings due to the above-mentioned reaction products is substantially based on its effectiveness in reducing internal friction in internal combustion engines, particularly gasoline engines. Thus, the above-mentioned reaction product functions essentially as a lubricity improver in the context of the present invention.

The reaction products prepared from hydrocarbyl-substituted dicarboxylic acids or anhydrides thereof and aminoguanidine or salts thereof are described in US Published Specification US 2009/0282731 Al and US 2010/0037514 A1 to improve the performance of diesel engines and to improve the performance of injectors Are described as additives for cleaning.

British patents GB 998 869 and GB 1 020 059 disclose that the reaction products prepared from polyisobutenyl succinic anhydride and aminoguanidine bicarbonate are also suitable as surfactant additives in gasoline fuels.

European Patent Specification EP 0 310 367 A1 describes that the reaction product prepared from polyisobutenylsuccinic anhydride and aminoguanidine bicarbonate protects the copper and copper alloy in the diesel engine when present in motor oil.

The spark-ignition internal combustion engine is preferably understood to mean a gasoline engine which is generally ignited by a spark plug. In addition to conventional 4- and 2-stroke gasoline engines, spark-ignition internal combustion engines also include other engine types, such as Wankel engines. (LPG) or compressed natural gas (" LPG "), such as a conventional gasoline type, in particular a gasoline type according to EN 228, a Flex fuel with 75 to 85% CNG ").

However, the use of reaction products prepared from (a) the hydrocarbyl-substituted dicarboxylic acids or anhydrides thereof and (b) the nitrogen compounds of the formula (I) of the present invention are also suitable for use in newly developed internal combustion engines such as natural- Quot; HCCI "

The nitrogen compound of formula (I) for the reactive component (a) is guanidine, substituted guanidine or a salt thereof. Possible hydrocarbyl radicals in such compounds include 1 to 20, especially 1 to 12, especially 1 to 8 carbon atoms. The hydrocarbyl radical may contain a minor amount of hetero and / or halogen atoms such as oxygen and / or nitrogen atoms and / or may contain functional groups such as hydroxyl groups, carboxyl groups, carboxyl ester groups, cyano groups, / RTI > is intended to mean a hydrocarbyl radical of any structure which includes, but is not limited to, those radicals, including, but not limited to, The hydrocarbyl radical may be saturated or unsaturated in nature; May have a linear or branched structure; Aromatic and / or heterocyclic sub-structures.

Nitrogen-containing compound (I) may have two such hydrocarbyl or may have a radical, or for R ¹ or R ² only one such hydrocarbyl radicals for R ¹ and R ^2, if in this case the latter remaining The substituent is hydrogen. However, preferably both substituents R < ¹ > and R < ² > are both hydrogen, i.e. the compound is unsubstituted aminoguanidine.

Possible hydrocarbyl radicals for R ¹ and / or R ² are preferably linear or branched alkyl or alkenyl radicals, especially those having 1 to 8, preferably 1 to 4 carbon atoms, such as methyl Propyl, n-butyl, sec-butyl, isobutyl, tert-butyl, Butenyl, hexyl, hexyl, heptyl, heptyl, heptyl, heptyl, heptyl, heptyl, heptyl, heptyl, heptyl, heptyl, Heptadecyl, octadecyl (stearyl), oleyl, linolyl, linolenyl, nonadecyl, eicosyl, or the appropriate isomers thereof.

In addition, the possible hydrocarbyl radicals for R ¹ and / or R ² can also refer to cycloalkyl radicals such as cyclopentyl, cyclohexyl, 2-, 3- or 4-methylcyclohexyl or cycloheptyl have.

In addition, possible hydrocarbyl radicals for R ¹ and / or R ² are also radicals such as aryl, alkaryl or arylalkyl radicals such as phenyl, naphthyl, benzyl, 2-phenylethyl, Phenylbutyl, tolyl or o-, m- or p-xylyl.

When the nitrogen compound I is used in one of its salts, it is in particular a halide such as chloride or bromide, carbonate, hydrogencarbonate (bicarbonate), nitrate or orthophosphate. It is preferable to use a hydrogencarbonate (bicarbonate).

In a preferred embodiment, the nitrogen compound of component (b) is an unsubstituted aminoguanidine hydrogencarbonate.

The hydrocarbyl-substituted dicarboxylic acids or anhydrides thereof of component (a) generally have saturated C ₂ - to C ₁₀ -dicarboxylic acids as base skeletons or anhydrides thereof. The dicarboxylic acid or anhydride thereof may have several, for example two or three, hydrocarbyl substituents, but preferably only one hydrocarbyl substituent. Anhydrides are typically in the cyclic form when anhydrides are formed in the molecule. 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 likewise suitable.

In a preferred embodiment, the hydrocarbyl-substituted dicarboxylic acid used as reaction component (a) is based on succinic acid or anhydride thereof. More particularly, the corresponding succinic anhydride of formula II is also suitable herein:

Wherein R ³ represents a hydrocarbyl radical having 8 to 250 carbon atoms. Hydrocarbyl radicals may also contain hetero atoms and / or halogen atoms, such as oxygen and / or nitrogen atoms, in minor amounts herein, and / or may contain hydroxyl groups, carboxyl groups, carboxyl ester groups, cyano groups, nitro groups and / Or a sulfo group, but is understood to mean a hydrocarbyl radical of any structure wherein the predominant hydrocarbon character of the radical is not impaired by them. The hydrocarbyl radical is generally alkyl, alkenyl, cycloalkyl, aryl, heteroaryl, aralkyl or alkylaryl radical. In the case of a long-chain hydrocarbyl radical, it may be an olefin polymer such as those based on polyethylene, polypropylene or polyisobutylene.

In a preferred embodiment, the hydrocarbyl radical in component (a), i.e. the R ³ radical, is a linear or branched C ₈ - to C ₄₀ -alkyl or -alkenyl radical or a polyisobutylene radical having 24 to 250 carbon atoms Lt; / RTI >

A linear or branched C ₈ - to C ₄₀ -alkenyl radical and a polyisobutenyl radical are generally obtained by thermal ene reaction of an unsubstituted dicarboxylic acid or an anhydride thereof with long-chain? -Olefins , An olefin double bond is obtained at the?,? Positions of the hydrocarbyl side chain. For such a purpose, the reactants are generally heated to a temperature of from 150 to 250 캜. Subsequently, the alkenyl radical can be hydrogenated with the corresponding saturated alkyl radical.

Useful C ₈ - to C ₄₀ -alkenyl radicals, especially C ₁₀ - to C ₂₄ -alkenyl radicals are, for example, 1-nonenyl, 1-decenyl, 1-undecenyl, Decene, 1-tetradecenyl, 1-pentadecenyl, 1-hexadecenyl, 1-octadecenyl, 1-eicosenyl and oligoisobutene such as di-, tri-, tetra- or pentaisobutene from a manufacturing or technical α- olefin mixtures, such as C ₂₀ -C ₂₄ -α- alkenyl radical to the corresponding prepared from olefins.

When a polyisobutenyl radical is present, it preferably contains from 24 to 250, in particular from 28 to 180, in particular from 36 to 80, carbon atoms, or accordingly its number average molecular weight M _n is preferably from 330 to < RTI ID = 3500, in particular 390 to 2500, in particular 500 to 1100. Such polyisobutenyl radicals are generally prepared from highly reactive polyisobutene, i.e., polyisobutene having a high proportion of terminal vinylidene double bonds, generally at least 60%, especially at least 70%, especially at least 80%.

The succinylation degree of polyisobutenylsuccinimide (" PIBSA ") thus obtained, i.e. the molar ratio of succinic anhydride unit to polyisobutene unit, is generally from 0.8 to 2.0, in particular from 1.0 to 1.3. Therefore, it is possible that two succinic anhydride units are bonded to one polyisobutene chain.

The reaction products obtained from (a) hydrocarbyl-substituted dicarboxylic acids or anhydrides thereof and (b) nitrogen compounds I are often mixtures of different compounds of different structures. The contents of such a mixture are particularly suitable for the preparation of compounds comprising an imide formed from the primary amino group of I, for example a compound IIIa and / or one or two aminotriazole moieties, for example R ¹ = R ² = H Compound IIIb can be:

The reaction product of the present invention prepared from (a) a hydrocarbyl-substituted dicarboxylic acid or anhydride thereof and (b) a nitrogen compound I is useful as a catalyst for the production of spark-ignition internal combustion engines, Are particularly suitable as additives, have good miscibility with other fuel additives, and do not have any significant tendency to form water and emulsions. The advantageous properties mentioned are exhibited to a certain extent when used in gasoline fuels with the additional use of a fuel additive with surfactant action.

Accordingly, the present invention also relates to a process for the preparation of a reaction product comprising at least one of the reaction products of the present invention prepared from a gasoline fuel in a large amount and comprising (a) a hydrocarbyl-substituted dicarboxylic acid and (b) There is provided a fuel composition containing a trace amount of at least one fuel additive having a surfactant action.

Generally, the amount of such one or more of the reaction products of the invention in gasoline fuels is from 10 to 5000 ppm by weight, more preferably from 20 to 2000 ppm, even more preferably from 30 to 1000 ppm, especially from 40 to 500 ppm, For example, 50 to 300 ppm.

Useful gasoline fuels include all conventional gasoline fuel compositions. A typical representative example that may be mentioned herein is the Eurosuper base fuel, which is commercially available EN 228. In addition, the gasoline fuel compositions of the specification according to WO 00/47698 are also of use in the present invention. In addition, in the context of the present invention, gasoline fuels may also be used as alcohol-containing gasoline fuels, particularly those containing ethanol-containing gasoline fuels such as those described in WO 2004/090079, for example Flex ("E85") containing 85 vol.% Ethanol, as well as ethanol generally distilled azeotropically, with about 96 vol% C ₂ H ₅ OH and about 4 vol% H ₂ O Quot; E100 " fuel type.

The reaction products of the present invention prepared from (a) a hydrocarbyl-substituted dicarboxylic acid or anhydride thereof and (b) the nitrogen compound I can be added to a specific base fuel alone or in the form of a fuel additive package. Such a package is a fuel additive concentrate and generally comprises not only solvents but also one or more fuel additives which differ from the reaction products of the present invention and have a surfactant action, a series of additional constituents as auxiliary additives, in particular carrier oils, Antioxidants or stabilizers, antistatic agents, metallocenes, metal deactivators, solubilizers, markers and / or dyes, which are known to those skilled in the art.

Surfactants or surfactant additives, hereinafter referred to as component (D), are generally referred to as immersion inhibitors for fuels. Surfactant additives are preferably both hydrophilic substances having at least one hydrophobic hydrocarbyl radical and at least one polar moiety having a number average molecular weight (M _n ) of 85 to 20,000, especially 300 to 5,000, especially 500 to 2,500.

In a preferred embodiment, the fuel composition of the present invention contains at least one representative selected from the following as the at least one fuel additive (D), which is different from the reaction product of the present invention and has a surfactant action:

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

(Db) optionally together with a hydroxyl group, a nitro group;

(Dc) a mono- or polyamino group (with one or more nitrogen atoms having basic properties);

(Dd) a carboxyl group or an alkali metal or alkaline earth metal salt thereof;

(De) sulfo group or an alkali metal or alkaline earth metal salt thereof;

(Df), a hydroxyl group, a mono-alkylene part-or poly-amino polyoxyalkylene -C ₂ -C ₄ which terminates by a, or a carbamate by a (at least one is nitrogen having basic characteristics);

(Dg) carboxyl ester group;

A moiety derived from (Dh) 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.

The number average molecular weight (M _n ) of the hydrophobic hydrocarbon radicals in the surfactant additive, which ensures a suitable solubility in the fuel composition, is 85 to 20,000, especially 300 to 5,000, especially 500 to 2,500. Typical hydrophobic hydrocarbyl radicals particularly useful in conjunction with the polar moieties (Da), (Dc), (Dh) and (Di) are alkyl or alkenyl radicals of relatively long chain, in particular those having an M _n of 300 to 5,000, , In particular from 700 to 2,300, polypropenyl, polybutenyl and polyisobutenyl radicals.

Examples of such groups of surfactant additives include:

The additives containing mono- or polyamino groups (Da) are preferably polypropenes or polybutenes based on polyisobutenes or polyisobutenes based on polyisobutenes with M _n of 300 to 5000 (i.e. mainly with internal double bonds) - or polyalkenepolyamines. When the additive preparation proceeds from polybutene or polyisobutene having predominantly internal double bonds (generally in the beta and gamma positions), one possible route of preparation is either by chlorination and subsequent amination, or by air or ozone By the oxidation of the double bond used and subsequent amination under a reducing (hydrogenation) atmosphere. Here, the amines used for the amination can be, for example, ammonia, monoamines or polyamines such as dimethylaminopropylamine, ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine. Corresponding additives based on polypropene are described in particular in WO-A-94/24231.

Further preferred additives containing a monoamino group (Da) are hydrogenation of the reaction product of a polyisobutene having an average degree of polymerization P of 5 to 100 with a mixture of nitrogen oxides or nitrogen oxides, especially as described in WO-A-97/03946 Product.

Further preferred additives containing the monoamino group (Da) are compounds obtainable by reaction with an amine from a polyisobutene epoxide, as described in DE-A-196 20 262, and subsequent dehydration and reduction of the amino alcohol .

The additives containing a nitro group (Db), optionally in combination with a hydroxyl group, preferably have an average degree of polymerization P of from 5 to 100 or 10, preferably of from 5 to 100 or 10, as described in particular in WO-A-96/03367 and WO- To 100 carbon atoms and a mixture of nitrogen oxides or nitrogen oxides and oxygen. The reaction products are generally selected from the group consisting of pure nitropolyisobutene (e.g., alpha, beta-dinitropoliisobutene) and mixed hydroxy nitropoliisobutene (e.g., alpha -nitro- beta -hydroxypolyisobutene Tungsten).

Mono- or additive containing a hydroxyl group (Dc) with poly amino group is particularly, especially having preferably predominantly terminal double bond as described in EP-A-476 485 M _n of 300 to 5000 in Is the reaction product of polyisobutene epoxide obtainable from polyisobutene with ammonia or mono- or polyamines.

The additive containing a carboxyl group or an alkali metal or alkaline earth metal salt (Dd) thereof is preferably a C ₂ -C ₄₀ -olefin having a total molecular weight of from 500 to 20,000 and all or part of its carboxyl group is an alkali metal or alkaline earth metal salt , And any remaining carboxyl groups are copolymers with maleic anhydride which react with alcohols or amines. Such additives are described in particular in EP-A-307 815. Such additives are mainly provided to prevent the valve seat from being worn out, and are advantageously used in combination with conventional fuel surfactants such as poly (iso) butene amine or polyether amine as described in WO-A-87/01126 Can be used in combination.

The additive containing sulfo group or its alkali metal or alkaline earth metal salt (De) is preferably an alkali metal or alkaline earth metal salt of alkylsulfosuccinate as described in EP-A-639 632 in particular. The additive is mainly provided to prevent the valve seat from being worn out, and can advantageously be used in combination with a conventional fuel surfactant such as poly (isobuteneamine) or polyether amine.

The additives containing polyoxy-C ₂ -C ₄ -alkylene moieties (Df) are preferably C ₂ -C ₆₀ -alkanols, C ₆ -C ₃₀ -alkanediol, mono- or di-C ₂ -C _30-alkyl amine, C ₁ -C ₃₀ -alkyl cyclohexanol or C ₁ -C ₃₀ - alkyl phenol, a hydroxyl group or an amino group of 1 to 30 mol per mol of ethylene oxide and / or propylene oxide and / Or butylene oxide, and, in the case of polyether amines, polyether or polyether amines obtainable by subsequent reductive amination with ammonia, monoamines or polyamines. These 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, the products also have carrier oil properties. Typical examples of these are the corresponding reaction products with tridecanolbutoxylate, isotridecanolbutoxylate, isononylphenol butoxylate and polyisobutanol butoxylate and propoxylate and also with ammonia.

The additive containing carboxyl ester groups (Dg) is preferably selected from esters of mono-, di- or tricarboxylic acids with long-chain alkanols or polyols, especially those described in DE-A-38 38 918 The minimum viscosity at 100 ° C is 2 mm ² / s. The mono-, di- or tricarboxylic acids used may be aliphatic or aromatic acids, and particularly suitable ester alcohols or ester polyols are, for example, long chain representatives having 6 to 24 carbon atoms. Typical representatives of esters are adipates, phthalates, isophthalates, terephthalates and trimellitates of isooctanol, isodecanol and isotridecanol. Such products also have carrier oil properties.

Additives derived from succinic anhydride and containing moieties (Dh) with hydroxyl and / or amino and / or amido and / or imido groups are preferably derived from corresponding derivatives of alkyl- or alkenyl-substituted succinic anhydrides and Especially corresponding polyisobutenyl succinic anhydrides obtainable by reaction of maleic anhydride with a conventional or highly reactive polyisobutene having M _n of 300 to 5000 through a thermal path or through chlorinated polyisobutene . Of particular interest in this context are derivatives with aliphatic polyamines, such as ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine. The moieties having hydroxyl and / or amino and / or amido and / or imido groups are, for example, carboxylic acid groups, acid amides of monoamines, acid amides of di- or polyamines with free amines in addition to amide functional groups, acids And succinic acid derivatives having an amide functional group, carboximides with monoamines, carboximides with di- or polyimines having free amines in addition to imide functional groups, or with di- or polyamines with two succinic acid derivatives . ≪ / RTI > Such fuel additives are described in particular in US-A-4 849 572.

Surfactant additives from group Dh are preferably reaction products of alkyl- or alkenyl-substituted succinic anhydrides, especially polyisobutenylsuccinic anhydride (" PIBSA ") with amines and / or alcohols. Thus, they are derivatives derived from alkyl-, alkenyl- or polyisobutenylsuccinic anhydrides and have amino and / or amido and / or imido and / or hydroxyl groups. It is obvious that the reaction products can be obtained not only when substituted succinic anhydrides are used but also when substituted succinic acids or suitable acid derivatives such as succinyl halides or succinic acid esters are used.

The fuel to which the additive is added preferably contains at least one surfactant based on polyisobutenyl-substituted succinimide. The imides with aliphatic polyamines are of particular interest. Particularly preferred polyamines are ethylenediamine, diethylenetriamine, triethylenetetramine, pentaethylenehexamine, especially tetraethylenepentamine. The number average molecular weight M _n of the polyisobutenyl radical Is preferably 500 to 5,000, more preferably 500 to 2,000, especially about 1000.

Additives containing moieties (Di) obtained by Mannich reaction of substituted phenols with aldehydes and mono- or polyamines are preferably selected from polyisobutene-substituted phenols, formaldehyde and mono- or polyamines such as ethylenediamine, diethylene tri Amine, triethylenetetramine, tetraethylenepentamine, or dimethylaminopropylamine. The polyisobutenyl-substituted phenol may be derived from conventional or highly reactive polyisobutene having M _n of 300 to 5000. The above " polyisobutene Mannich base " is described in particular in EP-A-831 141.

The fuel composition of the present invention comprises at least one fuel additive that is different from the reaction product of the present invention and has a surface-active activity and is generally selected from Groups (Da) to (Di) More preferably from 20 to 2000, even more preferably from 30 to 1000 ppm, especially from 40 to 500 ppm, for example, from 50 to 250 ppm.

The aforementioned surfactant additives (D) are preferably used in combination with one or more carrier oils. In a preferred embodiment, the fuel composition of the present invention contains at least one carrier oil in minor amounts, in addition to one or more of the reaction products of the present invention and one or more fuel additives that are different from the reaction products of the present invention and have a surfactant action.

Suitable mineral carrier oils are, for example, fractions obtained from crude oil processing such as brightstock or base oil having a viscosity of the order of 500 to 2000 SN; They are also aromatic hydrocarbons, paraffinic hydrocarbons and alkoxyalkanols. Quot; hydrocrack oil " (obtained from natural mineral oil hydrogenated with a catalyst under high pressure and having an isobaric range in the range of about 360 to 500 < 0 > C, isomerized and also deparaffinated A vacuum distillate cut) is likewise useful. Mixtures of the above-mentioned mineral carrier oils are likewise suitable.

Examples of suitable synthetic carrier oils are selected from the group consisting of polyolefins (poly-alpha-olefins or poly (internal olefins)), (poly) esters, (poly) alkoxylates, polyethers, aliphatic polyetheramines, Starting polyethers, alkylphenol-initiated polyether amines and carboxyl esters of long-chain alkanols.

An example of a suitable polyolefin is an olefin polymer with an M _n of 400 to 1800, especially based on polybutene or polyisobutene (hydrogenated or hydrogenated).

Examples of suitable polyethers or polyetheramines are preferably C ₂ -C ₆₀ -alkenols, C ₆ -C ₃₀ -alkanediol, mono- or di-C ₂ -C ₃₀ -alkylamines, C ₁ -C ₃₀ -Alkylcyclohexanol or C ₁ -C ₃₀ -alkylphenol with 1 to 30 mol of ethylene oxide and / or propylene oxide and / or butylene oxide per hydroxyl group or amino group and reacting the polyetheramine Is a compound comprising a polyoxy-C ₂ -C ₄ -alkylene moiety obtainable by subsequent reductive amination with ammonia, monoamine or polyamine. 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, the polyetheramine used may be a poly-C ₂ -C ₆ -alkylene oxide amine or a functional derivative thereof. Typical examples thereof are the corresponding reaction products with tridecanolbutoxylate or isotridecanolbutoxylate, isononylphenol butoxylate and also with polyisobutenebutoxylate and propoxylate, and also with ammonia.

Examples of carboxyl esters of long-chain alkanols are in particular esters with long-chain alkanols or polyols of the mono-, di- or tricarboxylic acids mentioned in particular in DE-A-38 38 918. The mono-, di- or tricarboxylic acid used may be an aliphatic or aromatic acid; Suitable ester alcohols or polyols are, in particular, long chain representatives having, for example, from 6 to 24 carbon atoms. Typical representatives of esters are adipates, phthalates, isophthalates, terephthalates and trimellitates of isooctanol, isononanol, isodecanol and isotridecanol, such as di (n- or isotridecyl) phthalate to be.

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- .

Particularly suitable examples of suitable synthetic carrier oils include about 5 to 35, for example about 5 to 30, C ₃ -C ₆ -alkylene oxide units such as propylene oxide, n-butylene oxide and isobutyl Lt; / RTI > is an alcohol-initiated polyether having one or more selected from the group consisting of ethylene oxide units, Non-limiting examples of suitable starting alcohols are phenols substituted with long chain alkanols or long chain alkyls, wherein the long chain alkyl radicals are especially straight or branched C ₆ -C ₁₈ -alkyl radicals. Preferred examples include tridecanol and nonylphenol.

A further suitable synthetic carrier oil is an alkoxylated alkylphenol as described in DE-A-101 02 913.

A preferred carrier oil is a synthetic carrier oil, and particularly preferred is a polyether.

When a carrier oil is further used, it is added in an amount of preferably 1 to 1000 ppm, more preferably 10 to 500 ppm, particularly 20 to 100 ppm, based on the weight of the added fuel of the present invention.

In a preferred embodiment, the fuel composition of the present invention comprises, in addition to one or more reaction products of the invention, one or more fuel additives which are different from the reaction products of the present invention and have a surfactant action, and optionally one or more Carrier oil, and at least one corrosion inhibitor.

Suitable corrosion inhibitors as such auxiliary additives are, for example, succinic acid esters, in particular with polyols, fatty acid derivatives, such as oleic acid esters, oligomerized fatty acids and substituted ethanolamines.

Suitable emulsifying agents as further auxiliary additives are, for example, alkali metal and alkaline earth metal salts of alkyl-substituted phenol- and naphthalenesulfonates and alkali metal and alkaline earth metal salts of fatty acids and also alcohol alkoxylates such as alcohol ethoxylates Phenol alkoxylates such as tert-butylphenol ethoxylate or tert-pentylphenol ethoxylate, condensation products of fatty acids, alkyl phenols, ethylene oxide and propylene oxide, such as ethylene oxide-propylene Oxide block copolymers, polyethyleneimines and polysiloxanes.

Suitable dehyenes as further auxiliary additives are, for example, alkoxylated phenol-formaldehyde condensates.

Suitable foam inhibitors as additional co-additives are, for example, polyether-modified polysiloxanes.

Suitable antioxidants as further auxiliary additives are, for example, substituted phenols such as 2,6-di-tert-butylphenol and 2,6-di-tert-butyl-3-methylphenol, For example N, N'-di-sec-butyl-p-phenylenediamine.

Suitable metal deactivators as additional ancillary additives are, for example, salicylic acid derivatives, such as N, N'-disalicylidene-1,2-propanediamine.

Particularly suitable solvents for fuel additive packages are, for example, non-polar organic solvents, especially aromatic and aliphatic hydrocarbons such as toluene, xylene, " white spirit " ), Exxol (ExxonMobil) and Solvent Naphtha. Also useful herein are blends with non-polar organic solvents, particularly mentioned, in particular alcohols such as tert-butanol, isoamyl alcohol, 2-ethylhexanol and 2-propylheptanol.

When the stated auxiliary additives and / or solvents are additionally used in gasoline fuels, they are used in conventional amounts.

The present invention also relates to a process for the preparation of a reaction product which comprises (a) a hydrocarbyl-substituted dicarboxylic acid or anhydride thereof and (b) a reaction product of the invention prepared from a nitrogen compound of the formula (I) Lt; RTI ID = 0.0 > fuel additive < / RTI > Alternatively, the additive concentrates of the present invention may contain the additional auxiliary additives mentioned above.

The reaction product of the present invention is present in the additive concentrate of the present invention in an amount of from 1 to 99% by weight, more preferably from 15 to 95% by weight, especially from 30 to 90% by weight, based on the total weight of the concentrate in each case. The one or more fuel additives which are different from the abovementioned reaction products and have a surfactant activity are in each case preferably from 1 to 99% by weight, more preferably from 5 to 85% by weight, in particular from 10 to 70% by weight, based on the total weight of the concentrate, By weight of the additive concentrate of the present invention.

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

Example  1: Mixed performance

And maleic anhydride with number average molecular weight M _n of 1,000, the terminal vinylidene polyisobutenyl succinic anhydride and aminoguanidine obtained in the column en reaction (200 ℃) of the polyisobutene is 85% of the content of double bond X hydrogen carbonate The reaction product (" RP1 ") prepared from Nate was prepared similarly to Example 1 of US 2009/0282731 A1 using Solvesso ^TM 150 (manufacturer: ExxonMobil) as diluent.

Additive concentrates were prepared by simple mixing of the ingredients listed below using the reaction product so prepared (" RP1 "):

400 중량부의 본 발명의 반응 생성물 RP1 (Solvesso 150 중 50중량%)

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

390 중량부 (중합체 함량) 의 통상적인 계면활성제 첨가제 구성성분 (M_n = 1000 인 폴리이소부텐 기재의 폴리이소부텐 모노아민)

390 parts by weight (polymer content) of a conventional surfactant additive component (polyisobutene monoamine based on polyisobutene having M _n = 1000)

310 중량부의, 알콜-출발 폴리에테르 기재의 시판 캐리어 오일

310 parts by weight of an alcohol-derived polyether-based commercial carrier oil

270 중량부의, 희석제로서의 Solvent Naphtha

270 parts by weight of Solvent Naphtha as a diluent

470 중량부의, 추가 희석제로서의 2-프로필헵타놀

470 parts by weight of 2-propylheptanol as an additional diluent

4 중량부의 시판 디헤이저 구성성분 (알콕실레이트화 페놀-포름알데히드 축합물 기재)

4 parts by weight of commercially available diheter components (based on alkoxylated phenol-formaldehyde condensate)

The above-mentioned components were able to be mixed with each other without any problems to provide a clear liquid, and its consistency remained stable over several days.

For comparison, was prepared the additive concentrate "AC2", which the active ingredients of the reaction product RP1 of the present invention, the commercially available prior art lubricity improver ( "RP2"), i.e., polyisobutenyl succinic anhydride (M _n = 1000 the polyisobutenyl TEN substrate) and tetraethylenepentamine were replaced with the same amount of imide. After mixing together, RP2 was present as a cloudy liquid, and after a few days the precipitate separated.

Example  2: Emulsion  Performance

The additive concentrates AC1 (invention) and AC2 (comparative) were added to a typical Eurosuper base fuel, which is a commercially available EN 228 as a gasoline fuel, and the dosage of the lubricity improving agents RP1 (invention) and RP2 (comparative) In an amount so as to be 390 ppm. According to the ASTM D 1094 phase separation test, water was added to the system and the phase separation behavior was evaluated. After 5 minutes, AC1 provided two distinct, clearly separated phases (phase separation class 1 according to ASTM D 1094), but after 5 minutes AC2 provided an emulsion in the water phase and turbid fuel phase (according to ASTM D 1094 Phase separation class: 4).

Example  3: Fuel economy

The US Environmental Protection Agency Test Protocol, C.F.R., using gasoline fuels manufactured on the basis of commercially available base fuels with AC1 added at the dosage rates described in Example 2, In accordance with Title 40, Part 600, Subpart B, fuel economy was determined in a fleet test using three different vehicles. In each vehicle, at the doses described in Example 2, the fuel consumption was first determined using the fuel to which the additive was not added, and then the fuel consumption was determined using the same fuel containing the additive concentrate AC1. On average, for all cars used, the result was an average fuel savings of 1.3%.

Example  4: Intake valve clean performance

The intake valve deposit (" IVD ") was measured on a CEC F-20-98 in a Mercedes Benz M111 engine using two gasoline fuels with either AC1 (invention) or AC2 (comparative). The default for gasoline fuels without additive was 94 mg per valve, with a value of 2 mg per valve for gasoline fuels with AC1 (invention) and for gasoline fuels with AC2 (comparative) Giving a value of 6 mg.

Claims (9)

(a) a hydrocarbyl-substituted dicarboxylic acid or anhydride thereof having 8 to 250 carbon atoms in a hydrocarbyl radical, and (b) at least one reaction product prepared from a nitrogen compound of formula I or a salt of nitrogen compound I , And
An additive concentrate comprising at least one hydrophobic hydrocarbyl radical having a number average molecular weight (M _n ) of from 85 to 20,000 and at least one fuel additive having a surfactant action, the at least one affinity substance having at least one polar moiety ,
The additive concentrate being used as an additive in the fuel for reducing the fuel consumption used in the operation of the spark-ignition internal combustion engine or an additive used as an additive in the corresponding gasoline fuel for reducing the fuel consumption used in the operation of the natural ignition internal combustion engine Concentrate:

Wherein R ¹ and R ² are each independently hydrogen or a C ₁ - to C ₂₀ -hydrocarbyl radical. The additive concentrate of claim 1, wherein the hydrocarbyl-substituted dicarboxylic acid of component (a) is succinic acid or an anhydride thereof. The composition of claim 1, wherein the hydrocarbyl-substituent in component (a) is a linear or branched C ₈ - to C ₄₀ -alkyl or -alkenyl radical or a polyisobutenyl radical having 24 to 250 carbon atoms Additive concentrate. The additive concentrate according to claim 1, wherein the nitrogen compound of the component (b) is an unsubstituted aminoguanidine hydrogencarbonate. The additive concentrate according to claim 1, wherein the additive concentrate comprises at least one representative selected from (Da) to (Di) as a fuel additive having a surfactant action:
(Da) a mono- or polyamino group having up to 6 nitrogen atoms and at least one nitrogen atom having basic properties;
(Db) optionally together with a hydroxyl group, a nitro group;
(Dc) one or more nitrogen atoms together with a mono- or polyamino group having basic character, a hydroxyl group;
(Dd) a carboxyl group or an alkali metal or alkaline earth metal salt thereof;
(De) sulfonic acid group or an alkali metal or alkaline earth metal salt thereof;
Polyoxyethylene -C ₂ -C ₄ that by or poly amino group, or a carbamic terminated by a mate - - (Df) a hydroxyl group, a mono-with at least one nitrogen atom is a basic characteristic alkylene part;
(Dg) carboxyl ester group;
(Dh) a moiety derived from succinic anhydride and having at least one functional group selected from the group consisting of hydroxyl, amino, amido and imido;
(Di) moieties obtained by Mannich reaction of substituted phenols with aldehydes and mono- or polyamines. The additive concentrate of claim 1, further comprising at least one carrier oil as an additional fuel additive. The additive concentrate of claim 1, further comprising at least one corrosion inhibitor as an additional fuel additive. A fuel composition comprising a gasoline fuel and at least one additive concentrate according to any one of claims 1 to 7. delete