WO2001038463A1

WO2001038463A1 - Use of fatty acid salts of alkoxylated oligoamines as lubricity improvers for petroleum products

Info

Publication number: WO2001038463A1
Application number: PCT/EP2000/011102
Authority: WO
Inventors: Knut Oppenländer; Marco Bergemann; Klaus Mundinger; Dietmar Posselt; Siegbert Brand; Ansgar Eisenbeis
Original assignee: Basf Aktiengesellschaft
Priority date: 1999-11-19
Filing date: 2000-11-10
Publication date: 2001-05-31
Also published as: IL149198A0; CA2388065A1; MXPA02003836A; EP1230330A1; DE50006014D1; NZ519236A; HRP20020530A2; MY123415A; ZA200204851B; CZ20021730A3; IL149198A; ATE263825T1; EP1230330B1; HRP20020530B1; HUP0204038A2; AR028188A1; JP4713804B2; DK1230330T3; PT1230330E; NO20022319D0

Abstract

The invention relates to the use of fatty acid salts of alkoxylated oligoamines (I), whereby: A represents alkylene groups having 2 to 8 C atoms; R represents C7 to C23 alkyl groups or monounsaturated or polyunsaturated C7 to C23 alkenyl groups; Z represents C1 to C8 alkylene groupings, C3 to C8 cycloalkylene groupings or C6 to C12 arylene or aryl alkylene groupings; m represents 0 or a whole number ranging from 1 to 5, and the sum of all variables x has a value ranging from 50 % to 300 % of (m+3). Said fatty acid salts of alkoxylated oligoamines are used as lubricity improvers for petroleum products, especially for gasolines and middle distillates.

Description

Use of fatty acid salts of alkoxylated oligoamines as lubricity improvers for mineral oil products

description

The present invention relates to the use of fatty acid salts of alkoxylated oligoamines as lubricity improvers for mineral oil products, in particular for petrol and middle distillates, especially diesel fuels, and also additive concentrates for such mineral oil products and such mineral oil products themselves, which contain these fatty acid salts of alkoxylated oligoamines.

Carburetors and intake systems of gasoline engines, but also injection systems for fuel metering, are increasingly contaminated with contaminants caused by dust particles from the air, unburned hydrocarbon residues from the combustion chamber and the crankcase ventilation gases that are led into the carburetor.

These residues shift the air-fuel ratio at idle and in the lower part-load range, so that the mixture becomes leaner, the combustion incomplete and, in turn, the proportions of unburned or partially burned hydrocarbons in the exhaust gas increase and gasoline consumption increases.

It is known that in order to avoid these disadvantages, fuel additives are used to keep valves and carburetor or injection systems of gasoline engines clean (cf., for example: M. Rossenbeck in catalysts, surfactants, mineral oil additives, ed. J. Falbe, U. Hasserodt, p. 223, G. Thieme Verlag, Stuttgart 1978).

Such pure fuel additives (detergents), which can originate from a large number of chemical substance classes, such as polyalkenamines, polyetheramines, polybutene-Mannich bases or polybutensuccinimides, are generally used in combination with carrier oils and, in some cases, other additive components such as corrosion inhibitors and demulsifiers.

However, petrol fuels with and without such additive components usually show inadequate behavior in need of improvement with regard to their lubricity and wear protection properties in gasoline engines. Low-sulfur diesel fuels, which are being used more and more these days, also show lubricity problems which, for example, result in increased wear on the injection pumps. The lowering of the sulfur content in diesel fuels is necessary to reduce or avoid sulfur dioxide and particle emissions. To achieve low sulfur levels, the diesel fuels must be hydrogenated. This also destroys polar and multinuclear aromatic components in the fuel that cause the natural lubricating effect of the diesel fuel. Thus, as with petrol, there is a need for additives that increase the lubricity in the fuel efficiently (also known as "lubricity additives" or "friction modifiers").

Lubricity-improving additives known to date for petrol are, for example, fatty acids, such as. B. described in WO 98/11175, alkenyl succinic acid esters, bis (hydroxyalkyl) fatty amines and hydroxyacetamides. For diesel fuels in particular fatty acids and fatty acid derivatives, e.g. B. esters of glycerol with unsaturated fatty acids, or castor oil, as described in EP-B 605 857, used as lubricity-improving additives.

However, since the properties of the prior art mentioned are still in need of improvement in terms of their property profile, in particular with regard to their lubrication and wear protection effect, the object of the present invention was to provide better-effective lubricity improvers for mineral oil products, in particular for petrol and middle distillates.

Accordingly, the use of fatty acid salts of alkoxylated oligoamines of the general formula I

AO) _x - H [R - COO®] m + 1 (I)

in the the variables

A represents alkylene groups with 2 to 8 carbon atoms, R C to C ₃ alkyl groups or mono- or polyunsaturated

C- to C ₃ -alkenyl groups, which can additionally carry hydroxyl groups,

ZC ~ to Cs-alkylene groups, C ₃ - to C ₈ -cycloalkylene groups or C ₆ - to -CC ₂ arylene or arylalkylene groups,

m represents 0 or an integer from 1 to 5 and

the sum of all variables x has a value of 50% to 300% of (m + 3),

found as a lubricity improver for mineral oil products.

The compounds of formula I mentioned are already known as such. In U.S. 4,131,583 describes salts of particular unsaturated On- to C ₂₀ carboxylic acids with N, N, N ', N' -Tetrahydroxye- thyl-C ₂ ^_ C ₄ alkylenediamines, but these are only as corrosion inhibitors in aqueous Coating agents recommended for metal surfaces.

From JP-A 11/050076 it is known that N, N, N ', N' tetrakis (2-hydroxypropyl) ethylenediamine in the presence of fatty acids such as stearic acid or oleic acid in aqueous lubricating oil compositions such as cutting oil or grinding oil causes rust formation and prevents fungal attack and stabilizes the composition. An improvement in the lubricating effect is not mentioned here.

From JP-A 11/209773 aqueous lubricants for conveyor belts in the filling of bottles with beverages are known which contain fatty acid salts of alkanolamines such as N, N, N ', N' tetrakis (2-hydroxypropyl) ethylenediamine. For example, palmitic acid, tetradecanoic acid, oleic acid and lauric acid are mentioned as fatty acids.

Mineral oil products are to be understood here as fuels, operating materials, fuels and lubricating oils, which, however, are based not only on petroleum but also partly or completely on synthetic and / or naturally occurring raw materials. Examples of such raw materials are natural gas, methanol, ethanol, hard coal liquefaction products or rapeseed oil, which are processed into fuels or incorporated into petroleum-based fuels. The designated mineral oil products are generally practically water-free or contain water at least only in minor quantities. Examples of water-containing mineral oil products 38463 ₄ products are fuel emulsions such as diesel / water emulsions, which can usually contain up to approx. 35% by weight of water. Mineral oil products preferred for the present invention are, on the one hand, petrol fuels and, on the other hand, middle distillates such as, in particular, diesel fuels.

The alkylene group A 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 for A.

The longer-chain radical R occurring in the carboxylate anion denotes, for example, branched or preferably linear C - to C ₂₃ -, preferably Cn ~ to C ₂ ι, especially C ₁ 5 to C ₉ alkyl groups, which may additionally 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-tridecanoic acid, tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), stearic acid and octadecanoic acid (octadecanoic 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 longer-chain radical R occurring in the carboxylate anion preferably denotes mono- or polyunsaturated C ₇ to C ₃ radicals, in particular mono- or polyunsaturated Cn ~ to C ₂ ι ~, especially C ₁₅ - to cig alkenyl groups, which can also 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 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 variable Z means in particular C 1 -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-cyclo pentylidene or 1,3- or 1, 4-cyclohexylidene or C _ß - to Cs-arylene LEN or -Arylalkylengruppierungen 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 groups 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 (Variablen) of all variables x, mixtures of mono-, di- and / or trialkanolamines or pure trialkanolamines are based on the fatty acid salts used according to the invention as a cationic component. Examples of such alkanolamines are monoethanolamine, diethanolamin, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine and the associated mixtures. In this group, the oleic acid salt of triethanolamine (∑x = 3) is 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, the basis is 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 ', N' - tetrakis (2 '-hydroxyethyl) -1, 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-) reacted with 4 to 5 mol ethylene oxide or 1,2-propylene oxide ethylene) triamine of particular interest.

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

The number of alkylene oxide units (OA) introduced per amine molecule can correspond to the number of NH bonds in the underlying amine (∑x = m + 3). However, more or fewer OA units can also be installed. With over-stoichiometric incorporation, a triple alkoxylation per NH bond [300% of (m + 3)] is an upper limit with regard to the properties of the resulting fatty acid salts. With sub-stoichiometric incorporation, an average 50% alkoxylation [50% of (m + 3)] o A corresponding lower limit, in this case there are usually mixtures of species with different degrees of alkoxylation.

In a 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 used according to the invention can usually be easily prepared by alkoxylation of the underlying amines by customary methods and subsequent neutralization with the fatty acids of the formula R-COOH.

When using C 1 -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 of 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 in such a way 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. You 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 preparation of the fatty acid salts of the general formula I used in accordance with the invention usually requires significantly less effort and energy than in the case of conventional lubricity improvers of the prior art, in particular those based on amino the or esters, the production of which generally requires higher temperatures, longer reaction times and complicated work-up work to separate undesired by-products, which occur in particular in the case of condensation reactions.

The fatty acid salts of general formula I described are outstandingly suitable as lubricity additives ("lubrication additives", "friction modifiers") in mineral oil products, in particular in petrol and middle distillates, especially diesel fuels. The fatty acid salts I are generally highly effective and can therefore be used widely. When fatty acid salts I are used, the tendency for wear to occur in the parts of the machines and units operated with the mineral oil products is significantly reduced.

The fatty acid salts of the general formula I used in gasoline according to the invention can advantageously be used in combination with, in principle, all customary gasoline additives.

Usual petrol additives with detergent effect are for example:

(a) Polyisobutenamines which, according to EP-A 244 616, are obtained by hydroformylation of highly reactive polyisobutene with a number-average molecular weight of 300 to 5000 and subsequent reductive amination with ammonia, monoamines or polyamines such as dimethyleneaminopropylamine, ethylenediamine, diethylenetriamine or triethylenetetramine Tetraethylene pentamine are available;

(b) poly (iso) butenamines obtained by chlorination of polybutenes or polyisobutenes with double bonds predominantly in the β and γ position and subsequent amination with ammonia, monoamines or the polyamines mentioned under (a) above;

(c) poly (iso) butenamines which can be obtained by oxidation of double bonds in poly (iso) butenes with air or ozone to give carbonyl or carboxyl compounds and subsequent amination under reducing (hydrogenating) conditions;

(d) polyisobutenamines which are obtainable from polyisobutene epoxides according to DE-A 196 20 262 by reaction with amines and subsequent dehydration and reduction of the amino alcohols; (e) optionally hydroxyl-containing polyisobutenamines, which are obtainable according to WO-A 97/03946 by reacting polyisobutenes with an average degree of polymerization P = 5 to 100 with nitrogen oxides or mixtures of nitrogen oxides and oxygen and subsequent hydrogenation of these reaction products;

(f) Polyisobutenamines containing hydroxyl groups, which can be obtained according to EP-A 476 485 by reacting polyisobutene epoxides with ammonia, monoamines or the above-mentioned polyamines;

(g) Polyetheramines, which are obtained by reacting C ₂ - to C o ~ alkanols, C ₆ - to C ₃ o-alkanediols, mono-, di- or tri-C ₂ - to C ₃ o-alkylamines, Cι ~ to C ₃ o-alkylcyclohexanols or Cι ~ bis

C ₃ o-alkylphenols with 1 to 30 mol of ethylene oxide and / or propylene oxide and / or butylene oxide per hydroxyl or amino group and subsequent reductive amination with ammonia, monoamines or the above-mentioned polyamines are available - such products also meet the requirements of carrier oils th;

(h) "Polyisobutene Mannich bases", which in particular according to EP-A 831 141 or according to German patent applications Az. 199 48 111.3 and 199 48 114.8 can be obtained by reacting polyisobutene-substituted phenols with aldehydes and monoamines or the above-mentioned polyamines;

(i) polypropylene amines according to WO 94/24231, which are obtainable by metallocene-catalyzed propene oligomerization and subsequently the steps of hydroformylation and reductive amination mentioned under (a) above;

(j) additives containing carboxylic acid ester groups, preferably based on esters of mono-, di- or tricarboxylic acids with long-chain alcohols or polyols, in particular those with a minimum viscosity of 2 mm 2 / s at 100 ° C., as described in DE-A 38 38 918 are described as examples here adipates, phthalates, isophthalates, terephthalates and trimel - litates of iso-octanol, iso-nonanols, iso-decanols and iso-tridecanols - products of this type also fulfill carrier oil properties;

(k) Imides, amides, esters and ammonium and alkali metal salts of polyisobutene succinic anhydrides, which are obtainable from conventional or highly reactive polyisobutene and maleic anhydride by thermal means or via the chlorinated polyisobutene and in particular in the form of the derivatives aliphatic polyamines can be used - such gasoline fuel additives are described in particular in US Pat. No. 4,849,572.

Common gasoline additives with valve seat anti-wear properties include:

(1) Carboxyl groups or additives containing alkali metal or alkaline earth metal salts, in particular such as the copolymers of C ₄ -C ₄ -olefins with maleic anhydride with a total molar mass of 500 to 20,000 described in EP-A 307 815, the carboxyl groups of which are wholly or partly added the alkali metal or alkaline earth metal salts and a remaining radical of the carboxyl groups are reacted with alcohols or amines;

(m) Sulfonic acid groups or additives containing their alkali metal or alkaline earth metal salts, in particular such as the alkali metal or alkaline earth metal salts of alkyl sulfosuccinic acid esters described in EP-A 639 632.

In addition to and together with the aforementioned gasoline fuel additives (a) to (m), other customary carrier oils, additive components and auxiliaries can be combined with the fatty acid salts of the general formula I for use in gasoline fuels.

Examples of common carrier oils for petrol additives are mineral carrier oils (base oils), in particular those of the viscosity class "Solvent Neutral (SN) 500 to 2000", synthetic carrier oils based on olefin polymers with M _N = 400 to 1800, especially based on polybutene or polyisobutene. Base (hydrogenated or non-hydrogenated), of polyalphaolefins or poly-internalolefins and synthetic carrier oils based on alkoxylated long-chain alcohols or phenols. Mixtures of the carrier oils mentioned can of course also be used.

Fractions such as kerosene, naphtha or brightstock are also suitable as mineral carrier oils and / or diluents or solvents for petrol additives. Aromatic hydrocarbons, paraffinic (aliphatic) hydrocarbons and alkoxyalkanols are also suitable for this.

Of particular importance as carrier oils for gasoline fuel additives are polyetherols which, by reacting C ₂ -C ₃ -alkanols, C _ß -C o-alkanediols, mono-, di- or tri-C- to C ₃ o -alkylamines, Cι ~ to C ₃ o-alkylcyclohexanols or Cι ~ bis C ₃ o-alkylphenols with 1 to 30 mol ethylene oxide and / or propylene oxide and / or butylene oxide per hydroxyl or amino group are available. In particular, alcohol-initiated polyetherols with about 10 to 35, in particular 15 to 30, propylene and / or butylene oxide units are to be mentioned here; linear or branched C ₆ -C to alkanols are particularly suitable as starter alcohols.

Other common additive components and auxiliaries for gasoline fuels are corrosion inhibitors, for example based on ammonium salts of organic carboxylic acids which tend to form films, or heterocyclic aromatics for non-ferrous metal corrosion protection, antioxidants or stabilizers, for example based on amines such as p-phenylenediamine, dicyclohexylamine or derivatives thereof or phenols , 4-di-tert. -butylphenol or 3, 5-di-tert. -butyl-4-hydroxyphenylpropionic acid, demulsifiers, antistatic agents, metallocenes such as ferrocene or methylcyclopentadienylmanganese tricarbonyl and dyes (markers). Medium-chain linear or branched alkanols (with about 6 to 12 carbon atoms) are often used as solubilizers, for. B. 2-ethylhexanol. Sometimes amines are added to lower the pH of the fuel.

The fatty acid salts of the general formula I used in petrol according to the invention can also be used together with other lubricity improvers which are customary for this purpose, such as certain fatty acids, alkenylsuccinic acid esters, bis (hydroxyalkyl) fatty amines or hydroxyacetamides.

The carboxylic acids or fatty acids used as corrosion inhibitors or lubricity improvers can be present as monomeric or oligomeric, in particular dimeric, species. Mixtures of monomeric and di eren and optionally higher oligomeric species can also be present.

Combinations of the fatty acid salts of the general formula I used in petrol according to the invention with the detergents of the above-mentioned groups (a), (d) and (g), in particular with polyisobutenamines from group (a), are preferred. Particularly suitable polyisobutenamines (a) are those which are prepared by hydroformylation of highly reactive polyisobutenes having a number-average molecular weight of 500 to 2300, in particular 800 to 1500, especially 900 to 1200, and subsequent reductive amination with ammonia. The polyisobutenamines (a) are preferably combined with carrier oils, for example polyetherols or aliphatic or aromatic hydrocarbons, and optionally with the aforementioned corrosion inhibitors, antioxidants or stabilizers, demulsifiers, antistatic agents. tic agents, metallocenes and / or dyes used. A typical example of such a polyisobutenamine (a) is the product sold under the trade name Kerocom® PIBA by BASF Aktiengesellschaft.

All commercially available gasoline fuel compositions can be used as gasoline. The typical Eurosuper base fuel according to EN 228 should be mentioned here as a typical representative. Furthermore, the Az. 199 05 211.5 described petrol composition of interest.

The fatty acid salts of the general formula I used according to the invention in middle distillates can be used advantageously in all usual middle distillates.

These middle distillates, of which diesel fuels are the most important group, include petroleum raffinates, which usually have a boiling range of 100 to 400 ° C. These are mostly distillates with a 95% point up to 360 ° C or beyond. 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

Wt .-%. In addition, these middle distillates can also be heating oils with a sulfur content of at most 0.20% by weight, in particular at most 0.10% by weight, and aviation fuels.

The distillates mentioned are usually composed of components which are obtained from the atmospheric or vacuum distillation of petroleum or which are obtained from conversion processes, e.g. B. cracker, koker or visbreaker gas oil.

The middle distillates mentioned, above all diesel fuels, are distinguished by a low sulfur content, as a rule of a maximum of 0.05% by weight, in particular a maximum of 0.02% by weight, especially a maximum of 0.005% by weight, very particularly preferably at most 0.001% by weight.

The fatty acid salts of the general formula I used according to the invention in middle distillates, especially diesel fuels, can be incorporated therein as liquid pure substances or as liquid concentrates in a solvent or diluent. In principle, all substances mentioned above as such agents for use with gasoline fuel additives can be used as solvents or diluents. In particular, Mineral oil cuts such as naphtha, kerosene, diesel fuel and aromatic hydrocarbons such as solvent naphtha heavy, Solvesso® or Shellsol® are particularly suitable. These concentrates can be solutions or dispersions, with clear solutions being preferred. Mixtures of the solvents or diluents mentioned can also be used.

By using the solvents or diluents mentioned, in particular in a ratio by weight to the fatty acid salts I of 1:10 to 10: 1, in particular 1: 4 to 4: 1, especially 1: 2 to 2: 1 the solubility of the fatty acid salts of the general formula I used according to the invention can be improved. Such solutions or dilutions are advantageous when the middle distillate already contains further additives, when the mixing temperatures are low, when the metering device is not designed for low metering quantities or when mixtures with other middle distillates are to be produced.

The fatty acid salts of the general formula I used according to the invention in middle distillates can advantageously be used combined with in principle all common middle distillate or diesel fuel additives.

Common middle distillate or diesel fuel additives in this context are, in particular, detergents, corrosion inhibitors, dehazers, demulsifiers, antifoams ("antifoam"), antioxidants, metal deactivators, multifunctional stabilizers, cetane number improvers, combustion improvers, dyes, markers, solubilizers, other additives, and lubricants additives which improve the cold properties, such as flow improvers ("MDFI"), paraffin dispersants ("WASA") and their combination ("WAFI").

The present application also relates to a process for improving the lubricity of mineral oil products, in particular petrol and middle distillates, which is characterized in that effective amounts of fatty acid salts of alkoxylated oligoamines of the general formula I 1 to 6 are added to the mineral oil products.

The present invention furthermore relates to additive concentrates for mineral oil products, in particular for petrol and middle distillates, which contain the fatty acid salts of alkoxylated oligoamines of the general formula I in amounts of 0.05 to 50, in particular 0.1 to 30,% by weight, based on the total amount of the concentrates. These concentrates usually also contain the other additives, carrier oils, solution or diluents and / or auxiliaries. In the case of additive concentrates for petrol, these are, in particular, detergents and / or valve seat anti-wear agents, in particular the additives (a) to (m) listed above, and further components and auxiliaries customary for this, in particular carrier oils,

Corrosion inhibitors, antioxidants or stabilizers, demulsifiers, antistatic agents, metallocenes and dyes.

The present invention furthermore relates to mineral oil products, in particular gasoline and middle distillate compositions, which contain the fatty acid salts of alkoxylated oligoamines of the general formula I in effective amounts. Effective amounts are generally 1 to 1000 ppm by weight, in particular 5 to 500 ppm by weight, especially 10 to 250 ppm by weight, particularly preferably 20 to 100 ppm by weight, both for petrol and diesel fuel compositions .-ppm, based in each case on the total amount of the composition. These mineral oil products, in particular the gasoline and middle distillate compositions, usually contain, in addition to the fatty acid salts I used according to the invention, the additives, additive components and auxiliaries listed above.

The fatty acid salts of alkoxylated oligoamines of the general formula I are already highly effective in low concentrations in the mineral oil products as lubricity improvers and effectively prevent wear in the parts of the machines and units operated with the mineral oil products, for example in fuel inlet systems or injection pumps.

Furthermore, the fatty acid salts of alkoxylated oligoamines of the general formula I have good compatibility with lubricating oil, which is particularly important when used in diesel fuels. Due to the interaction of acid lubricity improvers (such as dimeric fatty acids) used to date with basic constituents of lubricating oil, which is known to be in contact with the fuel in gasoline and diesel engines, corresponding salts can separate out in the fuel and at undesired points in the engine or the injection system and Cause interference. This disadvantage is avoided by the use according to the invention of the fatty acid salts of alkoxylated oligoamines of the general formula I.

Also, the fatty acid salts of alkoxylated oligoamines of the general formula I used according to the invention have practically no tendency to form unwanted emulsions in the mineral oil products and are sufficiently stable to hydrolysis. The following examples are intended to illustrate the present invention without restricting it.

Preparation Examples

Example 1: Preparation of the bis-oleic acid salt of N, N, N ', N' -tetrakis (2'-hydroxypropyl) -1, 2-ethylenediamine

58.4 g (0.2 mol) of N, N, N ', N' -tetrakis (2'-hydroxypropyl) -1, 2-ethylenediamine (prepared by customary reaction of 1,2-ethylenediamine with 4 mol of propylene oxide in the presence of about 3% by weight of water, based on the amount of the amine used, at 100 to 110 ° C) were heated to a temperature of 60-80 ° C and within two hours with stirring at 110 , 4 g (0.4 mol) of oleic acid are added. The pH did not drop below 7. The mixture was then stirred for a further 2 hours at the specified temperature interval. The product obtained had an N titer of 2.39 mmol / g (calc. 2.37 mmol / g).

Example 2: Preparation of the bis-oleic acid salt of N, N, N ', N' -tetrakis (2'-hydroxyethyl) -1, 2-ethylenediamine

The title compound was prepared in analogy to Example 1 with the analogous amounts of N, N, N ', N' tetrakis (2'-hydroxyethyl) -1, 2-ethylenediamine.

applications

Example 3: Determination of the frictional wear values in petrol

A high frequency recrocating rig (HFRR) from PCS Instruments, London, was used to check the lubricity and wear in petrol. The measuring conditions have been adapted to the use of petrol. The applicability of this test method for petrol is indicated by the references D. Margaroni, Industrial Lubrication and Tribology, Vol. 50, No. 3, May / une 1998, pp. 108-118, and W. D. Ping, S. Korcek, H. Spikes, SAE Techn. Paper 962010, pp. 51-59 (1996).

The gasoline used here (OK) (typical gasoline in accordance with EN 228) was gently reduced to 50% by volume by distillation before the measurements. This 50% residue was used in the inspection in the wear measuring device to determine the blank value. According to the examples listed below, the other additives were added to this residue and the frictional wear values were determined according to the method given above. Right. The resulting frictional wear values (R) are given in micrometers (μm); the lower this value, the lower the wear that occurs.

The 50 vol.% Residue of a Eurosuper petrol OKI showed a blank value of R = 873 μm in the HFRR test, the 50 vol.% Residue of a comparable Eurosuper petrol OK2 gave a blank value of R = in the HFRR test 754 µm. The addition of 500 mg / kg of a commercially available petrol additive package Pl (based on a polyisobutenamine detergent, a synthetic carrier oil and a conventional corrosion inhibitor) or a commercially available petrol additive package P2 (analogous to Pl but with a different synthetic carrier oil) led to this each with friction wear values in the same order of magnitude. The addition of 50 mg / kg of the invention

Lubricity improvers from Examples 1 and 2 or from lubricity improvers known from the prior art resulted in correspondingly lower values, the products according to the invention mostly being significantly superior to those of the prior art. The values obtained are listed in Table 1 below.

Table 1: Frictional wear values R in petrol

added additives OK R [μm]

no OKI 873

500 mg / kg package Pl OKI 853

500 mg / kg package PI + 50 mg / kg product from example 2 OKI 686

no OK2 754

500 mg / kg package Pl OK2 717

500 mg / kg package Pl + 50 mg / kg

Product from Example 1 OK2 593

500 mg / kg package Pl + 50 mg / kg

Product from Example 2 OK2 634

500 mg / kg package Pl + 50 mg / kg comparative product OK2 659 500 mg / kg package P2 OK2 775

500 mg / kg package P2 + 50 mg / kg

Product from Example 1 OK2 680

500 mg / kg package P2 + 50 mg / kg

Product from Example 2 OK2 633

500 mg / kg package P2 + 50 mg / kg comparative product OK2 684

A commercial lubricant improver based on tall oil fatty acid according to WO 98/11175 was used as the comparative product.

Example 4: Determination of the frictional wear values in diesel fuels

Standard lubricity tests were carried out with an HFRR device from PCS Instruments, London, in which a steel ball rubs on a steel plate in the test fuel. ISO 12156-1 describes this method and has found its way into the diesel standard EN 590-1999. The limit here is an abrasion on the steel ball of a maximum of 460 μm. Unadditized low-sulfur diesel fuels can have frictional closure values R of typically 400 to 700 μm.

The test diesel fuels (DK1 to DK4) listed in Table 2 below had the characteristics indicated,

Table 2: Characteristics of the test diesel fuel

The sulfur content was determined in accordance with EN ISO 14 596. The following diesel fuel additives were used:

Additive A: product from Example 2 used according to the invention (undiluted)

Additive B: product from Example 1 used according to the invention (undiluted)

Additive C: as a comparison of commercially available lubricity improvers based on a mixture of a sterically hindered alkylphenol and a long-chain carboxylic acid

Additive D: as a comparison of commercially available lubricity improvers based on a mixture of a carboxylic acid amide and a natural fatty acid ester

Additive E: as a comparison of commercially available lubricity improvers based on a mixture of glycerol monooleate and glycerol monolinolate

Additive F: as a comparison of commercially available lubricity improvers based on a mixture of long-chain carboxylic acids

Table 3 below shows the results of the determination of the tear wear values R in the test diesel fuels. It is clear that the effect of products A and B used according to the invention exceeds that of market products C to F.

Table 3:

Tear wear values R [μm] in diesel fuel (WS 1.4 values measured HFRR according to ISO 12 156-1 at 60 ° C)

The values given in brackets indicate the respective dosage in vol.ppm.

Example 5: Lubricant compatibility

The tendency of an additive to form insoluble deposits with lubricating oil can be checked using various standardized laboratory tests. Here the test prescribed by DGMK was applied (German Scientific Society for Petroleum, Natural Gas and Coal e.V., Research Report 531 "Establishment of a catalog of criteria for testing lubricity additives in diesel fuels for refinery use", Hamburg 1998). 10 ml of motor oil (CEC RL 189; SAE 15W40) and 10 ml of additive are homogenized in a 500 ml flask. After 72 hours at 90 ° C., the mixture is cooled and assessed optically. This mixture is made up to 500 ml with diesel fuel and filtered through a 0.8 μm filter (SEDAB regulation). The occurrence of gel or sediment and the exceeding of a filtration time of 300 seconds leads to "Fail". By contrast, "pass" means that the test is passed.

Table 4 below with the results of this test illustrates that the lubricity improvers A and B used according to the invention are not expected to have any negative interactions with lubricating oil.

Table 4: Lubricating oil compatibility tests according to DGMK FB 531

As a further comparative additive G, a commercially available dimeric ■ fatty acid was used.

Claims

claims

1. Use of fatty acid salts of alkoxylated oligoamines of the general formula I

AO) _x - H [R- COO ^θ ] _{m + 1} (:

in the the variables

stand for alkylene groups with 2 to 8 carbon atoms.

RC - to C ₂ alkyl groups or mono- or polyunsaturated C - to C ₂₃ alkenyl groups, which can additionally carry hydroxyl groups,

C 1 ~ to C ₈ alkylene groups, C ₃ to C ₈ cycloalkylene groups or C ₆ to Cχ ₂ arylene or arylalkylene groups,

m represents 0 or an integer from 1 to 5 and

the sum of all variables x has a value of 50% to 300% of (m + 3),

as a lubricity improver for mineral oil products.

Use of fatty acid salts of alkoxylated oligoamines of the general formula I according to Claim 1, in which the variables A are 1, 2-ethylene, 1, 2-propylene or 1,

2-butylene groups are available.

3. Use of fatty acid salts of alkoxylated oligoamines of the general formula I according to claim 1 or 2, in which the variables R mono- or polyunsaturated C ₁₅ - bis

Cι ₉ alkenyl groups, which may additionally carry hydroxyl groups.

4. Use of fatty acid salts of alkoxylated oligoamines of the general formula I according to claims 1 to 3, in which the variables Z are polymethylene groups of the formula - (CH ₂ ) _n - with n = 2 to 6.

5. Use of fatty acid salts of alkoxylated oligoamines of the general formula I according to claims 1 to 4, in which the variable m stands for the number 1 or 2.

6. Use of fatty acid salts of alkoxylated oligoamines of the general formula I according to claims 1 to 5, in which the sum of all variables x has a value of 75% to 125% of (m + 3).

7. Use of fatty acid salts of alkoxylated oligoamines of the general formula I according to claims 1 to 6 as lubricity improvers in petrol and middle distillates.

8. A method for improving the lubricity of mineral oil products, in particular of petrol and middle distillates, characterized in that the mineral oil products are added effective amounts of fatty acid salts of alkoxylated oligoamines of the general formula I according to claims 1 to 6.

9. additive concentrates for mineral oil products, in particular for petrol and middle distillates, containing fatty acid salts of alkoxylated oligoamines of the general formula I according to claims 1 to 6 in amounts of 0.05 to 50 wt .-%.

10. Mineral oil products, in particular gasoline and middle distillate compositions, containing in effective amounts fatty acid salts of alkoxylated oligoamines of the general formula I according to claims 1 to 6.