DE10313883A1 - Additive mixture to improve the lubricity properties of mineral oil products - Google Patents

Abstract

The present invention relates to an additive mixture which contains at least one aliphatic monocarboxylic acid, at least one polycyclic carboxylic acid and at least one copolymer of lower olefins and unsaturated esters. Furthermore, the invention relates to the use of this additive mixture for the additivation of mineral oil products, also fuel oil and lubricant compositions and concentrates which contain this additive mixture.

Description

The present invention relates to an additive mixture containing at least one aliphatic monocarboxylic acid, at least a polycyclic carboxylic acid and at least one copolymer of lower olefins and unsaturated Contains esters. The invention further relates to the use of this additive mixture for the additive of mineral oil products, Moreover Brennstofföl- and lubricant compositions and concentrates containing this Additive mixture included.

Efforts to reduce harmful Emissions from the combustion of fuels, especially from Diesel fuels, more recently, have focused on reducing of sulfur dioxide emissions and the reduction of particle emissions, especially in diesel exhaust. To reduce sulfur dioxide emissions the sulfur content in petrol and Middle distillates, such as diesel fuel or heating oil, by "hydrotreatment", in which the Fuel is treated with hydrogen, making it sulphurous Components reduced to hydrogen sulfide in the refineries lowered. An unwanted one A side effect of this desulfurization is the destruction of polyaromatic and polar Components in the fuel. This is especially true with diesel fuels negative effects since diesel injection systems are often lubricated with fuel are and due to the reduction in the natural lubricity of the Fuel wear especially in the area of high-pressure injection pumps. The wear problem becomes even more significant if the fuels are mixed with "gas to liquid" fuels (GTL fuels) or used with regenerative fuels such as bioethanol, because these components have no lubricating properties have.

To avoid wear sets one generally uses artificial lubricity improvers for the fuel to how fatty acid mixtures, their esters, amides or salts.

WO 98/04656 describes diesel fuels with a sulfur content of at most 500 ppm, which is used to improve the lubricity of an additive mixture of monocarboxylic acids and contains polycyclic acids. The improvement in lubricity achieved with this additive mixture however, is not yet satisfactory.

The EP 1 028 155 describes the use of copolymers of ethylene and unsaturated esters to improve the lubricity of conventional lubricity additives. However, the amounts of additive required to improve the lubricity sufficiently are unsatisfactorily high.

Object of the present invention was therefore to provide additive mixtures that improve lubricity of fuel oil and lubricant compositions even at lower dosing rates improve effectively.

Surprisingly it was found that the combination of monocarboxylic acids and polycyclic acids a synergistic with copolymers of lower olefins and unsaturated esters Effect regarding improving lubricity of fuel oil and has lubricant compositions.

Object of the present invention is therefore an additive mixture containing

• i) as component A at least one aliphatic Monocarboxylic acid,
• ii) as component B at least one polycyclic carboxylic acid and
• iii) as component C at least one copolymer of lower Olefins and unsaturated Esters.

In the context of the present invention, alkyl denotes both branched and linear alkyl groups. For example, C ₁ -C ₄ alkyl denotes methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl. C ₁ -C ₅ alkyl also denotes pentyl or neopentyl and other positional isomers. C ₁ -C ₈ alkyl also denotes, for example, hexyl, heptyl, octyl and 2-ethylhexyl and other positional isomers. C ₁ -C ₁₀ alkyl also denotes nonyl, decyl and their positional isomers. C ₁ -C ₁₇ alkyl also denotes undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and positional isomers of these radicals.

In the context of the present invention, alkenyl denotes linear or branched, mono- or polyunsaturated alkenyl radicals. For example, C ₂ -C ₅ alkenyl represents vinyl, 1-propenyl, allyl, butenyl, isobutenyl, butadienyl, pentenyl or pentadienyl.

In the context of the present invention, aryl denotes in particular optionally substituted phenyl, benzyl, tolyl or naphthyl. Suitable substituents are, for example, C ₁ -C ₄ alkyl, OH and OC ₁ -C ₄ alkyl.

Within the scope of the present invention denotes the term "aliphatic Monocarboxylic acid "both the monocarboxylic acid itself as well as their derivatives, which are selected from carboxylic acid esters, the reaction products of carboxylic acids with primary, secondary and tertiary Amines and polyamines, the carboxylic acid ammonium salts, amides, imides and include amidines, and nitriles. It is preferably but the carboxylic acid self.

Within the scope of the present application denotes the term "polycyclic Carboxylic acid "both the carboxylic acid itself as well as their derivatives, which are also selected for these acids from carboxylic acid esters, the reaction products of carboxylic acids with primary, secondary and tertiary Amines and polyamines, the carboxylic acid ammonium salts, amides, imides and include amidines, and nitriles. It is preferably but the carboxylic acid self.

Aliphatic monocarboxylic acid it is preferably a saturated one or unsaturated linear or branched monocarboxylic acid with 12 to 24 carbon atoms, particularly preferably with 16 to 20 carbon atoms and especially with 18 carbon atoms in the carboxylic acid part of the molecule. Especially the monocarboxylic acid is preferred linear.

A is preferred as component A. Mixture of saturated and unsaturated aliphatic monocarboxylic acids used. A mixture of at least one is particularly preferred a saturated one, at least a monounsaturated and / or at least one polyunsaturated aliphatic monocarboxylic acid. Specifically, the saturated ones and unsaturated carboxylic acids always the same chain length on.

In a particularly preferred embodiment is used as component A, a mixture of at least one saturated aliphatic monocarboxylic acid, at least one monounsaturated aliphatic monocarboxylic acid and at least one polyunsaturated aliphatic monocarboxylic acid. In particular have at least 95%, especially at least 99% of the carboxylic acids same chain length on. Specifically the molar mixing ratio of saturated carboxylic acids too unsaturated carboxylic acid to polyunsaturated carboxylic acids 1 5-7: 4-6. However, mixtures are also suitable in which the molar mixing ratio of saturated carboxylic acids too many times unsaturated carboxylic acid unsaturated carboxylic acids 1: 5-55: 6-65 and preferably 1: 8-45: 15-35.

Examples of suitable saturated aliphatic Monocarboxylic acids are lauric acid, Tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, tubercolostearic acid, nonadecanoic acid, arachic acid, behenic acid and Lignoceric. examples for suitable unsaturated aliphatic monocarboxylic acids are palmitoleic acid, oleic acid and erucic (monounsaturated), Linoleic acid (double unsaturated), linolenic and elaeostearic acid (triple unsaturated), arachidonic acid (four times unsaturated), clupanodonic (Five times unsaturated) and docosahexaenoic acid (six times unsaturated). Is preferred as saturated aliphatic monocarboxylic acid palmitic or stearic acid used. Among the unsaturated Monocarboxylic acids are oleic acid, linoleic acid, linolenic acid and eleostearic prefers.

The polycyclic carboxylic acid it is preferably at least two 5- or 6-membered, saturated or unsaturated Cyclen comprehensive about two adjacent carbon atoms condensed ring system, where at least one cycle through at least one carboxyl group or by at least one carboxyl derivative which is selected from carboxylic ester groups, the reaction products of carboxyl groups with primary, secondary and tertiary Amines and polyamines, the ammonium carboxylates, carboxamides, imides and amidines, and nitriles, substituted and wherein each Cycle optionally contains a heteroatom selected from O and N.

worin
X für ein Kohlenstoffatom oder für ein Heteroatom, das ausgewählt ist unter O und N, steht, wobei in jedem Cyclus nur ein X für ein Heteroatom stehen darf und wobei die Bindung zwischen zwei Ringatomen X sowohl eine Einfachbindung als auch eine Doppelbindung sein kann;
R¹⁵, R¹⁶, R¹⁷ und R¹⁸ unabhängig voneinander für H, C₁-C₅-Alkyl, C₂-C₅-Alkenyl oder Aryl stehen, wobei R¹⁵ und R¹⁶ bzw. R¹⁷ und R¹⁸ gemeinsam mit den Ringatomen X, an die sie gebunden sind, einen Cyclus bilden können, der gesättigt oder ungesättigt sein, ein Heteroatom, das ausgewählt. ist unter O und N, enthalten, und durch einen gesättigten oder ungesättigten aliphatischen Kohlenwasserstoffrest mit ein bis vier Kohlenstoffatomen oder durch einen Hydroxyrest substituiert sein kann; und
Z für COOH, COOR¹⁹, CN oder ein Carboxylderivat, das bei der Umsetzung von Carbonsäure mit Aminen entsteht, steht.In a preferred embodiment, the polycyclic carboxylic acid has the general formula V.

wherein
X stands for a carbon atom or for a heteroatom, which is selected from O and N, where in each cycle only one X may represent a heteroatom and where the bond between two ring atoms X can be either a single bond or a double bond;
R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ independently of one another are H, C ₁ -C ₅ alkyl, C ₂ -C ₅ alkenyl or aryl, where R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ together with the ring atoms X to which they are attached can form a cycle which may be saturated or unsaturated, a heteroatom which is selected. is contained under O and N, and by a saturated or unsaturated aliphatic hydrocarbon radical having one to four carbon atoms or can be substituted by a hydroxy radical; and
Z stands for COOH, COOR ¹⁹ , CN or a carboxyl derivative which is formed in the reaction of carboxylic acid with amines.

R ¹⁹ stands for C ₁ -C ₈ alkyl which is interrupted by one or more groups which are selected from O and NR ²⁰ and / or by one or more groups which are selected from OR ²¹ and NR ²² R ²³ , may be substituted, wherein R ²⁰ , R ²¹ , R ²² and R ²³ are defined as R ¹⁹ or are H, or R ¹⁹ is C ₂ -C ₅ alkenyl.

Carboxyl derivatives in the implementation of carboxyl groups with amines are those mentioned above, d. H. Ammonium carboxylates, carboxamides, imides and amidines. Preferably these are ammonium carboxylates or carboxamides. Especially these ammonium salts or amides are preferably derived from amines from that selected include 2-ethylhexylamine, N, N-dibutylamine, ethylenediamine, diethylenetriamine, Triethylene tetramine and tetraethylene pentamine.

If R ¹⁵ and R ¹⁶ or R ¹⁷ and R ^{18 form a} ring together with the ring atoms X to which they are bonded, it is preferably a 5- or 6-ring, particularly preferably a carbocyclic 5- or 6-ring and especially a carbocyclic 6-ring. The ring can. be saturated or simple, double or triple unsaturated. The ring is preferably by at least one C ₁ -C ₄ alkyl group, in particular by methyl or isopropyl, by a C ₂ -C ₅ alkenyl group, in particular by vinyl, by an optionally substituted exocyclic double bond, in particular by a dimethyl-substituted exocyclic double bond and / or substituted by a hydroxy group.

R ¹⁵ and R ¹⁶ are preferably H or methyl. Both R ¹⁵ and R ¹⁶ are particularly preferably methyl. R ¹⁵ is more preferably attached to a bridging carbon atom. In particular, R ¹⁶ and Z are bonded to the same atom X, where X represents a carbon atom.

R ¹⁷ and R ¹⁸ preferably form a 5 or 6 ring with the X atoms to which they are attached, particularly preferably around a carbocyclic 5 or 6 ring and in particular around a carbocyclic 6 ring, ie the X atoms to which they are attached are carbon atoms. The ring can be saturated or single, double or triple unsaturated. The ring is preferably by at least one C ₁ -C ₄ alkyl group, in particular by methyl or isopropyl, by a C ₂ -C ₅ alkenyl group, in particular by vinyl, by an optionally substituted exocyclic double bond, in particular by a dimethyl-substituted exocyclic double bond and / or substituted by a hydroxy group.

worin
A für einen C₂-C₄-Alkylenrest, insbesondere für Ethylen, 1,2- oder 1,3-Propylen, 1,2-, 2,3-, 3,4-, 1,3- oder 1,4-Butylen steht,
X für O oder NR²⁰ steht,
worin R²⁰ für H oder C₁-C₄-Alkyl steht,
Y für H, OR²¹ oder NR²²R²³ steht,
worin R²¹ wie R²² definiert ist und R²² und R²³ für H, C₁-C₄-Alkyl oder C₁-C₄-Hydroxyalkyl stehen, und
n für eine Zahl von 1 bis 3 steht.In the radical R ¹⁹ there is C ₁ -C ₈ alkyl which is interrupted by one or more groups which are selected from O and NR ²⁰ and optionally by one or more groups which are selected from OR ²¹ and NR ²² R ²³ , is substituted, preferably for a radical of the formula

wherein
A for a C ₂ -C ₄ alkylene radical, in particular for ethylene, 1,2- or 1,3-propylene, 1,2-, 2,3-, 3,4-, 1,3- or 1,4- Butylene stands,
X represents O or NR ²⁰ ,
wherein R ^{20 is} H or C ₁ -C ₄ alkyl,
Y represents H, OR ²¹ or NR ²² R ²³ ,
wherein R ²¹ is defined as R ²² and R ²² and R ^{23 are} H, C ₁ -C ₄ alkyl or C ₁ -C ₄ hydroxyalkyl, and
n stands for a number from 1 to 3.

In the radical R ¹⁹ , C ₁ -C ₈ -alkyl which is substituted by one or more groups selected from OR ²¹ and NR ²² R ²³ , preferably represents C ₂ -C ₆ -alkyl, which is substituted by one to three Hydroxy groups and / or by one to three radicals NR ²² R ^{23 is} substituted. In particular, it stands for 2-hydroxyethyl, 2- or 3-hydroxypropyl, 2-, 3- or 4-hydroxybutyl, 2,3-dihydroxypropyl, 3-hydroxymethyl-5-hydroxypentyl, trihydroxyneopentyl, 2-aminoethyl, 3-aminopropyl, 2 -N- (hydroxyethyl) aminoethyl, 2-N-bis (hydroxyethyl) aminoethyl and the like.

The ester group COOR ¹⁹ is preferably derived from an alcohol R ¹⁹ OH, which is selected from primary alcohols having 1 to 8 carbon atoms, such as methanol, ethanol, propanol, isopropanol, n-butanol, sec-butanol, isobutanol, tert-butanol, pentanol , Allyl alcohol, furthermore polyols with 2 to 8 carbon atoms and 2 to 5 OH groups, such as ethylene glycol, propylene glycol, glycerol, trimethylolpropane and pentaerythritol, and primary, secondary and tertiary amino alcohols with 2 to 9 carbon atoms and 1 to 3 OH groups, such as diethanolamine and triethanolamine.

Z is preferably COOH.

X preferably represents a carbon atom.

worin X, Z, R¹⁵, R¹⁶, R¹⁷ und R¹⁸ wie vorstehend definiert sind. Die Aussagen bezüglich der bevorzugten Definition dieser Reste gelten hier entsprechend.In a further preferred embodiment, the polycyclic carboxylic acid has the general formula VI

wherein X, Z, R ¹⁵ , R ¹⁶ , R ¹⁷ and R ^{18 are} as defined above. The statements regarding the preferred definition of these residues apply accordingly here.

It is preferably the polycyclic carboxylic acid or the corresponding derivative by an acid of formula V.

It is particularly preferred in the polycyclic carboxylic acid or the corresponding derivative of the formula V by a resin acid or a resin acid derivative.

Preferred resin acid or its derivatives are abietic dihydroabietic tetrahydroabietic, dehydroabietic neoabietic, pimaric, levopimaric acid, palustrinic, Parastric acid or Derivatives of these acids.

Resin acids are common by distillation of natural Resins obtained from trees containing resin, especially conifers, wins, received.

The polycyclic described above carboxylic acids and their mixture with aliphatic monocarboxylic acids are in WO 98/04656 to which reference is hereby made in full.

In component C, the copolymer preferably contains structural units of the formulas I and II -CHR ¹ -CR ² R ³ - (I) -CHR ⁴ -CR ⁵ R ⁶ - (II), wherein
R ¹ , R ² and R ³ independently of one another represent H, methyl or ethyl,
R ^{4 represents} H, C ₁ -C ₄ alkyl or COOR ⁷ ,
R ^{5 represents} H or methyl,
R ^{6 stands} for COOR ⁷ or OOCR ⁸ ,
R ^{7 represents} a linear or branched C ₁ -C ₁₇ alkyl radical, and
R ^{8 represents} H or R ⁷ ,
and optionally structural units of the formula III and / or IV -CHR ⁹ -CR ¹⁰ R ¹¹ - (III ) -CHR ¹² -CR ¹³ R ¹⁴ - (IV) contains what
R9, R ¹⁰ and R ^{11 are} independently defined as R ¹ , R ² and R ³ ,
R ¹² is defined as R ⁴ ,
R ¹³ is defined as R ⁵ and R ¹⁴ is defined as R ⁶ ,
the structural units I and III and the structural units II and IV are each different from one another.

In the structural units of the formula I, R ¹ , R ² and R ^{3 are} preferably H; that is, the structural units I preferably correspond to copolymerized ethylene.

In the structural units of formula II, R ⁷ preferably represents a linear C ₁ -C ₁₀ alkyl radical, particularly preferably a linear C ₁ -C ₄ alkyl radical, such as methyl, ethyl, n-propyl or n-butyl, and especially for Methyl. Alternatively, R ⁷ preferably represents a branched C ₃ -C ₁₇ alkyl radical, particularly preferably a branched C ₃ -C ₁₀ alkyl radical. In particular, there is at least one branch on a carbon atom which is α or β to the carboxyl group. Examples of such radicals are isopropyl, isobutyl, tert-butyl, neopentyl, neohexyl, neoheptyl, neooctyl, neononyl and neodecyl.

In the structural units of the formula II, R ⁶ preferably represents OOCR ⁸ .

R ⁸ is preferably a linear C ₁ -C ₁₀ alkyl radical, particularly preferably a C ₁ -C ₁₀ alkyl radical. Alternatively, R ⁸ preferably represents a branched C ₃ -C ₁₇ alkyl radical, particularly preferably a branched C ₃ -C ₁₀ alkyl radical. In particular, there is at least one branch on a carbon atom which is α or β to the carboxyl group. Preferred branched C ₃ -C ₁₀ alkyl radical are isopropyl, isobutyl, tert-butyl, neopentyl, neohexyl, neoheptyl, neooctyl, neononyl and neodecyl and in particular neooctyl, neononyl and neodecyl.

However, R ⁸ in the structural units of the formula II particularly preferably represents a linear C ₁ -C ₁₀ -alkyl radical, in particular methyl, ethyl, pentyl or heptyl and especially methyl.

R ⁴ preferably represents H or methyl, particularly preferably H.

R ⁵ preferably represents H.

The repetition unit is particularly preferred of formula II for polymerized vinyl acetate, vinyl propionate, vinyl hexanoate or Vnyloctanoate and especially for Vinyl acetate.

• – R⁹ und R¹⁰ stehen beide für H und R¹¹ steht für Methyl oder Ethyl, d.h. die Wiederholungseinheiten III entsprechen einpolymerisiertem Propylen oder n-Butylen;
• – R⁹ und R¹⁰ stehen beide für Methyl und R¹¹ steht für H; d.h. die Wiederholungseinheiten III entsprechen einpolymerisiertem 2-Butylen;
• – R⁹ steht für H und R¹⁰ und R¹¹ stehen beide für Methyl; d.h. die Wiederholungseinheiten III entsprechen einpolymerisiertem Isobutylen.

The following combinations of the radicals R ⁹ , R ¹⁰ and R ^{11 are} preferred in the structural units of the formula III:

• - R ⁹ and R ¹⁰ both represent H and R ¹¹ represents methyl or ethyl, ie the repeating units III correspond to polymerized propylene or n-butylene;
• - R ⁹ and R ¹⁰ are both methyl and R ¹¹ is H; ie the repeating units III correspond to polymerized 2-butylene;
• - R ⁹ is H and R ¹⁰ and R ¹¹ are both methyl; ie repeating units III correspond to polymerized isobutylene.

In the structural units of the formula IV, R ¹⁴ preferably represents OOCR ⁸ . R ⁸ is preferably a branched C ₃ -C ₁₇ alkyl radical, particularly preferably a branched C ₃ -C ₁₇ alkyl radical. In particular, there is at least one branch on a carbon atom which is α or β to the carboxyl group. Preferred branched C ₃ -C ₁₀ alkyl radicals are isopropyl, isobutyl, tert-butyl, neopentyl, neohexyl, neoheptyl, neooctyl, neo nonyl and neodecyl and in particular neooctyl, neononyl and neodecyl.

R ¹² preferably represents 13 or methyl, particularly preferably H.

R ¹³ preferably represents H.

The repetition unit is particularly preferred IV for polymerized vinyl neononanoate or vinyl neodecanoate.

The copolymer of component C contains the structural units of formula I in an amount of preferably 65 to 99 mol%.

The structural units of the formula II are preferably in an amount of 1 to 35 mol%, particularly preferred from 1 to 30 mol% and in particular from 1 to 25 mol%, based on the total copolymer.

The structural units of the formula III are preferably in an amount of 0 to 20 mol%, particularly preferred from 0 to 10 mol% and in particular from 0 to 5 mol%, based on the total copolymer contained in the copolymer.

The structural units of the formula IV are preferably in an amount of 0 to 20 mol%, particularly preferred from 0 to 10 mol% and in particular from 0 to 5 mol%, based on the total copolymer contained in the copolymer.

The copolymer of component C preferably has a number average molecular weight M _n of 1000 to 10000, particularly preferably from 1000 to 5000.

Component C can also have several of the copolymers described above, which then have to be different. The difference can be both in the type of polymerized monomers and also in the amount in which the same monomers are polymerized are, or consist in the molecular weight of the copolymers.

In particular, the copolymer contains the component C essentially none, i.e. H. at the most 1% by weight, particularly preferably at most 0.5% by weight, based on the total weight of the copolymer, copolymerized Repetition units of formulas III and IV.

It is particularly preferred as a component C used a copolymer of ethylene and vinyl acetate. ethylene is in the copolymer in an amount of preferably 65 to 96 mol%, particularly preferably from 75 to 94 mol%, based on the Total copolymer, before. Accordingly, the residual content of the copolymer exists from vinyl acetate repeat units.

The copolymers of component C can be obtained, for example, by direct copolymerization of the monomers, and the ester group of the copolymerized ethylenically unsaturated ester in the copolymer can be changed by transesterification or by hydrolysis and subsequent reesterification. Such copolymers are described, for example, in WO 01/38461, EP-A 1 028 155 . EP-A 0 743 974 and WO 96/18708, to which reference is hereby made in full.

The weight ratio of component B to component A in the additive mixture preferably 1: 2 to 1:99, particularly preferably 1: 4 to 1:99 and especially 1:30 to 1:99.

The weight ratio of a mixture of components A and component B to component C is preferably 1: 250 to 10: 1, particularly preferably 1:20 to 5: 1 and in particular 1:10 to 4: 1.

Another object of the present invention is the use of the above described NEN additive mixture for the additivation of mineral oil products.

The additive mixture is particularly preferred to improve the lubricity properties petroleum products used.

The mineral oil products are preferably around fuel oils and lubricants.

Suitable fuel oils are Fuels, e.g. B. petrol and middle distillates, such as diesel fuels, fuel oil, especially heating oil EL, or kerosene, with diesel fuel and heating oil preferred are.

It deals with diesel fuels for example, oil refinements, the usual have a boiling range of 100 to 400 ° C. These are mostly distillates with a 95% point up to 360 ° C or even above out. You can but also so-called "Ultra Low Sulfur Diesel "or" City Diesel " by a 95% point of, for example, a maximum of 345 ° C and one Sulfur content of up to 0.005% by weight or through a 95% point of, for example, 285 ° C and a sulfur content of at most 0.001% by weight. In addition to through Refining available Diesel fuels are those made by Fischer-Tropsch processes or analogous processes from synthesis gas, e.g. B. by coal liquefaction or gas liquefaction ("gas to liquid" (GTL) fuels), available are suitable. Mixtures of the above are also suitable Diesel fuels with regenerative fuels, such as biodiesel, z. B. FAME, or bioethanol.

The additive mixture according to the invention is particularly preferred for the additivation of diesel fuels with low sulfur content, d. H. with a sulfur content of less than 0.05% by weight, preferably less than 0.02% by weight, in particular less than 0.005% by weight and especially less than 0.001 wt .-% sulfur, as well as for additives of heating oils with low sulfur content, d. H. with a sulfur content of less than 0.20% by weight, preferably less than 0.10% by weight, in particular less than 0.05% by weight and especially less than 0.005% by weight sulfur.

Another subject of the present Invention is a fuel composition containing a bulk of a hydrocarbon fuel oil and an effective amount of the additive mixture according to the invention and optionally at least one further additive. Regarding the preferred fuel oils is based on the above directed.

The additive mixture according to the invention is in the fuel oil preferably in an amount of 1 to 1000 ppm by weight, particularly preferably from 10 to 500 ppm by weight and in particular from 50 to 200 ppm by weight on the total amount of additive fuel oil.

Another subject of the present Invention is a lubricant composition containing one effective amount of an additive mixture according to the invention, a lubricant and optionally at least one further additive.

The invention also relates to an additive concentrate containing the additive mixture according to the invention, at least one solution or diluent and optionally at least one further additive.

Suitable diluents are, for example, fractions obtained in petroleum processing, such as kerosene, naphtha or brightstock. Also suitable are aromatic and aliphatic hydrocarbons, alkoxyalkanols and C ₁ -C ₁₀ alkanols, such as methanol, ethanol, propanol, isopropanol, butanol, pentanol, hexanol, heptanol, octanol, 2-ethylhexanol, nonanol, decanol and their positional isomers. In the case of middle distillates, particularly preferred diluents for diesel fuels, naphtha, kerosene, diesel fuels, aromatic hydrocarbons such as heavy solvent naphtha, Solvesso ^® or Shellsol ^® , alkanols such as 2-ethylhexanol, and mixtures of these solvents and diluents.

The additive mixture according to the invention is in the concentrates preferably in an amount of 0.1 to 80% by weight, particularly preferably from 1 to 70% by weight and in particular from 20 up to 60% by weight, based on the total weight of the concentrate.

Suitable additives in the fuel according to the invention or concentrate in addition to the additive mixtures according to the invention could be, especially for Diesel fuels include detergents, corrosion inhibitors, Dehazer, demulsifiers, antifoam ("Antifoam"), antioxidants, metal deactivators, multifunctional stabilizers, cetane number improvers, combustion improvers, Dyes, markers, solubilizers, Antistatic, other common lubricity, improving the cold properties Additives such as flow improvers ("MDFI"), paraffin dispersants ("WASA") and the combination of the the latter two additives ("WAFI"); and are, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition on CD-ROM, 1997, Wiley-VCH, Weinheim, Additives for Diesel Fuel.

To the usual lubricity improvers belong for example carboxylic acids, especially fatty acids, their esters, especially with polyols, mixtures of these acids and Esters, ash-free burning N-acyl compounds, such as polyalkenylsuccinic acid amides, Mixtures of the aforementioned acids and / or esters with these N-acyl compounds, such as, for example WO 96/23855 describes bis (hydroxyalkyl) fatty amines or hydroxyacetamide.

Suitable flow improvers include, for example, oil-soluble, polar nitrogen compounds, such as ammonium salts and / or amides of mono- or polycarboxylic acids or sulfonic acids, copolymers of ethylene and unsaturated carboxylic acid esters, comb polymers, saturated hydrocarbons, poly (meth) acrylic acid and mixtures of the flow improvers mentioned.

Preferred flow improvers are comb polymers whose side chains contain at least 6, preferably at least 10, atoms. Preferred comb polymers are, for example, in US Pat EP 1 028 155 to which reference is hereby made in full.

Mixtures of polar Nitrogen compounds, such as ammonium salts and / or amides of mono- or polycarboxylic acids or sulfonic acids, with copolymers of ethylene and unsaturated carboxylic acid esters and optionally with comb polymers, as described, for example, in of WO 95/33805 are preferred.

• a) 5 bis 95 Gew.-% mindestens eines Umsetzungsprodukts einer mindestens eine tertiäre Aminogruppe aufweisende Poly(C₂-C₂₀-Carbonsäure) mit sekundären Aminen und
• b) 5 bis 95 Gew.-% mindestens eines Umsetzungsprodukts aus Maleinsäureanhydrid und einem primären Alkylamin

verwendet. Solche Paraffindispergatoren sind beispielsweise in der WO 00/23541 beschrieben, auf die hiermit in vollem Umfang Bezug genommen wird.Mixtures of are preferably used as paraffin dispersants

• a) 5 to 95 wt .-% of at least one reaction product of a poly (C ₂ -C ₂₀ carboxylic acid) having at least one tertiary amino group with secondary amines and
• b) 5 to 95 wt .-% of at least one reaction product of maleic anhydride and a primary alkylamine

used. Such paraffin dispersants are described, for example, in WO 00/23541, to which reference is hereby made in full.

Another subject of the present Invention is the use of component C to increase the lubricity improver Effect of a mixture of components A and B. The above Definitions and explanations to preferred components A, B and C and to their mixing ratios apply here correspondingly.

Finally, the subject of the present Invention a method for producing a fuel oil or Lubricant composition in which a fuel oil or a Lubricant with components A, B and C that are as above are defined, in a mixture or separately, simultaneously or successively offset.

The statements made above in terms of suitable and preferred fuel oil and lubricant compositions, Fuel oils Lubricants and components A, B and C apply here accordingly.

The fuel oil or the lubricant can with the additive mixture according to the invention, in which all three components A, B and C are included become. Alternatively, you can them with a mixture of two components and with the third separate Component or with the three components A, B and C in separate Shape. With the last two alternatives, the Add the separated components simultaneously or one after the other take place, the order in the successive Addition is arbitrary.

The synergistically effective combination of components A, B and C in the additive mixture according to the invention leads to a significant improvement in the lubricity of additives petroleum products compared to prior art additives. The following Examples are intended to illustrate the invention without, however, it limit.

The tests described below were carried out with the following diesel fuels (DK):

• – als Komponenten A und B ("Komponente AB"): ein kommerziell erhältliches Gemisch aus gesättigten und ungesättigten Monocarbonsäuren und Harzsäuren der Bezeichnung Sylfat; Arizona Chemicals
• – als Komponente C – C1: ein Ethylen-Vinylacetat-Copolymer mit einem durchschnittlichen Vinylacetat-Gehalt von 26 Gew.-% – C2: eine Mischung aus Additiv C1 mit einem Ethylen-Vinylacetat-Copolymeren mit einem durchschnittlichen Vinylacetat-Gehalt von 30 Gew.-%. – C3: eine Mischung aus Additiv C1 mit einem Co-Additiv (Ethylendiamintetraessigsäure amidiert mit einem Ditalgfettamin) in einem Gewichtsverhältnis von 4:3. – C4: eine Mischung aus Additiv C1 mit dem Co-Additiv aus C3 und einem weiteren Co-Additiv (Kondensat aus Bernsteinsäureanhydrid mit einem C₁₀-C₁₈-Alkylamin) in einem Gewichtsverhältnis von 20:12:3.

The following components were used for the additives

• - As components A and B ("component AB"): a commercially available mixture of saturated and unsaturated monocarboxylic acids and resin acids called Sylfat; Arizona Chemicals
• - As component C - C1: an ethylene-vinyl acetate copolymer with an average vinyl acetate content of 26% by weight - C2: a mixture of additive C1 with an ethylene-vinyl acetate copolymer with an average vinyl acetate content of 30% by weight. -%. C3: a mixture of additive C1 with a co-additive (ethylenediaminetetraacetic acid amidated with a ditallow fatty amine) in a weight ratio of 4: 3. - C4: a mixture of additive C1 with the co-additive from C3 and another co-additive (condensate of succinic anhydride with a C ₁₀ -C ₁₈ alkylamine) in a weight ratio of 20: 12: 3.

The lubricity of non-additive, of additized with only one component AB or C and additivated according to the invention Basic fuels were tested with the HFRR test according to ISO 12156-1 and the observed lubricity compared. The WS determined in each case is in the following table 1.4 μm value lists which represents the size of the wear scar. A WS (wear scar) value of less than 460 μm indicates sufficient Lubricity.

The combination of components according to the invention A and B led with C. to a significant improvement in the lubricity of diesel fuels compared to the combination of components A and B.

Claims (24)

Additive mixture containing i) as a component A at least one aliphatic monocarboxylic acid, ii) as a component B at least one polycyclic carboxylic acid and iii) as a component C at least one copolymer of lower olefins and unsaturated Esters. Additive mixture according to claim 1, wherein the aliphatic Monocarboxylic acid a saturated or unsaturated, linear or branched monocarboxylic acid with 12 to 24 carbon atoms is. Additive mixture according to claim 2, wherein the aliphatic Monocarboxylic acid a saturated or unsaturated Monocarboxylic acid with 16 to 20 carbon atoms. Additive mixture according to one of the preceding claims, wherein as component A a mixture of saturated and unsaturated aliphatic monucarboxylic acids is used. Additive mixture according to claim 4, wherein the saturated and the unsaturated aliphatic monocarboxylic acids the same chain length exhibit. Additive mixture according to one of the preceding claims, wherein the polycyclic carboxylic acid an over two carbon atoms condensed ring system of at least two 5- or 6-membered, saturated or unsaturated Cycles is where at least one cycle is by at least one carboxylic acid group and where each cycle optionally has a heteroatom, selected under O and N, contains. The additive mixture according to claim 6, wherein the polycyclic carboxylic acid a resin acid is. Additive mixture according to one of the preceding claims, wherein in component C the copolymer has structural units of the formulas I and II -CHR ¹ -CR ² R ³ - (I) -CHR ⁴ -CR ⁵ R ⁶ - (II), wherein R ¹ , R ² and R ^{3 are} independently H, methyl or ethyl, R ^{4 is} H, C ₁ -C ₄ alkyl or COOR ⁷ , R ^{5 is} H or methyl, R ^{6 is} COOR ⁷ or OOCR ⁸ stands for R ^{7 stands} for a linear or branched C ₁ -C ₁₇ alkyl radical, and R ^{8 stands} for H or R ⁷ , and optionally structural units of the formulas III and / or IV -CHR ⁹ -CR ¹⁰ R ¹¹ - (III) -CHR ¹² -CR ¹³ R ¹⁴ - (IV) contains wherein R ⁹ , R ¹⁰ and R ^{11 are} independently defined as R ¹ , R ² and R ³ , R ¹² is defined as R ⁴ , R ¹³ is defined as R ⁵ and R ¹⁴ is defined as R ⁶ , wherein the structural units I and III and the structural units II and IV are each different from one another. Additive mixture according to claim 8, wherein R ¹ , R ² and R ^{3 are} H. Additive mixture according to one of claims 8 or 9, wherein R ^{6 is} OOCR ⁸ . Additive mixture according to claim 10, wherein R ^{8 stands} for a linear C ₁ -C ₁₇ alkyl radical or for a branched C ₃ -C ₁₇ alkyl radical, wherein there is at least one branch on a carbon atom which is α or β to the carboxyl group stands. Additive mixture according to claim 11, wherein R ^{8 is} methyl. Additive mixture according to one of claims 8 to 12, wherein R ⁴ and R ^{5 are} H. Additive mixture according to one of claims 8 to 13, wherein R ¹⁰ and / or R ^{11 are} methyl and R ^{9 is} H. Use of the additive mixture, as in a of the preceding claims is defined for the additive of mineral oil products. Use according to claim 15 to improve the Lubricity properties of petroleum products. Fuel oil composition, containing a major amount of a hydrocarbon fuel oil and one effective amount of an additive mixture as defined in one of the Expectations 1 to 14 and optionally at least one further additive. Fuel oil composition according to claim 17 or use according to one of claims 15 or 16, the fuel oil being diesel fuel, heating oil or kerosene is. Fuel oil composition according to claim 18 with a sulfur content of the fuel oil of at most 500 ppm. Fuel oil composition according to one of the claims 18 or 19 or use according to claim 18, wherein the diesel fuel by refining or by Fischer-Tropsch processes from synthesis gas available is, or is a mixture of such fuels and optionally is mixed with regenerative fuels. Lubricant composition containing an effective one Amount of additive mixture as defined in one of the claims 1 to 14 and a lubricant and optionally at least one another additive. Additive concentrate containing an additive mixture as defined in one of the claims 1 to 14 and at least one diluent and optionally at least one further additive. Use of a component C, as in a of claims 1 or 8 to 14 is defined to increase the lubricity-improving Effect of a mixture of components A and B, as in one of claims 1 to 7 are defined. Process for the preparation of a fuel oil composition as defined in one of the claims 17 to 20 or a lubricant composition as defined in claim 21, wherein one with a fuel oil or a lubricant components A, B and C, which are as in one of claims 1 to 14 are defined, in a mixture or separately, simultaneously or in succession added.