EP1752513B1 - Mineral oils having improved conductivity and cold flow properties - Google Patents

Abstract

A mineral oil composition comprises at least one alkylphenolaldehyde resin and, based on the alkylphenol resin, 0.05-10 wt.% of at least one salt of an aromatic base and of a sulfonic acid. Independent claims are also included for: (1) mineral oil distillate having a conductivity of more than 50 pS/m, which comprises the above composition, or having an aromatics content of less than 25 wt.% and comprising 5-5000 ppm of the above composition; (2) improving the electrical conductivity of a mineral oil distillate having an aromatics content of less than 25 wt.%, comprising adding at least a portion of the composition to the mineral distillate to provide the mineral oil with improved electrical conductivity; and (3) improving the cold flowability of a mineral oil distillate having a sulfur content less than 350 ppm, comprising adding to the mineral oil distillate the above composition.

Description

The present invention relates to the use of alkylphenol-aldehyde resins and salts of organic aromatic bases with sulfonic acids to improve the conductivity of low-sulfur mineral oil distillates, and the additive mineral oil distillates.

The content of mineral oil distillates in sulfur-containing compounds and aromatics must be lowered further and further in the course of tightening environmental legislation. The refinery processes used to produce specification-compliant mineral oil grades, however, also remove other polar and aromatic compounds. As a side effect, the electrical conductivity of these mineral oil distillates is greatly reduced. As a result, electrostatic charges, as they occur in particular under high flow rates, for example when pumping in lines and filters in the refinery, in the distribution chain as well as the consumer, can not be compensated. Such potential differences between the oil and its environment, however, carry the risk of spark discharge, which can lead to spontaneous combustion or explosion of flammable liquids. Therefore, additives are added to such oils with low electrical conductivity, which increase the conductivity and facilitate the potential equalization between the oil and its environment. A conductivity greater than 50 pS / m is generally considered sufficient for the safe handling of mineral oil distillates. Methods for determining the conductivity are described, for example, in DIN 51412-T02-79 and ASTM 2624.

A class of compounds used in mineral oils for a variety of purposes are alkylphenol resins and their derivatives, which can be prepared by condensation of alkyl-containing phenols with aldehydes under acidic or basic conditions. For example, alkylphenol resins are described as Cold flow improvers, lubricity improvers, oxidation inhibitors, corrosion inhibitors and asphalt dispersants and alkoxylated alkylphenol resins are used as demulsifiers in crude oils and middle distillates. Furthermore, alkylphenol resins are used as stabilizers for jet fuel. Resins of benzoic acid esters with aldehydes or ketones are also used as cold additives for fuel oils. However, the effect of the known resins and the additive systems containing them is not yet satisfactory, especially in many low-sulfur or sulfur-free oils.

GB-A-2 305 437 and GB-A-2 308 129 disclose alkylphenol-formaldehyde resins as pour point depressants for waxy liquids such as diesel, lubricating oil, hydraulic oil, crude oils. The condensation of the alkylphenols with formaldehyde in a ratio of 2: 1 to 1: 1.5 can be carried out in the presence of acidic catalysts such as sulfuric acid, sulfonic acids or carboxylic acids. The resin can then be treated with NaOH as needed to convert the acidic catalyst to the sodium salt and separate by, for example, filtration. In the examples, working with concentrated sulfuric acid, which is filtered off after the condensation as the sodium salt.

EP-A-0 857 776 discloses the use of alkylphenol resins in combination with ethylene copolymers and nitrogen-containing paraffin dispersants to improve the cold properties of middle distillates. The condensation of the resins can be carried out under catalysis by inorganic or organic acids, which optionally remain after not further specified neutralization in the product. In the examples, the condensation of the resins takes place under catalysis by alkylbenzenesulfonic acid, which is subsequently neutralized with KOH or NaOH.

EP-A-1 088 045 discloses that alkylphenol resins can be combined with amines bearing at least one hydrocarbon radical. According to the examples, these are salts of alkylphenol resins in which just under half of the phenolic OH groups are neutralized with secondary alkylamines.

EP-A-0 381 966 discloses a process for the preparation of novolacs by condensation of phenols with aldehydes with azeotropic culling of Water. Suitable catalysts are strong mineral acids, especially sulfuric acid and its acidic derivatives. These can be neutralized before working up the reaction mixture, preferably with metal hydroxides or amines. In the examples, all is catalyzed with sulfuric acid, which is then neutralized with sodium hydroxide solution.

EP-A-0 311 452 discloses alkylphenol-formaldehyde condensates as refrigerants for fuels and lubricating oils. The catalyst used is p-toluenesulfonic acid, which remains as such in the resin.

EP-A-1482024 discloses condensates of p-hydroxybenzoic acid esters and aldehydes or ketones as cold additives for fuel oils. The condensation takes place here in the presence of acidic catalysts such as p-toluenesulfonic acid, which remain as such in the product.

In the context of the present invention, alkylphenol resins are understood as meaning all polymers which are accessible by condensation of an alkyl radical-carrying phenol with aldehydes or ketones. The alkyl radical can be bonded directly to the aryl radical of the phenol via a C-C bond or via functional groups such as esters or ethers.

As catalysts for the condensation reactions of alkylphenol and aldehyde in addition to carboxylic acids such as acetic acid and oxalic acid in particular strong mineral acids such as hydrochloric acid, phosphoric acid and sulfuric acid and sulfonic acids are common catalysts. Usually, these remain after completion of the reaction as such or in neutralized form in the product.

From the prior art it is known to neutralize the catalyst used for the condensation of the alkylphenol resin with a base. In practice, bases such as sodium hydroxide or potassium hydroxide are usually used, which lead to the formation of sodium or potassium salts of these strong acids. For use as fuel additives, however, such salts are undesirable because they precipitate out of the oil in crystalline form and lead or filter clogging cause combustion as well as unwanted residue (ash).
Object of the present invention was thus to find an additive for improving both the conductivity and the cold properties of mineral oil distillates.

Surprisingly, it has now been found that mineral oils which contain phenol resins carrying alkyl radicals can be significantly improved in their electrical conductivity by adding small amounts of oil-soluble salts of organic aromatic bases and sulfonic acids. The effect achievable with salts of aromatic bases is also more pronounced than with corresponding alkali metal salts and ammonium salts based on aliphatic amines. Presumably, the salt formation in the mixtures according to the invention is much more selective and the weak in comparison to alkali metal bases and aliphatic amines aromatic bases prefer a salt formation with the strong sulfonic acids and less with the only weakly acidic phenolic OH groups. The oils thus additized show a greatly increased conductivity and are thus much safer to handle.

Furthermore, it has been found that by adding small amounts of oil-soluble salts of aromatic bases and sulfonic acids at the same time the effectiveness of the alkyl radicals carrying phenol-aldehyde resins as cold additives, especially as paraffin dispersants, is increased and also after prolonged storage of the alkylphenol-aldehyde resin or a alkylphenol Aldehyde resin-containing additive package is retained. Presumably, this is due to a suppression of the decomposition of the alkylphenol resins to intensely colored phenoxy and phenoxonium radicals.

The invention thus relates to compositions comprising at least one alkylphenol resin (constituent I) and, based on the alkylphenol resin, from 0.005 to 10% by weight of at least one salt of an aromatic base and a sulfonic acid (constituent II).

The invention further relates to mineral oil distillates having a sulfur content of less than 350 ppm, containing 5 to 500 ppm of a composition comprising at least one alkylphenol resin (constituent I) and, based on the alkylphenol resin, 0.05 to 10 wt .-% of at least one salt of an aromatic base and a sulfonic acid (component II).

Another object of the invention is the use of compositions comprising at least one alkylphenol resin (component I) and, based on the alkylphenol resin, 0.05 to 10 wt .-% of at least one salt of an aromatic base and a sulfonic acid (component II), for improving the electrical conductivity of mineral oil distillates having a sulfur content of less than 350 ppm.

Another object of the invention is the use of compositions comprising at least one alkylphenol resin (component I) and, based on the alkylphenol resin, 0.05 to 10 wt .-% of at least one salt of an aromatic base and a sulfonic acid (component II), for improving the cold flowability of mineral oil distillates having a sulfur content of less than 350 ppm.

The sulfonic acid salts of the invention can be added to the mineral oil distillate or the alkylphenol-aldehyde resin as such. They are preferably prepared by reacting the sulphonic acid used as the catalyst for the acidic condensation of the alkylphenol-aldehyde resin with the corresponding aromatic base in the presence of the alkylphenol-aldehyde resins. Alternatively, they can be prepared by reacting an aromatic base used as catalyst for basic condensation of the alkylphenol-aldehyde resin with corresponding sulfonic acids in the presence of the alkylphenol-aldehyde resins.

Preferably, the compositions according to the invention, based on the alkylphenol resin, 0.05 to 5 wt .-% and in particular 0.1 to 5 wt .-% such as 0.5 to 4 wt .-% of at least one salt of an aromatic base and a sulfonic acid.

The mineral oil distillates according to the invention preferably contain from 10 to 150 and especially from 10 to 100 ppm of at least one alkylphenol resin and from 0.1 to 5% by weight, particularly preferably 0.5 to 5 wt .-%. such as 1 to 4 wt .-% of at least one sulfonic acid salt based on the alkylphenol resin.

To improve the conductivity and / or cold flowability of mineral oil distillates, preference is given to using compositions comprising at least one alkylphenol resin and, based on the alkylphenol resin, 0.1 to 5 wt .-%, particularly preferably 0.5 to 5 wt .-% such as 1 to 4 wt .-% of at least one salt of an aromatic base and a sulfonic acid.

The mineral oil distillates of the invention which are improved in their electrical conductivity have an electrical conductivity of preferably at least 50 pS / m, especially of at least 70 pS / m, for example of at least 90 pS / m.

Particularly suitable sulfonic acids for the preparation of the sulfonic acid salts are all oil-soluble compounds containing at least one sulfonic acid group and at least one saturated or unsaturated, linear, branched and / or cyclic hydrocarbon radical having 1 to 40 carbon atoms and preferably having 3 to 24 carbon atoms. Particularly preferred are aromatic sulfonic acids, especially alkylaromatic mono-sulfonic acids having one or more C ₁ -C ₂₈ -alkyl radicals and in particular those having C ₃ -C ₂₂ -alkyl radicals. The alkylaromatic sulfonic acids preferably carry one or two alkyl radicals, in particular an alkyl radical. The underlying aryl groups are preferably monocyclic and bicyclic, in particular monocyclic. In a preferred embodiment, the aryl groups carry no carboxyl groups, and especially they carry only sulfonic acid and alkyl groups. Suitable examples are methanesulfonic acid, butanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, xylenesulfonic acid, 2-mesitylenesulfonic acid, 4-ethylbenzenesulfonic acid, isopropylbenzenesulfonic acid, 4-butylbenzenesulfonic acid, 4-octylbenzenesulfonic acid; Dodecylbenzenesulfonic acid, didodecylbenzenesulfonic acid, naphthalenesulfonic acid. Mixtures of these sulfonic acids are suitable. Oil-soluble here means that said compounds are at least 1 wt .-% soluble in aromatic solvents such as toluene.

Suitable aromatic bases are in particular oil-soluble compounds which are a cyclic, durchkonjugiertes hydrocarbon skeleton with 4n + 2 π-electrons, where n is an integer between 1 and 6, preferably between 2 and 4 and in particular 1 or 2, and at least one capable of salt formation Heteroatom included. This heteroatom may e.g. be part of the aromatic ring system in so-called heteroaromatics, but it may also be bound to this ring. It is preferably part of the aromatic ring system. Suitable heteroatoms are nitrogen, oxygen and sulfur, particularly preferred heteroatom is nitrogen. Preferably, at least one free electron pair of the heteroatom is not involved in the formation of the aromatic π-electron system.

The aromatic system may be mono-, di- or even polycyclic. It preferably contains one or more five- and / or six-membered rings with a π-electron septet. It is particularly preferably monocyclic and five- or six-membered. It may carry further substituents such as, for example, alkyl, alkylene and / or phenyl radicals, but also functional groups such as, for example, hydroxy, ester, amide and / or amino groups, provided these do not impair salt formation. Optionally present alkyl and alkenyl radicals may be linear, branched or cyclic and linked to the aromatic system at one or two sites.

Examples of suitable aromatic monocyclic bases are pyridine, picoline, lutidine, collidine, nicotinamide, dihydroquinoline, aminopyridine, aniline, N, N-dimethylaniline, toluidine, phenylenediamine, pyrimidine, pyrazine, pyridazine, imidazole, pyrazole, histamine, triazine, triazole, oxazole, Isoxazole, thiazole and isothiazole, and p-phenylenediamine, 2- (N, N-dimethylamino) pyridine, 4- (N, N-dimethylamino) pyridine and 2,4-diamino-6-hydroxypyrimidine.

Suitable aromatic polycyclic bases are, for example, quinoline, isoquinoline, 6-methylquinoline, 2-aminoquinoline, 5-dimethylaminochinoline, 7-dimethylaminoquinoline, benzimidazole, purine, cinnoline, phthalazine, quinazoline, quinoxaline, acridine, phenanthroline and phenazine and 1,5-diaminonaphthalene. 1,8-diaminonaphthalene and diaminoquinazoline.

Particularly preferred bases are mono- and bicyclic nitrogen-containing aromatics such as pyridine, quinoline, imidazole and derivatives thereof.

The sulfonic acid salts of the invention are prepared by reacting the sulfonic acids with 0.8 to 10 moles of aromatic base, preferably 0.9 to 5 moles of aromatic base, more preferably 0.95 to 2 moles of aromatic base, such as about equimolar. In particular, in the case of polybasic sulfonic acids and / or bases, the number of moles of the total acid and base groups reacted is considered. The additives according to the invention and the mineral oil distillates containing them can accordingly also contain more than equimolar amounts of aromatic base, based on the sulfonic acid. Alkylphenol-aldehyde resins are known in principle and, for example in the Rompp Chemie Lexikon, 9th edition, Thieme Verlag 1988-92, Volume 4, p 3351 et seq. described. Particularly suitable according to the invention are those alkylphenol-aldehyde resins which are derived from alkylphenols having one or two alkyl radicals in the ortho and / or para position to the OH group. Particularly preferred as starting materials are alkylphenols which carry at least two hydrogen atoms capable of condensation with aldehydes on the aromatic and in particular monoalkylated phenols. Particularly preferably, the alkyl radical is in the para position to the phenolic OH group. The alkyl radicals (which are understood as meaning in general hydrocarbon radicals as defined below for the constituent 1) may be identical or different in the alkylphenol-aldehyde resins which can be used in the process according to the invention, they may be saturated or unsaturated and have 1 to 200, preferably 1 to 20, in particular 4-16, such as 6-12 carbon atoms; it is preferably n-, iso- and tert-butyl, n- and iso-pentyl, n- and iso-hexyl, n- and iso-octyl, n- and iso-nonyl-, n - and iso-decyl, n- and iso-dodecyl, tetradecyl, hexadecyl, octadecyl, tripropenyl, tetrapropenyl, poly (propenyl) - and poly (isobutenyl) radicals. In a preferred embodiment, mixtures of alkylphenols having different alkyl radicals are used for the preparation of the alkylphenol resins. For example, resins based on butyphenol on the one hand and octyl, nonyl and / or dodecylphenol in a molar ratio of 1:10 to 10: 1 on the other hand have proven particularly useful.

Suitable alkylphenol resins may also contain or consist of structural units of other phenol analogs such as salicylic acid, hydroxybenzoic acid and derivatives thereof such as esters, amides and salts.

Suitable aldehydes for the alkylphenol-aldehyde resins are those having 1 to 12 carbon atoms and preferably those having 1 to 4 carbon atoms such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, 2-ethylhexanal, benzaldehyde, glyoxalic acid and their reactive equivalents such as paraformaldehyde and trioxane. Particularly preferred is formaldehyde in the form of paraformaldehyde and especially formalin.

The molecular weight of the alkylphenol-aldehyde resins measured by gel permeation chromatography against poly (styrene) standards in THF is preferably 500-25,000 g / mol, more preferably 800-10,000 g / mol and especially 1,000-5,000 g / mol such as 1500-3,000 g / mol. The prerequisite here is that the alkylphenol-aldehyde resins, at least in application-relevant concentrations of 0.001 to 1 wt .-% are oil-soluble.

worin R⁵ für C₁-C₂₀₀-Alkyl oder C₂-C₂₀₀-Alkenyl, O-R⁶ oder O-C(O)-R⁶, R⁶ für C₁-C₂₀₀-Alkyl oder C₂-C₂₀₀-Alkenyl und n für eine Zahl von 2 bis 100 steht, enthalten. R⁶ steht bevorzugt für C₁-C₂₀-Alkyl oder C₂-C₂₀-Alkenyl und insbesondere für C₄-C₁₆-Alkyl oder C₂-C₂₀-Alkenyl wie beispielsweise für C₆-C₁₂-Alkyl oder C₂-C₂₀-Alkenyl. Besonders bevorzugt steht R⁵ für C₁-C₂₀-Alkyl oder -Alkenyl und insbesondere für C₄-C₁₆-Alkyl oder -Alkenyl wie beispielsweise für C₆-C₁₂-Alkyl oder -Alkenyl. Bevorzugt steht n für eine Zahl von 2 bis 50 und speziell für eine Zahl von 3 bis 25 wie beispielsweise eine Zahl von 5 bis 15.In the context of the invention, these are alkylphenol-formaldehyde resins, the oligo- or polymers having a repetitive structural unit of the formula

wherein R ^{5 is} C ₁ -C ₂₀₀ alkyl or C ₂ -C ₂₀₀ alkenyl, OR ⁶ or OC (O) -R ⁶ , R ^{6 is} C ₁ -C ₂₀₀ alkyl or C ₂ -C ₂₀₀ alkenyl and n is a number from 2 to 100. R ⁶ is preferably C ₁ -C ₂₀ -alkyl or C ₂ -C ₂₀ -alkenyl and in particular C ₄ -C ₁₆ -alkyl or C ₂ -C ₂₀ -alkenyl, for example C ₆ -C ₁₂ -alkyl or C C ₂ -C ₂₀ alkenyl. R ^{5 is} particularly preferably C ₁ -C ₂₀ -alkyl or -alkenyl and in particular C ₄ -C ₁₆ -alkyl or alkenyl, such as for example C ₆ -C ₁₂ alkyl or alkenyl. Preferably, n is a number from 2 to 50 and especially a number from 3 to 25, such as a number from 5 to 15.

For use in middle distillates such as diesel and fuel oil alkylphenol-aldehyde resin with C ₂ -C _40, particularly preferred are alkyl radicals of the alkylphenol, preferably with C ₄ -C ₂₀ alkyl radicals such as C ₆ -C ₁₂ alkyl radicals. The alkyl radicals can be linear or branched, preferably they are linear. Particularly suitable alkylphenol-aldehyde resins are derived from linear alkyl radicals having 8 and 9 C atoms.

Particularly preferred for use in gasoline and jet fuel are alkylphenol-aldehyde resins whose alkyl radicals carry 4 to 200 carbon atoms, preferably 10 to 180 carbon atoms, and oligomers or polymers of olefins having 2 to 6 carbon atoms, such as .alpha for example, derived from poly (isobutylene). They are thus preferably branched. The degree of polymerization (n) here is preferably between 2 and 20, preferably between 3 and 10 alkylphenol units.

These alkylphenol-aldehyde resins are accessible by known methods, for example by condensation of the corresponding alkylphenols with formaldehyde, ie with 0.5 to 1.5 moles, preferably 0.8 to 1.2 moles of formaldehyde per mole of alkylphenol. The condensation can be carried out solvent-free, but preferably it is carried out in the presence of an inert or only partially water-miscible inert organic solvent such as mineral oils, alcohols, ethers and the like. Particularly preferred are solvents which can form azeotropes with water. As such solvents in particular aromatics such as toluene, xylene diethylbenzene and higher-boiling commercial solvent mixtures such as ®Shellsol AB, and solvent naphtha are used. The condensation is preferably carried out between 70 and 200 ° C such as between 90 and 160 ° C. It is usually catalyzed by 0.05 to 5 wt .-% bases or acids. Thus, for example, the condensation catalyzed by aromatic bases such as, for example, pyridine, with subsequent neutralization by means of organic sulfonic acid leads to the mixtures according to the invention. According to the invention, the catalysis by organic sulfonic acids, which after completion of the condensation with aromatic bases to the oil-soluble sulfonic acid salts according to the invention are reacted.

For ease of handling, the compositions according to the invention are preferably used as concentrates which contain from 10 to 90% by weight and preferably from 20 to 60% by weight of solvent. Preferred solvents are higher-boiling aliphatic hydrocarbons, aromatic hydrocarbons, alcohols, esters, ethers and mixtures thereof.

The additives of the invention increase the conductivity of mineral oils such as gasoline, kerosene, jet fuel, diesel, and low sulfur fuel oil of less than 350 ppm, especially less than 50 ppm, such as less than 10 or less than 5 ppm. At the same time, they improve the cold properties, in particular of middle distillates such as kerosene, jet fuel, diesel and heating oil.

The additives according to the invention may also be added to mineral oil distillates for improving cold flowability in combination with further additives such as, for example, ethylene copolymers, polar nitrogen compounds, comb polymers, polyoxyalkylene compounds and / or olefin copolymers.

The present invention thus provides a new additive package which simultaneously improves the cold properties and antistatic properties of low sulfur mineral oils.

If the additives according to the invention are used for mineral oil distillates, then in a preferred embodiment they contain, in addition to the constituents I and II, one or more of the constituents III to VII.

Thus, they preferably contain copolymers of ethylene and olefinically unsaturated compounds as constituent III. Suitable ethylene copolymers are, in particular, those which, in addition to ethylene, contain 6 to 21 mol%, in particular 10 to 18 mol%, of comonomers.

The olefinically unsaturated compounds are preferably vinyl esters, acrylic esters, methacrylic esters, alkyl vinyl ethers and / or alkenes, it being possible for the abovementioned compounds to be substituted by hydroxyl groups. One or more comonomers may be included in the polymer.

The vinyl esters are preferably those of the formula 1

CH ₂ = CH-OCOR ¹ (1)

wherein R ^{1 is} C ₁ to C ₃₀ alkyl, preferably C ₄ to C ₁₆ alkyl, especially C ₆ to C ₁₂ alkyl. In a further embodiment, said alkyl groups may be substituted with one or more hydroxyl groups.

In a further preferred embodiment, R ^{1 is} a branched alkyl radical or a neoalkyl radical having 7 to 11 carbon atoms, in particular having 8, 9 or 10 carbon atoms. Particularly preferred vinyl esters are derived from secondary and especially tertiary carboxylic acids whose branching is in the alpha position to the carbonyl group. Suitable vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl hexanoate, vinyl heptanoate, vinyl octanoate, vinyl pivalate, vinyl 2-ethylhexanoate, vinyl laurate, vinyl stearate and versatic acid esters such as vinyl neononanoate, vinyl neodecanoate, vinyl neoundecanoate.

In a further preferred embodiment, these ethylene copolymers contain vinyl acetate and at least one further vinyl ester of the formula 1 in which R ^{1 is} C ₄ to C ₃₀ -alkyl, preferably C ₄ to C ₁₆ -alkyl, especially C ₆ - to C ₁₂ -alkyl ,

The acrylic esters are preferably those of the formula 2

CH ₂ = CR ² -COOR ³ (2)

wherein R ^{2 is} hydrogen or methyl and R ^{3 is} C ₁ - to C ₃₀ -alkyl, preferably C ₄ - to C ₁₆ -alkyl, especially C ₆ - to C ₁₂ -alkyl. Suitable acrylic esters include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n- and Iso-butyl (meth) acrylate, hexyl, octyl, 2-ethylhexyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl (meth) acrylate and mixtures of these comonomers. In a further embodiment, said alkyl groups may be substituted with one or more hydroxyl groups. An example of such an acrylic ester is hydroxyethyl methacrylate.

The alkyl vinyl ethers are preferably compounds of the formula 3

CH ₂ = CH-OR ⁴ (3)

wherein R ^{4 is} C ₁ - to C ₃₀ -alkyl, preferably C ₄ - to C ₁₆ -alkyl, especially C ₆ - to C ₁₂ -alkyl. Examples which may be mentioned are methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether. In a further embodiment, said alkyl groups may be substituted with one or more hydroxyl groups.

The alkenes are preferably simple unsaturated hydrocarbons having 3 to 30 carbon atoms, especially 4 to 16 carbon atoms and especially 5 to 12 carbon atoms. Suitable alkenes include propene, butene, isobutylene, pentene, hexene, 4-methylpentene, octene, diisobutylene and norbornene and its derivatives such as methylnorbornene and vinylnorbornene. In a further embodiment, said alkyl groups may be substituted with one or more hydroxyl groups.

Particular preference is given to terpolymers which, apart from ethylene, have from 3.5 to 20 mol%, in particular from 8 to 15 mol% of vinyl acetate and from 0.1 to 12 mol%, in particular from 0.2 to 5 mol%, of at least one longer-chain and preferably branched one Vinyl esters such as vinyl 2-ethylhexanoate, vinyl neononanoate or vinyl neodecanoate, the total comonomer content being between 8 and 21 mol%, preferably between 12 and 18 mol%. Further particularly preferred copolymers contain, in addition to ethylene and 8 to 18 mol% of vinyl esters, 0.5 to 10 mol% of olefins such as propene, butene, isobutylene, hexene, 4-methylpentene, octene, diisobutylene and / or norbornene.

Preferably, these ethylene-co- and terpolymers have melt viscosities at 140 ° C of from 20 to 10,000 mPas, especially from 30 to 5,000 mPas, especially of 50 up to 2,000 mPas. The means of ¹ H-NMR spectroscopy, certain degrees of branching are preferably between 1 and 9 CH _3/100 CH ₂ groups, especially between 2 and 6 CH _3/100 CH ₂ groups, which do not stem from the comonomers.

Preference is given to using mixtures of two or more of the abovementioned ethylene copolymers. Particularly preferably, the polymers underlying the mixtures differ in at least one characteristic. For example, they may contain different comonomers, have different comonomer contents, molecular weights and / or degrees of branching.

The mixing ratio between the additives according to the invention and ethylene copolymers as constituent III can vary within wide limits depending on the application, with the ethylene copolymers III often representing the greater proportion. Such additive mixtures preferably contain from 2 to 70% by weight, preferably from 5 to 50% by weight, of the inventive additive combination of I and II and from 30 to 98% by weight, preferably from 50 to 95% by weight, of ethylene copolymers. The oil-soluble polar nitrogen compounds (constituent IV) which are suitable according to the invention as further constituents are preferably reaction products of fatty amines with compounds which contain an acyl group. The preferred amines are compounds of the formula NR ⁶ R ⁷ R ⁸ , in which R ⁶ , R ⁷ and R ^{8 may be} identical or different, and at least one of these groups is C ₈ -C ₃₆ -alkyl, C ₆ - C ₃₆ -cycloalkyl, C ₈ -C ₃₆ -alkenyl, in particular C ₁₂ -C ₂₄ -alkyl, C ₁₂ -C ₂₄ -alkenyl or cyclohexyl, and the other groups are either hydrogen, C ₁ -C ₃₆ -alkyl, C ₂ -C ₃₆ alkenyl, cyclohexyl, or a group of the formulas - (AO) _x -E or - (CH ₂ ) _n -NYZ, where A is an ethyl or propyl group, x is a number from 1 to 50, E = H, C ₁ -C ₃₀ -alkyl, C ₅ -C ₁₂ -cycloalkyl or C ₆ -C ₃₀ -aryl, and n = 2, 3 or 4, and Y and Z independently of one another are H, C ₁ -C ₃₀ Alkyl or - (AO) _x -E mean. The alkyl and alkenyl radicals can be linear or branched and contain up to two double bonds. They are preferably linear and substantially saturated, ie they have iodine numbers of less than 75 gl ₂ / g, preferably less than 60 gl ₂ / g and in particular between 1 and 10 gl ₂ / g. Particularly preferred are secondary fatty amines in which two of the groups R ⁶ , R ⁷ and R ^{8 are} C ₈ -C ₃₆ -alkyl, C ₆ -C ₃₆ -cycloalkyl, C ₈ -C ₃₆ -alkenyl, in particular C ₁₂ -C ₂₄ alkyl, C ₁₂ -C ₂₄ alkenyl or cyclohexyl. Suitable fatty amines are, for example Octylamine, decylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, eicosylamine, behenylamine, didecylamine, didodecylamine, ditetradecylamine, dihexadecylamine, dioctadecylamine, dieicosylamine, dibehenylamine and mixtures thereof. Specifically, the amines contain chain cuts based on natural raw materials such as coco fatty amine, tallow fatty amine, hydrogenated tallow fatty amine, dicocosfettamine, ditallow fatty amine and di (hydrogenated tallow fatty amine). Particularly preferred amine derivatives are amine salts, imides and / or amides such as, for example, amide ammonium salts of secondary fatty amines, in particular dicocosfettamine, ditallow fatty amine and distearylamine. Particularly preferred paraffin dispersants as constituent IV contain at least one acyl group converted to an ammonium salt. Specifically, they contain at least two, for example at least three or at least four and in the case of polymeric paraffin dispersants also five or more ammonium groups.

By acyl group is meant here a functional group of the following formula:

> C = O

Suitable carbonyl compounds for the reaction with amines are both monomeric and polymeric compounds having one or more carboxyl groups. In the case of the monomeric carbonyl compounds, preference is given to those having 2, 3 or 4 carbonyl groups. They can also contain heteroatoms such as oxygen, sulfur and nitrogen. Examples of suitable carboxylic acids are maleic, fumaric, crotonic, itaconic, succinic, C ₁ -C ₄₀ -alkenylsuccinic, adipic, glutaric, sebacic, and malonic acids and benzoic, phthalic, trimellitic and pyromellitic acid, nitrilotriacetic acid , Ethylenediaminetetraacetic acid and their reactive derivatives such as esters, anhydrides and acid halides. Copolymers of ethylenically unsaturated acids, such as, for example, acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid, have proven particularly suitable as polymeric carbonyl compounds, particular preference is given to copolymers of maleic anhydride. Suitable comonomers are those which impart oil solubility to the copolymer. Oil-soluble means here that the copolymer dissolves without residue in the mineral oil distillate to be added after reaction with the fatty amine in practice-relevant metering rates. Suitable comonomers are, for example Olefins, alkyl esters of acrylic acid and methacrylic acid, alkyl vinyl esters and alkyl vinyl ethers having 2 to 75, preferably 4 to 40 and in particular 8 to 20 carbon atoms in the alkyl radical. In the case of olefins, the carbon number refers to the alkyl radical attached to the double bond. Particularly suitable comonomers are olefins with a terminal double bond. The molecular weights of the polymeric carbonyl compounds are preferably between 400 and 20,000, more preferably between 500 and 10,000, for example between 1,000 and 5,000.

Oil-soluble polar nitrogen compounds which have been obtained by reaction of aliphatic or aromatic amines, preferably long-chain aliphatic amines, with aliphatic or aromatic mono-, di-, tri- or tetracarboxylic acids or their anhydrides have proven particularly suitable (cf. US 4 211 534 ). Similarly, amides and ammonium salts of aminoalkylene polycarboxylic acids such as nitrilotriacetic acid or ethylenediaminetetraacetic acid with secondary amines are suitable as oil-soluble polar nitrogen compounds (cf. EP 0 398 101 ). Other oil-soluble polar nitrogen compounds are copolymers of maleic anhydride and α, β-unsaturated compounds which can optionally be reacted with primary monoalkylamines and / or aliphatic alcohols (cf. EP-A-0 154 177 . EP 0 777 712 ), the reaction products of Alkenylspirobislactonen with amines (see. EP-A-0 413 279 B1) and after EP-A-0 606 055 A2 reaction products of terpolymers based on α, β-unsaturated dicarboxylic acid anhydrides, α, β-unsaturated compounds and polyoxyalkylene ethers of lower unsaturated alcohols.
The mixing ratio between the additives of the invention and oil-soluble polar nitrogen compounds as constituent IV may vary depending on the application. Such additive mixtures preferably contain from 10 to 90% by weight, preferably from 20 to 80% by weight, of the inventive additive combination of I and II and from 10 to 90% by weight, preferably from 20 to 80% by weight, of oil-soluble polar nitrogen compounds.

beschrieben werden. Darin bedeuten

A

R', COOR', OCOR', R"-COOR', OR';

D

H, CH₃, A oder R";

E

H, A;

G

H, R", R"-COOR', einen Arylrest oder einen heterocyclischen Rest;

M

H, COOR", OCOR", OR", COOH;

N

H, R", COOR", OCOR, einen Arylrest;

R'

eine Kohlenwasserstoffkette mit 8 bis 50 Kohlenstoffatomen;

R"

eine Kohlenwasserstoffkette mit 1 bis 10 Kohlenstoffatomen;

m

eine Zahl zwischen 0,4 und 1,0; und

n

eine Zahl zwischen 0 und 0,6.

As a further component suitable comb polymers (component V), for example, by the formula

to be discribed. Mean in it

A

R ', COOR', OCOR ', R "-COOR', OR ';

D

H, CH _3, A or R ";

e

H, A;

G

H, R ", R" -COOR ', an aryl radical or a heterocyclic radical;

M

H, COOR ", OCOR", OR ", COOH;

N

H, R ", COOR", OCOR, an aryl radical;

R '

a hydrocarbon chain of 8 to 50 carbon atoms;

R "

a hydrocarbon chain of 1 to 10 carbon atoms;

m

a number between 0.4 and 1.0; and

n

a number between 0 and 0.6.

Examples of suitable polyoxyalkylene compounds (constituent VI) are esters, ethers and ethers / esters of polyols which carry at least one alkyl radical having 12 to 30 carbon atoms. When the alkyl groups are derived from an acid, the remainder is derived from a polyhydric alcohol; If the alkyl radicals come from a fatty alcohol, the remainder of the compound derives from a polyacid.

Suitable comb polymers are, for example, copolymers of ethylenically unsaturated dicarboxylic acids such as maleic or fumaric acid with other ethylenically unsaturated monomers such as olefins or vinyl esters such as vinyl acetate. Particularly suitable olefins are α-olefins having 10 to 24 carbon atoms such as 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and mixtures thereof. Even longer-chain olefins based on oligomerized C ₂ -C ₆ -olefins such as poly (isobutylene) with a high proportion of terminal double bonds are suitable as comonomers. Usually, these copolymers are at least 50% esterified with alcohols having 10 to 22 carbon atoms. Suitable alcohols include n-decen-1-ol, n-dodecan-1-ol, n-tetradecan-1-ol, n-hexadecan-1-ol, n-octadecan-1-ol, n-eicosan-1-ol and mixtures thereof. Particular preference is given to mixtures of n-tetradecan-1-ol and n-hexadcan-1-ol. Also suitable as comb polymers are poly (alkyl acrylates), poly (alkyl methacrylates) and poly (alkyl vinyl ethers) derived from alcohols containing 12 to 20 carbon atoms and poly (vinyl esters) derived from fatty acids containing 12 to 20 carbon atoms. Derive atoms.

Suitable polyols are polyethylene glycols, polypropylene glycols, polybutylene glycols and their copolymers having a molecular weight of about 100 to about 5000, preferably 200 to 2000. Also suitable are alkoxylates of polyols, such as glycerol, trimethylolpropane, pentaerythritol, neopentyl glycol, as well as from them Condensation accessible oligomers having 2 to 10 monomer units, such as Polyglycerol. Preferred alkoxylates are those having from 1 to 100, in particular from 5 to 50, mol of ethylene oxide, propylene oxide and / or butylene oxide per mole of polyol. Esters are especially preferred.

Fatty acids containing 12 to 26 carbon atoms are preferred for reaction with the polyols to form the ester additives, more preferably C ₁₈ to C ₂₄ fatty acids, especially stearic and behenic acid. The esters can also be prepared by esterification of polyoxyalkylated alcohols. Preference is given to completely esterified polyoxyalkylated polyols having molecular weights of from 150 to 2,000, preferably from 200 to 600. Particularly suitable are PEG-600 dibehenate and glycerol-ethylene glycol tribehenate.

Suitable olefin copolymers (constituent VII) as further constituent of the additive according to the invention can be derived directly from monoethylenically unsaturated monomers or can be prepared indirectly by hydrogenation of polymers derived from polyunsaturated monomers such as isoprene or butadiene. In addition to ethylene, preferred copolymers contain structural units which are derived from α-olefins having 3 to 24 carbon atoms and have molecular weights of up to 120,000 g / mol. Preferred α-olefins are propylene, butene, isobutene, n-hexene, isohexene, n-octene, isooctene, n-decene, isodecene. The comonomer content of α-olefins having 3 to 24 C atoms is preferably between 15 and 50 mol%, more preferably between 20 and 35 mol% and especially between 30 and 45 mol%. These copolymers can also be small amounts, eg up to 10 mol% further comonomers such as non-terminal olefins or non-conjugated olefins. Preferred are ethylene-propylene copolymers. The olefin copolymers can be prepared by known methods, for example by Ziegler or metallocene catalysts.

Other suitable olefin copolymers are block copolymers containing blocks of olefinically unsaturated aromatic monomers A and blocks of hydrogenated polyolefins B. Particularly suitable are block copolymers of the structure (AB) nA and (AB) m, where n is a number between 1 and 10 and m is a number between 2 and 10.

The additives can be used alone or together with other additives, e.g. with other pour point depressants or dewaxing aids, with antioxidants, cetane number improvers, dehazers, demulsifiers, detergents, dispersants, defoamers, dyes, corrosion inhibitors, lubricity additives, sludge inhibitors, odorants and / or cloud point depressants.

The mixing ratio between the inventive additive combinations of I and II and the further constituents V, VI and VII is generally in each case between 1:10 and 10: 1, preferably between 1: 5 and 5: 1.

The additives according to the invention increase the conductivity of mineral oil distillates such as gasoline, kerosene, jet fuel, diesel and heating oil, preferably having a low aromatic content of less than 21% by weight, in particular less than 19% by weight, especially less than 18% by weight. % such as less than 17% by weight. Since they also improve the cold flow properties, especially of mineral oil distillates such as kerosene, jet fuel, diesel and heating oil, their use can be achieved a significant saving in the total additives of the oils, since no additional conductivity improvers must be used. In addition, can be set in areas or at times in which due to the climatic conditions so far no cold additives are used by admixing paraffin-rich, cheaper mineral oil fractions such as Cloud Point and / or CFPP of the oils to be upgraded to higher, which the economy of the refinery improved. The additives of the invention also contain no Metals, which could lead to ashes during combustion and thus deposits in the combustion chamber or exhaust gas system and particulate pollutants in the environment.

The conductivity of the oils according to the invention does not drop when the temperature drops, and in many cases even a rise in conductivity not known from additives of the prior art has been observed with decreasing temperature, so that safe handling is ensured even at low ambient temperatures. Another advantage of the additives of the invention is the preservation of the electrical conductivity even during prolonged, that is several weeks storage of the additized oils. Moreover, in the range of the mixing ratios suitable according to the invention there are no incompatibilities between the constituents I and II, so that in contrast to the additives of the US 4,356,002 can be easily formulated as concentrates.

They are particularly suitable for improving the electrostatic properties of mineral oil distillates such as jet fuel, gasoline, kerosene, diesel and heating oil, which were subjected to a hydrogenation refining in order to reduce the sulfur content and therefore contain only small amounts of polyaromatic and polar compounds. The additives according to the invention are particularly advantageous in mineral oil distillates which contain less than 350 ppm of sulfur, more preferably less than 100 ppm of sulfur, in particular less than 50 ppm of sulfur and in special cases less than 10 ppm of sulfur. The water content of such oils is below 150 ppm, sometimes below 100 ppm, such as below 80 ppm. The electrical conductivity of such oils is usually below 10 pS / m and often even below 5 pS / m.

Particularly preferred mineral oil distillates are middle distillates. The middle distillate is in particular those mineral oils which are obtained by distillation of crude oil and boil in the range of 120 to 450 ° C, for example kerosene, jet fuel, diesel and fuel oil. Their preferred sulfur, aromatics and water contents are as already stated above. The compositions according to the invention are particularly advantageous in middle distillates which have 90% distillation points below 360 ° C., in particular 350 ° C. and in special cases below 340 ° C. Among aromatic compounds, the sum of mono-, di- and polycyclic aromatic compounds as determinable by HPLC according to DIN EN 12916 (Edition 2001). The middle distillates may also contain minor amounts, for example up to 40% by volume, preferably 1 to 20% by volume, especially 2 to 15, for example 3 to 10% by volume of the oils of animal and / or vegetable origin described in more detail below such as fatty acid methyl esters.

The compositions according to the invention are likewise suitable for improving the electrostatic properties of fuels based on renewable raw materials (biofuels). By biofuels is meant oils obtained from animal and preferably vegetable material or both, and derivatives thereof, which can be used as fuel and especially as diesel or fuel oil. These are, in particular, triglycerides of fatty acids having 10 to 24 carbon atoms and the fatty acid esters of lower alcohols, such as methanol or ethanol, which are obtainable by transesterification.

Examples of suitable biofuels are rapeseed oil, coriander oil, soybean oil, cottonseed oil, sunflower oil, castor oil, olive oil, peanut oil, corn oil, almond oil, palm kernel oil, coconut oil, mustard seed oil, beef tallow, bone oil, fish oils and used edible oils. Other examples include oils derived from wheat, jute, sesame, shea nut, arachis oil and linseed oil. The fatty acid alkyl esters, also referred to as biodiesel, can be derived from these oils by methods known in the art. Rapeseed oil, which is a mixture of glycerol esterified fatty acids, is preferred because it is available in large quantities and is readily available by squeezing rapeseed. Furthermore, the also widespread oils of sunflower and soybeans and their mixtures with rapeseed oil are preferred.

Particularly suitable as biofuels are lower alkyl esters of fatty acids. For example, commercially available mixtures of the ethyl, propyl, butyl and especially methyl esters of fatty acids having 14 to 22 carbon atoms, for example of lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, elaidic acid, petroselinic acid, ricinoleic acid, Elaeostearic, linoleic, linolenic, eicosanoic, gadoleic, docosanoic or erucic acid into consideration. Preferred esters have an iodine value of from 50 to 150 and in particular from 90 to 125. Mixtures with particularly advantageous properties are those which contain mainly, ie at least 50% by weight of methyl esters of fatty acids having 16 to 22 carbon atoms and 1, 2 or 3 double bonds contain. The preferred lower alkyl esters of fatty acids are the methyl esters of oleic, linoleic, linolenic and erucic acids.

The additives of the invention are also useful for improving the electrostatic properties of turbine fuels. These are fuels boiling in the temperature range of about 65 ° C to about 330 ° C and marketed, for example, under the designations JP-4, JP-5, JP-7, JP-8, Jet A and Jet A-1. JP-4 and JP-5 are disclosed in U.S. Pat. Military Specification MIL-T-5624-N and JP-8 in U.S. Pat. Military Specification MIL-T-83133-D specified; Jet A, Jet A-1 and Jet B are specified in the ASTM D1655.

Likewise, the additives of the invention are suitable for improving the electrical conductivity of hydrocarbons, which are used as solvents z. B. in the textile cleaning or for the production of paints and varnishes.

Examples

Table 1: Characterization of the test oils: The test oils used were current oils from European refineries. The CFPP value is determined in accordance with EN 116 and the determination of the cloud point in accordance with ISO 3015. The determination of the aromatic hydrocarbon groups is carried out in accordance with DIN EN 12916 (November 2001 edition) Test oil 1 Test oil 2 Test oil 3 distillation IBP [° C] 169 193 173 20% [° C] 223 229 208 90% [° C] 337 329 334 FBP [° C] 359 351 359 Cloud point [° C] -5.9 -5.7 -7.2 CFPP [° C] -11 -9 -9 sulfur [Ppm] 30 19 8th Density @ 15 ° C [g / cm ³ ] .8361 .8313 .8261 aromatics [Wt .-%] 18.4 18.2 18.5 of which mono [Wt .-%] 15.5 17.0 17.3 di [Wt .-%] 2.5 1.2 1.1 poly [Wt .-%] 0.4 0.1 0.1

(A)

Mischungen aus Alkylphenolharzen und Sulfonsäuresalzen

A1)

Sauer katalysiertes Nonylphenol-Formaldehydharz (Mw 1300 g/mol)
mit 2,2 Gew.-% Imidazolium-Dodecylbenzolsulfonat

A2)

Sauer katalysiertes Nonylphenol-Formaldehydharz (Mw 1300 g/mol)
mit 2,3 Gew.-% Pyridinium-Dodecylbenzolsulfonat

A3)

Sauer katalysiertes Nonylphenol-Formaldehydharz (Mw 2200 g/mol)
mit 2,0 Gew.-% Pyridinium-p-Toluolsulfonat

A4)

Sauer katalysiertes Dodecylphenol-Formaldehydharz (Mw 1400 g/mol)
mit 0,3 Gew.-% Imidazolium-Dodecylbenzolsulfonat

A5)

Alkalisch katalysiertes Dodecylphenol-Formaldehydharz (Mw 1450 g/mol)
mit 2,0 Gew.-% Pyridinium-p-Toluolsulfonat

A6)

Sauer katalysiertes Nonylphenol-Formaldehydharz (Mw 1300 g/mol);
(Vergleich).

A7)

Sauer katalysiertes Nonylphenol-Formaldehydharz (Mw 1300 g/mol) mit
1,6 Gew.-% Natrium-Dodecylbenzolsulfonat (Vergleich)

A8)

Sauer katalysiertes Nonylphenol-Formaldehydharz (Mw 1300 g/mol) mit
1,8 Gew.-% Tributylammonium-Dodecylbenzolsulfonat (Vergleich)

The following additives were used:

(A)

Mixtures of alkylphenol resins and sulfonic acid salts

A1)

Acid-catalyzed nonylphenol-formaldehyde resin (Mw 1300 g / mol)
with 2.2% by weight of imidazolium dodecylbenzenesulfonate

A2)

Acid-catalyzed nonylphenol-formaldehyde resin (Mw 1300 g / mol)
with 2.3% by weight of pyridinium dodecylbenzenesulfonate

A3)

Acid-catalyzed nonylphenol-formaldehyde resin (Mw 2200 g / mol)
with 2.0% by weight of pyridinium p-toluenesulfonate

A4)

Acid catalyzed dodecylphenol-formaldehyde resin (Mw 1400 g / mol)
with 0.3% by weight of imidazolium dodecylbenzenesulfonate

A5)

Alkaline-catalyzed dodecylphenol-formaldehyde resin (Mw 1450 g / mol)
with 2.0% by weight of pyridinium p-toluenesulfonate

A6)

Acid catalyzed nonylphenol-formaldehyde resin (Mw 1300 g / mol);
(Comparison).

A7)

Sauer catalyzed nonylphenol-formaldehyde resin (Mw 1300 g / mol) with
1.6% by weight of sodium dodecylbenzenesulfonate (comparative)

A8)

Sauer catalyzed nonylphenol-formaldehyde resin (Mw 1300 g / mol) with
1.8% by weight of tributylammonium dodecylbenzenesulfonate (comparative)

The mixtures A1) to A8) were used as 50% settings in Solvent Naphtha, a commercial mixture of high-boiling aromatic hydrocarbons.

Improvement of the electrical conductivity of middle distillates

For conductivity measurements, the additives were dissolved with the given concentration in 2 l of the test oil 1 with shaking. An electrical conductivity meter MLA 900 was used to determine the electrical conductivity in accordance with DIN 51412-T02-79. The unit of electrical conductivity is picosiemens / m (pS / m). A conductivity of at least 50 pS / m is generally considered sufficient for the safe handling of oils. Table 2: Electrical conductivity of test oil 1 with the addition of sulfonic acid salts example additive 0 ppm 1 ppm 2 ppm 3 ppm 1 (See) Imidazolium dodecylbenzenesulfonate 6 10 11 13 2 (Cf.) Pyridinium dodecylbenzenesulfonate 6 9 12 14 3 (Cf.) Pyridinium p-toluenesulfonate 6 9 12 16 4 (Cf.) Sodium dodecylbenzenesulfonate 6 8th 10 11 5 (Cf.) Tributylammonium dodecylbenzenesulfonate 6 9 11 13

For better comparability, the sulfonic acid salts were also used as 50% settings in solvent naphtha. Table 3: Electrical conductivity of test oil 1 with the addition of additives according to the invention example additive 0 ppm 50 ppm 100 ppm 150 ppm 6 A1 6 51 112 172 7 A2 6 54 105 151 8th A3 6 43 92 143 9 A5 6 46 98 157 10 (Cf.) A6 6 9 21 33 11 (Cf.) A7 6 10 24 37 12 (Cf.) A8 6 36 84 112

Effectiveness of the additives as cold flow improvers

To assess the effect of the additives according to the invention on the cold flow properties of middle distillates, the additives (A) according to the invention with various co-additives were used. The ethylene copolymers (B) and paraffin dispersants (C) used are commercial products with the characteristics given below.

The superior effectiveness of the additives according to the invention together with ethylene copolymers and paraffin dispersants for mineral oils and mineral oil distillates is described on the one hand by means of the CFPP test (Cold Filter Plugging Test according to EN 116).

• 150 ml der mit den in der Tabelle angegebenen Additivkomponenten versetzten Mitteldestillate wurden in 200 ml-Messzylindern in einem Kälteschrank mit -2°C/Stunde auf -13°C abgekühlt und 16 Stunden bei dieser Temperatur gelagert. Anschließend werden visuell Volumen und Aussehen sowohl der sedimentierten Paraffinphase wie auch der darüber stehenden Ölphase bestimmt und beurteilt. Eine geringe Sedimentmenge und eine trübe Ölphase zeigen eine gute Paraffindispergierung.

Furthermore, the paraffin dispersion in middle distillates is determined as follows in the short sediment test:

• 150 ml of the middle distillates mixed with the additive components indicated in the table were cooled to -13 ° C. in a cold cabinet at -2 ° C./hour in 200 ml graduated cylinders and stored at this temperature for 16 hours. Subsequently, the volume and appearance of both the sedimented paraffin phase and the oil phase above are visually determined and assessed. A Low sediment and a cloudy oil phase show a good paraffin dispersion.

In addition, the lower 20% by volume is isolated and the cloud point determined according to IP 3015. Only a small deviation of the cloud point of the lower phase (CP _KS ) from the blank value of the oil shows a good paraffin dispersion.

B1

Copolymer aus Ethylen und 13,6 mol-% Vinylacetat mit einer bei 140°C gemessenen Schmelzviskosität von 120 mPas; 65 %ig in Kerosin

B2

Terpolymer aus Ethylen, 13,7 mol-% Vinylacetat und 1,4 mol-% Neodecansäurevinylester mit einer bei 140°C gemessenen Schmelzviskosität von 98 mPas, 65 %ig in Kerosin.

B3

Mischung aus zwei Teilen B1 und einem Teil B2, 65 %ig in Kerosin

(B) Characterization of the ethylene copolymers used

B1

Copolymer of ethylene and 13.6 mol% of vinyl acetate with a measured at 140 ° C melt viscosity of 120 mPas; 65% in kerosene

B2

Terpolymer of ethylene, 13.7 mol% of vinyl acetate and 1.4 mol% of vinyl neodecanoate with a measured at 140 ° C melt viscosity of 98 mPas, 65% in kerosene.

B3

Mixture of two parts B1 and one part B2, 65% in kerosene

C1

Umsetzungsprodukt eines Dodecenyl-Spirobislactons mit einer Mischung aus primärem und sekundärem Talgfettamin, 60 %ig in Solvent Naphtha (hergestellt gemäß EP 0413279 )

C2

Umsetzungsprodukt eines Terpolymers aus C₁₄/₁₆-α-Olefin, Maleinsäureanhydrid und Allylpolyglykol mit 2 Equivalenten Ditalgfettamin, 50 %ig in Solvent Naphtha (hergestellt gemäß EP 0606055 )

C3

Umsetzungsprodukt aus Phthalsäureanhydrid und 2 Equivalenten Di(hydriertem Talgfett)amin, 50 %ig in Solvent Naphtha (hergestellt gemäß EP 0 061 894 )

C4

Umsetzungsprodukt aus Ethylendiamintetraessigsäure mit 4 Equivalenten Ditalgfettamin zum Amid-Ammoniumsalz, 50 %ig in Solvent Naphtha (hergestellt gemäß EP 0 398 101 )

Tabelle 4: Prüfung als Kaltfließverbesserer in Testöl 1 Beispiel Additive Testöl 1 (CP -5,9°C) A B C Sediment [Vol.-%] Aussehen Ölphase CPKS [°C] 13 (Vgl.) 50 ppm A6 350 ppm B1 100 ppm C2 4 trüb -3,6 14 (Vgl.) 40 ppm A6 350 ppm B1 80 ppm C2 7 wolkig -2,9 15 (Vgl.) 50 ppm A8 350 ppm B1 100 ppm C2 1 trüb -3,9 16 50 ppm A1 350 ppm B1 100 ppm C2 0 trüb -5,7 17 40 ppm A1 350 ppm B1 80 ppm C2 2 trüb -4,4 18 50 ppm A2 350 ppm B1 100 ppm C2 0 trüb -5,2 19 50 ppm A3 350 ppm B1 100 ppm C2 0 trüb -5,4 20 50 ppm A4 350 ppm B1 100 ppm C2 0 trüb -4,5 21 50 ppm A5 350 ppm B1 100 ppm C2 0 trüb -5,2 22 50 ppm A1 350 ppm B2 100 ppm C3 0 trüb -5,3 23 50 ppm A1 350 ppm B2 100 ppm C4 0 trüb -5,7 Tabelle 5: Prüfung als Kaltfließverbesserer in Testöl 2 Beispiel Additive Testöl 2 (CP -5,7°C) A B C Sediment [Vol.-%] Aussehen Ölphase CP_KS [°C] 24 (Vgl.) 50 ppm A6 200 ppm B1 100 ppm C2 5 klar 4,2 25 (Vgl.) 50 ppm A6 400 ppm B1 100 ppm C2 1 trüb -3,2 26 50 ppm A1 200 ppm B1 100 ppm C2 2 wolkig 1,4 27 50 ppm A2 400 ppm B1 100 ppm C2 0 trüb -5,2 28 50 ppm A3 400 ppm B1 100 ppm C2 0 trüb -4,9 29 50 ppm A5 400 ppm B1 100 ppm C2 0 trüb -5,1 30 50 ppm A1 200 ppm B2 100 ppm C3 0 trüb -5,3 31 50 ppm A1 200 ppm B2 100 ppm C4 0 trüb -5,2 Tabelle 6: Prüfung als Kaltfließverbesserer in Testöl 3 Die Bestimmung von CFPP-Wert und Paraffindispergierung im Kurzsedimenttest erfolgte nach Additivierung des Testöls mit 200 ppm Fließverbesserer B3 und 100 ppm Paraffindispergator C2. Beispiel Additiv A CFPP [°C] Sediment [Vol.-%] Aussehen Ölphase CPKS [°C] 32 (Vgl.) 50 ppm A6 -24 0 trüb -2,0 33 50 ppm A1 -26 0 trüb -4,5 34 50 ppm A2 -27 0 trüb -4,7 35 50 ppm A3 -28 0 trüb -4,1 36 50 ppm A4 -25 0 trüb -3,6 37 50 ppm A5 -27 0 trüb -3,9 (C) Characterization of the paraffin dispersants C used

C1

Reaction product of a dodecenyl spirobislactone with a mixture of primary and secondary tallow fatty amine, 60% in Solvent Naphtha (prepared according to EP 0413279 )

C2

Reaction product of a terpolymer of C _14/16 -α-olefin, maleic anhydride and di-tallow Allylpolyglykol with 2 equivalents, 50% (in Solvent Naphtha prepared according to EP 0606055 )

C3

Reaction product of phthalic anhydride and 2 equivalents of di (hydrogenated tallow fat) amine, 50% in solvent naphtha (prepared according to EP 0 061 894 )

C4

Reaction product of ethylenediaminetetraacetic acid with 4 equivalents of ditallow fatty amine to the amide ammonium salt, 50% in Solvent Naphtha (prepared according to EP 0 398 101 )

Table 4: Test as cold flow improver in test oil 1 example additives Test oil 1 (CP -5.9 ° C) A B C Sediment [vol.%] Appearance oil phase CPKS [° C] 13 (Cf.) 50 ppm A6 350 ppm B1 100 ppm C2 4 cloudy -3.6 14 (Cf.) 40 ppm A6 350 ppm B1 80 ppm C2 7 cloudy -2.9 15 (Cf.) 50 ppm A8 350 ppm B1 100 ppm C2 1 cloudy -3.9 16 50 ppm A1 350 ppm B1 100 ppm C2 0 cloudy -5.7 17 40 ppm A1 350 ppm B1 80 ppm C2 2 cloudy -4.4 18 50 ppm A2 350 ppm B1 100 ppm C2 0 cloudy -5.2 19 50 ppm A3 350 ppm B1 100 ppm C2 0 cloudy -5.4 20 50 ppm A4 350 ppm B1 100 ppm C2 0 cloudy -4.5 21 50 ppm A5 350 ppm B1 100 ppm C2 0 cloudy -5.2 22 50 ppm A1 350 ppm B2 100 ppm C3 0 cloudy -5.3 23 50 ppm A1 350 ppm B2 100 ppm C4 0 cloudy -5.7 example additives Test Oil 2 (CP -5.7 ° C) A B C Sediment [vol.%] Appearance oil phase CP _KS [° C] 24 (Cf.) 50 ppm A6 200 ppm B1 100 ppm C2 5 clear 4.2 25 (Cf.) 50 ppm A6 400 ppm B1 100 ppm C2 1 cloudy -3.2 26 50 ppm A1 200 ppm B1 100 ppm C2 2 cloudy 1.4 27 50 ppm A2 400 ppm B1 100 ppm C2 0 cloudy -5.2 28 50 ppm A3 400 ppm B1 100 ppm C2 0 cloudy -4.9 29 50 ppm A5 400 ppm B1 100 ppm C2 0 cloudy -5.1 30 50 ppm A1 200 ppm B2 100 ppm C3 0 cloudy -5.3 31 50 ppm A1 200 ppm B2 100 ppm C4 0 cloudy -5.2 example Additive A CFPP [° C] Sediment [vol.%] Appearance oil phase CPKS [° C] 32 (Cf.) 50 ppm A6 -24 0 cloudy -2.0 33 50 ppm A1 -26 0 cloudy -4.5 34 50 ppm A2 -27 0 cloudy -4.7 35 50 ppm A3 -28 0 cloudy -4.1 36 50 ppm A4 -25 0 cloudy -3.6 37 50 ppm A5 -27 0 cloudy -3.9

Long-term stability of the additives

The long-term stability of the additives according to the invention was tested on additives A1 and A2 directly after preparation for its performance in the short sediment test and compared with the effect of the same samples after storage at 50 ° C. for five weeks. For comparison, an alkylphenol-aldehyde resin without additive (A6) was tested under the same conditions. In contrast to the additive according to the invention, this had become significantly darker after storage.

The short sediment test was carried out in Test Oil 3 containing 200 ppm B3 and 100 ppm C1 with 50 ppm each of Resin A6, A1 and A2, respectively. Table 7: Short sediment test in test oil 3 example Additive A Test oil 3 (CP -7,2 ° C) CFPP [° C] Sediment [vol.%] Appearance oil phase CPKS [° C] 38 (Cf.) 50 ppm A6 (immediately) -24 0 cloudy -2.0 39 (Cf.) 50 ppm A6 (after 5 weeks) -22 2 cloudy 0.2 40 50 ppm A1 (immediately) -28 0 cloudy -4.5 41 50 ppm A1 (after 5 weeks) -27 0 cloudy -4.3 42 50 ppm A2 (immediately) -26 0 cloudy -4.7 43 50 ppm A2 (after 5 weeks) -26 0 cloudy -4.4

The experiments show that the additives according to the invention are superior to the additives of the prior art in terms of improving the cold flowability and in particular the paraffin dispersion of middle distillates. They bring about an improved paraffin dispersion or, alternatively, a comparable paraffin dispersion with a lower additive dosage. In addition, they show that the mixtures according to the invention simultaneously have a pronounced synergistic effect with regard to improving the electrical conductivity of middle distillates. In contrast, neither sulfonic acid salts alone nor alkylphenol resins alone have a significant influence on the conductivity of low-sulfur middle distillates. The mixtures according to the invention thus make it possible to improve the conductivity of oils doped with alkylphenol resins to more than 50 pS / m with only small amounts of sulfonic acid ammonium salt and thus to ensure safe handling of the additized oils.

Claims (16)

1. A composition comprising at least one alkylphenol resin (constituent I) and, based on the alkylphenol resin, from 0.05 to 10% by weight of at least one salt of an aromatic base and of a sulfonic acid (constituent II) wherein the alkylphenol-aldehyde resin has a repeating structural unit of the formula

   

   where R⁵ is C₁-C₂₀₀-alkyl or C₂-C₂₀₀-alkenyl, O-R⁶ or O-C(O)-R⁶, where R⁶ is C₁-C₂₀₀-alkyl or C₂-C₂₀₀-alkenyl, and n is from 2 to 100.
2. The composition as claimed in claim 1, wherein the aldehyde used for the condensation of the alkylphenol-aldehyde resin has from 1 to 12 carbon atoms.
3. The composition as claimed in claim 1 and/or 2, wherein the alkyl group of the alkylphenol-aldehyde resin has from 1 to 200 carbon atoms.
4. The composition as claimed in one or more of claims 1 to 3, wherein the molecular weight of the alkylphenol-aldehyde resins is from 400 to 20 000 g/mol.
5. The composition as claimed in one or more of claims 1 to 5, wherein the sulfonic acid used to prepare the sulfonates is oil-soluble, and contains at least one sulfonic acid group and at least one saturated or unsaturated, linear, branched and/or cyclic hydrocarbon radical having from 1 to 40 carbon atoms.
6. The composition as claimed in one or more of claims 1 to 5, wherein the aromatic bases used to prepare the sulfonates are oil-soluble compounds which contain a cyclic, through-conjugated hydrocarbon skeleton with 4n+2 π electrons and at least one heteroatom capable of salt formation.
7. The composition as claimed in claim 6, wherein the heteroatom capable of salt formation is part of the aromatic ring system.
8. The composition as claimed in one or more of claims 1 to 7, wherein copolymers of ethylene and from 6 to 21 mol% of vinyl esters, acrylic esters, methacrylic esters, alkyl vinyl ethers and/or alkenes are additionally present.
9. The composition as claimed in one or more of claims 1 to 8, wherein reaction products of compounds of the formula NR⁶R⁷R⁸, where R⁶, R⁷ and R⁸ may be the same or different and at least one of these groups is C₈-C₃₆-alkyl, C₆-C₃₆-cycloalkyl, C₈-C₃₆-alkenyl, in particular C₁₂-C₂₄-alkyl, C₁₂-C₂₄-alkenyl or cyclohexyl, and the remaining groups are either hydrogen, C₁-C₃₆-alkyl, C₂-C₃₆-alkenyl, cyclohexyl, or a group of the formulae -(A-O)_x-E or -(CH₂)_n-NYZ, where A is an ethyl or propyl group, x is from 1 to 50, E = H, C₁-C₃₀-alkyl, C₅-C₁₂-cycloalkyl or C₆-C₃₀-aryl, and n = 2, 3 or 4, and Y and Z are each independently H, C₁-C₃₀-alkyl or -(A-O)_x-E with compounds which have a functional group of the formula
   
           > C = O
   
   are additionally present.
10. The composition as claimed in one or more of claims 1 to 9, wherein comb polymers of the formula

    

    are additionally present, where

    A is R', COOR', OCOR', R"-COOR', OR';

    D is H, CH₃, A or R";

    E is H, A;

    G is H, R", R"-COOR', an aryl radical or a heterocyclic radical;

    M is H, COOR", OCOR", OR", COOH;

    N is H, R", COOR", OCOR, an aryl radical;

    R' is a hydrocarbon chain having from 8 to 50 carbon atoms;

    R" is a hydrocarbon chain having from 1 to 10 carbon atoms;

    m is between 0.4 and 1.0; and

    n is between 0 and 0.6.
11. The composition as claimed in one or more of claims 1 to 10, wherein polyoxyalkylene compounds which are esters, ethers and ether/esters and bear at least one alkyl radical having from 12 to 30 carbon atoms are additionally present.
12. The composition as claimed in one or more of claims 1 to 11, wherein copolymers which contain, in addition to structural units of ethylene, structural units which derive from α-olefins having from 3 to 24 carbon atoms and have molecular weights of up to 120 000 g/mol are additionally present.
13. A mineral oil distillate having a conductivity of more than 50 pS/m, which comprises compositions as claimed in one or more of claims 1 to 12.
14. A mineral oil distillate having an aromatics content of less than 25% by weight, and comprising from 5 to 5000 ppm of the composition as claimed in one or more of claims 1 to 12.
15. The use of compositions as claimed in one or more of claims 1 to 12 for improving the electrical conductivity of mineral oil distillates having an aromatics content of less than 25% by weight.
16. The use of compositions comprising at least one alkylphenol resin (constituent I) and, based on the alkylphenol resin, from 0.05 to 10% by weight of at least one salt of an aromatic base and of a sulfonic acid (constituent II) for improving the cold flowability of mineral oil distillates having a sulfur content of less than 350 ppm, wherein the alkylphenol-aldehyde resin has a repeating structural unit of the formula

    

    where R⁵ is C₁-C₂₀₀-alkyl or C₂-C₂₀₀-alkenyl, O-R⁶ or O-C(O)-R⁶, where R⁶ is C₁-C₂₀₀-alkyl or C₂-C₂₀₀-alkenyl, and n is from 2 to 100.