EP1230330B1 - Use of fatty acid salts of alkoxylated oligoamines as lubricity improvers for petroleum products - Google Patents

Description

The present invention relates to the use of fatty acid salts of alkoxylated oligoamines as lubricity improvers for petroleum products, especially for petrol and Middle distillates, especially diesel fuels, and such Mineral oil products themselves, which contain special fatty acid salts from alkoxylated Contain oligoamines.

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

These residues shift the air-fuel ratio in the Idling and in the lower part-load range, so that the mixture lean, the combustion of incomplete and again the proportions of unburned or partially burned hydrocarbons in the exhaust gas larger and gasoline consumption increases.

It is known that to avoid these disadvantages, fuel additives for keeping valves and carburetor or injection systems clean gasoline engines (see e.g. 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 one Numerous classes of chemical substances such as polyalkenamines, polyetheramines, Polybutene Mannich bases or polybutene succinimides can generally come in combination with Carrier oils and some other additive components such as corrosion inhibitors and demulsifiers for use.

Show petrol with and without such additive components however mostly an inadequate and improvement behavior with regard to their lubricity and wear protection properties in gasoline engines.

Also the low-sulfur diesel fuels used more and more these days show lubricity problems that arise, for example in increased wear on the injection pumps. The lowering of the sulfur content in diesel fuels is to reduce or avoid sulfur dioxide and particle emissions required. To achieve low sulfur levels the diesel fuels must be hydrogenated. Thereby are also polar and polynuclear aromatic components in the Fuel destroys the natural lubricating effect of the diesel fuel cause. So here too - as with the Petrol - a need for additives that increase lubricity increase in fuel efficiently (also as "Lubricity Additive" or "Friction Modifier").

Lubricity-improving agents previously known for petrol Additives are, for example, fatty acids, such as. B. in the WO 98/11175 describes 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 glycerin with unsaturated fatty acids, or castor oil, as in EP-B 605 857 as lubricity-improving Additives used.

However, since the means of the prior art mentioned in their Property profile, especially with regard to their lubrication and Wear protection effect, are still in need of improvement, lay the present invention has the object of being more effective Lubricity improver for mineral oil products, in particular for petrol and middle distillates.

in der die variablen

A

für Alkylengruppen mit 2 bis 8 C-Atomen stehen,

R

C₇- bis C₂₃-Alkylgruppen oder ein- oder mehrfach ungesättigte C₇- bis C₂₃-Alkenylgruppen, welche zusätzlich Hydroxylgruppen tragen können, bezeichnen,

Z

C₁- bis C₈-Alkylengruppierungen, C₃- bis C₈-Cycloalkylengruppierungen oder C₆- bis C₁₂-Arylen- oder -Arylalkylengruppierungen bedeuten,

m

für 0 oder eine ganze Zahl von 1 bis 5 steht und

die Summe aller Variablen x einen Wert von 50% bis 300% von (m+3) hat,
als Schmierfähigkeitsverbesserer für Mineralölprodukte gefunden.Accordingly, the use of fatty acid salts of alkoxylated oligoamines of the general formula I

in which the variable

A

represent alkylene groups with 2 to 8 carbon atoms,

R

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

Z

C ₁ to C ₈ alkylene groupings, C ₃ to C ₈ cycloalkylene groupings or C ₆ to C ₁₂ 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. US Pat. No. 4,131,583 describes salts of in particular unsaturated C ₁₁ -C ₂₀ -carboxylic acids with N, N, N ', N'-tetrahydroxyethyl-C ₂ -C ₄ -alkylenediamines, but these are used exclusively as corrosion inhibitors in aqueous coating compositions 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 prevents the formation of rust and fungus and stabilizes the composition. An improvement in Lubrication is not mentioned here.

JP-A 11/209773 describes aqueous lubricants for conveyor belts known when filling bottles with drinks, which Fatty acid salts of alkanolamines such as N, N, N ', N'-tetrakis (2-hydroxypropyl) ethylenediamine contain. As fatty acids, for example Palmitic acid, tetradecanoic acid, oleic acid and lauric acid called.

DE-B 1 047 526 recommends fatty acid salts of alkoxylated oligoamines as a remedy against the icing of the gasifier of gasoline engines. As a concrete connection in this regard, the mononaphthenate salt of N, N, N ', N'-tetrakis (2-oxypropyl) ethylenediamine called. However, there are no indications of a lubricating effect given this means.

US-A 3 429 673 discloses carboxylic acid salts of alkoxylated monoamines as corrosion inhibitors in fuel oils.

Among mineral oil products, fuels, operating materials, Fuels and lubricating oils are understood, but not only on petroleum but also partly or completely on synthetic and / or naturally occurring raw materials. Examples for such raw materials are natural gas, methanol, ethanol, Coal liquefaction products or rapeseed oil, which are used as fuels processed or incorporated into petroleum-based fuels become. The designated mineral oil products are usually practically anhydrous or at least only contain water in minor amounts. Examples of water-containing mineral oil products are fuel emulsions like diesel / water emulsions that can usually contain up to about 35% by weight of water. For the present invention preferred mineral oil products are for one petrol and the other middle distillates such as in particular Diesel fuels.

The alkylene group A is preferably derived from the corresponding ones 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 for 1,3-propylene, 1,4-butylene, 1,6-hexylene or 1,8-octylene stand. A can also be a mixture of various of the above Represent groupings. Are particularly preferred for A ethylene, 1,2-propylene or 1,2-butylene groups.

The longer-chain radical R occurring in the carboxylate anion denotes, for example, branched or preferably linear C ₇ - to C ₂₃ -, preferably C ₁₁ - to C ₂₁ -, especially C ₁₅ - to C ₁₉ -alkyl groups, which can additionally carry hydroxyl groups. Examples of 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), octadecanoic acid (stearic acid) and e. 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 ₂₃ radicals, in particular mono- or poly-unsaturated C ₁₁ to C ₂₁ , especially C ₁₅ to C ₁₉ 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 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 - to C ₄ -alkylene groupings such as methylene, 1,2-propylene, 1,2-butylene, 1,3-butylene or 2,3-butylene, C ₅ - to C ₆ -cycloalkylene groupings such as 1 , 3-cyclopentylidene or 1,3- or 1,4-cyclohexylidene or C ₆ - to C ₈ -arylene or -arylalkylene groupings such as 1,3- or 1,4-phenylene, 2-methyl-1,4-phenylene or 1,3- or 1,4-bismethylene phenylene.

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

If the variable m stands for 0, it is usually dependent on the Sum (Σ) of all variables x, mixtures of mono-, di- and / or Trialkanolamines or pure trialkanolamines according to the invention used fatty acid salts as a cationic component. Examples of such alkanolamines are monoethanolamine, diethanolamine, Triethanolamine, monoisopropanolamine, diisopropanolamine, Triisopropanolamine and the corresponding mixtures. In this The oleic acid salt of triethanolamine (Σx = 3) is of particular importance 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 are usually complete and / or partially alkoxylated dialkylenetriamines such as Di- (1,2-ethylene) -triamine, di- (1,3-propylene) -triamine or Di- (1,4-butylene) -triamine based. In this group are the bis oleic acid salts of N, N, N ', N'-tetrakis (2'-hydroxyethyl) -1,2-ethylenediamine (Σx = 4) and N, N, N ', N'-tetrakis (2'-hydroxypropyl) -1,2-ethylenediamine (Σx = 4) and the tris oleic acid salts of reacted with 4 to 5 mol of ethylene oxide or 1,2-propylene oxide Di- (1,2-ethylene) -triamine of particular interest.

However, it is also possible to use higher homologs of the alkylenediamines mentioned and dialkylenetriamines such as triethylenetetramine (m = 3), tetraethylene pentamine (m = 4) or pentaethylene hexamine (m = 5) as an amine component for those used according to the invention Based on fatty acid salts.

The number of alkylene oxide (OA) units introduced per amine molecule can be the number of N-H bonds in the underlying Correspond to amine (Σx = m + 3). However, it can also do more or less OA units can be installed. With superstoichiometric Incorporation is a triple alkoxylation per N-H bond [300% of (m + 3)] with regard to the properties of the resulting fatty acid salts an upper limit. With sub-stoichiometric installation a statistical average 50% alkoxylation [50% of (m + 3)] a corresponding lower limit, usually mixtures from species with different degrees of alkoxylation in front.

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

The general fatty acid salts used according to the invention Formula I can usually be easily by alkoxylation of the underlying amines by conventional methods and subsequent Establish neutralization with the fatty acids of the formula R-COOH.

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

The neutralization is usually carried out by heating the thus obtained alkoxylated amine with the corresponding stoichiometric or slightly sub-stoichiometric amount (i.e. 90 to 100 %, in particular 95 to 100% of theory) of fatty acid at temperatures from 30 to 100 ° C, especially 40 to 80 ° C, for a period of time from 15 minutes to 10 hours, especially 30 minutes to 5 hours. The neutralization reaction should be carried out that no carboxylic acid ester portions arise in the product. In many Cases can include both the alkoxylated amine and the fatty acid be used as liquids, which is the implementation of corresponding fatty acid salt designed particularly simple. The Order of combining alkoxylated amine and fatty acid is not critical, i.e. one can use both the alkoxylated amine and add the fatty acid as well as the fatty acid and add the alkoxylated amine.

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

The production of the fatty acid salts used according to the invention the general formula I usually requires significantly less effort and energy than with conventional lubricity improvers State of the art, especially in those based on amides or esters, which are usually produced at higher temperatures, longer reaction times and time-consuming refurbishment work to separate unwanted by-products, in particular occur in condensation reactions are necessary.

The fatty acid salts of general formula I described are suitable excellently as a lubricity improver ("Lubricity Additive", "Friction Modifier") in mineral oil products, especially in petrol and middle distillates, especially diesel fuels. The fatty acid salts I are general highly effective and therefore widely applicable. When using the Fatty acid salts I will tend to wear in the parts of the machines operated with the mineral oil products and aggregates significantly reduced.

The fatty acid salts used in petrol according to the invention of the general formula I can advantageously with In principle, all common gasoline additives are used in combination become.

(a) Polyisobutenamine, welche gemäß der EP-A 244 616 durch Hydroformylierung von hochreaktivem Polyisobuten des zahlengemittelten Molgewichtes von 300 bis 5000 und anschließende reduktive Aminierung mit Ammoniak, Monoaminen oder Polyaminen wie Dimethylenaminopropylamin, Ethylendiamin, Diethylentriamin, Triethylentetramin oder Tetraethylenpentamin erhältlich sind;

(b) Poly(iso)butenamine, welche durch Chlorierung von Polybutenen oder Polyisobutenen mit Doppelbindungen überwiegend in der β-und γ-Position und anschließende Aminierung mit Ammoniak, Monoaminen oder den oben unter (a) genannten Polyaminen erhältlich sind;

(c) Poly(iso)butenamine, welche durch Oxidation von Doppelbindungen in Poly(iso)butenen mit Luft oder Ozon zu Carbonyl- oder Carboxylverbindungen und anschließende Aminierung unter reduzierenden (hydrierenden) Bedingungen erhältlich sind;

(d) Polyisobutenamine, welche gemäß der DE-A 196 20 262 aus Polyisobutenepoxiden durch Umsetzung mit Aminen und nachfolgende Dehydratisierung und Reduktion der Aminoalkohole erhältlich sind;

(e) gegebenenfalls Hydroxylgruppen enthaltende Polyisobutenamine, welche gemäß der WO-A 97/03946 durch Umsetzung von Polyisobutenen mit einem mittleren Polymerisationsgrad P = 5 bis 100 mit Stickoxiden oder Gemischen aus Stickoxiden und Sauerstoff und anschließende Hydrierung dieser Umsetzungsprodukte erhältlich sind;

(f) Hydroxylgruppen enthaltende Polyisobutenamine, welche gemäß der EP-A 476 485 durch Umsetzung von Polyisobutenepoxiden mit Ammoniak, Monoaminen oder den oben genannten Polyaminen erhältlich sind;

(g) Polyetheramine, welche durch Umsetzung von C₂- bis C₃₀-Alkanolen, C₆- bis C₃₀-Alkandiolen, Mono-, Di- oder Tri-C₂- bis C₃₀-alkylaminen, C₁- bis C₃₀-Alkylcyclohexanolen oder C₁- bis C₃₀-Alkylphenolen mit 1 bis 30 mol Ethylenoxid und/oder Propylenoxid und/oder Butylenoxid pro Hydroxyl- bzw. Aminogruppe und anschließende reduktive Aminierung mit Ammoniak, Monoaminen oder den oben genannten Polyaminen erhältlich sind - derartige Produkte erfüllen auch Trägeröleigenschaften;

(h) "Polyisobuten-Mannichbasen", welche insbesondere gemäß EP-A 831 141 oder gemäß DE-A-199 48 111 und 199 48 114 durch Umsetzung von polyisobutensubstituierten Phenolen mit Aldehyden und Monoaminen oder den oben genannten Polyaminen erhältlich sind;

(i) Polypropylehamine gemäß WO 94/24231, welche durch metallocenkatalysierte Propen-Oligomerisierung und nachfolgend die oben unter (a) genannten Schritte der Hydroformylierung und reduktiven Aminierung erhältlich sind;

(j) Carbonsäureestergruppen enthaltende Additive, vorzugsweise auf Basis von Estern aus Mono-, Di- oder Tricarbonsäuren mit langkettigen Alkoholen oder Polyolen, insbesondere solchen mit einer Mindestviskosität von 2 mm2/s bei 100°C, wie sie in DE-A 38 38 918 beschrieben sind, als Beispiele können hier Adipate, Phthalate, iso-Phthalate, Terephthalate und Trimellitate des iso-Octanols, iso-Nonanols, iso-Decanols und iso-Tridecanols genannt werden - derartige Produkte erfüllen auch Trägeröleigenschaften;

(k) Imide, Amide, Ester und Ammonium- und Alkalimetallsalze von Polyisobutenbernsteinsäureanhydriden, welche aus konventionellem oder hochreaktivem Polyisobuten und Maleinsäureanhydrid auf thermischem Wege oder über das chlorierte Polyisobuten erhältlich sind und insbesondere in Form der Derivate mit aliphatischen Polyaminen eingesetzt werden können - derartige Ottokraftstoffadditive sind insbesondere in US-A 4 849 572 beschrieben.
Übliche Ottokraftstoffadditive mit ventilsitzverschleißhemmender Wirkung sind beispielsweise:

(l) Carboxylgruppen oder deren Alkalimetall- oder Erdalkalimetallsalze enthaltende Additive, insbesondere wie die in der EP-A 307 815 beschriebenen Copolymeren von C₂-C₄₀-Olefinen mit Maleinsäureanhydrid mit einer Gesamtmolmasse von 500 bis 20 000, deren Carboxylgruppen ganz oder teilweise zu den Alkalimetall- oder Erdalkalimetallsalzen und ein verbleibender Rest der Carboxylgruppen mit Alkoholen oder Aminen umgesetzt sind;

(m) Sulfonsäuregruppen oder deren Alkalimetall- oder Erdalkalimetallsalze enthaltende Additive, insbesondere wie die in der EP-A 639 632 beschriebenen Alkalimetall- oder Erdalkalimetallsalze von Sulfobernsteinsäurealkylestern.

Usual petrol additives with detergent effects are for example:

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

(b) poly (iso) butenamines which are obtainable 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 carbonyl or carboxyl compounds and subsequent amination under reducing (hydrogenating) conditions;

(d) polyisobutenamines which, according to DE-A 196 20 262, can be obtained from polyisobutene epoxides 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 are obtainable according to EP-A 476 485 by reacting polyisobutene epoxides with ammonia, monoamines or the above-mentioned polyamines;

(g) polyetheramines obtained by reacting C ₂ -C ₃₀ alkanols, C ₆ -C ₃₀ alkanediols, mono-, di- or tri-C ₂ -C ₃₀ -alkylamines, C ₁ -C ₃₀ -Alkylcyclohexanolen or C ₁ - to C ₃₀ -alkylphenols with 1 to 30 mol 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 - meet such products also carrier oil properties;

(h) "Polyisobutene Mannich bases", which are obtainable in particular according to EP-A 831 141 or DE-A-199 48 111 and 199 48 114 by reacting polyisobutene-substituted phenols with aldehydes and monoamines or the above-mentioned polyamines;

(i) Polypropylehamines 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 Adipates, phthalates, iso-phthalates, terephthalates and trimellitates of iso-octanol, iso-nonanols, iso-decanols and iso-tridecanols can be mentioned as examples here - products of this type also fulfill carrier oil properties;

(k) Imides, amides, esters and ammonium and alkali metal salts of polyisobutene succinic anhydrides, which can be obtained from conventional or highly reactive polyisobutene and maleic anhydride by thermal means or via the chlorinated polyisobutene and can be used in particular in the form of derivatives with aliphatic polyamines - such gasoline additives described in particular in US-A 4,849,572.
Common gasoline additives with valve seat wear-inhibiting effects include:

(l) Carboxyl groups or additives containing their alkali metal or alkaline earth metal salts, in particular such as the copolymers of C ₂ -C ₄₀ 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 petrol additives (a) bis (m) can further conventional carrier oils, additive components and Aid with the fatty acid salts of the general formula I for Combined use in petrol.

The usual carrier oils for petrol additives are, for example, mineral carrier oils (base oils), especially 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.

As mineral carrier oils and / or dilution or Solvents for petrol additives are also available at Fractions such as kerosene, naphtha or petroleum processing Brightstock suitable. Aromatic are also suitable for this Paraffinic (aliphatic) hydrocarbons Hydrocarbons and alkoxyalkanols.

Of particular importance as carrier oils for gasoline fuel additives are polyetherols which, by reacting C ₂ -C ₃₀ -alkanols, C ₆ -C ₃₀ -alkanediols, mono-, di- or tri-C ₂ -C ₃₀ -alkylamines, C ₁ to C ₃₀ alkylcyclohexanols or C ₁ to C ₃₀ 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 ₁₅ -alkanols are particularly suitable as starter alcohols.

Other common additive components and auxiliaries for petrol are corrosion inhibitors, for example based of film-forming ammonium salts of organic carboxylic acids or of 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 of phenols such as 2,4-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). As a mediator are often medium chain linear or branched Alkanols (with about 6 to 12 carbon atoms) are used, e.g. B. 2-ethylhexanol. Sometimes amines are also used to lower the pH of the Added fuel.

The fatty acid salts used in petrol according to the invention of the general formula I can also be used together with others usual lubricity improvers such as certain Fatty acids, alkenyl succinic acid esters, bis (hydroxyalkyl) fatty amines or hydroxyacetamides can be used.

The as corrosion inhibitors or lubricity improvers Carboxylic acids or fatty acids used can be used as monomers or oligomeric, in particular dimeric, species are present. It can also mixtures of monomeric and dimeric and possibly higher ones oligomeric species are present.

Combinations of the gasoline fuels according to the invention are preferred used fatty acid salts of the general formula I with the detergents of groups (a), (d) and (g) mentioned above, especially with polyisobutenamines of group (a). Particularly suitable Polyisobutenamines (a) are those which are produced by hydroformylation of highly reactive polyisobutenes of the number average Molecular weight of 500 to 2300, especially 800 to 1500, especially 900 to 1200, and subsequent reductive amination be made with ammonia. The polyisobutenamines (a) are preferably used together with carrier oils, for example polyetherols or aliphatic or aromatic hydrocarbons, and optionally with the aforementioned corrosion inhibitors, Antioxidants or stabilizers, demulsifiers, antistatic agents, Metallocenes and / or dyes used. As a a typical example of such a polyisobutenamine (a) is under the trade name Kerocom® PIBA from BASF Aktiengesellschaft to name distributed product.

All commercially available petrol compositions can be used as petrol are used. As a typical representative here the standard Euro super base fuel according to EN 228 is mentioned become. Furthermore, DE-A-199 is also here 05 211 described petrol composition of interest.

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

To these middle distillates, of which diesel fuels are the most important group, include petroleum refines, which are usually have a boiling range of 100 to 400 ° C. these are mostly distillates with a 95% point up to 360 ° C or above out. But this can also be called "ultra low sulfur" Diesel "or" City Diesel ", identified by a 95% point of, for example, a maximum of 345 ° C and a sulfur content of at most 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 use heating oils with a maximum sulfur content of 0.20% by weight, in particular a maximum of 0.10% by weight, as well as aviation fuels.

The distillates mentioned usually consist of components together that one from atmospheric or vacuum distillation from oil or from conversion processes, z. B. cracker, koker or visbreaker gas oil.

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

According to the invention in middle distillates, especially diesel fuels, fatty acid salts of the general formula I used herein as pure liquid substances or as liquid concentrates be incorporated in a solvent or diluent. In principle, as solvents or diluents all as such means for use with gasoline additives mentioned substances are used. especially mineral oil cuts such as naphtha, kerosene, Diesel fuel and aromatic hydrocarbons such as solvents Heavy naphtha, Solvesso® or Shellsol®. These concentrates can Be solutions or dispersions, with clear solutions preferred become. Mixtures of the solutions mentioned or Thinners are used.

By using the solvents or diluents mentioned, in particular in relation to the weight of the fatty acid salts I of 1:10 to 10: 1, especially from 1: 4 to 4: 1, especially from 1: 2 to 2: 1, the solubility of the fatty acid salts used according to the invention of the general formula I can be improved. Such solutions or dilutions are advantageous if the middle distillate already contains other additives when the mixing temperatures be low if the dosing device is not on low doses or if mixtures with other middle distillates to be produced.

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

Common middle distillate or diesel fuel additives are in this connection especially detergents, corrosion inhibitors, Dehazer, demulsifiers, anti-foaming agents ("Antifoam"), antioxidants, Metal deactivators, multifunctional stabilizers, Cetane number improvers, combustion improvers, dyes, Markers, solubilizers, antistatic agents, other common lubricity Additives as well as additives improving the cold properties such as Flow improvers ("MDFI"), paraffin dispersants ("WASA") and their Combination ("WAFI").

The present application also relates to a method for Improve the lubricity of mineral oil products, in particular of petrol and middle distillates, which thereby is characterized in that the mineral oil products are effective Amounts of fatty acid salts of alkoxylated oligoamines of the general Formula I 1 to 6 admits.

Additive concentrates for mineral oil products, especially for petrol and middle distillates, 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 wt .-%, based on the total amount of the concentrates. These contain concentrates usually also the other additives, carrier oils, solution or Diluents and / or auxiliaries. In the case of additive concentrates for petrol, these are especially detergents and / or valve seat anti-wear agents, especially the additives (a) to (m) listed above, and others therefor usual components and auxiliaries, 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 is the bis-oleic acid salt of N, N, N ', N'-tetrakis (2'-hydroxyethyl) -1,2-ethylenediamine or N, N, N ', N'-tetrakis (2'-hydroxypropyl) -1,2-ethylenediamine contained in effective amounts. Effective amounts are usually both at Ottoals also with diesel fuel compositions 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, in each case based on to understand the total amount of the composition. These petroleum products, especially the gasoline and middle distillate compositions, usually contain in addition to the invention fatty acid salts used in them include those listed above Additives, additive components and auxiliaries.

The fatty acid salts of alkoxylated oligoamines of the general Formula I are already in low concentrations in the mineral oil products highly effective as a lubricity improver and prevent wear in the parts of those with the mineral oil products operated machines and units, for example in Fuel intake systems or injection pumps, effectively before.

Furthermore, the fatty acid salts of alkoxylated oligoamines general formula I has good lubricating oil compatibility, which is particularly important when used in diesel fuels is. Through the interaction of previously used acidic lubricity improvers (such as dimeric fatty acids) basic components of lubricating oil, which is used in petrol and diesel engines is known to be in contact with the fuel, can corresponding salts in the fuel and undesirable Separate the engine or the injection system and Cause interference. This disadvantage is caused by the invention Use of the fatty acid salts of alkoxylated oligoamines of the general formula I avoided.

The fatty acid salts used according to the invention also tend to alkoxylated oligoamines of general formula I practically not to unwanted emulsion formation in the mineral oil products and are sufficiently stable to hydrolysis.

The following examples are intended to illustrate the present invention but without limiting 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 (Made by the usual 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 amine used, at 100 to 110 ° C) were heated to a temperature of 60-80 ° C and inside two hours with stirring with 110.4 g (0.4 mol) of oleic acid added. The pH did not drop below 7. Subsequently was stirred for 2 hours in 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 analogous to Example 1 with the analog Amounts of N, N, N ', N'-tetrakis (2'-hydroxyethyl) -1,2-ethylenediamine manufactured.

applications Example 3: Determination of the frictional wear values in petrol

For checking the lubricity or wear in petrol became a High Frequency Reciprocating Rig (HFRR) device from PCS Instruments, London. The measurement conditions have been adapted to the use of petrol. The applicability of this test method for petrol is by the references D. Margaroni, Industrial Lubrication and Tribology, Vol. 50, No. 3, May / June 1998, pp. 108-118, and W. D. Ping, S. Korcek, H. Spikes, SAE Techn. Paper 962010, pp. 51-59 (1996).

The petrol used here (OK) (typical petrol according to EN 228) were distilled before the measurements gently concentrated to 50% by volume. This 50% residue served when checking in the wear measuring device to determine the Blank value. This backlog was made according to the below given examples given the other additives and the Friction wear values were determined using the method given above. The resulting friction wear values (R) are in micrometers (µm) specified; the lower this value is, the lower is the wear that occurs.

The 50 vol.% Residue of a Eurosuper petrol OK1 resulted in a blank value of R = 873 µm in the HFRR test, the 50 vol.% Residue of a comparable Eurosuper petrol OK2 resulted in a blank value of R = in the HFRR test 754 µm. The addition of 500 mg / kg of a commercially available petrol additive package P1 (based on a polyisobutenamine detergent, a synthetic carrier oil and a common corrosion inhibitor) or a commercially available petrol additive package P2 (analogous to P1 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 each of the lubricity improvers according to the invention 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 clearly superior to those of the prior art. The values obtained are listed in Table 1 below. Frictional wear values R in petrol added additives OK R [µm] no OK1 873 500 mg / kg package P1 OK1 853 500 mg / kg package P1 + 50 mg / kg product from example 2 OK1 686 no OK2 754 500 mg / kg package P1 OK2 717 500 mg / kg package P1 + 50 mg / kg product from example 1 OK2 593 500 mg / kg package P1 + 50 mg / kg product from example 2 OK2 634 500 mg / kg package P1 + 50 mg / kg comparison 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

As a comparison product was a commercially available on tall oil fatty acid based lubricity improver according to WO 98/11175 used.

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, performed on a steel ball a steel plate in the test fuel rubs. ISO 12156-1 describes this method and has found its way into the diesel standard EN 590-1999. The limit here is abrasion on the steel ball from maximum of 460 µm. Unadditized low-sulfur diesel fuels friction lock values R of typically 400 up to 700 µm.

The test diesel fuels (DK1 to DK4) listed in Table 2 below had the characteristics indicated. Characteristics of the test diesel fuel DK 1 DK 2 DK 3 DK 4 quality [Mg / kg] EN 590 EN 590 EN 590 C-DK MK 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 Siedeanfang [° C] 170 176 175 184 20% by volume [° C] 235 214 218 219 95% by volume [° C] 363 352 343 280 Final boiling point [° C] 371 370 356 289

The sulfur content was determined in accordance with EN ISO 14 596.

Additiv A:
erfindungsgemäß eingesetztes Produkt aus Beispiel 2 (unverdünnt)

Additiv B:
erfindungsgemäß eingesetztes Produkt aus Beispiel 1 (unverdünnt)

Additiv C:
als Vergleich handelsüblicher Schmierfähigkeitsverbesserer auf Basis einer Mischung aus einem sterisch gehinderten Alkylphenol und einer langkettigen Carbonsäure

Additiv D:
als Vergleich handelsüblicher Schmierfähigkeitsverbesserer auf Basis einer Mischung aus einem Carbonsäureamid und einem natürlichen Fettsäureester

Additiv E:
als Vergleich handelsüblicher Schmierfähigkeitsverbesserer auf Basis einer Mischung aus Glycerinmonooleat und Glycerinmonolinolat

Additiv F:
als Vergleich handelsüblicher Schmierfähigkeitsverbesserer auf Basis einer Mischung langkettiger Carbonsäuren

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. Tear wear values R [µm] in diesel fuel (WS 1.4 values according to HFRR according to ISO 12 156-1 at 60 ° C) added additive DK1 DK2 DK3 DK 4 none 532 (0) 624 (0) 615 (0) 564 (0) Additive A 389 (50) 375 (50) 399 (75) 358 (200) 363 (100) Additive B 355 (50) 471 (50) 401 (75) 388 (200) 359 (100) Additive C 436 (50) 455 (50) - 435 (200) 330 (100) 453 (250) Additive D 517 (50) 474 (150) - 518 (150) 252 (200) 387 (200) added additive DK1 DK2 DK3 DK 4 Additive E 471 (50) 473 (100) 578 (250) 282 (50) 350 (350) Additive F - - 421 (75) -

The values given in brackets indicate the respective dosing quantity in vol.ppm.

Example 5: Lubricant compatibility

The tendency of an additive to precipitate insoluble with lubricating oil can be formed using various standardized laboratory tests be checked. Here was the test prescribed by DGMK applied (German Scientific Society for Petroleum, Natural gas and coal e.V., research report 531 "Preparation of a Criteria catalog for testing lubricity additives in diesel fuels for refinery use ", Hamburg 1998) 10 ml engine oil (CEC RL 189; SAE 15W40) and 10 ml additive homogenized in a 500 ml flask. After 72 hours at 90 ° C is cooled and visually assessed. You fill this mixture with Diesel fuel to 500 ml and filtered through a 0.8 µm filter (SEDAB regulation). The appearance of gel or sediment as well as exceeding a filtration time of 300 seconds leads to "fail". "Pass", on the other hand, means that the test passed is.

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. Lubricating oil compatibility tests according to DGMK FB 531 additive after 72 h at 90 ° C Filtration time [sec] rating without - 112 - Additive A clear 86 passport Additive B clear 89 passport Additive D (for comparison) cloudy > 300 Fail Additive G (for comparison) cloudy, not homogeneous, gel-like particles > 1800 Fail

As a further comparative additive G, a commercially available dimer was used Fatty acid used.

Claims (9)

1. The use of fatty acid salts of alkoxylated oligoamines of the formula I

   

   where

   A

   is an alkylene group of 2 to 8 carbon atoms,

   R

   is C₇- to C₂₃-alkyl or mono- or polyunsaturated C₇- to C₂₃-alkenyl, which may additionally carry hydroxyl groups,

   Z

   is a C₁- to C₈-alkylene group, C₃- to C₈-cycloalkylene group or C₆- to C₁₂-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 from 50 to 300% of (m+3),
   as lubricity enhancers for mineral oil products.
2. The use of fatty acid salts of alkoxylated oligoamines of the formula I as claimed in claim 1, in which A is a 1,2-ethylene, 1,2-propylene or 1,2-butylene group.
3. The use of fatty acid salts of alkoxylated oligoamines of the formula I as claimed in claim 1 or 2, in which R is a mono- or polyunsaturated C₁₅- to C₁₉-alkenyl group which may additionally carry hydroxyl groups.
4. The use of fatty acid salts of alkoxylated oligoamines of the formula I as claimed in any of claims 1 to 3, in which Z is a polymethylene group of the formula -(CH₂)_n-, where n is from 2 to 6.
5. The use of fatty acid salts of alkoxylated oligoamines of the formula I as claimed in any of claims 1 to 4, in which m is 1 or 2.
6. The use of fatty acid salts of alkoxylated oligoamines of the formula I as claimed in any of claims 1 to 5, in which the sum of all variables x is from 75% to 125% of (m+3).
7. The use of fatty acid salts of alkoxylated oligoamines of the formula I as claimed in any of claims 1 to 6 as lubricity enhancers in gasoline fuels and middle distillates.
8. A process for improving the lubricity of mineral oil products, in particular of gasoline fuels and middle distillates, wherein effective amounts of fatty acid salts of alkoxylated oligoamines of the formula I as claimed in any of claims 1 to 6 are added to the mineral oil products.
9. A mineral oil product, in particular a gasoline fuel or middle distillate composition, containing the bisoleic acid salt of N,N,N',N'-tetrakis(2'-hydroxyethyl)-1,2-ethylene-diamine or N,N,N',N'-tetrakis-(2'-hydroxypropyl)-1,2-ethylenediamine in effective amounts.