DE10239841A1 - Fuel and lubricant additive mixture, especially for reducing fuel injector coke deposits in diesel engines and reducing corrosive action of fuels, comprises (partially) neutralized fatty acid and detergent - Google Patents

Abstract

Additive mixture comprises a (partially) neutralized fatty acid and a detergent having a polar head group and a hydrophobic hydrocarbon group with a number-average molecular weight of 85-20000. Independent claims are also included for: (1) fuel composition comprising a hydrocarbon fuel, an additive mixture as above and optionally other additives; (2) lubricant composition comprising an additive mixture as above, a lubricant and optionally other additives; (3) additive concentrate comprising an additive mixture as above, a diluent and optionally other additives.

Description

The present invention relates to Additive mixtures containing, as component A, at least one additive with detergent action and at least one partially or completely neutralized as component B. Contain fatty acid. The invention further relates to the use of these additive mixtures for the additive of power and Lubricant compositions as well as fuel and lubricant compositions and concentrates containing this additive mixture.

Efforts to reduce harmful Emissions from the combustion of fuels, especially from Diesel fuels, more recently, have focused on reducing of sulfur dioxide emissions and the reduction of particle emissions, especially in diesel exhaust. To reduce sulfur dioxide emissions has been the sulfur content in Otto and Diesel fuels through "hydrotreatment", in which the fuel is treated with hydrogen, creating sulfur-containing components reduced to hydrogen sulfide, lowered in the refineries. An unwanted one A side effect of this desulfurization is the destruction of polyaromatic and polar Components in the fuel. This is especially true with diesel fuels negative effects as diesel engines are fuel lubricated and due to the reduction in the natural lubricity of the Fuel wear especially in the area of high-pressure injection pumps. The wear problem becomes even more significant when the fuels are mixed with "gas to liquid "fuels (GTL fuels) or with regenerative Fuels, such as bioethanol, are used because of these components no lubricity improving Possess properties.

To avoid wear sets in general, artificial lubricity improvers are added to the fuel, like fatty acid mixtures, their esters, amides or salts.

Furthermore, the fuels Detergents added, which fuel-related coke deposits in the area of the injection nozzles and holes, the u. a. in direct-injection high-performance systems such as "common rail "," pump nozzle " or "pump-line-nozzle" impair the optimal formation of a finely divided fuel spray and thereby increased Fuel consumption and emissions.

Additives with detergent action to improve the lubricity of fuels are for example in the WO-A-96/23855 described. The additive compositions described therein contain an ash-free burning N-acylated compound and a carboxylic acid or a carboxylic acid ester and are said to improve the lubricity.

The WO-A-01/38463 describes the use of fatty acid salts of alkoxylated oligoamines as lubricity improvers for mineral oil products.

A disadvantage of those in the prior art Additives or additive mixtures described is that to achieve a lubricity enhancer Effectively relatively high dosing rates are required.

Object of the present invention was therefore to provide additive mixtures that improve lubricity of fuel and lubricant compositions, even with lower ones Effectively improve dosing rates.

Surprisingly it was found that combinations of additives with detergent action and of partial or complete neutralized fatty acids a synergistic effect regarding improving lubricity and at the same time the detergent effect of fuel and lubricant compositions have.

Object of the present invention is accordingly an additive mixture containing

• i) as component A at least one additive with detergent action, which has at least one hydrophobic hydrocarbon radical with a number average molecular weight (M _n ) from 85 to 20,000 and at least one polar head group, and
• ii) at least one partially or completely neutralized as component B. Fatty acid.

The polar head group of the component A is preferably selected under

• (a) Mono- or polyamino groups with up to 6 nitrogen atoms, at least one nitrogen atom basic Has properties
• (b) nitro groups, optionally in combination with hydroxyl groups,
• (c) hydroxyl groups in combination with mono- or polyamino groups, where at least one nitrogen atom has basic properties,
• (d) polyoxy-C ₂ -C ₄ -alkylene groupings which are terminated by hydroxyl groups, mono- or polyamino groups, where at least one nitrogen atom has basic properties, or are terminated by carbamate groups,
• (e) carboxylic ester groups,
• (f) by Mannich reaction of substituted phenols with Aldehydes and mono- or polyamino groups and
• (g) from carboxylic anhydrides derived groups with hydroxy and / or amino and / or Amido and / or imido groups

Additives containing mono- or polyamino groups (a) are preferably polyalkene mono- or polyalkene-polyamines based on polypropene or on reactive (ie with predominantly terminal double bonds - mostly in the β- and γ-position) or conventional (ie with predominantly central double bonds) Polybutene or polyisobutene with M _N = 300 to 5,000. Such additives based on reactive polyisobutene, which from the polyisobutene, which can contain up to 20 wt .-% n-butene units, by hydroformylation and reductive amination with ammonia, monoamines or polyamines such as dimethylaminopropylamine, ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine can be produced in particular from the EP-A 244 616 known. If one starts from the production of the additives of polybutene or polyisobutene with predominantly central double bonds (mostly in the β and γ position), the production route by chlorination and subsequent amination or by oxidation of the double bond with air or ozone to form carbonyl or Carboxyl compound and subsequent amination under reductive (hydrogenating) conditions. The same amines as above for the reductive amination of the hydroformylated reactive polyisobutene can be used here for the amination. Corresponding additives based on polypropene are particularly in the WO-A 94/24231 to which reference is hereby made in full.

Further preferred additives containing monoamino groups (a) are the hydrogenation products of the reaction products of polyisobutenes with 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 to which reference is hereby made in full.

Further preferred additives containing monoamino groups (a) are the compounds obtainable from polyisobutene epoxides by reaction with amines and subsequent dehydration and reduction of the amino alcohols, as described in particular in DE-A 196 20 262 to which reference is hereby made in full.

Additives containing nitro groups, optionally in combination with hydroxyl groups, (b) are preferably reaction products of polyisobutenes having an 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 to which reference is hereby made in full. These reaction products are usually mixtures of pure nitropolyisobutanes (e.g., α, β-dinitropolyisobutane) and mixed hydroxynitropolyisobutanes (e.g. α-nitro-β-hydroxypolyisobutane).

Hydroxyl groups, optionally in combination with mono- or polyamino groups, (c) additives are, in particular, reaction products of polyisobutene epoxides, obtainable from polyisobutene preferably having predominantly terminal double bonds with M _N = 300 to 5,000, with ammonia, mono- or polyamines, as described in particular in EP-A 476 485 to which reference is hereby made in full.

Polyoxy-C ₂ - to C ₄ -alkylene (d) additives are preferably polyethers or polyetheramines which are obtainable by reaction of C ₂ - to C ₆₀ alkanols, C ₆ - to 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 ethylene oxide and / or propylene oxide and / or butylene oxide per hydroxyl group or amino group and, in the case of the polyether amines, by subsequent reductive Amination with ammonia, monoamines or polyamines are available. Such products are used in particular in EP-A 310 875 . EP-A 356 725 . EP-A 700 985 and US-A 4 877 416 to which reference is hereby made in full. In the case of polyethers, such products also have carrier oil properties. Typical examples of this are tridecanol or isotridecanol butoxylates, isononylphenol butoxylates and polyisobutenol butoxylates and propoxylates as well as the corresponding reaction products with ammonia.

Additives containing carboxylic acid ester groups (e) are preferably esters of mono-, di- or tricarboxylic acids with long-chain alkanols or polyols, in particular those with a minimum viscosity of 2 mm ² at 100 ° C., as described in particular in DE-A 38 38 918 to which reference is hereby made in full. Aliphatic or aromatic acids can be used as mono-, di- or tricarboxylic acids, and long-chain representatives with, for example, 6 to 24 carbon atoms are particularly suitable as ester alcohols or polyols. Typical representatives of the esters are adipates, phthalates, isophthalates, terephthalates and trimellitates of iso-octanol, iso-nonanol, iso-decanol and iso-tridecanol. Such products meet also carrier oil properties.

Additives containing groups (f) generated by conventional Mannich reaction of phenolic hydroxyl groups with aldehydes and mono- or polyamines are preferably reaction products of polyisobutene-substituted phenols with formaldehyde and primary mono- or polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine or dimethylaminopropylamine. Such "polyisobutene Mannich bases" are particularly in the EP-A 831 141 to which reference is hereby made in full.

Groupings derived from carboxylic anhydrides with hydroxy and / or Additives containing amino and / or amido and / or imido groups (g) are preferably corresponding derivatives of dicarboxylic acid anhydrides, particularly preferred of succinic anhydride.

It is particularly preferred in the polar grouping of component A by one of carboxylic anhydrides derived grouping with hydroxy and / or amino and / or amido and / or imido groups (g), in particular with amido and / or imido groups, d. H. around N-acyl groupings.

Component A is preferably one ashless burning acylated nitrogen compound (N-acyl compound) with a polar grouping (g).

Component A can, however, in addition to the preferred ashless burning acylated nitrogen compound (N-acyl compound) with a polar grouping (g) also one or contain more compounds that the combination of hydrophobic hydrocarbon residues with the polar groups mentioned above correspond to (a) to (f).

The hydrophobic hydrocarbon residue component A is preferably a homo- or Copolymer residue, the repeating units derived from monomers are selected are among propene, n-butene and isobutene and mixtures thereof.

The homo- or copolymer residue is particularly preferably a polyisobutene residue. In particular, the homo- or copolymer residue stands for a so-called "reactive" polyisobutene residue, which differs from the "low-reactive" polyisobutenes in the content of terminally arranged double bonds. Reactive polyisobutenes differ from low-reactive ones in that they have at least 50 mol%, preferably at least 60 mol% and particularly preferably at least 80 mol%, based on the total number of polyisobutene macromolecules, of terminally arranged double bonds. The terminally arranged double bonds can be both vinyl double bonds [-CH = C (CH ₃ ) ₂ ] and vinylidene double bonds [-CH ₂ -C (= CH ₂ ) -CH ₃ ]. Polyisobutenes which have uniform polymer skeletons are particularly preferred. Uniform polymer structures have, in particular, those polyisobutenes which are composed of at least 85% by weight, preferably at least 90% by weight and particularly preferably at least 95% by weight, of isobutene units. Such reactive polyisobutenes preferably have a number average molecular weight in the range from 200 to 20,000. Suitable for the production of fuel additives are in particular reactive polyisobutenes which have a number average molecular weight in the range from 300 to 3,000, particularly preferably 400 to 2,500 and very particularly preferably 500 to 1,500, for. B. a number average molecular weight of about 550, about 800, about 1 000 or about 2 300. Suitable for the production of lubricant additives are particularly reactive polyisobutenes which have a number average molecular weight in the range from 1000 to 15 000, particularly preferably 1300 to 12500 and very particularly preferably 2000 to 10,000, e.g. B, a number average molecular weight of about 1500, about 2000 or about 2300. The reactive polyisobutenes preferably also have a polydispersity of less than 3.0, in particular less than 1.9 and particularly preferably less than 1.7 or less 1.5 , Polydispersity is the quotient of the weight-average molecular weight M _W divided by the number-average molecular weight M _N.

Particularly suitable reactive polyisobutenes are e.g. B. the Glissopal brands from BASF AG, in particular Glissopal 1000 (M _N = 1,000) and Glissopal V 33 (M _N = 550) and Glissopal 2300 (M _N = 2,300) and their mixtures. Other number average molecular weights can be adjusted in a manner known in principle by mixing polyisobutenes of different number average molecular weights or by extractive enrichment of polyisobutenes of certain molecular weight ranges.

Component A is preferably an ash-free burning N-acyl compound which is derived from a polar group (g) substituted by a homo- or copolymer residue. Preferred polar groups (g) and preferred hydrophobic hydrocarbon radicals are those mentioned above. The ash-free burning acyl compound is particularly preferably an N-acyl compound derived from polyalkenylsuccinic anhydrides and especially from polyisobutenylsuccinic anhydrides. Of particular interest here are N-acyl compounds which can be obtained by reacting the anhydride with aliphatic polyamines, such as ethylene diamine, diethylene triamine, triethylene tetramine or tetraethylene pentamine. Such N-acyl compounds are particularly in US-A 4,849,572 to which reference is hereby made in full.

The polyisobutenyl succinic anhydride is, for example, by reaction of conventional or reactive polyisobutene with M _N = 300 to 5,000 with maleic anhydride by thermal means or via the chlorinated polyisobutene available.

The ash-free burning acylated nitrogen compound with polar grouping (g) can be obtained, for example, by reacting a carboxylic acid substituted with a hydrophobic hydrocarbon residue or a carboxylic acid derivative substituted with a hydrophobic hydrocarbon residue with an amine which has at least one NH or NH ₂ group. A carboxylic anhydride is preferably reacted.

As stated above, acts the carboxylic acid or with the carboxylic acid derivative particularly preferably a dicarboxylic acid or a dicarboxylic acid derivative, preferably a dicarboxylic anhydride, especially a succinic acid or a succinic acid derivative, preferably a succinic anhydride. Polyalkenylsuccinic acids or polyalkenylsuccinic acid derivatives are preferred, preferably polyalkenyl succinic anhydrides, especially polyisobutene succinic anhydride.

When converting dicarboxylic acids or Their derivatives, especially in the case of dicarboxylic acid anhydrides, with amines can be product mixtures arise, the dicarboxylic acid monoamides, dicarboxylic acid amides, Ammonium salts of dicarboxylic acid monoamides, Dicarbonsäuremonoamidmonoester, Amidines and dicarboxylic acid mono- and diimides. Both are suitable as component A. the individual acylation products mentioned and their mixtures. However, dicarboximides, in particular dicarboxylic monoimides, are preferred.

For the reaction with the carboxylic acid or the carboxylic acid derivative suitable amines are both monoamines, i. H. Amines with only one Amino function in the molecule, as well as polyamines, d. H. those with at least two amino functions in the molecule, suitable.

Suitable monoamines are both primary and secondary aliphatic amines with 3 to 10 carbon atoms, such as propylamine, Butylamine, pentylamine, hexylamine, octylamine, diethylamine, dipropylamine, Diisopropylamine, dibutylamine, cyclohexylamine, N-methylcyclohexylamine, N-ethylcyclohexylamine, piperidine, piperazine and morpholine. Suitable are also mixtures of monoamines, especially on an industrial scale accessible Amine mixtures, such as fatty amines, such as those found in Ullmanns Encyclopedia of Industrial Chemistry, 6th edition, 2000 electronic release, chapter "Amines, aliphatic", whereupon reference is hereby made in full.

However, polyamines are preferred used.

Suitable polyamines are, for example, those of the formula NR ¹ R ² R ³ , in which at least one of the radicals R ¹ , R ² or R ^{3 represents} a radical of the following formulas II, III or IV [(CR ⁴ R ⁵ ) _x -NR ⁶ -] _Y (CR ⁷ R ⁸ ) _z -NR ⁹ R ¹⁰ (II) [(CR ⁴ R ⁵ ) _x -O] _Y (CR ⁷ R ⁸ ) _z -NR ⁹ R ¹⁰ (III) or [(CR ⁴ R ⁵ ) _x -NR ⁶ ] _Y (CR ⁷ R ⁸ ) _z -OR ¹¹ (IV)
wherein
R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ¹¹ each independently represent H or C ₁ -C ₆ alkyl,
R ⁹ and R ¹⁰ each independently represent H, C ₁ -C ₆ alkyl or C ₁ -C ₆ hydroxyalkyl,
x and z each independently represent a number from 1 to 8 and
y represents a number from 0 to 8.

R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ¹¹ are preferably H or methyl.

Those radicals R ¹ , R ² and R ³ which do not represent a radical of the formula II, III or IV preferably stand for H, C ₁ -C ₆ alkyl, C ₁ -C ₆ hydroxyalkyl or for C ₃ - C ₈ cycloalkyl, where at least one of the radicals R ¹ , R ² and R ³ must stand for H.

In the above definition for the radicals R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ¹¹ , C ₁ -C ₆ alkyl is in particular methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl or hexyl.

C ₁ -C ₆ hydroxyalkyl stands in particular for the above-mentioned C ₁ -C ₆ alkyl radicals which are substituted by a hydroxy group.

C ₃ -C ₈ cycloalkyl stands in particular for cyclopropyl, cyclopentyl, methylcyclopentyl, cyclohexyl, methylcyclohexyl and cyclooctyl.

R ¹ and R ² are particularly preferably H and R ³ is a radical of the formula I in which R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ^{10 are} H.

Suitable polyamines are, for example, ethylenediamine, diethylenetriamine, triethylenetetramine, tetrae methylene pentamine, pentaethylene hexamine, propylene diamine, dipropylene triamine, tripropylene tetetramine, tetrapropylene pentamine, pentapropylene hexamine, butylene diamine, dibutylene triamine, tributylene tetramine, tetrabutylene pentamine, pentabutylene hexamine N, N-dimethylmethylene diamine, n, di-diamine, n, di-diamine, N, di-diamine, N, di-diamine, N, di-diamine, N, di-diamine, N, di-diamine, N, di-diamine, N, di-diamine, N, di-diamine -diamine, N, N-diethylethylene-l, 2-diamine, N, N-dipropylethylene-l, 2-diamine, N, N-dimethylpropylene-l, 3-diamine, N, N-diethylpropylene-l, 3-diamine , N, N-dipropylpropylene-l, 3-diamine, N, N-dimethylbutylene-l, 4-diamine, N, N-diethylbutylene-l, 4-diamine, N, N-dipropylbutylene-l, 4-diamine, N , N-dimethylpentylene-1,3-diamine, N, N-diethylpentylene-1,5-diamine, N, N-dipropylpentylene-1,5-diamine, N, N-dimethylhexylene-1,6-diamine, N, N -Diethylhexylene-1,6-diamine, N, N-dipropylhexylene-1,6-diamine, bis [(N, N-dimethylamino) methyl] amine, bis [(N, N-diethylamino) methyl] amine, bis [( N, N-dipropylamino) methyl] amine, bis [2- (N, N-dimethylamino) ethyl] amine, bis [2- (N, N-dipropylamino) ethyl] amine,
Bis [3- (N, N-dimethylamino) propyl] amine, bis [3- (N, N-diethylamino) propyl] amine, bis [3- (N, N-dipropylamino) propyl] amine, bis [4- ( N, N-dimethylamino) butyl] amine, bis [4- (N, N-diethylamino) butyl] amine,
Bis [4- (N, N-dipropylamino) butyl] amine, bis [5- (N, N-dimethylamino) pentyl] amine, bis [5- (N, N-diethylamino) pentyl] amine, bis [5- ( N, N-dipropylamino) pentyl] amine, bis [6- (N, N-dimethylamino) hexyl] amine,
Bis [6- (N, N-diethylamino) hexyl] amine, bis [6- (N, N-dipropylamino) hexyl] amine and the like. Such polyamides are described in Kirk-Othmer's "Encyclopedia of Chemical Technology", 2nd edition, volume 7, pages 22 to 37, Interscience Publishers, New York (1965, chapter "Ethylene amines".

Processes for the preparation of the above-mentioned N-acyl compounds are known to the person skilled in the art. A particularly suitable process for the preparation of polyalkenyl succinimides is in the German patent application DE-A-10123553.4 described, to which reference is hereby made in full. A polyalkenylsuccinic anhydride is first reacted with an alcohol or a phenol and then with an amine. Alternatively, the polyalkenyl succinic anhydride is reacted with the amine in the presence of an alcohol or a phenol.

For the production of polyalkenylsuccinimides suitable alcohols are preferably monohydric; are suitable, however also polyhydric alcohols.

Monohydric alcohols are preferred with 1 to 16 carbon atoms, such as methanol, ethanol, Propanol, isopropanol, butanol, sec-butanol, isobutanol, tert-butanol, 2-hydroxymethylfuran, amyl alcohol, isoamyl alcohol, vinyl carbinol, Cyclohexanol, n-hexanol, 6-caprylic alcohol, 2-ethylhexanol, N-decanol, lauryl alcohol, isoocytyl alcohol and their mixtures. Preferred alcohols are those with 6 to 16 Carbon atoms. 2-Ethylhexanol is particularly preferred.

Suitable phenols include phenol, Naphthol, (o, p) alkylphenols and salicylic acid.

Processes for the preparation of polyalkenyl-substituted carboxylic acids or their derivatives are known. This is how the German patent application describes it DE-A-10123553.4 the production of a polyolefin-substituted carboxylic acid or a derivative thereof by reacting a polyalkene with a monounsaturated acid or its derivative, the polyalkylene attaching to the double bond of the acid component in an en reaction.

Component B is preferably one partially or completely neutralized with amines Fatty acid.

worin
R für C₇-C₂₃-Alkyl oder ein- oder mehrfach ungesättigtes C₇-C₂₃-Alkenyl, die gegebenenfalls durch eine oder mehrere Hydroxygruppen substituiert sind, steht;
A für C₂-C₈-Alkylen steht;
Z für C₁-C₈-Alkylen, C₃-C₈-Cycloalkylen oder C₆-C₁₂-Arylen oder C₇-C₂₀-Arylalkylen steht;
m für eine Zahl von 0 bis 5 steht; und
x¹, x², X³ und x⁴ jeweils unabhängig für eine Zahl von 0 bis 24 stehen, wobei wenigstens ein x nicht für 0 steht,
und gegebenenfalls wenigstens eine weitere Fettsäure RCOOH, worin R wie vorstehend definiert ist.Component B particularly preferably comprises at least one fatty acid salt of the formula I.

wherein
R represents C ₇ -C ₂₃ alkyl or mono- or polyunsaturated C ₇ -C ₂₃ alkenyl, which are optionally substituted by one or more hydroxyl groups;
A represents C ₂ -C ₈ alkylene;
Z represents C ₁ -C ₈ alkylene, C ₃ -C ₈ cycloalkylene or C ₆ -C ₁₂ arylene or C ₇ -C ₂₀ arylalkylene;
m represents a number from 0 to 5; and
x ¹ , x ² , X ³ and x ⁴ each independently represent a number from 0 to 24, at least one x not representing 0,
and optionally at least one further fatty acid RCOOH, where R is as defined above.

Such fatty acid salts are for example in the WO 01/38463 to which reference is hereby made in full.

The longer-chain radical R which occurs in the carboxylate anion RCOO or in the fatty acid RCOOH denotes, for example, branched or preferably linear C ₇ - to C ₂₃ -, preferably C ₁₁ - to C ₂₁ -, especially C ₁₅ - to C ₁₉ -alkyl groups , which can also carry hydroxyl groups. Examples of basis The carboxylic acids are octanoic acid, 2-ethylhexanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid (lauric acid), tridecanoic acid, iso-tridecanoic acid, tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid) and eicosacid. The acids mentioned can be of natural or synthetic origin. Mixtures of the acids mentioned can also form the basis of the carboxylate anions.

However, the longer-chain radical R occurring in the carboxylate anion RCOO or in the fatty acid RCOOH preferably denotes mono- or polyunsaturated C ₇ to C ₂₃ radicals, in particular mono- or polyunsaturated C ₁₁ to C ₂₁ , especially C ₁₅ to C ₁₉ alkenyl groups, which can additionally carry hydroxyl groups. These unsaturated residues are preferably linear. In the case of polyunsaturated alkenyl groups, these preferably contain two or three double bonds. Examples of underlying carboxylic acids are elaidic acid, ricinoleic acid, linoleic acid and linolenic acid. Particularly good results are achieved with oleic acid. Mixtures of such unsaturated carboxylic acids with one another and with the above-mentioned saturated carboxylic acids can also form the basis of the carboxylate anions. Such mixtures are, for example, tall oil, tall oil fatty acid and rapeseed oil fatty acid. The unsaturated carboxylic acids and the mixtures mentioned are generally of natural origin.

The alkylene group A in compounds of formula I is preferably derived from corresponding alkylene oxides such as ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide and cis or trans-2,3-butylene oxide. However, it can also be used for 1,3-propylene, 1,4-butylene, 1,6-hexylene or 1,8-octylene. A can also be a mixture represent from different of the groupings mentioned. Especially be preferred for A ethylene, 1,2-propylene or 1,2-butylene groups.

The variable Z means in particular C ₁ - to C ₄ -alkylene groupings such as methylene, 1,2-propylene, 1,2-butylene, 1,3-butylene or 2,3-butylene, C ₅ - to C ₆ -cycloalkylene groupings such as 1 , 3-cyclopentylidene or 1,3- or 1,4-cyclohexylidene or C ₆ - to C ₈ -arylene or -arylalkylene groupings such as 1,3- or 1,4-phenylene, 2-methyl-l, 4-phenylene or 1,3- or 1,4-bismethylene phenylene.

However, the variable Z preferably means polymethylene groupings of the formula - (CH ₂ ) _n - with n = 2 to 8, in particular with n = 2 to 6, that is to say in particular 1,2-ethylene, 1,3-propylene, 1,4-butylene , 1,5-pentylene and 1,6-hexylene, but also 1,7-heptylene and 1,8-octylene.

If the variable m stands for 0, as a rule, depending on the sum (F) of all variables x ¹ , x ² and x ³ , mixtures of mono-, di- and / or trialkanolamines or pure trialkanolamines are the fatty acid salts used according to the invention based on cationic component. Examples of such alkanolamines are monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine and the associated mixtures. In this group, the oleic acid salt of triethanolamine is [(x ¹ + x ² + x ³ ) = 3; A = ethylene) of particular interest.

However, the variable m is preferably for the Number 1 or 2. For m = 1 lie completely and / or partially alkoxylated alkylenediamines such as 1,2-ethylenediamine, 1,3-propylenediamine or 1,4-butylenediamine. For m = 2 are usually complete and / or partially alkoxylated dialkylenetriamines such as di- (1,2-ethylene) -triamine, Di- (1,3-propylene) -triamine or di- (1,4-butylene) -triamine. In this group are the bis oleic acid salts of N, N, N ', N'-tetrakis (2'-hydroxyethyl) -1,2-ethylenediamine (Σx = 4) and N, N, N ', N'-tetrakis (2'-hydroxypropyl) -1,2-ethylenediamine (Σx = 4) as well the tris oleic acid salts of reacted with 4 to 5 moles of ethylene oxide or 1,2-propylene oxide Di- (1,2-ethylene) -triamine of particular interest.

However, it is also possible to have higher homologues of the alkylenediamines and dialkylenetriamines mentioned, for example Triethylene tetramine (m = 3), tetraethylene pentamine (m = 4) or pentaethylene hexamine (m = 5) as an amine component for those used according to the invention fatty acid salts taken as a basis.

In a preferred embodiment, the number x, ie the sum of x ¹ , x ² , x ³ and x ⁴ (Σx), of the alkylene oxide units (OA) introduced per amine molecule is the number of NH bonds in the underlying amine dependent and can correspond to the number of NH bonds (Σx = m + 3). However, more or fewer OA units can also be installed. With over-stoichiometric incorporation, triple alkoxylation per NH bond [300% of (m + 3)] is a preferred upper limit with regard to the properties of the resulting fatty acid salts. In the case of substoichiometric incorporation, a statistical average 50% alkoxylation [50% of (m + 3)] is a corresponding preferred lower limit; here mostly mixtures of species with different degrees of alkoxylation are present.

In a particularly preferred embodiment has the sum (Σ) of all variables x a value from 75% to 125% of (m + 3).

The fatty acid salts of the general formula I usually can easily by alkoxylation of the underlying amines according to the usual Methods and subsequent neutralization with the fatty acids of the formula Make RCOOH.

When using C ₂ to C ₄ alkylene oxides, the alkoxylation is expediently used for introducing the first alkylene oxide unit into the NH bond in the presence of small amounts of water (usually 0.5 to 5% by weight, based on the amount on amine used) without catalyst at temperatures from 80 to 140 ° C and for the introduction of further alkylene oxide units with the exclusion of water in the presence of basic catalysts such as alkali metal hydroxides, e.g. As sodium or potassium hydroxide, carried out at temperatures from 100 to 150 ° C.

The neutralization takes place in the Usually by heating the alkoxylated amine thus obtained with the appropriate stoichiometric or slightly sub-stoichiometric Quantity (i.e. 90 to 100%, especially 95 to 100% of theory) of fatty acid at temperatures from 30 to 100 ° C, in particular 40 to 80 ° C, for one Duration of 15 minutes to 10 hours, especially 30 minutes up to 5 hours. The neutralization reaction should be carried out that no Carbonsäureester Shares arise in the product. In many cases, both the alkoxylated Amine as well as the fatty acid as liquids are used, which is the implementation of the corresponding fatty acid salt designed particularly simple. The order of joining of alkoxylated amine and fatty acid is not critical, i.e. one can submit both the alkoxylated amine and the fatty acid admit as well the fatty acid submit and add the alkoxylated amine.

In principle, however, it is also possible that alkoxylated amine and the fatty acid as individual components, additive concentrates or mineral oil products add and let the salt formation take place there.

The molar ratio of component A to component B in the additive mixture preferably 1:10 to 10: 1, particularly preferably 1: 6 to 6: 1 and especially 1: 4 to 4: 1.

Another subject of the present The invention is the use of the additive mixture described above for the additives of fuel and lubricant compositions.

Suitable fuels are petrol and middle distillates, such as diesel fuel, heating oil or kerosene, with diesel fuel is preferred.

It deals with diesel fuels for example, oil refinements, the usual have a boiling range of 100 to 400 ° C. These are mostly distillates with a 95% point up to 360 ° C or even above out. You can but also so-called "Ultra Low Sulfur Diesel" or "City Diesel" be characterized by a 95% point of, for example, maximum 345 ° C and a maximum sulfur content of 0.005% by weight or a 95% point of, for example, 285 ° C and a sulfur content of at most 0.001% by weight. In addition to through Refining available Diesel fuels are those produced by coal gasification or gas liquefaction ("gas to liquid (GTL) fuels) are available. Suitable are also mixtures of the aforementioned diesel fuels with regenerative fuels such as biodiesel or bioethanol.

The additive mixture according to the invention is particularly preferred for the additivation of diesel fuels with low sulfur content, d. H. with a sulfur content of less than 0.05% by weight, preferably less than 0.02% by weight, in particular less than 0.005% by weight and especially less than 0.001 wt% sulfur.

The additive mixture according to the invention is particularly preferred to reduce combustion-related coke deposits in the area the injection system of diesel engines with and without direct fuel injection, preferably of diesel engines with direct fuel injection, used.

The additive mixture according to the invention is preferred also to reduce the corrosive effect of a fuel used.

Another subject of the present Invention is a fuel composition containing a bulk of a hydrocarbon fuel and an effective amount of the additive mixture according to the invention and optionally at least one further additive. Regarding the preferred fuels, reference is made to the above statements.

The additive mixture according to the invention is in the Fuel preferably in an amount of 1 to 1000 ppm by weight, particularly preferably from 10 to 500 ppm by weight and in particular from 50 to 200 ppm by weight, based on the total amount of additive Fuel, before.

Another subject of the present Invention is a lubricant composition containing one effective amount of an additive mixture according to the invention, a Lubricant and optionally at least one other additive.

The invention also relates to an additive concentrate containing the additive mixture according to the invention, at least one solution or diluent and optionally at least one further additive.

Suitable diluents are, for example in oil processing resulting fractions, such as kerosene, naphtha or brightstock. Suitable are beyond aromatic and aliphatic hydrocarbons and alkoxyalkanols. Preferred for middle distillates, especially for diesel fuels diluent used are naphtha, kerosene, diesel fuels, aromatic hydrocarbons, such as Solvent Naphtha heavy, Solvesso® or Shellsol® and mixtures this solution and diluents.

The additive mixture according to the invention is in the concentrates preferably in an amount of 0.1 to 80% by weight, particularly preferably from 1 to 70% by weight and in particular from 20 up to 60% by weight, based on the total weight of the concentrate.

Suitable additives which can be contained in the fuel or concentrate according to the invention in addition to the additive mixtures according to the invention, in particular for diesel fuels, include detergents s, corrosion inhibitors, dehazers, demulsifiers, anti-foaming agents ("Antifoam"), antioxidants, metal deactivators, multifunctional stabilizers, cetane improvers, combustion improvers, dyes, markers, solubilizers, antistatic agents, other customary lubricity improvers, the cold properties improving additives (such as "MD improvers") , Paraffin dispersants ("WASA") and the combination of the latter two additives ("WAFI").

The usual lubricity improvers include, for example, carboxylic acids, especially fatty acids, their esters, especially with polyols, mixtures of these acids and esters, ash-free N-acyl compounds, such as polyalkenylsuccinic acid amides, mixtures of the abovementioned acids and / or esters with these N-acyl compounds, for example in the WO 96/23855 bis (hydroxyalkyl) fatty amines or hydroxyacetamides.

Suitable flow improvers include, for example, oil-soluble, polar nitrogen compounds, such as ammonium salts and / or amides of mono- or polycarboxylic acids or sulfonic acids and their mixtures with copolymers of ethylene and unsaturated carboxylic acid esters and optionally comb polymers, as described in US Pat WO 95/33805 are described.

The synergistically effective combination of components A and B in the additive mixture according to the invention leads to a significant improvement in the lubricity of additives Fuels and a significant reduction in the corrosion effect of fuels and nozzle coking compared to prior art additives.

The following examples illustrate the invention, but without restricting it.

The tests described below were carried out with the following fuels:
- Diesel fuel according to DIN EN 590 with a sulfur content of 48 ppm: Diesel I
- Diesel fuel according to DIN EN 590 with a sulfur content of 15 ppm (ULSD): Diesel II
- Diesel fuel according to DIN EN 590 with a sulfur content of 4 ppm (MK1): Diesel III
- Blend from 5% biodiesel in 95% Diesel I: Blend I
- Blend from 8% ethanol in 91% Diesel I (1% stabilizer package): Blend II
- Gas to liquid fuel: GTL
- Blend from 20% GTL in 80% Diesel I: Blend III

1. Synthesis of the components of the additive mixture

1.1 Synthesis of a polyisobutene succinimide (Detergent I)

In a 1 liter three-necked flask 630 g polyisobutene succinic anhydride (Molecular weight of polyisobutene: 1000) (saponification number 95) mixed with 0.2 to 2 mol of 2-ethylhexanol and within 20 minutes to 80 ° C up to 160 ° C heated. 105 g (0.55 mol) of tetraethylene pentamine were added. The mixture was left at 90 ° to 150 ° C. to 180 ° C. Stir for 180 minutes. The alcohol subsequently became removed in vacuum.

1.2 Synthesis of a lubricity improver (Lubricity I)

58.4 g (0.2 mol) of N, N, N ', N'-tetrakis (2'-hydroxypropyl) -1,2-ethylenediamine (obtained from 1,2-ethylenediamine and 4 mol propylene oxide in the presence of 3% by weight of water based on the amount of the amine used) were at 60-80 ° C heated and 110.4 (0.4 mol) of oleic acid were added with stirring within two hours. The pH value did not drop below 7. This was followed by a further two hours touched. The product obtained had one N titer of 2.39 mmol / g.

2. Engine tests

In addition to the combinations according to the invention Detergens I and Lubricity I became commercially available detergents based on of polyisobutene succinimide called Detergent II and standard lubricity improvers acid-based with the designation Lubricity II or based on ester with the designation Lubricity III used and their performance with the combinations according to the invention from Detergent I and Lubricity I compared.

2.1 Nozzle coking in the Peugeot XUD 9 according to CEC-F23-A01

The flow reduction with 0.1 mm needle stroke ("flow restriction") of the above-mentioned unadditized basic fuels and fuel blends was carried out in a Peugeot XUD 9 test engine as part of the current 10 h test percentages determined according to CEC-F23-A01 and compared with the nozzle coking observed when using the additive fuels and fuel blends.

The additive fuels or Blends were made by adding the above Combinations of 80 mg / kg each Detergent I-II and 120 mg / kg of the lubricity improver Lubricity I-III received.

The following results were obtained:

 The combinations according to the invention from Detergens I and Lubricity I showed compared to those alone test results obtained with Detergent I improved by 6-9% Performance. With other combinations there were no significant changes observed.

2.2 Corrosion tests according to ASTM D 665 A / B

The corrosion behavior of the above Unadditized base fuels and fuel blends have been tested in steel fingers according to ASTM D 665 A in distilled water and ASTM D 665 B in synthetic Salt water checked and with that when using the additive fuels and fuel blends observed corrosion behavior compared.

The additive fuels or Blends were made by adding the above Combinations of 80 mg / kg each Detergent I-II and 120 mg / kg of the lubricity improver Lubricity I-III received.

The test results were evaluated in accordance with NACE TM-01-72
A ≅100 stainless
B ++ ≅ 0.1% or less of the total area rusted
B + ≅ 0.1 - 5% of the total area rusted
B ≅ 5 - 25% of the total area rusted
C ≅ 25 - 50% of the total area rusted
D ≅ 50 - 75% of the total area rusted
E ≅ 75 - 100% of the total area rusted

The following results were obtained:

The combinations of detergent I and lubricity I according to the invention showed in comparison to the test results obtained with Detergent I alone once again significantly improved performance. Minor improvements were observed with the other combinations tested.

2.3 Determination of lubricity according to HFRR

The lubricity of the unadditized Base fuels and fuel blends were tested in HFRR tests in accordance with ASTM D 6079-99 checked and compared to that when using the additive fuels and fuel blends observed lubricity.

The additive fuels or Blends were made by adding the above Combinations of 80 mg / kg each Detergent I and 120 mg / kg lubricity improver Lubricity I received. Each is shown in the table below determined WSl.4 [μm], which represents the size of the wear scar.

The following results were obtained:

The combinations of detergent according to the invention I and Lubricity I showed compared to those with Lubricity alone I obtained test results that improved performance by 5-25 μm.

Claims (20)

Additive mixture containing i) as component A at least one additive with detergent action, which has at least one hydrophobic hydrocarbon radical with a number average molecular weight (M _n ) from 85 to 20,000 and at least one polar head group, ii) as component B at least one partially or completely neutralized fatty acid , Additive mixture according to claim 1, wherein the polar head group of component A is selected from (a) mono- or polyamino groups having up to 6 nitrogen atoms, at least one nitrogen atom having basic properties, (b) nitro groups, optionally in combination with hydroxyl groups, (c) Hydroxyl groups in combination with mono- or polyamino groups, where at least one nitrogen atom has basic properties, (d) polyoxy-C ₂ -C ₄ -alkylene groups, through hydroxyl groups, mono- or polyamino groups, where at least one nitrogen atom has basic properties, or through carbamate groups are terminated, (e) carboxylic acid ester groups, (f) groups generated by Mannich reaction of substituted phenols with aldehydes and mono- or polyamino and (g) groups derived from carboxylic anhydrides with hydroxyl and / or amino and / or amido and / or imido groups. Additive mixture according to claim 2, wherein component A is an ash-free is burning acylated nitrogen compound. Additive mixture according to one of the preceding claims, wherein the hydrocarbon residue is a homo- or copolymer residue, the Repeat units are derived from monomers that are selected among propene, n-butene and isobutene and mixtures thereof. Additive mixture according to one of the preceding claims, wherein Component A by the reaction of a carboxylic acid or a carboxylic acid derivative with an amine which has at least one NH group. Additive mixture according to claim 5, wherein it is the carboxylic acid or in the carboxylic acid derivative a dicarboxylic acid or a dicarboxylic acid derivative is. Additive mixture according to claim 6, wherein it is the carboxylic acid or in the carboxylic acid derivative a polyalkenyl succinic acid or a polyalkenylsuccinic acid derivative. Additive mixture according to claim 7, wherein component A at least a polyalkenyl succinimide. Additive mixture according to one of the preceding claims, wherein the hydrocarbon residue derived from reactive polyisobutene is. Additive mixture according to one of the preceding claims, wherein in component B the fatty acid is neutralized with at least one amine. Additive mixture according to claim 10, wherein component B at least one fatty acid salt of formula I.

wherein R is C ₇ -C ₂₃ alkyl or mono- or polyunsaturated C ₇ -C ₂₃ alkenyl, which are optionally substituted by one or more hydroxyl groups; A represents C ₂ -C ₈ alkylene; Z represents C ₁ -C ₈ alkylene, C ₃ -C ₈ cycloalkylene or C ₆ -C ₁₂ arylene or C ₇ -C ₂₀ arylalkylene; m represents a number from 0 to 5; and x ¹ , x ² , x ³ and x ⁴ each independently represent a number from 0 to 24, at least one x not representing 0, and optionally comprising at least one further fatty acid RCOOH, in which R is as defined above. Additive mixture according to one of the preceding claims, wherein Component A and component B are present in a molar ratio of 1:10 to 10: 1. Use of the additive mixture as in one of the preceding Expectations is defined for the additive of fuel and lubricant compositions. Use according to claim 13 to reduce combustion-related Coke deposits in the area of the injection system of diesel engines with and without direct fuel injection. Use according to claim 13 to reduce the corrosive Effect of a fuel. Fuel composition containing a major amount of one Hydrocarbon fuel and an effective amount of an additive mixture as defined in one of the claims 1 to 12 and optionally at least one further additive. A fuel composition according to claim 16 or use according to one of the claims 13 to 15, the fuel being diesel fuel, heating oil or kerosene. Fuel composition or use according to claim 17, the diesel fuel being refined, coal gasified or gas liquefaction available is, or is a mixture of such fuels and optionally is mixed with regenerative fuels. Lubricant composition containing an effective amount an additive mixture as defined in one of the claims 1 to 12 and a lubricant and optionally at least one another additive. Additive concentrate, containing an additive mixture as defined in one of the claims 1 to 12 and at least one diluent and optionally at least one further additive.