EP1537192A1

EP1537192A1 - Additive mixture for fuel and lubricants

Info

Publication number: EP1537192A1
Application number: EP03794964A
Authority: EP
Inventors: Peter Schwab; Stephan Hüffer; Mirjam Herrlich-Loos; Siegbert Brand
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2002-08-29
Filing date: 2003-08-28
Publication date: 2005-06-08
Also published as: KR20050048619A; US20050268539A1; AU2003264123A1; CN1678719A; NO20050660L; DE10239841A1; WO2004024851A1; CA2497123A1

Abstract

The invention relates to additive mixtures containing at least one additive as component A with detergent effect and at least one partly- or completely-neutralised fatty acid as component B. The invention further relates to the use of said additive mixture for adding to fuel and lubricant compositions and fuel and lubricant compositions and concentrates containing said additive mixture.

Description

Additive mixture for fuels and lubricants

description

The present invention relates to additive mixtures which contain as component A at least one additive with detergent action and as component B at least one partially or completely neutralized fatty acid. Furthermore, the invention relates to the use of these additive mixtures for the additivation of fuel and lubricant compositions as well as fuel and lubricant compositions and concentrates which contain this additive mixture.

Efforts to reduce harmful emissions from the combustion of fuels, particularly diesel fuels, have recently focused on reducing sulfur dioxide emissions and reducing particulate emissions, particularly in diesel exhaust. In order to reduce sulfur dioxide emissions, the sulfur content in petrol and diesel fuels has been reduced in the refineries by "hydrotreatants", in which the fuel is treated with hydrogen, whereby sulfur-containing components are reduced to hydrogen sulfide. An undesirable side effect of this desulfurization is the destruction of polyaromatic and polar components in the fuel. This has negative effects, particularly in the case of diesel fuels, since diesel engines are fuel-lubricated and, due to the reduction in the natural lubricity of the fuel, wear increased, particularly in the area of high-pressure injection pumps. The wear problem becomes even more significant when the fuels are used in a mixture with "gas to liquid" fuels (GTL fuels) or with regenerative fuels such as bioethanol, since these components have no properties that improve lubricity.

In order to avoid wear, artificial lubricity improvers, such as fatty acid mixtures, their esters, amides or salts, are generally added to the fuel.

Detergents are also added to the fuels, which contain fuel-related coke deposits in the area of the injection nozzles and holes, which, among other things, are used in direct-injection high-performance systems. systems such as "co mon rail", "pump nozzle" or "pump line nozzle" should impair the optimal formation of a finely divided fuel mist and thereby lead to increased fuel consumption and emissions.

Additives with detergent action to improve the lubricity of fuels are described, for example, in WO-A-96/23855. 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.

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

A disadvantage of the additives or additive mixtures described in the prior art is that relatively high metering rates are required to achieve a lubricity-improving effect.

The object of the present invention was therefore to provide additive mixtures which effectively improve the lubricity of fuel and lubricant compositions, even at lower metering rates.

Surprisingly, it was found that combinations of additives with detergent action and of partially or completely neutralized fatty acids have a synergistic effect with regard to improving the lubricity and at the same time the detergent action of fuel and lubricant compositions.

The present invention accordingly relates to an additive mixture comprising

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 ) of 85 to 20,000 and at least one polar head group, and

ii) as component B at least one partially or completely neutralized fatty acid. The polar head group of component A is preferably selected from

5 (a) mono- or polyamino groups with 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,

15

(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,

20

(e) carboxylic ester groups,

(f) Groups generated by Mannich reaction of substituted phenols with aldehydes and mono- or polyamines and

25

(g) groups derived from carboxylic acid anhydrides with hydroxy and / or amino and / or amido and / or imido groups

'^"" Mono- or polyamino groups (a) containing additives are pre - ^■ -

30 preferably polyalkene mono- or polyalkene polyamines based on polypropene or 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 ad

35 -propellant additives on the basis of reactive polyisobutene which s from the polyisobutene containing up to 20 wt .-% of n-butene units can contain, by hydroformylation and reductive amination with ammonia, monoamine ^'or polyamines such as Dirnethylaminopropylamin, ethylenediamine, diethylenetriamine, triethylenetetramine or tetrahedral

40 ethylene pentamine can be produced are known in particular from EP-A 244 616. If one starts out from the production of additives from polybutene or polyisobutene with predominantly central double bonds (mostly in the β and γ position), the production route by chlorination and subsequent amine

45 tion or by oxidation of the double bond with air or ozone to the carbonyl or carboxyl compound and subsequent amination under reductive (hydrogenating) conditions. To amine tion, the same amines as above can be used for the reductive amination of the hydroformylated reactive polyisobutene. Corresponding additives based on polypropene are described in particular in 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 from polyisobutenes with an average degree of polymerization P = 5 to 100 with nitrogen oxides or mixtures of nitrogen oxides and oxygen, as are described in particular in WO-A 97/03946 which is hereby incorporated by reference in its entirety.

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. 0

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 5 and oxygen, as described in particular in WO-A 96/03367 and

WO-A 96/03479 are described, to which reference is hereby made in full. These reaction products are generally mixtures of pure nitropolyisobutenes (for example α, β-dinitro ^"" polyisobutene) and mixed hydroxynitropolyisobutenes (for example α-nitro-β-hydroxypolyisobutene).

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, is hereby incorporated in its entirety by reference. ^"

Additives containing polyoxy-C ₂ - to C ₄ -alkylene groupings (d) are preferably polyethers or polyetheramines which are obtained by reacting C ₂ - to Cβo-alkanols, C ₆ - to C ₃ o-alkanediols, mono- or di-C ₂ -C ₃₀ -alkylamines, -C-C ₃ o-alkylcyclohexanols or C- _L -Cso-alkylphenols with 1 to 30 mol of ethylene oxide and / or propylene oxide and / or butylene oxide per hydroxyl group or amino group and, in the case of the polyetheramines, by subsequent reductive _{A-discrimination} with ammonia, monoamines or polyamines available are. Products of this kind are described 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 are 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 also have carrier oil properties.

Additives containing groups (f) produced 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, triethylene tetramine, tetraethylene pentamine or dimethyl - - aminopropylamine. Such "polyisobutene Mannich bases" are described in particular in EP-A 831 141, to which reference is hereby made in full.

Groups derived from carboxylic anhydrides and containing hydroxyl and / or amino and / or amido and / or imido groups (g) are preferably corresponding derivatives of dicarboxylic anhydrides, particularly preferably succinic anhydride. ^* It goes without saying that the term "groups derived from car-" bonsäύreanhydriden ... "does not necessarily mean that the carboxylic acid anhydrides must actually be used. Of course, such groups can also by the implementation of other carboxylic acid derivatives, the possess the required activity, for example carboxylic acid halides, or also by the reaction of the carboxylic acid itself, if suitable activation measures are taken become. However, carboxylic anhydrides are particularly suitable derivatives for the conversion into the groups mentioned.

The polar group 5 of component A is particularly preferably a group derived from carboxylic anhydrides with hydroxyl and / or amino and / or amido and / or imido groups (g), in particular with amido and / or imido groups, i , H. around N-acyl groupings.

Component A is preferably an ash-free burning acylated nitrogen compound (N-acyl compound) with a polar grouping (g).

In addition to the preferred ash-free burning acylated nitrogen compound (N-acyl compound) with a polar grouping (g), component A can also contain one or more further compounds which are suitable for combining hydrophobic hydrocarbon radicals with the above-mentioned polar groupings (a ) to (f). 20

The hydrophobic hydrocarbon residue of component A is preferably a homo- or copolymer residue, the repeating units of which are derived from monomers selected from 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 residue which differs from so-called "reactive" poly-

30 isobutenes derived, which differ from the "low-reactive" polyisobutenes in the content of terminally arranged double bonds. Reactive polyisobutenes differ from low-reactivity in that they have at least 50 mol%, preferably at least 60 mol% and particularly preferably at least

35 80 mol%, based on the total number of polyisobutene macromolecules, have 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 ]. Especially preferred are

40 lyisobutenes which have uniform polymer skeletons. 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 preferably

45 polyisobutenes have a number average molecular weight in the range from 200 to 20,000. Reactive polyisobutenes are particularly suitable for the production of fuel additives. have an 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, e.g. Example a number average molecular weight of about 550, about 800, about 1000 or about 2 300 .. Suitable for _{manufacturing,} 5 position of lubricant additives are particularly reactive polyisobutenes which have a number average molecular weight in the range 1000 to 15,000, particularly preferably 1,300 to 12500 and most preferably 2000 to 10,000, e.g. B. a number average molecular weight of about 1500, about 2000 or about

10 2300. In addition, the reactive polyisobutenes preferably have a polydispersity of less than 3.0, in particular less than 1.9 and particularly preferably less than 1.7 or less than 1.5. Polydispersity is the quotient of the weight-average molecular weight M _w divided by the number-average

15 lower molecular weight M ^.

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. 5

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, 5 which can be obtained by reacting the anhydride with aliphatic polyamines, such as ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylene pentamine. Such N-acyl compounds are described in particular in US Pat. No. 4,849,572, to which reference is hereby made in full. 0

The polyisobutenyl succinic anhydride can be obtained, for example, by reacting conventional or reactive polyisobutene with M _N = 300 to 5000 with maleic anhydride by thermal means or via the chlorinated polyisobutene. Other polyalkenyl 5-succinic anhydrides can be prepared analogously. 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, the carboxylic acid or the carboxylic acid derivative is particularly preferably a dicarboxylic acid or a dicarboxylic acid derivative, preferably a dicarboxylic acid anhydride, in particular a succinic acid or a succinic acid derivative, preferably a succinic anhydride. Polyalkenylsuccinic acids or polyalkenylsuccinic acid derivatives are preferred, preferably polyalkenylsuccinic acid anhydrides, especially polyisobutenylsuccinic acid anhydride.

The reaction of dicarboxylic acids or their derivatives, in particular dicarboxylic acid anhydrides, with amines can result in product mixtures which comprise dicarboxylic acid monoamides, dicarboxylic acid diamides, ammonium salts of dicarboxylic acid monoamides, dicarboxylic acid monoamide monoesters, amidines and dicarboxylic acid monoamide. Both component acylation products and mixtures thereof are suitable as component A.

However, dicarboximides, in particular dicarboxylic monoimides, are preferred.

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

Suitable monoamines are both primary and secondary aliphatic amines with 3 to 10 carbon atoms, such as propylamine, butylamine, pentylamine, hexylain, octylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, cyclohexylamine, N-methylcyclohexylamine, N- Ethylcyclohexylamine, piperidine, piperazine and morpholine. Mixtures of monoamines are also suitable, in particular amine mixtures which are commercially available, such as fatty amines, as are described, for example, in Ullmanns Encyclopedia of Industrial Chemistry, 6th edition, 2000 electronic release, chapter "Amines, aliphatic", which is hereby incorporated in full reference is made.

However, polyamines are preferably 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

5 -H-CR R ⁵ ) _x -NR ⁶ -9-γ (CR ⁷ R ⁸ ) _z -NR ^Q Rl ° (II)

- CR ⁴ R ⁵ ) _x -0-hr (CR ⁷ R ⁸ ) _z -NR ⁹ R ¹⁰ (III) or

-H-CR ⁴ R ⁵ ) _X -NR ⁶ Y (CR ⁷ R ⁸ ) _Z -OR ¹¹ (i)

10 where

R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ¹¹ each independently represent H or Ci-Cg-alkyl, 15

R ⁹ and R ¹⁰ each independently represent H, Ci-C _ß- alkyl or Ci-Cg-hydroxyalkyl,

x and z each independently represent a number from 1 to 8, preferably 20 for 2 to 4 and in particular for 2 and

y represents a number from 0 to 8.

R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ¹¹ each independently represent preferably 25 for 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 are preferably H, Ci-Cβ-alkyl, C ₁ -C ₆ -hydroxyalkyl or 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, pen- 35 tyl or hexyl.

Ci-Cg-hydroxyalkyl stands in particular for the above-mentioned Ci-C _δ -alkyl radicals which are substituted by a hydroxy ^" group. ^J

R ¹ and R ² are particularly preferably H and R ³ is a radical of the formula II in which R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ^{10 are} H.

Suitable polyamines are, for example, ethylenediamine, diethylene-45 triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, propylene diamine, dipropylenetriamine, tripropylenetetramine, tetrapropylene pentamine, pentapropylene hexamine, butylene diamine, dibu tylene triamine, tributylene tetramine, tetrabutylene pentamine, pentabutylene hexamine N, N-dimethylmethylene diamine, N, -diethylmethylene diamine,, N-dipropylmethylene diamine, N, N-dimethylethylene-1,2-diamine, N, N-diethylethylene-1, 2- diamine, N, N-dipropylethylene-1,2-diamine, N, N-dimethylpropylene-1,3-diamine, N, N-diethylpropylene-1,3-diamine, N, N-dipropylpropylene-1,3-diamine ,, N-dimethylbutylene-1,4-diamine, N, -diethylbutylene-1,4-diamine, N, N-diprop-1-butylene-1,4-diamine, N, N-dimethylpentylene-1,5-diamine, N, N-diethylpentylene-1,5-diamine, N, -dipropylpentylene-1,5-diamine, N, N-dimethylhexylene-1,6-diamine, N, N-diethylhexylene-1,6-diamine, N, -dipropylhex -1,6-diamine, bis [2- (N, N-dimethylamino) ethyl] amine, bis [2- (N, N-diethylamino) ethyl] amine, bis [2- (N, N-dipropylamino) ethylamine, bis [3- (N, N-dimethylamino) propyl] amine, bis [3- (N, N-diethylamino) propyl] amine, bis [3- (, N-dipropylamino) propyl] amine, bis [ 4- (N, -dimethylamino) butyl] amine, bis [4- (N, -diethylamino) butyl] amine,

Bis [4- (N, N-dipropylamino) butyl] amine, bis [5- (N, N-dimethylamino) pentyl] amine, bis [5- (N, N-diethylamine) pentyl] amine, bis [ 5- (N, N-dipropylamino) pentyl] amine, bis [6- (N, N-dimethylamino) hexyl] amine, bis [6- (, N-diethylamino) hexyl] amine, bis [6- (N, N -Dipropylamino) hexyl] amine and the like. Such polyamines 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 polyalkenylsuccinimides is described in German patent application DE-A-10123553.4, to which reference is hereby made in full. A polyalkenylsuccinic anhydride is reacted first 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.

Alcohols suitable for the preparation of polyalkenylsuccinimides are preferably monohydric; however, polyhydric alcohols are also suitable.

Monohydric alcohols with 1 to 16 carbon atoms are preferably used, 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, isooctyl alcohol and mixtures thereof. 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. For example, German patent application DE-A-10123553.4 describes the preparation of a polyolefin-substituted carboxylic acid or a derivative thereof by reacting a polyalkene with a monounsaturated acid or its derivative, the polyalkylene forming in an en reaction attaches the double bond of the acid component.

Component B is preferably a fatty acid partially or completely neutralized with amines.

Component B particularly preferably comprises at least one fatty acid salt of the formula I.

_x3 -H [R-COO ^θ ] _{m + 1} (i)

wherein

R is C -C ₂₃ alkyl or mono- or polyunsaturated

C ₇ -C ₂₃ alkenyl, which is optionally substituted by one or more hydroxy groups;

represents C ₂ -Cs alkylene;

represents Ci-Cs-alkylene, C ₃ -Cs-cycloalkylene or C ₆ -Cι ₂ -arylene or C -C ₂ o-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-, where at least 'one x does not stand for 0,

and optionally at least one further fatty acid RCOOH, where R is as defined above.

Such fatty acid salts are described, for example, in WO 01/38463, to which reference is hereby made in full. The longer-chain radical R occurring in the carboxylate anion RC00 or in the fatty acid RCOOH denotes, for example, branched or preferably linear C to C ₂₃ , preferably Cn to C ₂ ,, especially C ₁₅ to Cig alkyl groups, which can also carry hydroxyl groups. Examples of the underlying carboxylic acids are octanoic acid, 2-ethylhexanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid (lauric acid), tridecanoic acid, iso-tri-decanoic acid, tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid and sticinoic acid. 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 occurring in the carboxylate anion or RCOO- in the fatty acid RCOOH relatively long-R designates preferably mono- or polyunsaturated C - to C ₂₃ radicals, in particular mono- or polyunsaturated C ₂ to C n χ-, in all C ₁₅ - to cig 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 also with the above-mentioned saturated ones can also be used

Carboxylic acids underlie 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 the formula I is preferably derived from corresponding alkylene oxides such as ethylene oxide, 1, 2-propylene oxide, 1,2-butylene oxide and ice or trans-2,3-butylene oxide. However, it can also represent 1,3-propylene, 1,4-butylene, 1,6-hexylene or 1,8-octylene. A can also represent a mixture of different of the groupings mentioned. A, ethylene, 1,2-propylene or 1,2-butylene groups are particularly preferred. -

The variable Z means in particular Ci 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 groups such as 1,3- or 1,4-phenylene, 2-methyl-1 , 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 (Σ) 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 as a 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 preferably stands for the number 1 or 2. For m = 1 there are completely and / or partially alkoxylated alkylenediamines such as 1,2-ethylenediamine, 1,3-propylenediamine or 1,4-butylenediamine. For m = 2 there are usually completely 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 ', ^y- tetrakis (2' -hydroxyethyl) -l, 2-ethylenediamine (∑x = 4) and N, N, N ', N' -Tetrakis (2'-hydroxypropyl) -1, 2-ethylenediamine (∑x = 4) and the tris-oleic acid salts of di- (1,2-ethylene reacted with 4 to 5 mol ethylene oxide or 1,2-propylene oxide ) -triamine of particular interest.

However, it is also possible to use higher homologs of the alkylene diamines and dialkylene triamines mentioned, such as, for example, triethylene tetramine (m = 3), tetraethylene pentamine (m = 4) or pentaethylene hexamine (m = 5), as the amine component for the fatty acid salts used according to the invention.

In a preferred embodiment, the number x, ie the sum of x ¹ , x ² , x ³ and x ⁴ (∑x), of the alkylene oxide units (OA) introduced per amine molecule is based on the number of NH bonds in the base Amine dependent and can correspond to the number of NH bonds (∑x = 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 sub-stoichiometric incorporation, an average 50% alkoxylation [50% of (m + 3)] is a corresponding preferred lower limit; in this connection then mostly mixtures of species with different degrees of alkoxylation are present.

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

The fatty acid salts of the general formula I can usually be prepared easily by alkoxylation of the underlying amines by customary methods and subsequent neutralization with the fatty acids of the formula RCOOH.

When using C ₂ -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 of 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, eg. As sodium or potassium hydroxide, carried out at temperatures from 100 to 150 ° C.

The neutralization is generally carried out by heating the alkoxylated amine thus obtained with the corresponding stoichiometric or slightly sub-stoichiometric amount (ie 90 to 100%, in particular 95 to 100% of theory) of fatty acid to temperatures of 30 to 100 ° C., in particular 40 to 80 ° C, for a period of 15 minutes to 10 hours, especially 30 minutes to 5 hours. The neutralization reaction should be carried out so that no carboxylic ester components are formed in the product. In many cases, both the alkoxylated amine and the fatty acid can be used as liquids, which makes the conversion to the corresponding fatty acid salt particularly simple. The order of combining alkoxylated amine and fatty acid is not critical, i.e. one can either add the alkoxylated amine and add the fatty acid or add the fatty acid and add the alkoxylated amine.

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

The molar ratio of component A to component B in the additive mixture is preferably 1:10 to 10: 1, particularly preferably 1: 6 to 6: 1 and in particular 1: 4 to 4: 1. Another object of the present invention is the use of the additive mixture described above for the additive of fuel and lubricant compositions.

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

Diesel fuels are, for example, petroleum refines, which usually have a boiling range from 100 to

Have 400 ° C. These are mostly distillates with a 95% point up to 360 ° C or even more. However, these can also be so-called "ultra low sulfur diesel" or "city diesel", characterized by a 95% point of, for example, a maximum of 345 ° C. and a sulfur content of a maximum of 0.005% by weight or by a 95% Point of, for example, 285 ° C. and a maximum sulfur content of 0.001% by weight. In addition to the diesel fuels obtainable by refining, those which are obtainable by coal gasification or gas liquefaction ("gas to liquid (GTL) fuels) 0 are also suitable. Mixtures of the aforementioned diesel fuels with regenerative fuels such as biodiesel or bioethanol are also suitable.

The additive mixture according to the invention is particularly preferred for the additization of diesel fuels with a low sulfur content, ie with a sulfur content of less than 0.05% by weight, preferably less than 0.02% by weight, in particular less than 0.005% by weight and "used fei." especially of less than 0.001 wt .-% sulfur ^{^'. ...} 0

The additive mixture according to the invention is particularly preferably used to reduce the combustion-related coke deposits in the area of the injection system of diesel engines with and without direct fuel injection, preferably of diesel engines with 5 direct fuel injection.

An additive mixture according to the invention also for encryption is preferably ^"'ringerung the corrosive effect of a fuel verwendet.-

Another object of the present invention is

Fuel composition comprising a main amount of a hydrocarbon fuel and an effective amount of the additive mixture according to the invention and optionally at least one further additive. With regard to the preferred fuels 5, reference is made to the above statements. The additive mixture according to the invention is preferably present in the fuel in an amount of 1 to 1000 ppm by weight, particularly preferably 10 to 500 ppm by weight and in particular 50 to 250 ppm by weight, based on the total amount. of the additive fuel.

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

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

Suitable diluents are, for example, fractions obtained in petroleum processing, such as kerosene, naphtha or brightstock. Aromatic and aliphatic hydrocarbons and alkoxyalkanols are also suitable. In the case of middle distillers, particularly preferred diluents used in diesel fuels, naphtha, kerosene, diesel fuels, aromatic hydrocarbons such as heavy solvent naphtha, Solves- so ^® or Shellsol ^® and mixtures of these solvents and diluents.

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

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, corrosion inhibitors, dehazers, demulsifiers, antifoams ("antifoam"), antioxidants, metal deactivators, multifunctional stabilizers , Cetane number improvers, combustion improvers, dyes, markers, solubilizers, antistatic agents, other ^" customary lubricity improvers, additives that improve the cold properties, such as flow improvers (" MDFI "), paraffin dispersants (" WASA ") and the combination of the latter two additives ( "WAFIs").

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 burning N-acyl compounds, such as polyalkenylsuccinic acid amides, mixtures of the aforementioned acids and / or esters with these N-acyl compounds, as described for example in 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 WO 95/33805 ,

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 fuels additized with it and to a significant reduction in the corrosion effect of fuels and the nozzle coking in comparison to additives of the prior art.

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

Examples

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 of 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

I. 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 of polyisobutenylsuccinic anhydride (molecular weight of the polyisobutene: 1000) (saponification number 95) were mixed with 0.2 to 2 mol of 2-ethylhexanol and within 20 minutes at 80 ° C to 160 ° C heated. 105 g (0.55 mol) of tetraethylene pentamine were added. It was left at 150 Stir ° C to 180 ° C for 90 to 180 minutes. The alcohol was then removed in vacuo.

1.2 Synthesis of a lubricity improver (Lubricity I) '

58.4 g (0.2 mol) of N, N, N ', N'-tetrakis (2' -hydroxypropyl) -l, 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 heated to 60-80 ° C. and 110.4 g (0.4 mol) of oleic acid were added with stirring within two hours. The pH did not drop below 7. The mixture was then stirred for a further two hours. The product obtained had an N titer of 2.39 mmol / g.

engine tests

In addition to the combinations according to the invention of detergent I and lubricity I, commercially available detergents based on polyisobutene succinimide with the name detergent II and customary lubricity improvers on the basis of acid with the name Lubricity II or ester-based with the name Lubricity III were used and their Performance compared with the combinations of detergent I and lubricity I according to the invention.

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 Unadditized base fuels and fuel blends were determined in a Peugeot XUD 9 test engine as part of the current 10 h test procedure in accordance with CEC-F23-A01 and compared with the nozzle coking observed when using the additive fuels and fuel blends. The additive fuels or blends were added by adding the above. Combinations of 80 mg / kg detergent I-II and 120 mg / kg of the lubricity improvers Lubricity I-III are obtained.

The following results were obtained: ^• - • ^• • ■

** Differences to the measured flow reduction without lubricity improver

The combinations of detergent I and lubricity I according to the invention showed a 6-9% improved performance compared to the test results obtained with detergent I alone. No significant changes were observed with other combinations.

2.2 Corrosion tests according to ASTM D 665 A / B

The corrosion behavior of the above unadditized base fuels and fuel blends was tested in steel finger tests in accordance with ASTM D 665 A in distilled water and ASTM D 665 B in synthetic salt water and compared with the corrosion behavior observed when using the additive fuels and fuel blends. The additive fuels or blends were obtained by adding the above combinations of 80 mg / kg detergent I-II and 120 mg / kg of the lubricity improvers Lubricity I-III. The evaluation of the test results was carried out in accordance with NACE TM-01-72

A s 100% rustproof

B ++ s 0.1% or less of the total area rusted B + ss 0.1 - 5% of the total area rusted B - 5 - 25% of the total area rusted C s 25 - 50% of the total area rusted D s 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 according to the invention

I showed a significantly improved performance compared to the test results obtained with Detergent I alone. Minor improvements were observed with the other combinations tested.

2.3 Determination of the lubricity according to HFRR

The lubricity of the unadditized basic fuels and fuel blends was tested in HFRR tests in accordance with ASTM D 6079-99 and compared with the lubricity observed when using the additive fuels and fuel blends. The additive fuels or blends were obtained by adding the above combinations of 80 mg / kg detergent I and 120 mg / kg ^! Lubricity improver Lubricity I obtained. The following table shows the determined WS1.4 [μm], which represents the size of the wear scar.

The following results were obtained:

** Differences to the measured WS1.4 values in [μm] without detergent

The combinations of detergent I and lubricity I according to the invention showed a performance improvement of 5-25 μm compared to the test results obtained with lubricity I alone.

Claims

claims

1. 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.

2. Additive mixture according to claim 1, wherein the polar head group of component A is selected from

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

(b) nitro groups, optionally in combination with hydroxyl groups,

(e) carboxylic ester groups,

(g) groups derived from carboxylic anhydrides with hydroxyl and / or amino and / or amido and / or imido groups.

3. Additive mixture according to claim 2, wherein component A is an ash-free burning acylated nitrogen compound.

4. Additive mixture according to one of the preceding claims, wherein 5 the hydrocarbon radical is a homo- or copolymer radical, the repeat units of which are derived from monomers which are selected from propene, n-butene and isobutene and mixtures thereof.

5. Additive mixture according to one of the preceding claims, wherein component A is obtainable by reacting a carboxylic acid or a carboxylic acid derivative with an amine which has at least one NH group.

15 6. Additive mixture according to claim 5, wherein the carboxylic acid or the carboxylic acid derivative is a dicarboxylic acid or a dicarboxylic acid derivative.

7. Additive mixture according to claim 6, wherein the carboxylic acid or the carboxylic acid derivative is a polyalkenyl succinic acid or a polyalkenyl succinic acid derivative.

8. The additive mixture according to claim 7, wherein component A comprises at least one polyalkenyl succinimide.

9. Additive mixture according to one of the preceding claims, wherein the hydrocarbon radical is derived from reactive polyisobutene.

30

10. Additive mixture according to one of the preceding claims, wherein in component B the fatty acid is neutralized with at least one amine.

35 11. Additive mixture according to claim 10, wherein component B at least one fatty acid salt of formula I.

40) _x3 -H [R-COO ^ö ] _{m + 1} (i)

45 where R represents CC ₂₃ alkyl or mono- or polyunsaturated CC ₂₃ alkenyl, which are optionally substituted by one or more hydroxyl groups;

5 A represents C ₂ -C ₈ alkylene;

Z is -C ₈ alkylene, C ₃ -C ₈ cycloalkylene or Cg-C ₁₂ arylene or C ₇ -C ₂ o-arylalkylene;

10 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,

15 and optionally at least one further fatty acid RCOOH, where R is as defined above,

includes.

20 12. 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.

13. Use of the additive mixture as defined in one of the preceding claims for the additization of

Fuel and lubricant compositions.

14. Use according to claim 13, for reducing the combustion-related coke deposits in the area of the injection system.

30 stems of diesel engines with and without direct fuel injection.

15. Use according to claim 13, for reducing the corrosive effect of a fuel.

35

16. A fuel composition containing a main amount of a hydrocarbon fuel and an effective amount of an additive mixture as defined in any one of claims 1 to 12 and optionally at least one further additive.

40 fabric.

17. A fuel composition according to claim 16 or use according to any one of claims 13 to 15, wherein the fuel is diesel fuel, heating oil or kerosene.

45

18. A fuel composition or use according to claim 17, wherein the diesel fuel is obtainable by refining, coal gasification or gas liquefaction, or is a mixture of such fuels and is optionally mixed with regenerative fuels.

19. Lubricant composition containing an effective amount of an additive mixture as defined in one of claims 1 to 12 and a lubricant and optionally at least one further additive.

20. Additive concentrate containing an additive mixture as defined in one of claims 1 to 12 and at least one diluent and, if appropriate, at least one further additive.