WO2004085580A1

WO2004085580A1 - Additive mixture for improving the lubricating properties of mineral oil products

Info

Publication number: WO2004085580A1
Application number: PCT/EP2004/003253
Authority: WO
Inventors: Siegbert Brand; Wolfgang Ahlers; Ansgar Eisenbeis; Peter Schwab; Irene Trötsch-Schaller
Original assignee: Basf Aktiengesellschaft
Priority date: 2003-03-27
Filing date: 2004-03-26
Publication date: 2004-10-07
Also published as: DE10313883A1

Abstract

The 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 consisting of low olefins and of unsaturated esters. The invention also relates to the use of this additive mixture for adding to mineral oil products, in particular, to both fuel oil compositions and lubricant compositions, and relates to concentrates that all contain this additive mixture.

Description

Additive mixture to improve the lubricity properties of mineral oil products

description

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.

Efforts to reduce harmful emissions from the combustion of fuels, particularly diesel fuels, have recently focused on reducing sulfur dioxide emissions and reducing particulate emissions, particularly in diesel exhaust. To reduce sulfur dioxide emissions, the sulfur content in petrol and middle distillates, such as diesel or heating oil, has been reduced in the refineries by "hydrotreatmentent", in which the fuel is treated with hydrogen, whereby sulfur-containing components are reduced to hydrogen sulfide lowered. An undesirable side effect of this desulfurization is the destruction of polyaromatic and polar components in the fuel. This has a negative impact, particularly in the case of diesel fuels, since diesel injection systems are often lubricated with fuel and, due to the reduction in the natural lubricity of the fuel, wear has increased, particularly in the area of high-pressure injection pumps. The wear problem becomes even more significant if the fuels are used in a mixture with "gas to liquid" fuels (GTL fuels) or with regenerative fuels such as bioethanol, since these components have no properties that improve lubricity.

In order to avoid wear, artificial lubrication improvers, such as fatty acid mixtures, their esters, amides or salts, are generally added to the fuel. WO 98/04656 describes diesel fuels with a sulfur content of at most 500 pp, which contains an additive mixture of monocarboxylic acids and polycyclic acids to improve the lubricity. However, the improvement in lubricity achieved with this additive mixture is still not satisfactory.

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.

The object of the present invention was therefore to provide additive mixtures which effectively improve the lubricity of fuel oil and lubricant compositions, even at lower metering rates.

It has surprisingly been found that the combination of monocarboxylic acids and polycyclic acids with copolymers of lower olefins and unsaturated esters has a synergistic effect with regard to improving the lubricity of fuel oil and lubricant compositions.

The present invention therefore relates to an additive mixture comprising

i) at least one aliphatic monocarboxylic acid as component A,

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. Ci-Cs-alkyl also designates pentyl or neopentyl and other positional isomers. Ci-Cs-alkyl also designates, for example, hexyl, heptyl, octyl and 2-ethylhexyl and other positional isomers. C 1 -C ₀ alkyl also denotes wonyl, decyl and their positional isomers. Cχ-Cχ-alkyl also denotes ündecyl, dodecyl, tridecyl, Tetradecyl, pentadecyl, hexadecyl, heptadecyl and positional isomers of these residues.

In the context of the present invention, alkenyl denotes linear or branched, mono- or polyunsaturated alkenyl residues. For example, C ₂ -Cs-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 ₄ alkyl, OH and 0 -C -C ₄ alkyl.

In the context of the present invention, the term “aliphatic monocarboxylic acid” denotes both the monocarboxylic acid itself and its 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, Include imides and amidines, and nitriles. However, it is preferably the carboxylic acid itself.

In the context of the present application, the term “polycyclic carboxylic acid” denotes both the carboxylic acid itself and its 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 amidines include, and nitriles. However, it is preferably the carboxylic acid itself.

The aliphatic monocarboxylic acid is preferably a saturated 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. The monocarboxylic acid is particularly preferably linear.

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

Examples of suitable saturated aliphatic monocarboxylic acids are lauric acid, tridecanoic acid, myisic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, tuberculostearic acid, nonadecanoic acid, arachic acid, behenic acid and lignoceric acid. Examples of suitable unsaturated aliphatic monocarboxylic acids are palmitoleic acid, oleic acid and erucic acid (mono-unsaturated), linoleic acid (mono-unsaturated), linolenic acid and elaeostearic acid (tri-unsaturated), arachidonic acid (four-times unsaturated), clupanodonic acid (five-times unsaturated) and do- (six-times unsaturated) unsaturated). Palmitic acid or stearic acid is preferably used as the saturated aliphatic monocarboxylic acid. Among the unsaturated monocarboxylic acids, oleic acid, linoleic acid, linolenic acid and elaeostearic acid are preferred.

The polycyclic carboxylic acid is preferably a ring system which comprises at least two 5- or 6-membered, saturated or unsaturated cycles and is condensed via two adjacent carbon atoms, at least one cycle being selected by at least one carboxyl group or by at least one carboxyl derivative is substituted among carboxylic acid ester groups, the reaction products of carboxyl groups with primary, secondary and tertiary amines and polyamines, which include ammonium carboxylates, carboxamides, imides and amidines, and nitriles, and where each cycle optionally contains a heteroatom selected from 0 and N.

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 0 and N, where in each cycle only one X may stand for a heteroatom and 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 represent H, Ci-Cs-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 is saturated or unsaturated, contain a heteroatom which is selected from 0 and N, and by a saturated or unsaturated aliphatic hydrocarbon radical having one to four carbon atoms or by egg - A hydroxy residue can be substituted; 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 Ci-Cg-alkyl which is interrupted by one or more groups which are selected from 0 and NR ²⁰ and / or by one or more groups which are selected from OR ²¹ and NR ²² R ²³ can be, where 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 which are formed in the reaction of carboxyl groups with amines are those mentioned above, ie ammonium carboxylates, carboxamides, imides and amidines. These are preferably ammonium carboxylates or carboxamides. These ammonium salts or amides are particularly preferably derived from amines which are selected from 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 attached, it is preferably a 5- or 6-ring, particularly preferably a carbocyclic 5 - Or 6-ring and especially see a carbocyclic 6-ring. The ring can be saturated or single, double or triple unsaturated. The ring is preferably by at least one Cx-C ^ 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 bound 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 atoms X to which they are attached, particularly preferably a carbocyclic 5 or 6 ring and in particular a carbocyclic 6 ring, ie the atoms X to which they are attached are carbon atoms. The ring can be saturated or single, double or triple unsaturated. The ring is preferably through at least one C ₁ -C ₄ -alkyl group, in particular through methyl or isopropyl, through a C ₂ -C ₅ -alkenyl group, in particular through vinyl, through an optionally substituted exocyclic double bond, in particular through a dimethyl-substituted exocyclic double bond and / or substituted by a hydroxy group.

The radical R ¹⁹ is Ci-Cg-alkyl which is interrupted by one or more groups selected from 0 and NR ²⁰ and optionally substituted by one or more groups selected from OR ²¹ and NR ²² R ²³ , preferably for a radical of the formula

-r-A-XH-n-A-Y

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 0 or NR ²⁰ , wherein R ^{20 is} H or C ₁ -C ₄ alkyl,

Y represents H, OR ²¹ or NR ² R ²³ ,

wherein R ²¹ is defined as R ²⁰ and R ²² and R ²³ for H,

-CC ₄ alkyl or -C ₄ -hydroxyalkyl, and

n stands for a number from 1 to 3.

In the R ¹⁹ radical, Ci-Cg-alkyl, which is substituted by one or more groups selected from OR ²¹ and NR ²² R ²³ , is preferably C ₂ -Cg-alkyl, which is substituted by one to three hydroxyl groups and / or is substituted by one to three radicals NR ²² R ²³ . 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, further 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.

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.

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

The polycyclic carboxylic acid or the corresponding derivative of the formula V is particularly preferably a resin acid or a resin acid derivative.

Preferred resin acid or its derivatives are abietic acid, dihydroabietic acid, tetrahydroabietic acid, dehydroabietic acid, neoabietic acid, pimaric acid, laevopimaric acid, palustric acid, paraastric acid or derivatives of these acids.

Resin acids are usually obtained by distillation of natural resins obtained from trees containing resin, in particular from conifers.

The polycyclic carboxylic acids described above and their mixture with aliphatic monocarboxylic acids are described 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 ⁵ - (II),

wherein

R ¹ 'R ² and R ³ independently of one another are H, methyl or ethyl, R ^{4 represents} H, -CC 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 4 -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 ^{1: L} - (HI)

-CHR ¹² -CR ¹³ R ¹⁴ - (IV)

contains what

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 ,

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 ₄ -alkyl radical, particularly preferably a linear C 1 -C ₄ -alkyl radical, such as methyl, ethyl, n-propyl or n-butyl, and especially methyl. Alternatively, R ⁷ is preferably a branched C ₃ -Cι alkyl, more preferably a branched C ₃ -Cιo ^_A lkylrest. In particular, there is at least one branch on a carbon atom that 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 preferably represents a linear C 1 -C 4 -alkyl radical, particularly preferably a C 1 -C ₁ -alkyl radical. Alternatively, R ^{8 is} preferably a branched C ₃ -Cχ alkyl radical, particularly preferably a branched C ₃ -Cι ₀ 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 -Cιo alkyl are isopropyl, isobutyl, tert-butyl, neopentyl, neohexyl, Neoheptyl, Neooctyl, Neononyl and neodecyl and particularly Neooctyl, Neononyl and neodecyl.

However, R ⁸ in the structural units of the formula II is particularly preferably 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 repeating unit of the formula II particularly preferably stands for polymerized vinyl acetate, vinyl propionate, vinyl hexanoate or vinyl octanoate and in particular for vinyl acetate.

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 preferably represents a branched C ₃ -C ₇ -alkyl radical, particularly preferably a branched C ₃ -C-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 1 -C 10 -alkyl radicals are isopropyl, isobutyl, tert-butyl, neopentyl, neohexyl, neoheptyl, neooctyl, neo- nonyl and neodecyl and especially neooctyl, neononyl and neodecyl.

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

R ¹³ preferably represents H.

The repeating unit IV particularly preferably stands for polymerized vinyl neononanoate or vinyl neodecanoate.

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

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

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

The structural units of the formula IV are preferably present in the copolymer in an amount of 0 to 20 mol%, particularly preferably 0 to 10 mol% and in particular 0 to 5 mol%, based on the total 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 contain several of the copolymers described above, in which case these must be different. The difference can exist both in the type of polymerized monomers and in the amount in which the same monomers are polymerized in, or in the molecular weight of the copolymers.

In particular, the copolymer of component C contains essentially no, ie at most 1% by weight, particularly preferably at most 0.5% by weight, based on the total weight of the copolymer, of copolymerized repeating units of the formulas III and IV. A copolymer of ethylene and vinyl acetate is particularly preferably used as component C. Ethylene is present in the copolymer in an amount of preferably 65 to 96 mol%, particularly preferably 75 to 94 mol%, based on the total copolymer. Accordingly, the residual content of the copolymer consists of vinyl acetate repeating units.

The copolymers of component C can be obtained, for example, by direct copolymerization of the monomers, it being possible for the ester group of the copolymerized ethylenically unsaturated ester in the copolymer to 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 is preferably 1: 2 to 1:99, particularly preferably 1: 4 to 1:99 and in particular 1:30 to 1:99.

The weight ratio of a mixture of component 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 additive mixture described above for the additivation of mineral oil products.

The additive mixture is particularly preferably used to improve the lubricity properties before mineral oil products.

The mineral oil products are preferably fuel oils and lubricants.

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

Diesel fuels are, for example, petroleum raffinates, which usually have a boiling range of 100 to 400 ° C. These are mostly distillates with a 95% point up to 360 ° C or beyond. However, these can also be so-called "ultra low sulfur diesel" or "city diesel", characterized by a 95% point of, for example, a maximum of 345 ° C. and a sulfur content of a maximum of 0.005% by weight or by a 95% point of, for example, 285 ° C. and a sulfur content of maximum 0.001% by weight. In addition to the diesel fuels obtainable by refining, those that are produced by Fischer-Tropsch processes or analog processes from synthesis gas, e.g. B. by coal liquefaction or gas liquefaction ("gas to liquid" (GTL) fuels) are available, suitable. Mixtures of the aforementioned diesel fuels with regenerative fuels, such as biodiesel, for. B. FAME, or bioethanol.

The additive mixture according to the invention is particularly preferred for additizing diesel fuels with a low sulfur content, ie. 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% by weight of sulfur, and for the addition of Low sulfur fuel oils, 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 of sulfur.

Another object of the present invention is a

Fuel composition comprising a main amount of a hydrocarbon fuel oil and an effective amount of the additive mixture according to the invention and optionally at least one further additive. With regard to the preferred fuel oils, reference is made to the above statements.

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

Another object of the present invention is a lubricant composition containing an 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 solvent or diluent and, if appropriate, 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 Cι-C Alko-alkanols, such as methanol, ethanol, propanol, isopropanol, butanol, pentanol, He- xanol, heptanol, octanol, 2-ethylhexanol, nonanol, decanol and their positional isomers. In middle distillates, in particular in diesel fuels preferred diluent used are naphtha, kerosene, diesel fuels, aromatic hydrocarbons, such as Solvent Naphtha heavy, Solvesso or Shellsol ^®, Al alkanols such as 2-ethyl hexanol, and mixtures of these solvents and diluents.

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

Suitable additives which can be contained in the fuel or concentrate according to the invention in addition to the additive mixtures according to the invention, in particular for diesel fuels, include detergents, corrosion inhibitors, dehazers, demulsifiers, antifoam ("antifoam"), antioxidants, metal deactivators, multifunctional stabilizers, cetane number improvers , Combustion improvers, dyes, markers, solubilizers, antistatic agents, other customary lubricity improvers, additives which improve the cold properties, such as flow improvers ("MDFI"), paraffin dispersants ("WASA") and the combination of the latter two additives ("WAFI") ); and are described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition on CD-ROM, 1997, Wiley-VCH, Weinheim, Additives for Diesel Fuel.

The usual lubricity improvers include, for example, carboxylic acids, especially fatty acids, their esters, especially with polyols, mixtures of these acids and esters, ash-free N-acyl compounds, such as polyalkenylsuccinic acid amides, mixtures of the abovementioned acids and / or esters with these N-acyl compounds, such as they are described, for example, in WO 96/23855, bis (hydroxyalkyl) fatty amines or hydroxyacetamides.

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 aforementioned flow improvers.

Preferred flow improvers are comb polymers whose side chains contain at least 6, preferably at least 10, atoms. Preferred comb polymers are described, for example, in 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 WO 95/33805, are also preferred.

Mixtures of are preferably used as paraffin dispersants

a) 5 to 95% by weight of at least one reaction product of a poly (C ₂ -C ₂ o- ₎ having at least one tertiary amino group

Carboxylic acid) 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 object of the present invention is the use of component C to increase the lubricity-improving effect of a mixture of components A and B. The above definitions and explanations for preferred components A, B and C and their mixing ratios apply accordingly here.

Finally, the present invention relates to a method for producing a fuel oil or lubricant composition, in which a fuel oil or a lubricant with components A, B and C, which are defined as described above, is mixed or separately, simultaneously or in succession.

The statements made above with regard to suitable and preferred fuel oil and lubricant compositions, fuel oils, lubricants and components A, B and C apply accordingly here.

The fuel oil or the lubricant can be mixed with the additive mixture according to the invention, in which all three components A, B and C are contained. Alternatively, they can be mixed with a mixture of two components and with the third separate component or with the three components A, B and C in separate form. In the last two alternatives, the addition of the separate components can be carried out simultaneously or sequentially otherwise, the order in the sequential 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 mineral oil products additized therewith in comparison to additives of the prior art.

The following examples are intended to illustrate the invention without, however, restricting it.

Examples

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

CP = cloud point

CFPP: Cold Filter Plugging Point

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

-Cl: an ethylene-vinyl acetate copolymer with an average vinyl acetate content of 26% by weight

-C2: a mixture of additive Cl with an ethylene-vinyl acetate copolymer with an average vinyl acetate content of 30% by weight. -C3: a mixture of additive Cl with a co-additive (ethylenediaminetetraacetic acid amidated with a ditallow fatty amine) in a weight ratio of 4: 3.

-C4: a mixture of additive Cl with the co-additive from C3 and another co-additive (condensate of succinic anhydride with a Cio-Cie-alkylamine) in a weight ratio of 20: 12: 3.

The lubricity of non-additive, of additive with only one component AB or C and of additive according to the invention was tested with the HFRR test according to ISO 12156-1 and the observed lubricity was compared. The following table shows the WS 1.4 μm value, 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 A and B with C according to the invention led to a significant improvement in the lubricity of the diesel fuels compared to the combination of components A and B.

Claims

claims

1. Additive mixture containing

i) at least one aliphatic monocarboxylic acid as component A,

ii) as component B at least one polycyclic carboxylic acid and

2. Additive mixture according to claim 1, wherein the aliphatic monocarboxylic acid is a saturated or unsaturated, linear or branched monocarboxylic acid having 12 to 24 carbon atoms.

3. Additive mixture according to claim 2, wherein the aliphatic monocarboxylic acid is a saturated or unsaturated monocarboxylic acid having 16 to 20 carbon atoms.

4. Additive mixture according to one of the preceding claims, wherein a mixture of saturated and unsaturated aliphatic monocarboxylic acids is used as component A.

5. Additive mixture according to claim 4, wherein the saturated and the unsaturated aliphatic monocarboxylic acids have the same chain length.

6. Additive mixture according to one of the preceding claims, wherein the polycyclic carboxylic acid is a ring system condensed over two carbon atoms from at least two 5- or 6-membered, saturated or unsaturated cycles, at least one cycle being substituted by at least one carboxylic acid group and wherein each Cycle optionally contains a heteroatom selected from O and N.

7. The additive mixture according to claim 6, wherein the polycyclic carboxylic acid is a resin acid. 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-CR ⁵ R ⁶ - (II),

wherein

R ¹ 'R ² and R ³ independently of one another are H, methyl or ethyl,

R ^{4 represents} H, -CC ₄ alkyl or COOR ⁷ ,

R ^{5 represents} H or methyl,

R ^{6 stands} for COOR ⁷ or OOCR ⁸ ,

R ⁷ for a linear or branched C _! -C ₁₇ alkyl radical, and

R ^{8 represents} H or R ⁷ ,

and optionally structural units of the formulas III and / or IV

-CHR ⁹ -CR ¹⁰ R ^{1: L} - (III)

-CHR ¹² -CR ¹³ R ¹⁴ - (IV)

contains what

R ⁹ , R ¹⁰ and R ^{11 are defined} independently of one another like R ¹ , R ² and R ³ ,

Ri2 _we R4 is defined

R ¹³ is defined as R ⁵ and

R ¹⁴ is defined as R ⁶ ,

9. Additive mixture according to claim 8, wherein R ¹ «- R ² and R ^{3 are} H.

10. Additive mixture according to one of claims 8 or 9, wherein R ⁶ 5 is OOCR ⁸ .

11. The additive mixture according to claim 10, wherein R ^{8 represents} a linear C 1 -C ₇ -alkyl radical or a branched C ₃ -Ci ₇ -alkyl radical, with at least one branch on a carbon

10 lenstoffatom, which is α- or ß-to the carboxyl group.

12. Additive mixture according to claim 11, wherein R ^{8 is} methyl.

15 13. Additive mixture according to one of claims 8 to 12, wherein R ⁴ and R ^{5 are} H.

14. Additive mixture according to one of claims 8 to 13, wherein R ¹⁰ and / or R ^{11 are} methyl and R ^{9 is} H.

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15. Use of the additive mixture as defined in any one of the preceding claims for the additization of mineral oil products.

25 16. Use according to claim 15 to improve the lubricity properties of mineral oil products.

17. A fuel oil composition containing a major amount of a hydrocarbon fuel oil and an effective amount of one

30 additive mixture as defined in one of claims 1 to 14 and optionally at least one further additive.

18. Fuel oil composition according to claim 17 or use 35 according to one of claims 15 or 16, wherein it is

Fuel oil delt diesel fuel, heating oil or kerosene han _¬.

19. A fuel oil composition according to claim 18 with a sulfur content of the fuel oil of at most 500 ppm.

20. Fuel oil composition according to one of claims 18 or 19 or use according to claim 18, wherein the diesel fuel by refining or by Fischer-Tropsch process

45 is available from synthesis gas, or a mixture of such Is fuel and is optionally mixed with regenerative fuels.

21. Lubricant composition containing an effective amount

5 an additive mixture according to the definition in one of claims 1 to 14 and a lubricant and optionally at least one further additive.

22. Additive concentrate containing an additive mixture according to the

10 Definition in one of claims 1 to 14 and at least one diluent and optionally at least one further additive.

23. Use of a component C, as defined in one of claims 15 1 or 8 to 14, to increase the lubricity-improving effect of a mixture of components A and B, which are as defined in one of claims 1 to 7.

24. A method of making a fuel oil composition as defined in any one of claims 17 to 20 or, a lubricant composition as defined in claim 21, which comprises a fuel oil or a lubricant having components A, B and C as in one the

25 claims 1 to 14 are defined, in a mixture or separately, simultaneously or in succession.

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