SK7002002A3 - Use of fatty acid salts of alkoxylated oligoamines as lubricity improvers for petroleum products - Google Patents

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

Technical field

The present invention relates to the use of salts of fatty acids and alkoxylated oligoamines as lubricity enhancers for petroleum products, in particular for petroleum fuels and intermediate distillates, in particular diesel fuel, and additive concentrates for such petroleum products, and such petroleum products themselves containing these salts. fatty acids and alkoxylated oligoamines.

BACKGROUND OF THE INVENTION

Carburetors and gasoline engine intake systems, as well as fuel injection systems, are increasingly polluted with airborne dust particles, unburnt hydrocarbon residues from the combustion chamber, and crankcase breather gases entering the carburetor.

These residues shift the air to fuel ratio during idling and lower partial load, so the mixture becomes poorer, combustion incomplete and the amount of unburned or partially burned hydrocarbons in the exhaust gas increases and gasoline consumption increases.

It is known that these disadvantages can be avoided by using fuel additives to maintain valve and carburetor cleanliness or gasoline engine injection systems (e.g., M. Rossenbeck in Katalysatoren, Tenside, Mineralôladditive, ed. J. Falbe, U. Hasserodt, page 223, G). Thieme Verlag, Stuttgart 1978).

Such fuel additives (detergents) that maintain cleanliness and can come from a large number of chemical classes, such as polyalkenamines, polyetheramines, polybutene Mannich bases or polybutenylsuccinimides, are generally used in combination with carrier oils and in some cases other additives such as corrosion inhibitors and demulsifiers.

However, gasoline fuels with and without such additives generally exhibit inadequate behavior with the need for improvement due to their lubricity and anti-wear properties in gasoline engines.

The low sulfur diesel fuel increasingly used today also causes lubricity problems, which lead, for example, to more wear in the injection pumps. Reducing the sulfur content of diesel is needed to reduce or prevent sulfur dioxide and smoke emissions. Diesel fuel must be hydrogenated to achieve a low sulfur content. As a result, the polar and multi-core aromatic components in the fuel that are responsible for the natural lubricating effect of diesel fuel are also discarded. Here again, as in the case of gasoline fuels, there is a need for additives which sufficiently increase the lubricity in the fuel (also referred to as lubricants or friction modifiers).

Lubricant enhancers for gasoline fuels known to date are, for example, the fatty acids described, for example, in WO 98/11175, alkenyl succinic esters, bis (hydroxyalkyl) fatty amines and hydroxyacetamides. In the case of diesel fuel, in particular, fatty acids and fatty acid derivatives, for example glycerol esters of unsaturated fatty acids or castor oil, are used as lubricity-improving additives, as described in EP-B 605 857.

However, since the prior art materials are unsatisfactory in their property profile, in particular in relation to their lubricating and anti-wear effect, it is an object of the present invention to provide more effective lubricity enhancers for petroleum products, especially gasoline fuels and middle distillates.

SUMMARY OF THE INVENTION

We have found that this goal can be achieved with fatty acid salts and alkoxylated oligoamines of formula I

where [R-COO] m + 1 (D

A is an alkylene group having 2 to 8 carbon atoms,

R is C ₇ -C ₂₃ -alkyl or mono- or polyunsaturated C ₇ -C ₂₃ alkenyl, which may additionally carry hydroxyl groups,

Z is up to a C ₈ -alkylene group, a C ₃ to C ₈ -cycloalkylene group or a C ₆ to C ₁₂ -arylene or arylalkylene group, m is 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 lubricity enhancers for petroleum products.

The compounds of the formula I are known per se. U.S. Pat. No. 4,131,583 discloses salts of especially unsaturated _υ - to C ₂₀ carboxylic acids with Ν, Ν, Ν ', Ν -tetrahydroxyethyl-C ₂ -C ₄ -alkylenediamines, which are only recommended as corrosion inhibitors in coating materials on aqueous bases for metal surfaces.

JP-A 11/050076 discloses that N, N, N ', N'-tetrakis (2-hydroxypropyl) ethylenediamine in the presence of fatty acids such as stearic or oleic acid in aqueous lubricating oil compositions such as cutting oil or milling oil, prevents rust formation and fungal attacks and stabilizes the composition. Improvement of the lubricating effect is not mentioned there.

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

Petroleum products are to be understood here as motor fuels, operating materials, combustion fuels and lubricating oils, which are, however, not only based on petroleum but also partly or entirely on the basis of synthetic and / or naturally occurring raw materials. Examples of such raw materials are natural gas, methanol, ethanol, coal liquefaction products or rapeseed oil, which are processed to form fuels or added to petroleum-based fuels. The specified petroleum products are generally virtually anhydrous or contain water at least in small quantities. Examples of water-containing petroleum products include fuel emulsions, for example, oil and water emulsions, which may typically contain up to about 35% water by weight. The petroleum products preferred for the present invention are, on the one hand, gasoline fuels and, on the other hand, middle distillates, in particular diesel.

The alkylene group A is preferably derived from the corresponding alkylene oxides, such as ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide and cis- or trans-2,3-butylene oxide. However, it can also be 1,3-propylene, 1,4-butylene, 1,6-hexylene or 1,8-octylene. It may also be a mixture of different groups from the above groups. A is particularly preferably an ethylene, 1,2-propylene or 1,2-butylene group.

The relatively long-chain radical R occurring in the carboxylate anion is, for example, branched or preferably linear C ₇ - to C ₂₃ -alkyl, preferably C _n - to C ₂₁ -alkyl, in particular C ₁₅ - to C ₁₉ -alkyl which may also to carry hydroxyl groups. Examples of source carboxylic acids are octanoic acid, 2-ethylhexanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid (lauric acid), tridecanoic acid, isotridecanoic acid, tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid) and eicosanoic acid. These acids may be of natural or synthetic origin. Carboxylate anions can also be based on mixtures of these acids.

However, the relatively long chain of the R radical occurring in the carboxylate anion is preferably a mono- or polyunsaturated C ₇ -C ₂₃ radical, in particular a mono or polyunsaturated C ₁ -C ₂ ralkenyl, in particular C ₁₅ -C ₁₉ -alkenyl, which it may additionally carry hydroxyl groups. These unsaturated radicals are preferably linear. In the case of polyunsaturated alkenyl groups, these preferably contain two or three double bonds. Examples of source carboxylic acids are elaidic acid, ricinoleic acid, linoleic acid and linolenic acid. Particularly good results are obtained with oleic acid. The carboxylate anions may also be based on mixtures of such unsaturated carboxylic acids with each other and also with the above-mentioned saturated carboxylic acids. Such mixtures are, for example, tall oil, tall oil fatty acid, and rapeseed oil fatty acid. Said unsaturated carboxylic acids and said mixtures are generally of natural origin.

Z is in particular a C 1 -C ₄ -alkylene group, for example methylene, 1,2-propylene,

1,2-butylene, 1,3-butylene or 2,3-butylene, _C, - to C ₆ -cycloalkylen, e.g., 1,3-cyclopentylidene and 1,3-cyclohexylidene, or 1,4-or C ₆ - to _C8 arylene and arylalkylene groups, such as 1,3- or 1,4-phenylene, 2-methyl-

1,4-phenylene or 1,3- or 1,4-bismethylene-phenylene.

However, Z is preferably a polymethylene group of the formula - (CH 2 n -), wherein n is from 2 to 8, in particular from 2 to 6, i.e. especially 1,2-ethylene, 1,3-propylene, 1,4-butylene, , 5-pentylene and 1,6-hexylene, but also 1,7-heptylene and 1,8-octylene.

m is 0, the fatty acid salts used according to the invention are generally dependent on the sum (Σ) of all x variables based on mixtures of mono-, di- and / or trialkanolamines or pure trialkanolamines as cationic components. Examples of such alkanolamines are monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine and the respective mixtures. Of particular interest in this group is the oleic acid triethanolamine salt (Σχ =

3).

Preferably, however, m is 1 or 2. For m = 1, the base is completely or partially alkoxylated alkylenediamines such as 1,2-ethylenediamine, 1,3-propylenediamine or 1,4-butylenediamine. For ηΐ = 2, the base generally consists of fully and / or partially alkoxylated dialkylene triamines such as di (1,2-ethylene) triamine, di (1,3-propylene) triamine or di (1,4-butylene) triamine. Of particular interest in this group are the salts of bisoleic acid and N, N, N ', N'-tetrakis (2'-hydroxyethyl) -1,2-ethylenediamine (Σχ = 4) and N, N, N', N'-tetrakis (2'-hydroxypropyl) -1,2-ethylenediamine (Σχ = 4) and trisoleic acid and di (1,2-ethylene) triamine salts reacted with 4-5 moles of ethylene oxide or 1,2-propylene oxide.

However, higher homologues of these alkylenediamines and dialkylenetriamines, for example tetraethylenetetramine (m = 3), tetraethylenepentamine (m = 3), may also be used as the source amine component for the fatty acid salts of the invention.

4) or pentaethylenehexamine (m = 5).

The number of alkylene oxide units (OA) introduced per amine molecule may correspond to the number of N-H bonds in the source amine (Σχ = m + 3). However, it is also possible to incorporate more or less OA units. In the case of nadstoichiometric incorporation, the upper limit is triple alkoxylation per N-H bond [300% z (m + 3)] with respect to the properties of the fatty acid salts obtained. In the case of substoichiometric incorporation, the relevant lower limit is the average 50% alkoxylation [50% of (m + 3)]; however, mixtures of molecules with different degrees of alkoxylation are then present.

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

The fatty acids used according to the invention and formula I can conveniently be readily prepared by alkoxylation of the source amines by conventional methods followed by neutralization with fatty acids of formula R-COOH.

When using _the C - to C ₄ -alkylénoxidy, alkoxylation is preferably carried out in the presence of small amounts of water (at most from 0.5 to 5% by weight, based on the amount of the amine), without catalyst, at 80 to 140, in introducing a first alkylene oxide unit into the NH bond, and in the absence of water, in the presence of basic catalysts, for example alkali metal hydroxides, e.g. sodium hydroxide or potassium hydroxide at 100 to 150 ° C with the introduction of additional alkylene oxide units.

The neutralization is generally carried out by heating the obtained alkoxylated amines with the corresponding stoichiometric or slightly sub-stoichiometric amount (i.e. from 90 to 100%, in particular from 95 to 100% of the theoretical amount) of the fatty acid to a temperature of 30 to 100 ° C, especially 40 to 80 ° C. over a period of 15 minutes to 10 hours, in particular from 30 minutes to 5 hours. The neutralization reaction should be carried out so that no carboxylic ester fractions are present in the product. In many cases, both an alkoxylated amine and a fatty acid can be used in the form of liquids, making the reaction to the corresponding fatty acid salt particularly simple. The order in which the alkoxylated amine and the fatty acid are combined is not critical. Either the alkoxylated amine may first be taken and the fatty acid may be added, or the fatty acid may be taken first and the alkoxylated amine may be added.

In principle, however, it is also possible to add the alkoxylated amine and the fatty acid as individual components to the additive or petroleum product concentrates and allow the salt to form there.

Generally, the preparation of the fatty acid salts used according to the invention and formula I generally requires considerably less effort and energy than conventional prior art lubricity enhancers, especially those based on amides or esters, which generally require longer reaction times and expensive processing procedures for precipitating unwanted by-products, which occur in particular in the case of condensation reactions.

The described fatty acid salts of the formula I are very suitable as lubricity enhancers (lubricants, lubricity modifiers) in petroleum products, in particular in gasoline fuels and in middle distillates, in particular diesel. Fatty acids I are generally highly effective and thus widely applicable. When fatty acids I are used, the tendency to wear occurring in parts of machines and units operating with petroleum products is substantially reduced.

The fatty acid salts used according to the invention in gasoline fuels and formula I can advantageously be used in combination with essentially all conventional gasoline fuel additives.

Examples of conventional detergent fuel additives are:

(a) polyisobutyl amines obtainable by EP-A 244 616 by hydroformylation of a high-reactive polyisobutene having a number average molecular weight of 300 to 5000 and subsequent reductive amination with ammonia, monoamines or polyamines such as dimethyleneamininopropylamine, ethylenediamine, diethylenetriamine, diethylenetriamine, diethylenetriamine, diethylenetriamine, poly (iso) butenamines obtainable by chlorination of polybutenes or polyisobutenes with double bonds predominantly in the β and γ position, followed by amination with ammonia, monoamines or polyamines listed under (a) above;

(c) poly (iso) butenamines obtainable by oxidation of double bonds in poly (iso) butenes with air or ozone to form carbonyl or carboxyl compounds and subsequent amination under reducing (hydrogenation) conditions;

(d) polyisobutyl amines obtainable according to DE-A 196 20 262 from polyisobutene epoxides by reaction with amines and subsequent dehydration and reduction of amino alcohols;

(e) polyisobutyl amines which may contain a hydroxyl group and which, according to WO-A 97/03946, can be obtained by reacting polyisobutenes with an average degree of polymerization of P from 5 to 100 with nitrogen oxides or mixtures of oxides of nitrogen and oxygen and subsequent hydrogenation of these reaction products;

(f) hydroxyl-containing polyisobutyl amines obtainable according to EP-A 476 485 by reaction of polyisobutene epoxides with ammonia, monoamines or the aforementioned polyamines;

(g) polyetheramines obtainable by reaction of C ₂ -C ₃₀ -alkanols, C ₆ -C ₃₀ alkanediols, mono-, di- or tri-C ₂ -C ₃₀ -alkylamines, C ₁ -C 6 -alkylcyclohexanols or C 1 -C _30- alkylphenols having 1 to 30 moles of ethylene oxide and / or propylene oxide and / or butylene oxide per hydroxyl or amino group followed by reductive amination with ammonia, monoamines or the aforementioned polyamines; such products may also have carrier oil properties;

(h) polyisobutene Mannich bases, which can be obtained in particular according to

EP-A 831 141 or according to German patent applications 199 48 111.3 and 199 48 114.8 by reacting polyisobutenesubstituted phenols with aldehydes and monoamines or the aforementioned polyamines;

(i) the polypropylenamines of WO 94/24231, obtainable by the metallocene catalyzed propene oligomerization followed by the hydroformylation and reductive amination steps mentioned above under (a);

(j) additives containing carboxylic ester groups, preferably based on esters of mono-, di- or tricarboxylic acids with long-chain alcohols or polyols, in particular those having a minimum viscosity of 2 mm ² / s at 100 ° C as described DE-A 38 38 918; examples include adipates, phthalates, isophthalates, terephthalates and trimellitates of isooctanol, isononanol, isodecanol and isotridecanol; such products also have carrier oil properties;

(k) imides, amides, esters and ammonium and alkali metal salts of polyisobutenylsuccinic anhydrides, obtainable from conventional or high-reactive polyisobutene and maleic anhydride by the thermal method or via chlorinated polyisobutene, and may be used, in particular, as derivatives with aliphatic polyamines; such additives for gasoline fuels are described in particular in US-A 4,849,572.

Examples of conventional gasoline fuel additives that inhibit valve seat wear are:

(1) additives containing carboxyl groups or their alkali or alkaline earth metal salts, in particular the copolymers of C ₂ -C ₄₀ -olefins with maleic anhydride, as described in EP-A 307 815 and having a total molecular weight of from 500 to 20 000 and wherein some or all of the carboxyl groups have been reacted to form alkali or alkaline earth metal salts and the remainder of the carboxyl groups have been reacted with alcohols or amines;

(m) additives containing sulfo groups or their alkali metal or alkaline earth metal salts, in particular alkali metal or alkaline earth metal salts with alkyl sulfosuccinates, which salts are described in EP-A 639 632.

In addition to the aforementioned additives to gasoline fuels (a) to (m) and together with them, other conventional carrier oils, admixture components and excipients can be combined with the fatty acid salts of formula I for use in gasoline fuels.

Examples of conventional carrier oils for gasoline fuel additives are mineral carrier oils (base oils), in particular oils of the viscosity class "Solvent Neutral (SN) 500 to 2000", synthetic olefin polymer carrier oils with M _n = 400 to 1800, in particular based on polybutene or polyisobutene (hydrogenated or non-hydrogenated), and based on poly-alpha-olefins or poly-internal-olefins, and synthetic carrier oils based on long-chain alkoxylated alcohols or phenols. It is, of course, also possible to use mixtures of said carrier oils.

Fractions obtained in the treatment of petroleum, for example petroleum, naphtha or heavy oil lubricant, are also suitable as mineral carrier oils and / or diluents or solvents for gasoline fuel additives. Aromatic hydrocarbons, paraffinic (aliphatic) hydrocarbons and alkoxyalkanols are also suitable for this purpose.

Of particular importance as carrier oils for gasoline fuel additives are polyetherols, which are obtainable by reaction of C ₂ -C ₃₀ alkanols, C ₆ -C ₃₀ -alkanediols, mono-, di- or tri-C ₂ -C ₃₀ -alkylamino, C ₁ -C ₃₀ -alkylcyclohexanols or Ο, -Ο-alkylphenols with 1 to 30 moles of ethylene oxide and / or propylene oxide and / or butylene oxide per hydroxyl or amino group. Particular examples here are alcohol-initiated polyetherols having from about 10 to 35, in particular from 15 to 30, propylene oxide and / or butylene oxide units; particularly suitable initiating alcohols are the linear or branched C ₆ -C ₁₅ alkanols.

Other conventional additive components and auxiliaries for gasoline fuels are corrosion inhibitors, for example based on ammonium salts of organic carboxylic acids, which salts tend to form films, or heterocyclic aromatics for corrosion protection of non-ferrous metals, antioxidants or stabilizers, for example based on amines such as amines is, for example, penylenediamine, dicyclohexylamine or derivatives thereof, or based on phenols, such as 2,4-di-tert-butylphenol or 3,5-di-tert-butyl-411 hydroxyphenylpropionic acid, demulsifiers, antistatic agents, metallocenes such as ferrocene or methylcyclopentadienylmanganetricarbonyl, and markers. Linear or branched medium chain alkanols (having, for example, from 6 to 12 carbon atoms) are often used as solubilizers, e.g. 2-ethylhexanol.

Sometimes amines are also added to lower the pH of the fuel.

The fatty acid salts used according to the invention in gasoline fuels and formula I can also be used together with other lubricity enhancers customary for this purpose, such as, in particular, fatty acids, alkenyl succinic esters, bis (hydroxyalkyl) fatty amines or hydroxyacetamides.

The carboxylic acids or fatty acids used as corrosion inhibitors or lubricity enhancers may be present as monomeric or oligomeric, especially dimeric molecules. Mixtures of monomeric and dimeric and, if necessary, higher oligomeric molecules may also be present.

Preference is given to combinations of the fatty acid salts used according to the invention in gasoline fuels and of formula I with detergents of groups (a), (d) and (g) above, in particular with the polyisobutynamines of group (a). Particularly suitable polyisobutyl amines (a) herein are those prepared by hydroformylating high reactive polyisobutenes with a number average molecular weight of from 500 to 2300, in particular from 800 to 1500, preferably from 900 to 1200, followed by reductive amination with ammonia. The polyisobutyl amines (a) are preferably used together with carrier oils, for example polyetherols or aliphatic or aromatic hydrocarbons, and, if necessary, the aforementioned corrosion inhibitors, antioxidants or stabilizers, demulsifiers, antistatic agents, metallocenes and / or markers. A typical example of such polyisobutamine (a) is the product sold under the trade name Kerocom® PIBA by BASF Aktiengesellschaft.

Suitable gasoline fuels are all commercial gasoline fuel compositions. A typical example here is the commercial base fuel Eurosuper according to

EN 228. The gasoline fuel composition described in German patent application 199 05 211.5 is also of interest here.

The fatty acid salts used according to the invention in intermediate distillates and formula I can advantageously be used in all conventional intermediate distillates.

These middle distillates, of which diesel fuel is the most important group, include refined petroleum products, which usually have a boiling range of 100 to 400 ° C. They are generally distillates having a boiling point of 95% to 360 ° C or higher. However, it may also be ultra-low-sulfur or urban diesel having a boiling point of, for example, not more than 345 ° C of 95% and a sulfur content of not more than 0,005% by weight, or a boiling point of 95%, for example of 285 ° C. % of sulfur not more than 0,001%. In addition, these middle distillates may be fuel oils with a sulfur content of not more than 0.20%, preferably not more than 0.10% by weight and aviation fuel.

Said distillates usually consist of components obtained from the distillation of mineral oil under atmospheric or reduced pressure, or obtained from conversion processes, for example gas oil from cracking, coking or viscosity reduction by fine cracking.

Said middle distillates, in particular diesel fuels, are distinguished by a low sulfur content, generally not more than 0.05, preferably not more than 0.02, more preferably not more than 0.005 and most preferably not more than 0.001% by weight.

The fatty acid salts used according to the invention in middle distillates, in particular diesel fuels and of formula I, can be used here as pure liquid substances or as liquid concentrates in a solvent or diluent. In principle, all of the above substances as such compositions for use with gasoline fuel additives may be used herein as solvents or diluents. Particularly suitable are petroleum fractions such as crude naphtha, kerosene, naphtha and aromatic hydrocarbons, for example heavy solvent naphtha, Solvesso® or Shellsol®. These concentrates may be solutions or dispersions, with clear solutions being preferred. Mixtures of the solvents or diluents mentioned may also be used.

By using said solvents or diluents, in particular in a weight ratio to fatty acid salts I of from 1: 10 to 10: 1, preferably from 1: 4 to 4: 1, more preferably from 1: 2 to 2: 1, the solubility can be improved the fatty acid salts used according to the invention and formula I. Such solutions or dilutions are advantageous when the middle distillate already contains further additives, when the mixing temperatures are low, when the dosing agent is not low-dosed, or when mixtures are to be prepared with other middle distillates.

I

The fatty acid salts used according to the invention in middle distillates and formula I can advantageously be used in combination with essentially all conventional middle distillate or diesel fuel additives.

Conventional additives to middle distillates or diesel in this context are, in particular, detergents, corrosion inhibitors, clarifiers, demulsifiers, antifoams, antioxidants, metal deactivators, multifunctional stabilizers, cetane number improvers, combustion enhancers, colorants, markers, solubilizers, , other conventional lubricants and additives that improve low temperature properties, such as flow enhancers (MDFI), paraffin dispersants (WASA) and combinations thereof (WAFI).

The present application also relates to a process for improving the lubricity of petroleum products, in particular gasoline fuels and intermediate distillates, wherein effective amounts of salts of fatty acids and alkoxylated oligoamines of formula I are added to the petroleum products.

The present invention further relates to additive concentrates for petroleum products, in particular for petroleum fuels and middle distillates, containing fatty acid salts and alkoxylated oligoamines of the formula I in amounts of from 0.05 to 50, preferably from 0.1 to 30% by weight, based on total amount of concentrates. These concentrates usually also contain the aforementioned other additives, carrier oils, solvents or diluents and / or excipients. In the case of gasoline fuel additive concentrates, these are in particular detergents and / or valve seat wear inhibiting compositions, in particular additives (a) to (m) above, and further components and auxiliaries customary for this purpose, in particular carrier oils, corrosion inhibitors, antioxidants or stabilizers, demulsifiers, antistatic agents, metallocenes and markers.

The present invention further relates to petroleum products, in particular gasoline fuel and middle distillate compositions which contain fatty acid salts and alkoxylated oligoamines of formula I in effective amounts. As a rule, effective amounts are to be understood in the case of gasoline compositions and in the case of oil compositions 1 to 1000, preferably 5 to 500, more preferably 10 to 250 and most preferably 20 to 100 ppm by weight in each case relative to the total amount of the composition. These petroleum products, in particular gasoline fuel and middle distillate compositions, generally contain the abovementioned additives, ingredient components and excipients in addition to the fatty acid salts I used according to the invention.

Salts of fatty acids and alkoxylated oligoamines of formula I are highly effective as lubricity enhancers even at low concentrations in petroleum products and effectively protect against wear on parts of machinery and systems operating with petroleum products, such as fuel intake systems or injection pumps.

In addition, the fatty acid salts of the alkoxylated oligoamines of formula I have good compatibility with lubricating oil, which is particularly important when used in diesel fuels. Due to the interaction of lubricity enhancers (eg dimeric fatty acids) used hitherto with the base components of the lubricating oil, which are in contact with the fuel in gasoline and diesel engines, the respective salts may be stored in the fuel and on unwanted surfaces of the engine or injection system. cause malfunctions. This disadvantage can be avoided by new uses of fatty acid salts and alkoxylated oligoamines of formula I.

Moreover, the salts of the fatty acids and alkoxylated oligoamines of the formula I which are used according to the invention have virtually no tendency to undesirably form emulsions in petroleum products and are sufficiently stable to hydrolysis.

The following examples illustrate the invention without limiting its scope.

DETAILED DESCRIPTION OF THE INVENTION

Example 1: Preparation of Bisoleic Acid Salt and 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 conventional reaction of 1,2-ethylenediamine with 4 mol of propylene oxide in the presence of approximately 3 % by weight (based on the amount of amine used) of water at 100-110 ° C) was heated to 60-80 ° C and mixed with 110.4 g (0.4 mol) oleic acid over 2 hours with stirring. During this procedure the pH did not drop below 7. Stirring was then continued for a further 2 hours at the indicated temperature range. The product obtained had an N titer of 2.39 mmol / g (calculated 2.37 mmol / g).

Example 2: Preparation of Bisoleic Acid Salt and N, N, N ', N'-tetrakis (2'-hydroxyethyl) -1,2-ethylenediamine

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

Examples of use

Example 3: Determination of friction corrosion values in gasoline fuel

A high frequency reciprocating rig (HFRR) from PCS Instruments, London, was used to test for lubricity or wear in gasoline fuels. The measurement conditions were adapted to the use of gasoline fuels. The suitability of this test method for petrol fuel is demonstrated by D. Margaroni, Industrial Lubrication and Tribology, Vol. 50, no. 3, May / June 1998, pages 108-118, and W. D. Ping, S. Korcek, H. Spikes, SAE Techn. Taper 962010, pages 51-59 (1996).

The gasoline fuel (GF) used herein (typically gasoline according to EN 228) was vaporized to 50% by volume distillation under mild conditions for measurement. This 50% residue was used in a test in a wear measuring instrument to determine the baseline. Additional ingredients were added to this residue according to the examples below and friction corrosion values were determined according to the above method. The friction corrosion values obtained (F) are given in micrometres (pm); the lower this value, the lower the resulting wear.

The 50% by volume residue of Eurosuper GF1 gasoline gave a default value of F = 873 pm in the HFRR test, while a 50% by volume of comparable Eurosuper GF2 gasoline fuel gave a default value of F = 754 pm in the HFRR test. Adding 500 mg / kg of a commercial finished fuel additive blend P1 (based on polyisobutynamine detergent, synthetic carrier oil and conventional corrosion inhibitor) or a commercial finished fuel blend additive P2 (analogous to P1 but with other synthetic carrier oil) to the remainder in any case, it resulted in friction corrosion values of the same order of magnitude. The addition of in each case 50 mg / kg of the novel lubricity enhancers of Examples 1 and 2 or of the prior art lubricity enhancers resulted in correspondingly lower values, the new products generally being substantially better than the prior art compositions. The values obtained are shown in Table 1.

Table 1: Friction corrosion values F in petrol fuel

Additive added GF R [μπι] any GF1 873 500 mg / kg of mixture P1 GF1 853 500 mg / kg of P1 + 50 mg / kg of the product of Example 2 GF1 686 no GF2 754 500 mg / kg of mixture P1 GF2 717 500 mg / kg of P1 + 50 mg / kg of the product of Example 1 GF2 593 500 mg / kg of P1 + 50 mg / kg of the product of Example 2 GF2 634 500 mg / kg of P1 + 50 mg / kg comparative product GF2 659 500 mg / kg of mixture P2 GF2 775 500 mg / kg of P2 + 50 mg / kg of the product of Example 1 GF2 680 500 mg / kg of P2 + 50 mg / kg of the product of Example 2 GF2 633 500 mg / kg of P2 + 50 mg / kg comparative product GF2 684

In each case, a tall oil fatty acid lubricating agent and according to WO 98/11175 was used as a comparative product.

Example 4: Determination of friction corrosion values in diesel fuels

Standard lubricity tests were performed using an HFRR instrument from PCS Instruments, London, in which a steel ball is rubbed against a steel plate in the fuel being tested. This method is described in ISO 12156-1 and has also been introduced in the EN 590-1999 diesel standard. The limit given here is a steel ball abrasion of not more than 460 μιτι. Low sulfur, unadditioned diesel fuels may have frictional corrosion values of F typically from 400 to 700 μιτι.

The diesel oils tested (DF1 to DF4) listed in Table 2 had the characteristics listed.

Table 2: Characteristics of diesel fuels tested

DF 1 DF2 DF3 DF4 quality [Mg / kg] EN 590 EN 590 EN 590 C-DKMK 1 Sulfur content [kg / m ³ ] 180 700 430 6 density [° C] 841.3 835.6 830.6 810.6 CP [° C] -6 -6 -7 -31 CFPP [° C] -9 -10 -10 -32 Initial boiling point [° C] 170 176 175 184 20% vol [° C] 235 214 218 219 95% vol [° C] 363 352 343 280 Final boiling point [° C] 371 370 356 289

The sulfur content was determined according to EN ISO 14 596.

The following diesel fuel additives were used:

Additive A:

the product of Example 2 used according to the invention (undiluted)

Additive B:

the product of Example 1 used according to the invention (undiluted)

Additive C:

for comparison commercial means for improving lubricity based on a mixture of sterically hindered alkylphenol and a long chain carboxylic acid

Additive D:

for comparison, a commercial lubricity enhancer based on a mixture of carboximide and a natural fatty ester

Additive E:

for comparison commercial composition for improving lubricity based on a mixture of glyceryl monooleate and glyceryl monolinoleate

Additive F:

for comparison, a commercial composition for improving lubricity based on a long chain carboxylic acid mixture

Table 3 below shows the results of determining the friction corrosion values F in the test diesel fuels. It is clear that the effect of products A and B used according to the invention is better than that of commercial products C to F.

Table 3:

Friction corrosion values F (pm) in diesel (WS 1.4 HFRR values according to ISO 12 156-1 at 60 ° C)

Additive added DF1 DF2 DF3 DF4 no 532 (1) 624 (1) 615 (1) 565 (0) Additive A 389 (49) 375 (49) 363 (99) 399 (74) 358 (201) Additive B 355 (49) 471 (49) 359 (99) 401 (74) 388 (199) Additive C 436 (49) 455 (49) 330 (99) - 435 (201) 453 (250) Additive D 517 (49) 474 (151) 252 (199) - 518 (150) 387 (201) Additive E 471 (49) 473 (99) 282 (49) 578 (250) 350 (350) Additive F - - 421 (74) -

The values in brackets represent the dose in ppm by volume.

Example 5: Compatibility with lubricating oil

The tendency of the additive to form insoluble precipitates with lubricating oil can be checked by various standardized laboratory tests. Here, the test prescribed by DGMK (Deutsche Wissenschaftliche Gesellschaft für Erdol, Erdgas und Kohle e.V., Research Board 531) was used. According to this procedure, 10 ml of engine 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 was cooled and visually evaluated. This mixture is made up to 500 ml with diesel oil and filtered through a 0.8 µm filter (SEDAB specification). The occurrence of a gel or sediment and a filtering time exceeding 300 seconds leads to a "non-compliant" result. On the other hand, 'compliant' means that the test requirements have been met.

Table 4 below, which contains the results of this test, illustrates the fact that the A and B lubricity enhancers used according to the invention are unlikely to have any adverse interactions with the lubricating oil.

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

additive for 72 h at 90 ° C Filtration time [s] Rating no - 112 - Additive A v / cire 86 suits Additive B clear 89 suits Additive D (for comparison) turbid > 300 does not Additive G (for comparison) turbid, non-homogeneous, gel-like particles > 1800 does not

Commercial dimer fatty acid was used as another comparative additive G.

f f 2002 2002

Claims (10)

PATENT CLAIMS Use of fatty acid salts and alkoxylated oligoamines of formula I H - (OA) _{XX -} H - (OA) _{X -} [R - COO] _m + - | (D where A is an alkylene group having 2 to 8 carbon atoms, R. is C ₇ -C ₂₃ -alkyl or mono- or polyunsaturated C ₇ -C ₂₃ alkenyl, which may additionally carry hydroxyl groups, Z is a C 1 -C ₈ -alkylene group, a C ₃ -C ₈ -cycloalkylene group or a C ₆ -C ₁₂ -arylene or arylalkylene group, m is an integer from 1 to 5 and the sum of all variables x is from 50 to 300% of (m + 3) as lubricity enhancers for petroleum products. Use of fatty acid salts and alkoxylated oligoamines of formula I according to claim 1, wherein A is a 1,2-ethylene, 1,2-propylene or 1,2-butylene group. Use of fatty acid salts and alkoxylated oligoamines of formula I according to claim 1 or 2, wherein R is a mono- or polyunsaturated C ₁₅ - C ₁₉ alkenyl group which may further carry hydroxyl groups. Use of salts of fatty acids and alkoxylated oligoamines of formula I according to any one of claims 1 to 3, wherein Z is a polymethylene group of formula (CH ₂ ) _n -, wherein n is from 2 to 6. Use of fatty acid salts and alkoxylated oligoamines of formula I according to any one of claims 1 to 4, wherein m is 1 or 2. Use of fatty acid salts and alkoxylated oligoamines of formula I according to any one of claims 1 to 5, wherein the sum of all variables x is from 75% to 125% of (m + 3). Use of fatty acid salts and alkoxylated oligoamines of formula I according to any one of claims 1 to 6 as lubricity enhancers in gasoline fuels and middle distillates. Process for improving the lubricity of petroleum products, in particular gasoline fuels and middle distillates, characterized in that effective amounts of the fatty acid salts and alkoxylated oligoamines of the formula I according to any one of claims 1 to 6 are added to the petroleum products. Additive concentrate for petroleum products, in particular for petroleum fuels and middle distillates, characterized in that it contains salts of fatty acids and alkoxylated oligoamines of the formula I according to any one of claims 1 to 6 in amounts of from 0.05 to 50% by weight. Petroleum product, in particular a gasoline fuel or middle distillate composition, characterized in that it contains salts of the fatty acids and alkoxylated oligoamines of the formula I according to any one of claims 1 to 6 in effective amounts.