JP2003514979A - Use of fatty acid salts of alkoxylated oligoamines as lubricity improvers for petroleum products - Google Patents

Abstract

(57) Use of fatty acid salts of alkoxylated oligoamines of the formula (I) as lubricity improvers for petroleum products, in particular gasoline and middle distillates, wherein A is a C atom 2 to eight is an alkylene group having, R represents _C 7 _{-C 23} - alkenyl group, Z is _{C 1 ~C 8 - - C 7} ~C 23 alkyl group or one or more unsaturated alkylene group, C ₃ -C ₈ - arylene cycloalkylene group or _C 6 _{-C 12} - or - means an aryl alkylene group, m is 0 or an integer from 1 to 5, and the sum of all variables x (m + 3) 50 to 300% of the above).

Description

Detailed Description of the Invention

The present invention relates to the use of fatty acid salts of alkoxylated oligoamines as lubricity improvers for petroleum products, especially gasoline and middle distillates, especially diesel fuels, and additives for such petroleum products. It relates to concentrates as well as petroleum products of this kind themselves containing fatty acid salts of alkoxylated oligoamines.

The carburetor and inlet system of an Otto engine, and the injection system for fuel supply, depend on dust particles from the air, unburned hydrocarbon residue from the combustion chamber, and crankshaft case exhaust gas introduced into the carburetor. It is gradually contaminated by the resulting impurities.

[0003] These residues shift the air-fuel ratio to idle and to the low partial load region, so that the mixture becomes lean, the combustion is incomplete and again the proportion of unburned or partially burned hydrocarbons in the exhaust gas. Fuel consumption will increase, and gasoline consumption will increase.

To avoid these disadvantages, it is known to use fuel additives to keep the valves and carburetors or injection systems of Otto engines clean (
For example M.Rossenbeck in Katalysatoren, Tenside, Mineraloeladditive, Hrsg.J.Fa
Lbe, U. Hasselodt, p. 223, G. Thieme Verlag, Stuttgart 1978).

Such clean maintenance fuel additives (detergents), which may be derived from a number of chemical groups such as polyalkene amines, polyether amines, polybutene-Mannich bases or polybutene-succinimides, are generally carrier oils and monohydrates. The parts can be used in combination with further additive components such as corrosion inhibitors and defoamers.

However, many gasolines with and without such additive components exhibit inadequate and improved properties with respect to their lubricity or wear properties in Otto engines.

The low-sulfur diesel fuels that are being used more and more today also exhibit lubricity problems which lead to high wear, for example on injection pumps. In order to reduce or avoid sulfur dioxide and particulate emissions, the sulfur content in diesel fuel must be reduced. In order to achieve a low sulfur content, it is necessary to hydrogenate diesel fuel. This also decomposes polar and polynuclear aromatic components in the fuel, which give the diesel fuel a natural lubricating effect. Therefore, also in this case, as in the case of gasoline, there is a need for additives (also referred to as “lubricity additives” and “friction modifiers”) that effectively enhance the lubricity in the fuel.

Conventionally known lubricity improving additives for gasoline are, for example, WO 98/111.
75, fatty acids, alkenyl succinates, bis (hydroxyalkyl) aliphatic amines and hydroxyacetamide. In diesel fuels, in particular, fatty acids and fatty acid derivatives as described in EP-B605857, for example esters of glycerin with unsaturated fatty acids or castor oil, are used as lubricity improving additives.

However, since the abovementioned agents of the prior art still have room for improvement in their characteristic profiles, in particular their lubricating and antiwear properties, the subject of the invention is the petroleum products, in particular gasoline and intermediates. It was to provide a more effective lubricity improver for distillates.

[0010]   Correspondingly, the general formula I:

[0011]

[Chemical 2]

[Wherein A is a substituent or variable is an alkylene group having 2 to 8 C atoms, and R is a C ₇ -C ₂₃ -alkyl group optionally having a hydroxyl group or one or more unsaturated _C 7 _{-C 23} - alkenyl group, Z is _C 1 -C ₈ - alkylene _group, C 3 ~C ₈ - cycloalkylene group, or a _C 6 ~
C ₁₂ - arylene - or - means an aryl alkylene group, m is 0 or an integer from 1 to 5, and the sum of all variables x alkoxylation of] has a value 50 to 300% of the (m + 3) It has been discovered to use fatty acid salts of oligoamines as lubricity improvers for petroleum products.

The abovementioned compounds of formula I are already known compounds. US Pat. No. 4,131,583 describes in particular salts of unsaturated C ₁₁ -C ₂₀ -carboxylic acids with N, N, N ′, N′-tetrahydroxyethyl-C ₂ -C ₄ -alkylenediamines, which are It is exclusively recommended as a corrosion inhibitor in aqueous coatings for metal surfaces.

From JP-A11 / 050076, N, N, N ′, N′-tetrakis- (2-
(Hydroxypropyl) -ethyldiamine suppresses rust generation and mold damage in an aqueous lubricating oil composition such as cutting oil or grinding oil in the presence of fatty acid such as stearic acid or oleic acid, and It is known to stabilize.
No improvement in lubricity is mentioned here.

From JP-A 11/209773 is known an aqueous lubricant (Gleitmittel) for a belt conveyor in the filling of beverages into bottles, which is N, N, N ′, N ′.
-Contains fatty acid salts of alkanolamines such as tetrakis- (2-hydroxypropyl) -ethylenediamine. Fatty acids include, for example, palmitic acid, tetradecanoic acid, oleic acid and lauric acid.

Petroleum products here mean power fuels, motor vehicle fuels, fuels and lubricating oils, but these are not only petroleum, but also partially or completely synthetic and / or naturally derived raw materials. Based on. Examples of such feedstocks are natural gas, methanol, ethanol, coal-liquefied products or rapeseed oil, which are processed into fuels or added to petroleum-based fuels. The petroleum products mentioned are usually virtually water-free or contain at least small amounts of water. Examples of water-containing petroleum products are fuel emulsions, such as diesel / water emulsions, which may usually contain up to about 35% by weight water. The petroleum products which are advantageous according to the invention are, on the one hand, gasoline and, on the other hand, middle distillates, in particular diesel fuel.

The alkylene group A is preferably a corresponding alkylene oxide, such as ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide and cis-.
Alternatively, it is derived from trans-2,3-butylene oxide. But these are 1,
It may be 3-propylene, 1,4-butylene, 1,6-hexylene or 1,8-octylene. A may likewise be a mixture of different radicals mentioned above. Ethylene-, 1,2-propylene- or 1,2-butylene groups are particularly preferred for A.

[0018] carboxylate - The long chain group R present in the anion, for example, additionally hydroxyl groups C ₇ linear is also be branched or preferably a -C 23 _-, preferably C ₁₁ -C ₂₁ -, in particular _C 15 _{-C 19} - alkyl group. Examples of base 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 eicosanoic acid. The acids may be of natural or synthetic origin. Mixtures of the above acids may be the basis for the carboxylate anion.

The long-chain radical R present in the carboxylate-anion is, however, preferably one or more unsaturated C ₇ -C ₂₃ -radicals, which may additionally have a hydroxyl group, in particular. _C 11 of one or more unsaturated _{-C 21} -, in particular _C 15 _{-C 19} - an alkenyl group. The unsaturated groups are preferably linear. In a multiple unsaturated alkenyl group,
These preferably have 2 or 3 double bonds. Examples of base carboxylic acids are elaidic acid, ricinoleic acid, linoleic acid and linolenic acid. Particularly good results can be achieved with oleic acid. Mixtures of such unsaturated carboxylic acids with one another and with the abovementioned saturated carboxylic acids may also be the basis of the carboxylate-anion. Such mixtures are, for example, tall oil, tall oil fatty acids and rapeseed oil fatty acids. The unsaturated carboxylic acids and the mixtures are usually of natural origin.

[0020]   The substituent Z is especially C₁~ C_FourAn alkylene group such as methylene, 1,2-propyi
Len, 1,2-butylene, 1,3-butylene or 2,3-butylene, C₅~ C ₆ -Cycloalkylene groups, such as 1,3-cyclopentyridine or 1,3- or
Or 1,4-cyclohexylidene or C₆~ C₈-Arylene-or-Ari
Alkylene groups such as 1,3- or 1,4-phenylene, 2-methyl-1
Represents 4-phenylene or 1,3- or 1,4-bismethylenephenylene
.

However, the substituent Z is preferably a polymethylene group of the formula: — (CH ₂ ) _n — (where n = 2-8, in particular n = 2-6), ie especially 1,2- It represents ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene and 1,6-hexylene, as well as 1,7-heptylene and 1,8-octylene.

When the variable m is 0, it is usually mono-, depending on the sum (Σ) of all the substituents x.
Mixtures of di- and / or trialkanolamines or pure trialkanolamines are the base as the cationic constituent of the fatty acid salts used according to the invention. Examples of such alkanolamines are monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine and the corresponding mixtures. Of these groups, the oleate of triethanolamine (Σx = 3) is of particular importance.

However, the variable m is preferably a number 1 or 2. At m = 1, a completely and / or partially alkoxylated alkylenediamine, such as 1,2-ethylenediamine, 1,3-propylenediamine or 1,4-butylenediamine, is based. When m = 2, a nearly completely and / or partially alkoxylated dialkylenetriamine, such as di- (1,2-ethylene) -triamine, di- (1,3-propylene) -triamine or di- ( The base is 1,4-butylene) -triamine. In these groups, N, N, N ', N'-tetrakis- (2
′ -Hydroxyethyl) -1,2-ethylenediamine (Zx = 4) and N, N
, N ′, N′-tetrakis- (2′-hydroxypropyl) -1,2-ethylenediamine (Σx = 4) bis-oleate and ethylene oxide or 1
Of particular interest is the tris-oleate of di- (1,2-ethylene) -triamine reacted with 4-5 mol of 2,2-propylene oxide.

However, the higher homologues of the above alkylenediamines and dialkylenetriamines, such as triethylenetetramine (m = 3), tetraethylenepentamine (m
= 4) or pentaethylenehexamine (m = 5) can also be the basis of the amine component for the fatty acid salts used in the present invention.

The number of alkylene oxide units (OA) introduced per amine molecule may correspond to the number of N—H-bonds in the base amine (Σx = m + 3). However, it is also possible to introduce more or less OA-units. Introduced above stoichiometry is an upper limit for the properties of fatty acid salts that results in a 3-fold alkoxylation per NH bond [300% of ((m + 3)]]. For sub-stoichiometric introduction, a statistical average of 50% alkoxylation [50% of (m + 3)] is the corresponding lower limit,
In this case, there is a mixture of species with varying degrees of high alkoxylation.

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

The fatty acid salts of the general formula I used according to the invention can usually be prepared easily by the alkoxylation of the base amine in a conventional manner, followed by neutralization with the formula: R—COOH.

If C ₂ -C ₄ -alkylene oxides are used, the alkoxylation is advantageously carried out in the introduction of the first alkylene oxide units into the NH bond by using a small amount of water (often the amount of amine used). In the presence of 0.5 to 5% by weight), at a temperature of 80 to 140 ° C. without a catalyst, and with the introduction of further alkylene oxide units, under exclusion of water, the alkali metal hydroxide It is carried out in the presence of such basic catalysts, for example sodium or potassium hydroxide, at temperatures of 100 to 150 ° C.

Neutralization is usually carried out with a corresponding or slightly less than stoichiometric amount of the alkoxylated amine thus obtained (ie 90-100% of stoichiometric amount, in particular 95-100%).
) With fatty acid at a temperature of 30 to 100 ° C., in particular 40 to 80 ° C. for 15 minutes to 10 hours, in particular 30 minutes to 5 hours. This neutralization reaction should be carried out so that no carboxylic acid ester component is formed in the product. In many cases both alkoxylated amines and fatty acids can be used as liquids, which makes the reaction to the corresponding fatty acid salts particularly simple. The order of addition of alkoxylated amine and fatty acid is not critical. That is, the alkoxylated amine can be charged in advance and the fatty acid can be added, or the fatty acid can be charged in advance and the alkoxylated amine can be added.

However, it is also possible in principle to add the alkoxylated amine and the fatty acid as individual components to the additive concentrate or petroleum product, for the salt formation to take place there.

Its production is more difficult than in the conventional lubricity improvers of the prior art, especially at high temperatures, long reaction times and especially the laborious work-up operations for removing the unwanted by-products formed in the condensation reaction. The production of the fatty acid salts of the general formula I used according to the invention is carried out with considerably less effort and energy than on the basis of the amides or esters required by the.

The abovementioned fatty acid salts of the general formula I are outstandingly suitable for improving the lubricity of petroleum products, in particular gasoline and middle distillates, in particular diesel fuel (“lubrication additives”, “friction modifiers”).
Is suitable as The fatty acid salt I generally has a high activity and can therefore be widely used. The use of fatty acid salt I significantly reduces the tendency for wear and agglomeration to occur on components of machines operating on petroleum products.

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

Customary gasoline additives having a cleaning action are, for example: (a) hydroformylation of highly reactive polyisobutenes having a number average molecular weight of 300 to 5000 according to EP-A 24461, followed by ammonia, monoamines or polyamines, For example, polyisobuteneamine obtained by reductive amination with dimethyleneaminopropylamine, ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine; (b) polybutene having a double bond mainly in the β- and γ-positions or Poly (iso) buteneamine obtained by chlorinating polyisobutene followed by amination with ammonia, a monoamine or the polyamines mentioned above under (a); (c) emptying the double bond in poly (iso) butene. Or poly (iso) buteneamine obtained by oxidation with ozone to a carbonyl- or carboxyl compound and subsequent amination under reducing (hydrogenation) conditions; (d) Reaction with amine from polyisobutene epoxide according to DE-A 19620262. A polyisobuteneamine obtained by dehydration and subsequent reduction of the amino alcohol; (e) Polyisobutene having an average degree of polymerization P = 5-100 according to WO-A 97/03946 consisting of nitric oxide or nitric oxide and oxygen. React with the mixture,
A polyisobutene amine optionally containing a hydroxyl group, obtained by subsequent hydrogenation of this reaction product; (f) according to EP-A476485, a polyisobutene epoxide and ammonia,
Hydroxyl-containing polyisobuteneamines obtained by reacting a monoamine or a _{polyamine; (g) C 2 ~C 30} - _alkanols, C 6 _{-C 30} - alkanediol, mono- -
, Di- or tri-C ₂ -C ₃₀ -alkylamines, C ₁ -C ₃₀ -alkylcyclohexanols or C ₁ -C ₃₀ -alkylphenols with ethylene oxide and / or propylene oxide and / or per hydroxyl- or amino group Polyether amines obtained by reacting with 1 to 30 mol of butylene oxide followed by reductive amination with ammonia, monoamines, or the polyamines mentioned above, such products also having carrier oil properties; (h) especially EP-A831141 or German patent application Az. 19948111
． 3 and 19948114.8, a "polyisobutene-Mannich base" obtained by reacting a polyisobutene-substituted phenol with an aldehyde and a monoamine or a polyamine as described above; (i) metallocene-catalyzed propene-oligomerization followed by WO94 / 2 obtained by hydroformylation and reductive amination in the step mentioned in (a)
Polypropylene amines according to 4231; (j) Carboxylic ester group-containing additives based on esters consisting of mono-, di- or tricarboxylic acids and long-chain alcohols or polyols, in particular DE-A 3838918. Minimum viscosity 2 mm ² / s (1
(At 00 ° C.), by way of example in this case iso-octanol, iso-nonanol, iso-decanol and iso-tridecanol adipates, phthalates, iso-phthalates, terephthalates and trimellitates. (K) Obtained from conventional or highly reactive polyisobutene and maleic anhydride by heat or via chlorinated polyisobutene, and in particular in the form of derivatives with aliphatic polyamines. The imides, amides, esters and ammonium- and alkali metal salts of polyisobutene succinic anhydrides which can be used under US Pat. No. 4,948,572 are described in particular in US Pat.

Customary gasoline additives having a valve position antiwear effect are, for example: (l) The carboxyl groups whose total or partial alkali metal radicals are described in EP-A307815. Or an alkaline earth metal salt in which the remaining groups of the carboxyl group are reacted with an alcohol or an amine.
Additives containing carboxyl groups or their alkali metal or alkaline earth metal salts, such as copolymers of C ₂ -C ₄₀ -olefins having 000 with maleic anhydride; (m) especially in EP-A 639632. Additives containing sulphonic acid groups or their alkali metal or alkaline earth metal salts, such as the alkali metal or alkaline earth metal salts of the mentioned sulfosuccinic acid alkyl esters.

In addition to and in addition to the gasoline additives (a) to (m) above, further conventional carrier oils, additive components and auxiliaries for use in gasoline with fatty acid salts of the general formula I Can be combined with.

Customary carrier oils for gasoline additives are, for example, mineral-based carrier oils (base oils), especially the viscosity class “solvent neutral”.
t Neutral; SN) 500-2000 ", based on olefin polymers having M _N = 400-1800, in particular (hydrogenated or non-hydrogenated) polybutene- or polyisobutene-based polyalphaolefins or polyinterolefins Mention may be made of synthetic carrier oils based on as well as synthetic carrier oils based on alkoxylated long-chain alcohols or phenols.
Of course, it is also possible to use mixtures of the abovementioned carrier oils.

Also suitable as mineral carrier oils and / or diluents or solvents for gasoline additives are the fractions produced during petroleum processing, such as kerosene, naphtha or bright stock. To this end, aromatic hydrocarbons, paraffinic (
Aliphatic) hydrocarbons and alkoxyalkanols are preferred.

[0039] In this case as a carrier oil for gasoline _additive, C 2 _{-C 30} - _alkanols, C 6 _{-C 30} - alkanediol, mono-, - di - or tri _-C 2 _{-C 3 0} - alkylamines, C ₁ -C ₃₀ - alkyl cyclohexanol or _C 1 ~
1 to ₃₀ per C ₃₀ -alkylphenol and hydroxyl or amino group
Of particular importance are the polyetherols obtained by reacting with 30 mol of ethylene oxide and / or propylene oxide and / or butylene oxide. In particular, mention may be made here of polyetherols starting from alcohols which have about 10 to 35, in particular 15 to 30 units of propylene and / or butylene oxide units, the starting alcohols being in this case particularly linear. or branched _C 6 _{-C 15} - alkanol is preferred.

Other conventional additive components and auxiliaries for gasoline are corrosion inhibitors based on ammonium salts of organic carboxylic acids or heterocyclic aromatic compounds which have a tendency to form films, for example in nonferrous metal corrosion protection. Based on amines such as p-phenylenediamine, dicyclohexylamine or derivatives thereof or phenols such as 2,4-di-t-butylphenol or 3,5-di-t-butyl-4-hydroxyphenylpropionic acid. Antioxidants or stabilizers, antifoams, antistatic agents, metallocenes such as ferrocene or methylcyclopentadienyl manganese tricarbonyl as well as dyes (markers). Medium-chain linear or branched alkanols (having about 6 to 12 C atoms), such as 2-ethylhexanol, are often used as dissolution mediators. Sometimes amines are also used to lower the pH value of the fuel.

The fatty acid salts of the general formula I used according to the invention in gasoline are the other conventional lubricity improvers for this purpose, for example certain fatty acids, alkenyl succinic acid esters, bis (hydroxyalkyl) aliphatic amines. Alternatively, it can be used together with hydroxyacetamide.

The carboxylic acids or fatty acids used as corrosion inhibitors or lubricity improvers may be present as monomers or oligomers, especially as dimer species. Mixtures of monomers and dimers and optionally higher oligomeric species may also be present.

Fatty acid salts of the general formula I used in gasoline according to the invention and the groups (a) above,
Preference is given to the combination with the detergents of (d) and (g), in particular of the polyisobutenamine of group (a). Particularly suitable polyisobutenamine (a) is in this case
Number average molecular weight 500 to 2300, especially 800 to 1500, especially 900 to 12
It was prepared by hydroformylating 00 highly reactive polyisobutene followed by reductive amination with ammonia. The polyisobutenamine (a) is preferably used together with a carrier oil such as polyetherol or an aliphatic or aromatic hydrocarbon, and optionally the abovementioned corrosion inhibitors, antioxidants or stabilizers, defoamers, antistatic agents. , Metallocenes and / or dyes. A typical example of such a polyisobutenamine (a) is a trade name Kerocom (
Mention may be made of the products sold by BASF Aktiengesellschaft under the registered trademark PIBA.

As gasoline, it is possible to use all commercially available gasoline compositions. Typical representatives in this case are the Eurosuper Grundkraftstoff, customary in the market according to EN288. Furthermore, in this case, the German patent application Az. The gasoline composition described in 19905211.5 is also important.

The fatty acid salts used in the middle distillates according to the invention can advantageously be used in all customary middle distillates.

Among these middle distillates, of which diesel fuel is the most important group, are petroleum raffinates, which usually have a boiling range of 100-400 ° C. This is usually
It is a distillate with a 95% point of 360 ° C. and above. However, this means, for example, that the 95% point at a maximum of 345 ° C. and the maximum sulfur content of 0.005 mass% are
Or it may be, for example, the so-called “Ultra Low Sulfur Diesel” or “City Diesel”, which is characterized by a 95% point at 285 ° C. and a sulfur content of at most 0.001% by weight. Furthermore, these middle distillates may be fuel oils having a sulfur content of at most 0.20% by weight, in particular at most 0.10% by weight, as well as aviation fuels.

The above-mentioned distillates usually consist of components obtained from atmospheric pressure of petroleum-or vacuum distillation, or from the conversion process, for example cracking-, coke ovens- or visbreaking gas oils.

The abovementioned middle distillates, in particular diesel fuel, are usually up to 0.05% by weight, in particular up to 0.02% by weight, in particular up to 0.005% by weight, very preferably up to 0.00% by weight.
It is characterized by a low sulfur content of 1% by weight.

The fatty acid salts of the general formula I used according to the invention in middle distillates, especially diesel fuels, are used here as liquid refining substances or as liquid concentrates in solvents or diluents. You can In this case, it is possible in principle to use, as solvent or diluent, all the substances mentioned above as agents, such as are used with gasoline additives. In particular, petroleum components such as naphtha, kerosene, diesel fuel and aromatic hydrocarbons such as solvents, heavy naphtha, Solvesso® or Shellsol® are preferred. These concentrates can be solutions or dispersions, preference being given to clear solutions. It is also possible to use mixtures of the solvents or diluents mentioned.

The abovementioned solvents or diluents are used in particular in a weight ratio to the fatty acid salt I of 1:10 to 10: 1, in particular 1: 4 to 4: 1, especially 1: 2 to 2: 1. By doing so, the solubility of the fatty acid salt of general formula I used in the present invention can be improved. This may be the case if the middle distillate already contains other additives, if the mixing temperature is low, if addition control is not achieved at low dosages, or if a mixture with other middle distillates is to be produced. Such dissolution or dilution is advantageous.

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

The customary middle distillate or diesel fuel additives are in this connection in particular detergents, corrosion inhibitors, dehazers, defoamers, antifoams (“Antifoam”).
), Antioxidants, metal deactivators, multifunctional stabilizers, cetane number improvers, combustion improvers, dyes, markers, dissolution mediators, antistatic agents, other conventional lubricity additives and low temperature properties. Improving additives such as flow improvers (“MDFI”; Fliessverbesserer
), Paraffin dispersants (“WASA”) and combinations thereof (“WAFI”).
)).

The object of the present application is also a method for improving the lubricity of petroleum products, in particular gasoline and middle distillates, which is of the general formula I according to any one of claims 1 to 6. It is characterized in that a fatty acid salt of an alkoxylated oligoamine is added to a petroleum product in an effective amount.

The object of the present invention is furthermore the addition of the fatty acid salts of alkoxylated oligoamines of the general formula I in an amount of 0.05 to 50% by weight, in particular 0.1 to 30% by weight, based on the total amount of the concentrate. Additive concentrates for petroleum products, especially gasoline and middle distillates, contained. These concentrates usually also contain the other additives mentioned above, carrier oils, solvents or diluents and / or auxiliaries. In the case of additive concentrates for gasoline, this is in particular detergents and / or valve position antiwear agents, in particular the additives (a) to (m) mentioned above, and other components and auxiliary substances customary for this purpose. Agents, especially carrier oils, corrosion inhibitors, antioxidants or stabilizers, defoamers, antistatic agents, metallocenes and dyes.

A further object of the present invention is petroleum products, in particular gasoline and middle distillate compositions, which contain an effective amount of fatty acid salts of alkoxylated oligoamines of the general formula I. An effective amount is usually 1 to 1000 mass ppm, in particular 5 to 500 mass ppm, in particular 10 to 10 mass% of the total composition of both the gasoline composition and the diesel fuel composition.
250 ppm by weight, particularly preferably 20 to 100 ppm by weight. These petroleum products, in particular gasoline and middle distillate compositions, usually contain, in addition to the fatty acid salts I used therein according to the invention, the abovementioned additives, additive components and auxiliaries.

The fatty acid salts of alkoxylated oligoamines of the general formula I have a high effectiveness as lubricity improvers even at low concentrations in petroleum products and are members of machines operating on petroleum products, such as fuel inlet systems. Or effectively prevent wear and agglomeration on the injection pump.

Furthermore, the fatty acid salts of alkoxylated oligoamines of the general formula I have a good lubricating oil compatibility, which is particularly important when used in diesel fuel.
The interaction of conventionally used acidic lubricity improvers (eg, dimer fatty acids) with the basic components of lubricating oils that come into contact with the fuel, as is known in Otto and diesel engines, in the fuel and in the engine and injection. Corresponding salts build up in the undesired areas of the system, causing damage. This disadvantage is avoided when the fatty acid salts of alkoxylated oligoamines of the general formula I are used according to the invention.

The fatty acid salts of the alkoxylated oligoamines of the general formula I used according to the invention do in fact have no tendency to form undesired emulsions in petroleum products and have sufficient hydrolytic stability.

[0059]   The following examples illustrate the invention in more detail, but do not limit it.

Production Example Example 1: N, N, N ', N'-tetrakis- (2'-hydroxypropyl) -1
Preparation of bis-oleate of 2,2-ethylenediamine N, N, N ', N'-tetrakis- (2'-hydroxypropyl) -1,2-
58.4 g (0.2 mol) of ethylenediamine (1,2-ethylenediamine and 4 mol of propylene oxide were reacted in the conventional manner at 100 to 110 ° C. in the presence of about 3% by weight of water, based on the weight of amine used. Was heated to a temperature of 60 to 80 ° C., and 110.4 g (0.4 mol) of oleic acid was added over 2 hours with stirring. At this time, the pH value did not drop below 7. Subsequently, the mixture was further stirred within the above temperature range for 2 hours. The product obtained had an N-titer of 2.39 mmol / g (calculated 2.37 mmol / g).

Example 2: N, N, N ', N'-tetrakis- (2'-hydroxyethyl) -1,
Preparation of bis-oleate of 2-ethylenediamine The title compound was prepared in the same manner as in Example 1 in the same amount as N, N, N ', N'-tetrakis- (2
Prepared using'-hydroxyethyl) -1,2-ethylenediamine.

Example of Use Example 3: Measurement of Wear Value on Gasoline To investigate lubricity or wear on gasoline, PCS Instruments (London) High Frequency Reciprocating Rig (H)
FRR) -the instrument was used. The measurement conditions were adapted to the use of gasoline. The applicability of this test method for gasoline is described in the literature D. Margaroni, Industrial Lubication and
Tribology, Vol.50, No.3, May / June 1998, 108-118 and WDPing, S.Korc
ek, H. Spikes, SAE Techn. Paper 96 2010, 51-59 (1996).

The gasoline (OK) used here (typical gasoline according to EN 228) was carefully concentrated by distillation to 50% by volume before measurement. This 50% residue was used to establish blank test values during the investigation with the wear measuring device. Further additives were added to this residue in accordance with the examples below and the wear values were determined by the method described above.
The resulting wear value (R) is stated in micrometers (μm). The lower this value, the less wear has occurred.

The 50% by volume balance of Euro Super-Gasoline OK1 is HFRR-test and R =
Comparable Euro Super-Gasoline OK2, yielding a blank value of 873 μm
The 50% by volume residue of HFRR-test gave a blank value of R = 754 μm. To this are commercially available gasoline additives P1 (based on polyisobutene amine detergents, synthetic carrier oils and conventional corrosion inhibitors) or commercially available gasoline additives-
Packet P2 (similar to P1, but with other synthetic carrier oils) 500 mg /
Each addition of kg produced a wear value on the same scale. The lubricity improver of the present invention from Examples 1 and 2 or the lubricity improvers known from the prior art are each added to 50 m.
The addition of g / kg produced correspondingly lower values, but the products according to the invention far exceeded those according to the prior art. The values achieved are then listed in Table 1.

Table 1: Abrasion values on gasoline R Additives added OK R [μm] none OK1 873 packet P1 500 mg / kg OK1 853 packet P1 500 mg / kg + product from example 2 50 mg / kg OK1 686 none OK2 754 packet P1 500 mg / kg OK2 717 packet P1 500 mg / kg + product 50 mg / kg from example 1 OK2 593 packet P1 500 mg / kg + product 50 mg / kg from example 2 OK2 634 packet P1 500 mg / kg + comparative product 50 mg / Kg OK2 659 packet P2 500 mg / kg OK2 775 packet P2 500 mg / kg + product 50 mg / kg from example 1 OK2 680 packet P2 500 mg / kg + product 50 mg / k from example 2 g OK2 633 Packet P2 500 mg / kg + comparison product 50 mg / kg OK2 684 As comparison product, a commercial lubricity improver based on tall oil fatty acids according to WO 98/11175 was used, respectively.

Example 4: Determination of wear values on diesel fuel A conventional lubricity-test was carried out using a HFRR-device from PCS Instruments (London), with steel balls on a steel plate in the test fuel. I rubbed with. This method is ISO12
156-1 and complies with the diesel standard EN 590-1999. In this case, as a limit value, a maximum wear of steel balls of 460 μm is specified. Additive-free low sulfur diesel fuels may typically have a wear value R of 400-700 μm.

The tests listed in Table 2 below-diesel fuels (DK1 to DK4) showed the described properties.

[0068]

[Table 1]

[0069]   Sulfur content was measured according to EN ISO 14596.

The following diesel fuel additives were used: Additive A: product used according to the invention from Example 2 (undiluted) Additive B: product used according to the invention from Example 1 (Undiluted), Additive C: Commercially available lubricity improver based on a mixture of sterically hindered alkylphenols and long chain carboxylic acids as a comparison, Additive D: Carboxylic amides and natural fatty acid esters as a comparison Commercially available lubricity improver based on a mixture consisting of: Additive E: As a comparison, a commercial lubricity improver additive F based on a mixture consisting of glycerin monooleate and glycerin monolinoleate: As a comparison A commercially available lubricity improver based on a mixture of long chain carboxylic acids.

The following Table 3 shows the measurement results of the wear value R in the test diesel fuel. It is clear that the effects of the products A and B used according to the invention are superior to those of the commercial products C to F.

[0072]

[Table 2]

[0073]   The values in parentheses indicate the respective addition amounts in ppm by volume.

Example 5 Lubricating Oil Compatibility The tendency of additives to form insoluble precipitates with lubricating oils can be investigated in various standardized laboratory tests. In this case the test described by DGMK was applied (Deutsche Wissenschaftliche Gesellschaft fuer Erdoel, Erdgas und Kohle.
eV, Forschungsbericht 531 "Aufstellung eines Kriterienkataloges zur Tes
tung von Lubricity Additiven in Dieselkraftstoffen fuer den Raffinerieei
nsatz ", Hamburg 1998). In this case, engine oil (CEC RL 189;
10 ml of SAE 15W40) and 10 ml of additives are homogenized in a 500 ml flask. After 72 hours at 90 ° C., it is cooled and evaluated visually. The mixture is supplemented with diesel fuel to 500 ml and filtered through a 0.8 μm filter (SEDAB-formulation). The occurrence of gel or precipitate as well as exceeding the filtration time of 300 seconds is a "fail". On the other hand, “pass” means that the test is satisfied.

The following Table 4, together with the results of this test, shows the lubricity improver A used according to the invention.
The reason for this is that B and B are not expected to have a negative interaction with the lubricating oil.

[0076]

[Table 3]

[0077]   Commercially available dimer fatty acids were used as further comparative additives G.

[Procedure for Amendment] Submission for translation of Article 34 Amendment of Patent Cooperation Treaty

[Submission date] January 7, 2002 (2002.1.7)

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be amended] Claims

[Correction method] Change

[Contents of correction]

[Claims]

[Chemical 1] [Wherein A is a substituent or variable is an alkylene group having 2 to 8 C atoms, R is a C ₇ -C ₂₃ -alkyl group which may additionally have a hydroxyl group or one or more _C 7 _{-C 23} saturated - represents an alkenyl group, Z is _C 1 -C ₈ - alkylene _group, 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 all the sums of the variables x have a value of 50 to 300% of (m + 3)]. Use of fatty acid salts.

─────────────────────────────────────────────────── ─── Continued front page    (81) Designated countries EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, I T, LU, MC, NL, PT, SE, TR), OA (BF , BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, G M, KE, LS, MW, MZ, SD, SL, SZ, TZ , UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AE, AG, AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, B Z, CA, CH, CN, CR, CU, CZ, DE, DK , DM, DZ, EE, ES, FI, GB, GD, GE, GH, GM, HR, HU, ID, IL, IN, IS, J P, KE, KG, KP, KR, KZ, LC, LK, LR , LS, LT, LU, LV, MA, MD, MG, MK, MN, MW, MX, MZ, NO, NZ, PL, PT, R O, RU, SD, SE, SG, SI, SK, SL, TJ , TM, TR, TT, TZ, UA, UG, US, UZ, VN, YU, ZA, ZW (72) Inventor Klaus Mundinger             Limburger Hofshi, Germany             Larstraße 28 (72) Inventor Dietmar Posselt             Federal Republic of Germany Heidelberg Twi             -Gelhauser Landstrasse 7 (72) Inventor Siegbert Brandt             Federal Republic of Germany Speyer Zank             To-Clara-Clooster-Wake 6 (72) Inventor Ansgar Eisenvice             Federal Republic of Germany Georges Marien             Hutte Birk-Hahnweg 17 F-term (reference) 3G013 BA00

Claims (10)

[Claims] 1. A compound of general formula I: as a lubricity improver for petroleum products. [Wherein A is a substituent or variable is an alkylene group having 2 to 8 C atoms, R is a C ₇ -C ₂₃ -alkyl group which may additionally have a hydroxyl group or one or more _C 7 _{-C 23} saturated - represents an alkenyl group, Z is _C 1 -C ₈ - alkylene _group, C 3 -C ₈ - cycloalkylene group, or a _C 6 ~
C ₁₂ - arylene - or - means an aryl alkylene group, m is 0 or an integer from 1 to 5, and the sum of all variables x alkoxylation of] has a value 50 to 300% of the (m + 3) Use of fatty acid salts of oligoamines. 2. A fatty acid salt of an alkoxylated oligoamine of the general formula I according to claim 1, wherein the substituent A is a 1,2-ethylene group, a 1,2-propylene group or a 1,2-butylene group. use. 3. The general formula I according to claim 1 or 2, wherein the substituent R represents one or more unsaturated C ₁₅ -C ₁₉ alkenyl groups which may additionally have a hydroxyl group. Use of fatty acid salts of alkoxylated oligoamines. Wherein the substituent Z has the formula :-( _{CH 2) n} - (where represents the n = 2 to 6) polymethylene group of the general formula I according to any one of claims 1 to 3 Use of fatty acid salts of alkoxylated oligoamines. 5. Use of a fatty acid salt of an alkoxylated oligoamine of general formula I according to any one of claims 1 to 4, wherein the variable m is a number of 1 or 2. 6. Fatty acids of alkoxylated oligoamines of general formula I according to any one of claims 1 to 5, wherein the sum of all variables x has a value of 75% to 125% of (m + 3). Use of salt. 7. Use of a fatty acid salt of an alkoxylated oligoamine of general formula I according to any one of claims 1 to 6 as a lubricity improver in gasoline and middle distillates. 8. A method for improving the lubricity of petroleum products, in particular gasoline and middle distillates, wherein the fatty acid salt of an alkoxylated oligoamine of the general formula I according to any one of claims 1 to 6 is used. A method for improving the lubricity of a petroleum product, which comprises adding an effective amount to the petroleum product. 9. The general formula I according to claim 1, in an additive concentrate for petroleum products, in particular gasoline and middle distillates.
Additive concentrate for petroleum products, characterized in that it contains the fatty acid salt of the alkoxylated oligoamine according to claim 1 in an amount of 0.05 to 50% by weight. 10. Petroleum products, especially gasoline compositions and middle distillate compositions, in which an effective amount of a fatty acid salt of an alkoxylated oligoamine of general formula I according to any one of claims 1 to 6 is used. Petroleum products characterized by being contained in.