ES2219415T3 - EMPLOYMENT OF SALTS OF FATTY ACIDS OF ALCOXYLED OLIGOAMINS AS IMPROVEMENTS OF THE LUBRICATION CAPACITY FOR MINERAL OIL PRODUCTS. - Google Patents

Abstract

Use of fatty acid salts of alkoxylated oligóamines of the general formula I in which the variables A means alkylene groups with 2 to 8 carbon atoms, R means alkyl groups with 7 to 23 carbon atoms alkenyl groups once or several times unsaturated with 7 to 23 carbon atoms, which may additionally carry hydroxyl groups, Z means alkylene groups with 1 to 8 carbon atoms, cycloalkylene groups with 3 to 8 carbon atoms or arylene or arylalkylene groups with 6 to 12 atoms carbon, m means 0 or an integer from 1 to 5, and the sum of all variables x has a value of 50% up to 300% of (m + 3), as lubricant capacity enhancers for oil products mineral.

Description

Use of oligoamine fatty acid salts alkoxylated as lubricant enhancers for mineral oil products.

The present invention relates to the use of fatty acid salts of alkoxylated oligoamines as improvers of lubrication capacity for mineral oil products, particularly for Otto fuels and medium distillates, particularly diesel fuels, as well as oil products  mineral of this type, which contain special salts of fatty acids of alkoxylated oligoamines.

The carburetor and intake systems of Otto engines, but also injection systems for the fuel dosage, are increasingly loaded by impurifications, which are caused by air foam particles, hydrocarbon remains do not burn combustion enclosure and gases  ventilation of the crankshaft housing made to reach the carburetor.

These residual products alter the proportion of air-fuel in the empty gear and in the lower part load sector, so that the mix will be more poor, combustion will be more incomplete and parts of unburned or partially burned hydrocarbons in the gas escape will be again bigger and gasoline consumption increases

It is known, which are used to avoid these additive drawbacks for the fuel for cleaning the valves and carburetor or injection systems of Otto engines (see, for example: M. Rossenbeck in Katalysatoren, Tenside, Mineralöladditive, editor J. Falbe, U. Hasserodt, page 223, G. Thieme Verlag, Stuttgart 1978).

Additives for cleaning fuels this type (detergents), which can come from a large number of classes of chemical substances, such as polyalkyleneamines, polyethermines, Mannich bases of polybutene or polybutensuccinimides, generally applied in combination with carrier oils and partly with other components additives, such as corrosion inhibitors and demulsifiers.

Otto fuels with and without components additives of this type show, however, often a insufficient behavior and susceptible to improvements regarding their properties of lubricating capacity and protection against wear on Otto engines.

Also sulfur-poor diesel fuels nowadays always more used show capacity problems lubricant, which are noticed, for example, in increased wear on injection pumps. The decrease in sulfur content in Diesel fuels are necessary for reduction or for avoidance of sulfur dioxide and particulate emissions. For get reduced sulfur contents, they have to be hydrogenated Diesel fuels In this case they are also destroyed polar and aromatic polynuclear components in the fuel, that cause the natural lubricating effect of diesel fuel. There is, therefore, also in this case - as in the Otto fuels - a demand for additives, which increases the fuel lubrication capacity efficiently (also referred to as "Lubricity Additive" or "Friccion Modifier ").

The additives improving the capacity of lubrication currently known for Otto fuels, are, by example, fatty acids, such as, for example, described by WO 98/11175, esters of alkenyl succinic acid, fatty amines of bis (hydroxyalkyl) and hydroxyacetamides. For fuels Diesel particularly used fatty acids and derivatives of fatty acids, for example glycerin esters with fatty acids unsaturated, or castor oil, as described by the EP-B 605 857, as improving additives for lubrication capacity

As the agents of the prior art are, however, still susceptible to improvements in their profile of properties, particularly regarding its lubrication effect and of wear protection, existed for the present invention the task of making capacity enhancers available lubrication with greater efficiency for oil products minerals, particularly for Otto fuels and distillates media.

Therefore the use of salts was found of fatty acids of alkoxylated oligoamines of the general formula I

one

in which mean the variables

To alkylene groups with 2 to 8 atoms of carbon,

R alkyl groups with 7 to 23 carbon atoms or once or several times unsaturated alkenyl groups with 7 to 23 carbon atoms, which can additionally carry groups hydroxyl,

Z alkylene groups with 1 to 8 atoms of carbon, cycloalkylene groups with 3 to 8 carbon atoms or clusters of arylene or arylalkylene with 6 to 12 atoms of carbon,

m 0 or an integer from 1 to 5, and

the sum of all variables x has a value from 50% to 300% of (m + 3), as capacity enhancers of lubrication for mineral oil products.

The compounds mentioned in the Formula I. Acid salts are described by US 4 131 583 carboxylic acids with 11 to 20 carbon atoms particularly unsaturated with N, N, N ', N'-tetrahydroxyethylalkylenediamines with 2 a 4 carbon atoms, but they are recommended exclusively as corrosion inhibitors in coating agents aqueous for metal surfaces.

It is known by JP-A 11/050076, what N, N, N ', N'-tetrakis- (2-hydroxypropyl) -ethylenediamine prevents in the presence of fatty acids, such as stearic acid or acid oleic in aqueous compositions of lubricating oils, such as oil cutting or grinding oil corrosion formation and attack of fungi and stabilizes the composition. An improvement of the effect Lube is not mentioned in the publication.

JP-A 11/209773 is known aqueous lubricants for conveyor belts in the packaging of bottles with drinks, containing fatty acid salts of alkanolamines, such as N, N, N ', N'-tetrakis- (2-hydrociopropyl) -ethylenediamine. As fatty acids there are mentioned, for example, palmitic acid, acid tetradecanoic, oleic acid and lauric acid.

DE-B-1 047 526 recommends fatty acid salts of alkoxylated oligoamines as anti-freezing agents carburetor engines gasoline. As specific compound in this regard the salt of mononaftenate N, N, N ', N'-tetrakis- (2-oxypropyl) -ethylenediamine. There is, however, no reference to the lubricating effect of these agents.

US-A 3 429 673 offers salts of the carboxylic acid of alkoxylated monoamines as inhibitors against corrosion in combustible oils.

They have to be understood by oil products combustible minerals, fuels, diesel and lubricating oils, that are based, however, not only on oil but also on partly or completely in raw materials of synthetic origin and / or natural. Examples of raw materials of this type are gas natural, methanol, ethanol, stone coal liquefaction products or rapeseed oil, which is transformed into fuels or is incorporated into petroleum based fuels. The products of Mineral oil denominated are generally- and practically anhydrous or They contain water at least only in secondary quantities. The Examples of mineral oil products, which contain water, are fuel emulsions, such as diesel / water emulsions, which they can usually contain up to about 35% by weight of water. Preferred mineral oil products for The present invention are, on the one hand, Otto fuels and, for other part, middle distillates, as particularly combustible Diesel.

The alkylene A group is derived preferably of corresponding alkylene oxides, such as oxide of ethylene, 1,2-propylene oxide, 1,2-butylene and cis- or oxide trans-2,3-butylene. May mean, however, also 1,3-propylene, 1,4-butylene, 1,6-hexylene or 1,8-octylene. A can also represent a mixture, constituted by different groups mentioned. I know particularly preferred for ethylene groups, 1,2-propylene or 1,2-butylene.

The rest R of longer chain, which appears in the carboxylated anion, determines, for example, alkyl groups branched or preferably linear with 7 to 23, preferably with 11 to 21 and especially with 15 to 19 carbon atoms, which can additionally carry hydroxyl groups. Examples for acids carboxylics, which form the base, are octanoic acid, acid 2-ethylhexanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid (lauric acid), acid tridecanoic acid, iso-tridecanoic acid, acid tetradecanoic (myristic acid), hexadecanoic acid (acid palmitic acid), octadecanoic acid (stearic acid) and acid Eicosanic The acids mentioned can be of natural origin or synthetic. They may also form mixtures, consisting of acids cited for carboxylate anions.

The rest R of longer chain, which appears in the carboxylate anion, however, preferably called moieties once or several times unsaturated with 7 to 23 carbon atoms, particularly once or several times unsaturated alkenyl groups with 11 to 21 carbon atoms and especially with 15 to 19 atoms of carbon, which can additionally carry hydroxyl groups. These  unsaturated residues are preferably linear. In the case of several times unsaturated alkenyl groups contain the same preferably two or three double bonds. Examples of acids carboxylics, which form the base, are elaidinic acid, acid ricinoleic, linoleic acid and linoleic acid. Particularly Good results are achieved with oleic acid. They can form base of carboxylate anions also mixtures, consisting of acids unsaturated carboxylic acids of this type with each other and also with the saturated carboxylic acids mentioned above. Mixtures of these types are, for example, talol, talol fatty acid and acid rapeseed fat. The unsaturated carboxylic acids mentioned and the Cited mixtures are generally of natural origin.

The variable Z means particularly alkylene groups with 1 to 4 carbon atoms, such as methylene, 1,2-propylene, 1,2-butylene, 1,3-butylene or 2,3-butylene, cycloalkylene groups with 5 a 6 carbon atoms, such as 1,3-cyclopentylidene or 1,3- or 1,4-cyclohexylidene or arylene groupings or arylalkylene with 6 to 8 carbon atoms, such as 1,3- or 1,4-phenylene, 2-methyl-1,4-phenylene or 1,3-or 1,4-bismethylenephenylene.

The variable Z means, however, preferably polymethylene clusters of the formula - (CH 2) n - with n = 2 to 8, particularly with n = 2 to 6, particularly 1,2-ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene and 1,6-hexylene, a part, however, also 1,7-heptylene and 1,8-octylene.

In the case that the variable m 0 means, they generally form the base as a cationic component, depending on of the sum (\ Sigma) all variables x, mixtures, constituted by mono-, di- and / or pure trialkanolamines or trialkanolamines for the fatty acid salts used according to the invention. The Examples of alkanolamines of this type are monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine as well as the respective mixtures In this group the acid salt is of particular interest triethanolamine oleic (Sigmax = 3).

The variable m means, however, the number 1 or 2. For m = 1 they form a complete alkylenediamine base- and / or partially alkoxylated, such as 1,2-ethylenediamine, 1,3-propylenediamine or 1,4-butylenediamine. For m = 2 form often based fully 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 of particular interest are acid salts bis-oleic of N, N, N ', N'-tetrakis- (2'-hydroxyethyl) -1,2-ethylenediamine  (\ Sigmax = 4) and N, N, N ', N'-tetrakis- (2'-hydroxypropyl) -1,2-ethylenediamine  (\ Sigmax = 4) as well as acid salts tris-oleic of di- (1,2-ethylene (-triamine reacted with 4 to 5 mole of ethylene oxide or oxides of 1,2-propylene.

It is, however, also possible to make form base higher homologs of the cited alkylenediamines and dialkylenetriamines, such as, for example, triethylenetetramine (m = 3), tetraethylenepentamine (M = 4) or pentaethylenehexamine (m = 5) as amine component for fatty acid salts used according to the invention.

The number of alkylene oxide units introduced (OA) per molecule of amine may correspond to number of the N-H bonds in the amine, which form base (\ Sigmax = m + 3). They can be incorporated, however, also more or less units of OA. In over-stoichiometric incorporation  the upper limit forms a triple alkoxylation by bond of N-H [300% of (m + 3)] in reference to Properties of the resulting fatty acid salts. If of a stoichiometric incorporation missing is in the mean statistic a corresponding lower limit an alkoxylation to 50% [50% of (m + 3)], in this case they are then present at often mixtures, consisting of species with degrees of differently high alkoxylation.

In a preferred form of execution it shows the sum (\ Sigma) of all variables x a value of 75% up to 125% of (m + 3).

The fatty acid salts used according to the invention of the general formula I can be obtained customarily- and easily by alkoxylation of the amines, which form the base, according to usual methods and following neutralization with acids fatty acids of the formula R-COOH.

In the use of alkylene oxides with 2 to 4 carbon atoms the alkoxylation is conveniently carried out for the introduction of the first alkylene oxide unit in the N-H bond in the presence of small amounts of water (often 0.5 to 5% by weight, based on the amount of amine used) without catalyst at temperatures from 80 up to 140ºC and for the introduction of other oxide units of alkylene with water exclusion in the presence of catalysts basic, such as alkali metal hydroxides, for example hydroxide sodium or potassium, at temperatures from 100 to 150 ° C.

The neutralization is generally carried out by heating the alkoxylated amine thus obtained with the correspondingly stoichiometric amount or slightly stoichiometric missing (ie 90 to 100%, particularly from 95 to 100% of theory) of fatty acid to temperatures from 30 to 100 ° C, particularly from 40 up to 80 ° C, for a time of 15 minutes up to 10 hours, particularly from 30 minutes to 5 hours. The reaction of neutralization would have to be carried out in such a way that they form percentages of carboxylic acid esters in the product. In many cases both alkoxylated amine and also fatty acid as liquids. what does the reaction for give the corresponding fatty acid salt particularly simple. The order of the alkoxylated amine and fatty acid binding is not critical, that is, both the alkoxylated amine and put together the fatty acid as well as arrange the fatty acid and put together the alkoxylated amine.

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

Obtaining fatty acid salts used according to the invention of the general formula I requires often clearly less effort and energy than in improvers customary lubricating capacity of the prior art, particularly in those based on amides or esters, in whose obtaining generally requires higher temperatures, longer reaction times and laborious work of processing for the separation of unwanted by-products, which appear particularly in condensation reactions.

The described fatty acid salts of the general formula I serve excellently as improvers of the lubricating capacity ("Lubricity Additive", "Friction Modifier ") in mineral oil products, particularly in Otto fuels and in middle distillates, especially in fuels Diesel. The salts of fatty acids I are generally- and highly effective and with this widely usable. In the use of fatty acid salts I clearly reduces the tendency to appearance of wear on machine parts and aggregates Powered with mineral oil products.

The fatty acid salts used in Otto fuels according to the invention of the general formula I can be used advantageously and combined with mainly all usual fuel additives Otto.

The usual additives for Otto fuels with detergent effect are, for example:

(to)

Polyisobutenamines, obtainable according to EP-A 244 616 by hydroformylation of highly reactive polyisobutene with an average molecular weight in number from 300 to 5000 and following reductive amination with ammonia, monoamines or polyamines, such as dimethylaminopropylamine, ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine;

(b)

Poly (iso) butenamines, obtainable by chlorination of polybutenes or polyisobutenes with double bonds mostly in the β and γ position and following amination with ammonia, monoamines or polyamines cited above in (a);

(c)

Poly (iso) butenamines, obtainable by oxidation of double bonds in poly (iso) butenes with air or ozone to give compounds carbonyl or carboxyl and following amination under conditions reducing agents (hydrogenating agents);

(d)

Polyisobutenamines, obtainable according to DE-A 196 20 262 from polyisobutenepoxides by reaction with amines and subsequent dehydration and reduction of the amino alcohols;

(and)

Polyisobutenamines, which contain, in given case, hydroxyl groups, obtainable according to the WO-A 97/03946 by reaction of polyisobutenes with an average degree of polymerization P = 5 to 100 with monoxide of nitrogen or mixtures of nitrogen monoxide and oxygen and following hydrogenation of these reaction products;

(F)

Polyisobutenamines, which contain hydroxyl groups, obtainable according to EP-A-476 485 by reaction of polyisobutenepoxides with ammonia, monoamines or polyamines previously cited;

(g)

Polyethermines, obtainable by reaction of alkanols with 2 to 30 carbon atoms, alkanediols with 6 to 30 carbon atoms, mono-, di- or trialkylamines with 2 to 30 carbon atoms, alkylcyclohexanols with 1 to 30 carbon atoms or alkylphenols with 1 to 30 atoms of carbon with 1 to 30 mol of ethylene oxide and / or propylene oxide and / or butylene oxide per hydroxyl group or amino and following reductive amination with ammonia, monoamines or polyamines previously cited - products of this type also comply with the properties of carrier oils;

(h)

"Bases of Polyisobutene Mannich "obtainable particularly according to EP-A 831 141 or according to DE-A-199 48 111 and 199 48 114 by reaction of polyisobutensubstituted phenols with aldehydes and monoamines or of the aforementioned polyamines;

(i)

Polypropyleneamines according to WO 94/24231, obtainable by oligomerization of metallocencatalized propene and then the steps previously cited of (a) hydroformylation and amination reductive;

(j)

Additives, which contain carboxylic acid ester groups, preferably at ester base of mono-, di- or tricarboxylic acids with long chain alcohols or polyols, particularly those with a minimum viscosity of 2 mm 2 / s at 100 ° C, as described by DE-A 38 38 918; as examples can be cited in this case adipates, phthalates, iso-phthalates, iso-octanol terephthalates and trimellitates, iso-nonanol, iso-decanoles e iso-tridecanoles - products of this type they also meet the properties of carrier oils;

(k)

Imides, amides, esters and ammonium and alkali metal salts of anhydrides from polyisobutensucinic acid, obtainable from polyisobutene conventional or highly reactive and maleic acid anhydride of thermally or through chlorinated polyisobutene and that can particularly used in the form of derivatives with polyamines aliphatic - Otto fuel additives of this type are particularly described by US-A 4 849 572.

The usual Otto fuel additives With wear inhibitory effect of the valve seats are, for example:

(l)

Additives, which they contain carboxyl groups or their alkali metal or metal salts alkaline earth, particularly as the copolymers described by EP-A 307 815 of olefins with 2 to 40 atoms of carbon with maleic acid anhydride with a total mass molecular from 500 to 20 000, whose carboxyl groups are totally or partially transformed to give metal salts alkaline or alkaline earth metal and a residual remainder of the carboxyl groups are transformed with alcohols or amines;

(m)

Additives, which they contain sulfonic acid groups or their alkali metal salts or of alkaline earth metal, particularly as metal salts alkaline or alkaline earth metal of alkyl esters of acid sulfosuccinic as described by EP-A 639 632

In addition and together with the additives of Otto fuels cited from (a) to (m) may combine other usual carrier oils, additive components and agents auxiliaries with the fatty acid salts of the general formula I for use in Otto fuels.

As usual carrier oils for additives Otto fuels have to be mentioned, for example, oils mineral carriers (basic oils), particularly those of 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 (hydrogenated or non-hydrogenated), of polyalphaolefins or of polynternalolefins as well as synthetic carrier oils to base of alkoxylated alcohols of long chains or phenols. Naturally, mixtures consisting of the cited carrier oils.

As mineral carrier oils and / or diluents or solvents for Otto fuel additives serve also fractions, which occur in oil processing, like kerosene, naphtha or brighstock. They also serve in this case aromatic hydrocarbons, paraffinic (aliphatic) hydrocarbons and alkoxyalcohols.

Of particular importance as carrier oils for additives for Otto fuels are in this case polyether, which are obtainable by reaction of alkanols with 2 to 30 atoms carbon, alkanediols with 6 to 30 carbon atoms, mono-, di- or trialkylamines with 2 to 30 carbon atoms, alkylcyclohexanols with 1 to 30 carbon atoms or alkylphenols with 1 to 30 atoms of carbon with 1 to 30 mol of ethylene oxide and / or propylene oxide and / or butylene oxide per hydroxyl or amino group. Particularly, polyetherols have to be cited in this case. initiated by alcohol with approximately 10 to 35, particularly 15 to 30 propylene and / or butylene units; as initiation alcohols in this case they serve particularly linear or branched alkanols with 6 to 15 carbon atoms.

Other usual active components and agents Otto fuel auxiliaries are corrosion inhibitors, for example based on ammonium salts with a tendency to form organic carboxylic acid or aromatic films heterocyclics in the anticorrosive protection of heavy metals not ferrous antioxidants or stabilizers, for example based on amines, such as p-phenylenediamine, dicyclohexylamine or derivatives thereof or phenols, such as 2,4-diterc.-butylphenol or acid 3,5-di-tert-butyl-4-hydroxyphenylpropionic,  demulsifiers, antistatic agents, metallocenes, such as ferrocene or methylcyclopentadienylmanganesotricarbonyl, as well as dyes (Marker) Solubilizers are often used linear alkanols or branched of medium chains (with approximately 6 to 12 atoms carbon), for example 2-ethylhexanol. Sometimes it they also use amines to reduce the pH value of the fuel.

The fatty acid salts used according to the invention in Otto fuels of formulas I can be used also in conjunction with other capacity enhancers usual lubricant in this case, such as certain acids fatty, esters of alkenyl succinic acid, fatty amines of bis (hydroxyalkyl) or hydroxyacetamides.

The carboxylic acids or fatty acids used as corrosion inhibitors or capacity enhancers lubricant may be present as monomer species or oligomers, particularly dimers. They may also be present. mixtures, consisting of monomer and dimer species and, in case given, higher oligomers.

Acid salt combinations are preferred greases used in Otto fuels according to the invention of the general formula I with the detergents of the groups above cited (a), (d) and (g), particularly with polyisobutenamines of group A). Particularly suitable polyisobutenamines (a) are in this case those, which are obtained by hydroformylation of highly reactive polyisobutenes with an average molecular weight in number from 500 to 2300, particularly from 800 to 1500, about all from 900 to 1200, and following reductive amination with ammonia. The polyisobutenamines (a) are preferably used in jointly with carrier oils, for example polyetherols or aliphatic or aromatic hydrocarbons, and, where appropriate, with corrosion inhibitors mentioned above, antioxidants or  stabilizers, demulsifiers, antistatics, metallocenes and / or dyes As a typical example for a polyisobutenamine of This type (a) must mention the product marketed under the trade name Kerocom® PIBA of the firm BASF AG.

They can be used as Otto fuels they can all current Otto fuel compositions are used in trade. As a typical representative, the Eurosuper basic fuel current in the market according to EN 228. In addition, the fuel composition is also of interest here Otto described by DE-A-199 05 211.

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

To the middle distillates of this type, of which diesel fuels represent the most important group, they belong refined petroleum, which usually have a boiling range of 100 to 400 ° C. These are often distillates with a point of 95% up to 360 ° C or more. The they can also be called "Ultra Low Sulfur Diesel "or" City Diesel ", characterized by a point of a 95% of, for example, a maximum of 345 ° C and a sulfur content of a maximum of 0.005% by weight or for a point of 95% of, for example, 285 ° C and a sulfur content of a maximum of 0.001% in weigh. In addition, these distillates can also be diesel with a sulfur content of a maximum of 0.20% by weight, particularly of a maximum of 0.10% by weight, as well as fuel for aviation.

The aforementioned distillates are usually composed by components, which are obtained from atmospheric distillation or from oil vacuum or conversion processes occur, such as, for example, cracker, coker or visbraker diesel.

The above-mentioned distillates, particularly Diesel fuels, stand out for a low sulfur content, generally of a maximum of 0.05% by weight, particularly of a maximum of 0.02% by weight, especially a maximum of 0.005% by weight and very especially preferred of a maximum of 0.001% in weight.

The fatty acid salts of the formula I, used in middle distillates according to the invention, particularly in diesel fuels, they can be incorporated here as substances pure liquids or as liquid concentrates in a solubilizer or in a diluent. As solubilizers or diluents can be used in this case in principle all the substances mentioned previously as agents of this type for use with additives of diesel fuels. Particularly they serve oil mixtures mineral, such as gasoline, kerosene, diesel fuel as well as aromatic hydrocarbons, such as Solvent heavy naphtha, Solvesso® or Shellsol®. These concentrates can be solutions or dispersions, preferring clear solutions. Mixtures can also be used of solvents or diluents.

For the use of solvents or diluents, particularly in the proportion by weight with the acid signals Fatty I from 1:10 to 10: 1, particularly from 1: 4 to 4: 1 and especially from 1: 2 to 2: 1, the solubility of the fatty acid salts used according to the invention of the formula general I. Solutions or dilutions of this type are then advantageous, if the middle distillate already contains others additives, yes the temperatures of incorporation by mixture are low, if the dosing device is not set to small dosage amounts or yes they have to be obtained mixtures, constituted with other middle distillates.

The fatty acid salts of the general formula I used in middle distillates according to the invention, can be used in an advantageous way with mainly all additives for medium distillates or diesel fuels usual.

The usual additives of medium distillates or well of diesel fuels are in this context particularly detergents, corrosion inhibitors, dehazer, demulsifiers, antifoams ("antifoam"), antioxidants, deactivators metallic, multifunctional stabilizers, index enhancers Cetane, combustion enhancers, marker dyes, solubilizers, antistatics, other Lubricity additives usual, as well as additives, which improve cold properties, such as flow improvers ("MDFI"), dispersants of paraffin ("WASA") and its combination ("WAFI").

The purpose of this application is also a procedure for improving the lubrication capacity of mineral oil products, particularly Otto fuels and middle distillates, characterized in that they are added to the products of mineral oil effective amounts of fatty acid salts of alkoxylated oligoamines of the general formulas I from 1 to 6.

Active concentrates for oil products ore, particularly for Otto fuels and distillates media, may contain oligoamine fatty acid salts alkoxylates of the general formula I in amounts of 0.05 to 50, particularly 0.1 to 30%, referred to the total amount of concentrates. These concentrates contain usually also the other additives indicated above, carrier oils, solvents or diluents and / or agents auxiliary In the case of additive concentrates for Otto fuels are these particularly detergents and / or agents to avoid wear for valve seats, especially the additives listed above from (a) to (m), as well as other components and usual auxiliary agents for the case, particularly carrier oils, corrosion inhibitors, antioxidants or stabilizers, demulsifiers, antistatics, metallocenes and dyes.

The object of the present invention are also mineral oil products, particularly compositions for Diesel fuel and for middle distillates, which contain salt of bis-oleic acid from N, N, N ', N'-tetrakis- (2'-hydroxyethyl) -1,2-ethylenediamine or of N, N, N ', N'-tetrakis- (2'-hydroxypropyl) -1,2-ethylenediamine in effective amounts. They are understood by effective amounts generally both in combinations of Otto fuels and also in diesel fuels 1 to 1000 ppm weight, particularly 5 to 500 ppm by weight, especially 10 up to 250 ppm by weight and especially 20 to 100 ppm in weight, respectively referred to the entire amount of the composition. These mineral oil products, particularly those compositions for Otto fuels and middle distillates, contain usually in addition to the fatty acid salts used in according to the invention the additives, additive components and auxiliary agents indicated above.

The fatty acid salts of oligoamines alkoxylates of the general formula I are already highly effective in small concentrations in mineral oil products like lubricant enhancers and effectively prevent the wear on machine parts and aggregates operated with mineral oil products, for example in intake systems for fuel or injection pumps.

They also show the fatty acid salts of alkoxylated oligoamines of the general form I a good compatibility with lubricating oils, which is important particularly in the use of diesel fuels. For the effect reciprocal of acidic lubricant enhancers currently used (as dimer fatty acids) with components Basic lubricating oil, which is in contact in Otto engines and Diesel, as is known, with the fuel, can be deposited corresponding salts in the fuel in unwanted locations in the engine or injection system and cause disturbances. East inconvenience is avoided by the use according to the invention of the salts of fatty acids of alkoxylated oligoamines of the general formula I.

Nor do the salts of practically lean fatty acids used according to the invention of oligoamines alkoxylates of the general formula I to an emulsion formation unwanted in mineral oil products and are sufficiently stable to hydrolysis.

The following examples have to explain the present invention without, however, limiting it.

Examples of obtaining Example 1 Obtaining the salt of bis-oleic acid from 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 (obtained by usual reaction of 1,2-ethylenediamine with 4 mol of propylene oxide in  presence of approximately 3% by weight of water, referred to the amount of the amine used, at 100 to 110 ° C) up to a temperature of 690 to 80 ° C and were reacted in the after two hours stirring with 110.4 g (0.4 mol) of acid oleic In this case the pH value did not fall below 7. A then stirred further in the temperature range indicated for 2 hours. The product obtained had a title of N 2.39 mMol / g (about 2.37 mMol / g).

Example 2 Obtaining the salt of bis-oleic acid from N, N, N ', N'. tetrakis- (2'-hydroxyethyl) -1,2-ethylenediamine

The title compound was obtained analogously. to example 1 with the analogous amount of N, N, N ', N'-tetrakis- (2'-hydroxyethyl) -1,2-ethylenediamine.

Application examples Example 3 Determination of friction wear values in Otto fuel

For checking the lubricating capacity or either of the wear on Otto fuels a High device was used Frequency Reciprocating Rig (HFRR) from PCS Instruments, London The measurement conditions were adapted to the use of Otto fuels. The applicability of this measurement method for Otto fuels are documented by literary sources D, Margaroni, Industrial Lubrication and Tribology, vo. 50, No. 3, May / June 1998, pp. 108 to 118, and W. D, Ping, s. Korcek, H. Spikes, SAE Techn. Paper 962010, pp. 51 to 59 (1996).

The Otto fuels used in this case (OK) (typical Otto fuels according to EN 228) were concentrated before Distillation measurements carefully up to 50% in volume This 50% residual product served in the verification in the wear measuring device for determining the blank value. To this residual product were added corresponding to the examples indicated below the other additives and wear values were determined by friction according to the method indicated above. Wear values The resulting friction (R) are indicated in micrometers (um); the The lower this value, the less the wear, which appears,

The residual product at 50% by volume of a Otto Eurosuper OK1 fuel threw a value in the HFRR test R = 873 µm blank; the residual product at 50% by volume of a comparable Otto Eurosuper OK2 fuel threw in the test of HFRR a white value of R = 754 µm. The addition of 500 mg / kg of a commercially available Otto P1 fuel additive package (based on a polyisobutenamine detergent, a carrier oil synthetic and of a habitual corrosion inhibitor) or of a Otto P2 current commercial fuel additive package (analogously to P1 but with another synthetic carrier oil) to this led respectively to friction wear values of the same magnitude. The addition of respectively 50 mg / kg of the lubrication capacity enhancers according to the invention of the Examples 1 and 2 or of known lubricating capacity improvers of the state of the art resulted with values correspondingly lower, where the products according to the invention were to those of the prior art often clearly superior. The values obtained are indicated in the following table 1.

TABLE 1 Friction wear values R in fuel Otto

two

As a comparative product was used respectively a lubricating capacity improver, which is commercially based talol fatty acid based on WO 98/11175.

Example 4 Determination of friction wear values in diesel fuels

Standard lubricity trials led to carried out using an HFRR device from PCS Instruments, London where it grazes a steel sphere on a steel plate in The test fuels. ISO 12156-1 describes this method and found in the Diesel EN standard 590-1999. As a limit a friction is set in the steel sphere of a maximum of 460 µm. The fuels Sulfur-poor diesel without additives may have values of friction wear R of typically 400 to 700 µm.

Diesel test fuels cited in the Next Table 1 (DK1 through DK4) showed the following features.

TABLE 2 Diesel fuel characteristics of test

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Sulfur content was determined according to EN ISO 14 596.

The following additives of Diesel fuels:

Additive TO

Product used according to the invention of the example 2 (not diluted).

Additive B

Product used according to the invention of the example 1 (undiluted).

Additive C

As a comparison a capacity improver commercially available lubricant based on a mixture, consisting of a sterically hindered alkylphenol and an acid long chain carboxylic.

Additive D

As a comparison a capacity improver commercially available lubricant based on a mixture, consisting of an carboxylic acid amide and an acid ester Natural fatty

Additive AND

As a comparison a capacity improver commercially available lubricant based on a mixture, constituted by glycerin monooleate and monolinolate glycerin.

Additive F

As a comparison a capacity improver commercially available lubricant or base of a mixture, constituted by long chain carboxylic acids.

The following table 3 shows the results of the determination of friction wear values R in the Diesel test fuels. It is clear that the effect of The products A and B used according to the invention exceed those of Market products C to F.

TABLE 3 Friction wear values R [\ mum] in Diesel fuel (WS 1,4-values according to HFRR conforming to ISO 12 156-1 at 60 ° C)

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The values indicated in parentheses indicate the respective dosage amount in ppm volume.

Example 5 Compatibility of lubricating oil

The tendency of an additive to form with oil insoluble tank lubricant, can be checked with different standardized laboratory tests. In this case the test prescribed by DGMK (Deutsche Wissenschaftliche Gesellschaft für Erdöl, Erdgas und Kohle e.V., Forschungsbericht 531 "Aufstellung eines Kriterienkataloges zur Testung von Lubricity Additiven in Dieselkraftstoffen für den Raffinerieeinsatz ", Hamburg 1998). In this case, 10 ml of oil are homogenized motor (CEC RL 189; SAE 15W40) and 10 ml of additive in a flask with a capacity for 500 ml. After 72 hours at 90 ° C it is cooled and It is valued optically. This mixture is filled with diesel fuel up to 500 ml and filtered through a 0.8 µm filter (SEDAB indication). The appearance of gel or sediment as well as the exceeding a filtration time of 300 seconds leads to "fail." "Pass" means, on the contrary, that it is met essay.

The following table 4 with the results of these Tests illustrates that lubricant capacity improvers A and B employees according to the invention do not allow any effect to be expected Negative reciprocal with lubricating oil.

TABLE 4 Compatibility tests with lubricating oil according to DGMK FB 531

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Like other comparison additive G, a commercial dimer fatty acid.

Claims (9)

1. Use of fatty acid salts of alkoxylated oligoamines of the general formula I 6 in which the variables A means alkylene groups with 2 to 8 atoms of carbon, R means alkyl groups with 7 to 23 atoms of carbon alkenyl groups once or several times unsaturated with 7 to 23 carbon atoms, which can additionally carry groups hydroxyl, Z means alkylene groupings with 1 to 8 carbon atoms, cycloalkylene groups with 3 to 8 atoms carbon or arylene or arylalkylene groups with 6 to 12 carbon atoms, m means 0 or an integer from 1 to 5, and the sum of all variables x has a value from 50% to 300% of (m + 3), as capacity enhancers lubricant for mineral oil products. 2. Use of fatty acid salts of alkoxylated oligoamines of the general formula I according to the claim 1, where the variables A groups mean 1,2-ethylene, 1,2-propylene or 1,2-butylene. 3. Use of fatty acid salts of alkoxylated oligoamines of the general formula I according to the claim 1 or 2, wherein the variables R groups mean a or several times unsaturated with 15 to 19 carbon atoms, which they can additionally carry hydroxyl groups, 4. Use of fatty acid salts of alkoxylated oligoamines of the general formula I according to the claims 1 to 3, where the variables Z mean polymethylene clusters 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 the claims 1 to 4, where the variable m means the number 1 or two. 6. Use of fatty acid salts of alkoxylated oligoamines of the general formula I according to the claims 1 to 5, wherein the sum of all x variables at a value of 75% up to 125% of (m + 3). 7. Use of fatty acid salts of alkoxylated oligoamines of the general formula I according to the claims 1 to 6 as lubricant enhancers in Otto fuels and middle distillates. 8. Procedure for improving the lubricating capacity of mineral oil products, particularly Otto fuels and middle distillates, characterized in that effective amounts of fatty acid salts of alkoxylated oligoamines of the general formula I are added to the mineral oil products claims 1 to 6. 9. Mineral oil products, particularly Otto and medium distillate fuel compositions, containing the acid salt in effective amounts bis-oleic of N, N, N ', N'-tetrakis- (2'-hydroxyethyl) -1,2-ethylenediamine or of N, N, N ', N'-tetrakis- (2'-hydroxypropyl) -1,2-ethylenediamine.