EP1749874A2 - Mineral oils with improved conductivity and cold flowability. - Google Patents

Abstract

Improving the electrical conductivity of mineral oil distillate having water content of less than 150 ppm, involves adding a composition which comprises at least one alkylphenolaldehyde resin and 0.10-10 pbw at least one polar oil-soluble nitrogen compound, based on the alkylphenol-aldehyde resin, in such an amount that the mineral oil distillate has a conductivity of at least 50 pS/m. Improving the electrical conductivity of mineral oil distillate having water content of less than 150 ppm, involves adding a composition which comprises at least one alkylphenolaldehyde resin having formula (A) and 0.10-10 pbw at least one polar oil-soluble nitrogen compound, based on the alkylphenol-aldehyde resin, in such an amount that the mineral oil distillate has a conductivity of at least 50 pS/m. R 5>1-200C alkyl or 2-200C alkenyl, O-R 6> or O-C(O)-R 6>; R 6>1-200C-alkyl or 2-200C-alkenyl; n : 2-100. Independent claims are also included for: (1) improving the electrical conductivity of mineral oil distillate having a water content of less than 150 ppm, and comprising 0.1-200 ppm of at least one polar, oil-soluble nitrogen compound, comprising adding to the mineral oil distillate 0.1-200 ppm of at least one alkylphenol-aldehyde resin (A), so that the mineral oil distillate have a conductivity of at least 50 pS/m; and (2) mineral oil distillate having an aromatics content of less than 21 wt.%, a water content of less than 150 ppm, and a conductivity of at least 50 pS/m, and comprising 0.1-200 pm of at least one alkylphenol-aldehyde resin (A). [Image].

Description

The present invention relates to the use of alkylphenol-aldehyde resins and oil-soluble polar nitrogen compounds for improving the conductivity of low-water mineral oil distillates, as well as the additive mineral oil distillates.

The content of mineral oil distillates in sulfur-containing compounds and aromatic hydrocarbons must be further reduced as environmental legislation becomes more stringent. The refinery processes used to produce specification-compliant mineral oil grades, however, also remove other polar and aromatic compounds. Often it also reduces the capacity of the oils for water. 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. Particularly problematic is the increase in electrical conductivity at low temperatures, since the conductivity of organic liquids decreases with decreasing temperature and also the known additives show the same temperature dependence. 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 used as cold flow improvers, corrosion inhibitors and asphalt dispersants and alkoxylated alkylphenol resins 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.

Another group of mineral oil additives are polar oil-soluble nitrogen compounds, which are added in particular to winter diesel fuels as paraffin dispersants and counteract sedimentation of the paraffin crystals precipitating in the cold.

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.

US 4,356,002 discloses the use of alkoxylated alkylphenol resins as antistatics for hydrocarbons. With amino-containing copolymers of maleic anhydride and α-olefins, these lead to synergistically improved conductivities. The formulation of additive concentrates from these two classes of substance presents difficulties in that they are hardly miscible and thus form multiphase systems.

Most of the commercially used conductivity improvers contain as active ingredient component metal ions and / or polysulfones. Polysulfones are copolymers of SO ₂ and olefins. However, ash-forming and sulfur-containing additives are in principle undesirable for use in low-sulfur fuels. The effectiveness of the known as further additive component polar oil-soluble nitrogen compounds as a conductivity improver alone is insufficient and, as well as the combinations of these polar oil-soluble nitrogen compounds with alkoxylated alkylphenol according to US 4,356,002 with decreasing aromatics and water content of the oils to be added increasingly unsatisfactory. A subsequent addition of water leads in such oils but only to the dispersion of undissolved water, which does not contribute to increasing the conductivity but rather leads to increased corrosion and in the cold the risk of ice formation and consequent blockages of delivery lines and filters.

The object of the present invention was thus to find a superior over the prior art in its effectiveness additive for improving the electrical conductivity of mineral oil distillates with low water content, especially of low-aromatic mineral oil distillates, which also ensures safe handling of these oils even at low temperatures , In order to leave no residue during combustion, the additive should burn ashless and in particular contain no metals. In addition, it should also contain no sulfur compounds.

Surprisingly, it has now been found that low-mineral water oils can be significantly improved in their electrical conductivity by adding small amounts of phenolic resins (component I) and polar oil-soluble nitrogen compounds (component II). The conductivity is significantly increased by the combination of these two additive components than would be expected from the effect of the individual substances. In addition, the conductivity remains constant with decreasing temperature and in many cases even increases with decreasing temperature. The oils thus additized show a greatly increased conductivity and are therefore much safer to handle, especially at low temperatures.

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, enthält und, bezogen auf das Alkylphenol-Aldehydharz oder die Alkylphenol-Aldehydharze, 0,1 bis 10 Gewichtsteile mindestens einer polaren öllöslichen Stickstoffverbindung (Bestandteil II) enthalten, zur Verbesserung der elektrischen Leitfähigkeit von Mineralöldestillaten mit einem Wassergehalt von weniger als 150 ppm, in einer Menge so dass die Mineralöldestillate eine Leitfähigkeit vom mindestens 50 pS/m aufweisen.The invention thus relates to the use of compositions comprising at least one alkylphenol-aldehyde resin (component I), which is a structural element 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, and containing, based on the alkylphenol-aldehyde resin or the alkylphenol-aldehyde resins, 0.1 to 10 parts by weight of at least one polar oil-soluble nitrogen compound (component II), to improve the electrical conductivity of mineral oil distillates a water content of less than 150 ppm, in an amount such that the mineral oil distillates have a conductivity of at least 50 pS / m.

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, enthält und, bezogen auf das Alkylphenol-Aldehydharz oder die Alkylphenol-Aldehydharze, 0,1 bis 10 Gewichtsteile mindestens einer polaren, öllöslichen Stickstoffverbindung (Bestandteil II) enthalten, zusetzt, so dass die Mineralöldestillate eine Leitfähigkeit von mindestens 50 pS/m erreichen.Another object of the invention is a method for improving the electrical conductivity of mineral oil distillates having a water content of less than 150 ppm, by the mineral oil distillates compositions containing at least one alkylphenol-aldehyde resin (component I), which is a structural element 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, and, based on the alkylphenol-aldehyde resin or the alkylphenol-aldehyde resins, 0.1 to 10 parts by weight of at least one polar, oil-soluble nitrogen compound (Component II) are added, so that the mineral oil distillates reach a conductivity of at least 50 pS / m.

enthält, 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, zusetzt, so dass die Mineralöldestillate eine Leitfähigkeit von mindestens 50 pS/m aufweisen.Another object of the invention is a method for improving the electrical conductivity of mineral oil distillates having a water content of less than 150 ppm, containing 0.1 to 200 ppm of at least one polar, oil-soluble nitrogen compound by the mineral oil distillates 0.1 to 200 ppm at least an alkylphenol-aldehyde resin which is a structural element of the formula

in which 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, added, so that the mineral oil distillates have a conductivity of at least 50 pS / m.

enthält, 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, zur Verbesserung der elektrischen Leitfähigkeit von Mineralöldestillaten mit einem Wassergehalt von weniger als 150 ppm, die 0,1 bis 200 ppm mindestens einer polaren öllöslichen Stickstoffverbindung (Bestandteil II) enthalten, in einer Menge so dass die Mineralöldestillate eine Leitfähigkeit vom mindestens 50 pS/m aufweisen.Another object of the invention is the use of at least one alkylphenol-aldehyde resin (component I), which is a structural element of the formula

in which 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, to improve the electrical conductivity of mineral oil distillates having a water content of less than 150 ppm, the 0.1 to 200 ppm of at least one polar oil-soluble nitrogen compound (ingredient II) in an amount such that the mineral oil distillates have a conductivity of at least 50 pS / m.

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, enthält und 0,1 bis 200 ppm mindestens einer polaren öllöslichen Stickstoffverbindung (Bestandteil II) enthalten.Another object of the invention are mineral oil distillates having an aromatic content of less than 21 wt .-%, a water content of less than 150 ppm and a conductivity of at least 50 pS / m, the 0.1 to 200 ppm of at least one alkylphenol-aldehyde resin (component I), which is a structural element 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 from 2 to 100, and contains from 0.1 to 200 ppm of at least one polar oil-soluble nitrogen compound (Ingredient II).

In the context of the present invention, alkylphenol-aldehyde 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.

The compositions according to the invention preferably contain from 0.2 to 6 parts by weight, based on the alkylphenol resin or the alkylphenol-aldehyde resins, and especially from 0.3 to 3 parts by weight of at least one polar, oil-soluble nitrogen compound.

Preferred are 0.2 to 100 ppm and especially 0.25 to 25 ppm, such as 0.3 to 10 ppm, of at least one alkylphenol-aldehyde resin and 0.2 to 50 ppm and specifically, 0.25 to 25 ppm, such as 0.3 to 20 ppm, of at least one polar, oil-soluble nitrogen compound is used to improve electrical conductivity. It is particularly preferred to use a total of up to 100 ppm, preferably 0.2 to 70 ppm and especially 0.3 to 50 ppm of the combination of alkylphenol-aldehyde resin or alkylphenol-aldehyde resins and polar, oil-soluble nitrogen compound or nitrogen compounds.

Preferably, the mineral oil distillates of the invention contain from 0.2 to 100 ppm and especially from 0.25 to 25 ppm, such as from 0.3 to 10 ppm, of at least one alkylphenol-aldehyde resin and from 0.2 to 50 ppm and especially from 0.25 to 25 ppm, such as 0.3 to 20 ppm, of at least one polar, oil-soluble nitrogen compound. The mineral oil distillates according to the invention particularly preferably contain up to 100 ppm in total, preferably 0.2 to 70 ppm and especially 0.3 to 50 ppm of the combination of alkylphenol-aldehyde resin or alkylphenol-aldehyde resins and polar, oil-soluble nitrogen compound or nitrogen compounds.

Preferably, 0.2 to 100 ppm and especially 0.25 to 25 ppm, such as 0.3 to 10 ppm, of at least one alkylphenol-aldehyde resin is used to improve the electrical conductivity of mineral oil distillates, 0.2 to 50 ppm and especially 0 , 25 to 25 ppm, such as 0.3 to 20 ppm, of at least one polar, oil-soluble compound.

The mineral oil distillates of the invention which have improved electrical conductivity have an electrical conductivity of preferably at least 60, in particular at least 75 pS / m.

Alkylphenol-aldehyde resins as constituent I 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 to mean in general hydrocarbon radicals as defined below) 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 up to 200, preferably 1-20 , in particular 4-16, for example 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. Preferably, these radicals are saturated. 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 butylphenol on the one hand and octyl-, nonyl- and / or dodecylphenol on the other hand in a molar ratio of 1:10 to 10: 1 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 as determined by gel permeation chromatography in THF against poly (ethylene glycol) standards is preferably 400-20,000, in particular 800-10,000 g / mol and especially 2,000-5,000 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-Q₂₀₀-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 ―Alkenyl wie beispielsweise für C₆-C₁₂-Alkyl oder ―Alkenyl. Besonders bevorzugt steht R⁵ für C₁-C₂₀-Alkyl oder C₂-C₂₀―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 a preferred embodiment 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 -Q 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 -alkenyl, for example C ₆ -C ₁₂ -alkyl or -alkenyl. With particular preference R ^{5 is} C ₁ -C ₂₀ -alkyl or C ₂ -C ₂₀ -alkenyl and in particular C ₄ -C ₁₆ -alkyl or -alkenyl, 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.

Particularly preferred for use in middle distillates such as diesel and heating oil are alkylphenol-aldehyde resins having C ₂ -C ₄₀ -alkyl radicals of the alkylphenol, preferably having C ₄ -C ₂₀ -alkyl radicals such as, for example, 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 alkylphenols with linear alkyl radicals having 8 and 9 carbon atoms. The average molecular weight determined by GPC is preferably between 700 and 20,000, in particular between 1,000 and 10,000, for example between 2,000 and 3,500 g / mol.

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, more 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 be used. The condensation is preferably carried out between 70 and 200 ° C such as between 90 and 160 ° C. It is usually catalysed by 0.05 to 5 wt .-% bases or preferably by 0.05 to 5 wt .-% acids. As acidic catalysts 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. Particularly suitable catalysts are sulfonic acids which contain at least one sulfonic acid group and at least one saturated or unsaturated, linear, branched and / or cyclic hydrocarbon radical having 1 to 40 C atoms and preferably having 3 to 24 C 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. 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. Usually, these remain after completion of the reaction as such or in neutralized form in the product; Metal ions containing and thus ash-forming salts are usually separated.

The polar oil-soluble nitrogen compounds which are suitable as constituent II according to the invention 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 , wherein R ⁶ , R ⁷ and R ⁸ may be the same 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 remaining 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 is 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 . 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 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. 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 coconut fatty amine, tallow fatty amine, hydrogenated tallow fatty amine, dicoco fatty amine, di-tallow fatty amine and di (hydrogenated tallow fat) amine. Preferred amine derivatives are amine salts, imides and / or amides such as amide ammonium salts of secondary fatty amines, in particular dicocosfettamine, ditallow fatty amine and distearylamine. Particularly preferred polar oil-soluble nitrogen compounds as ingredient II contain at least one acyl group reacted to an ammonium salt. Specifically, they contain at least two, such as at least three or at least four, and in polymeric nitrogen compounds also five or more ammonium groups.

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

> C = O

Carbonyl compounds suitable for 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 500 and 50,000, more preferably between 1,000 and 20,000, for example between 2,000 and 10,000.

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 proved 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.

Particularly preferred as polar oil-soluble nitrogen compounds are reaction products of copolymers derived from ethylenically unsaturated dicarboxylic acids and α-olefins with secondary fatty amines.

Another group of particularly preferred polar oil-soluble nitrogen compounds as constituent II are acylated nitrogen compounds which are derived by reacting mono- as well as polycarboxylic acids having at least 10 carbon atoms or their reactive equivalents with amines which carry at least one acidic hydrogen atom. Carboxylic acid and amine are linked together via amide, imide, amidine or ammonium carboxylate function.

Suitable mono- and polycarboxylic acids are, for example, substituted succinic and propionic acids and their esters and anhydrides. The hydrocarbon radical of this acylating agent bonded via a C-C bond to the acyl group or acyl groups carries up to 400, preferably 30 to 50 C atoms. It is preferably an alkyl or alkenyl radical. Preferably, this is branched. It may contain one or two double bonds, preferably it is substantially saturated. It is derived from olefins such as, for example, dodecene, tetradecene, hexadecene, octadecene or eicosins, in particular having a terminal double bond and preferably homopolymers and copolymers of monoolefins and diolefins having 2 to 6 carbon atoms, such as ethylene, propylene, butene, isobutene, butadiene, Isoprene and 1-hexene off. Particularly preferred alkyl radicals are poly (isobutylenes). These are accessible, for example, by polymerization of a C ₄ refinery stream containing 35 to 75% by weight of butene-1 and 30 to 60% of isobutene in the presence of a Lewis catalyst such as aluminum trichloride.

Suitable amino compounds for the preparation of the acylated nitrogen compounds are, in addition to ammonia, amines with alkyl radicals having up to 30 carbon atoms, polyamines of the formula

(R ⁹⁾ ₂ N- [AN (R ^9)] _q - (R ⁹⁾

wherein each R ⁹ independently represents hydrogen or an alkyl or hydroxyalkyl radical having up to 24 carbon atoms, but wherein at least one R ^{9 is} hydrogen, q is an integer from 1 to 10 and A is an alkylene radical having 1 to 6 C atoms, as well as heterocycles substituted polyamines and aromatic polyamines. Particularly suitable are mixtures of polyamines, such as typically mixtures of poly (ethylene amines). Examples which may be mentioned: ethylenediamine, 1,2-propylenediamine, di (ethylene) triamine, tri (ethylene) tetramine, tetra (ethylene) pentamine, N- (2-hydroxyethyl) ethylenediamine, N, N ¹ -bis (2-hydroxyethyl ) ethylenediamine, N- (3-hydroxybutyl) tetra (methylene) diamine, N-2-aminoethylpiperazine, N-2 and N-3-aminopropylmorpholine, N-3- (dimethylamino) -propylpiperazine, 2-heptyl-3 ( 2-aminopropyl) imidazoline, 1,4-bis (2-aminoethyl) piperazine, 1- (2-hydroxyethyl) piperazine and various isomers of phenylenediamine and naphthalenediamine.

A typical and particularly preferred acylated nitrogen compound is prepared by reacting a poly (isobutylene) succinic anhydride or ester whose poly (isobutylene) moiety has between 50 and 400 carbon atoms with a mixture of poly (ethylene amines) containing from about 3 to 7 nitrogen atoms and about 1 to 6 ethylene units available.

Also, reaction products of unsaturated poly (isobutylene) having 50 to 400 carbon atoms with poly (ethylene amines) having about 3 to 7 carbon atoms and about 1 to 6 ethylene units and mixtures thereof are suitable as polar oil-soluble nitrogen compounds.

For easier 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, for example from 25 to 50% by weight of solvent. Preferred solvents are higher-boiling aliphatic, aromatic hydrocarbons, alcohols, esters, ethers and mixtures thereof. In the Concentrates may vary the mixing ratio between the alkylphenol-aldehyde resins of the invention as component I and nitrogen compounds as component II depending on the application. Such concentrates preferably contain from 0.1 to 10 parts by weight, preferably from 0.2 to 6 parts by weight, of the polar, oil-soluble nitrogen compound per part by weight of alkylphenol-aldehyde resin.

The compositions according to the invention increase the conductivity of mineral oils such as gasoline, kerosene, jet fuel, diesel and heating oil, in particular in oils with a low aromatic content of less than 21 wt .-%, in particular less than 19 wt .-%, especially less than 18 Wt .-% such as less than 17 wt .-% are beneficial. Since they simultaneously improve the cold properties, especially of middle distillates such as kerosene, jet fuel, diesel and heating oil, their use in areas or at times, in which due to the climatic conditions so far no paraffin dispersants are used, a significant saving in the total additive the oils can be achieved because no additional conductivity improvers must be used. At the same time, since the additives according to the invention improve the cold properties of the additized oils, e.g. Cloud point and / or CFPP of the oils to be added to be set higher, which improves the profitability of the refinery. The additives of the invention also contain no metals that could lead to ash during combustion and thus deposits in the combustion chamber or exhaust system and particle pollution of the environment.

To further increase the electrical conductivity of mineral oils, the additives according to the invention can also be used in combination with polysulfones. Suitable polysulfones are accessible by copolymerization of sulfur dioxide with 1-olefins having 6 to 20 carbon atoms such as 1-dodecene. They have molecular weights of from 10,000 to 1,500,000, preferably from 50,000 to 900,000 and especially from 100,000 to 500,000, measured by GPC against poly (styrene) standards. The preparation of suitable polysulfones is for example U.S. 3,917,466 known.

The additives of the invention may mineral oil distillates to improve the cold flowability in combination with other additives such as Ethylene copolymers, comb polymers, polyoxyalkylene compounds and / or olefin copolymers.

The present invention thus provides a new additive package which, in particular, improves the antistatic properties of aromatic-poor mineral oils by improving the cold properties.

The additives according to the invention for mineral oil distillates thus contain, in a preferred embodiment, in addition to the constituents I and II, one or more of the components III to VI.

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 isobutyl (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, wherein the total comonomer content of the terpolymers is preferably between 8 and 21 mol%, in particular between 12 and 18 mol%. Further particularly preferred copolymers contain, in addition to ethylene and 8 to 18 mol% of vinyl esters of C ₂ to C ₁₂ carboxylic acids, from 0.5 to 10 mol% of olefins such as propene, butene, isobutylene, hexene, 4-methylpentene, octene, diisobutylene and / or norbornene.

These ethylene copolymers and terpolymers preferably have melt viscosities at 140 ° C. of from 20 to 10,000 mPas, in particular from 30 to 5,000 mPas, especially from 50 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 5 to 50 wt .-% of the inventive additive combination of I and II and 30 to 98 wt .-%, preferably 50 to 95 wt .-% ethylene copolymers.

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.

Suitable comb polymers (constituent IV) can be obtained, 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.

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 their mixtures. Especially preferred are 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 having 12 to 20 carbon atoms and poly (vinyl esters) derived from fatty acids having 12 to 20 carbon atoms ,

Other suitable polyoxyalkylene compounds (constituent V) are, for example, esters, ethers and ethers / esters of polyols which carry at least one alkyl radical having 12 to 30 C 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 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 the thereof 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 VI) as a 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. Preferred copolymers contain, in addition to ethylene structural units derived from α-olefins having 3 to 24 carbon atoms and 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 carbon atoms is preferably between 15 and 50 mol%, more preferably between 20 and 35 mol% and especially between 30 and 45 mol%. These copolymers may also contain minor amounts, eg, up to 10 mol% of other 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, for example 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 additives for lowering the cloud point.
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 are suitable for improving the electrostatic properties and the cold flow properties of animal, vegetable or mineral oils. In particular, they increase the electrical conductivity of the additized oils and thus enable safe handling, for example during pumping and loading. 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 according to 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 those 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. They show particular advantages in low aromatics mineral oil distillates of less than 21% by weight, in particular less than 19% by weight, especially less than 18% by weight, for example less than 17% by weight. The water content of such oils is often 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. By aromatic compounds is meant the sum of mono-, di- and polycyclic aromatic compounds as determinable by HPLC according to DIN EN 12916 (2001 edition). The middle distillates may also contain minor amounts such as, 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 those below containing oils of animal and / or vegetable origin such as fatty acid methyl ester.

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. Here are, for example, commercially available mixtures of ethyl, propyl, butyl and especially methyl esters of fatty acids having 14 to 22 carbon atoms, for example of lauric, myristic, palmitic, palmitolic, stearic, oleic, elaidic, petroselic, ricinoleic, elaeostearic, linoleic, linolenic , Eicosanoic acid, gadoleic acid, docosanoic acid 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 are predominantly, ie at least Contain 50 wt .-% of methyl esters of fatty acids having 16 to 22 carbon atoms and 1, 2 or 3 double bonds. The preferred lower alkyl esters of fatty acids are the methyl esters of oleic, linoleic, linolenic and erucic acids.

The compositions according to the invention are also suitable 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:

Oils from European refineries were used as test oils. 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 (Cf.) distillation IBP [° C] 212 188 160 20% [° C] 244 249 229 90% [° C] 322 336 339 FBP [° C] 342 361 371 Cloud point [° C] -8.8 -12.5 4.6 Density @ 15 ° C [g / cm ³ ] .8302 .8264 .8410 Water content @ 20 ° C [Ppm] 25 35 185 sulfur content [Ppm] 4 6 173 elec. Conductivity @ 25 ° C [pS / m] 0 1 9 aromatics [Wt .-%] 14.8 16.9 29.9 of which mono [Wt .-%] 14.5 14.4 24.1 di [Wt .-%] 0.3 2.4 5.3 poly [Wt .-%] <0.1 0.1 0.5

1. (A) Charakterisierung der eingesetzten Alkylphenolharze
   • A1 Sauer katalysiertes Nonylphenol-Formaldehydharz (Mw 1.300 g/mol)
   • A2 Sauer katalysiertes Nonylphenol-Formaldehydharz (Mw 2.200 g/mol)
   • A3 Sauer katalysiertes Dodecylphenol-Formaldehydharz (Mw 2.600 g/mol)
   • A4 Alkalisch katalysiertes Dodecylphenol-Formaldehydharz (Mw 2.450 g/mol)
   • A5 Unter saurer Katalyse hergestelltes Alkylphenol-Formaldehydharz aus equimolaren Anteilen Nonylphenol und Butylphenol (Mw 2.900 g/mol)
   • A6 Mit 5 mol Ethylenoxid pro phenolischer OH-Gruppe alkoxiliertes Nonylphenolharz gemäß A2 (Vergleich).
2. (B) Charakterisierung der eingesetzten Stickstoffverbindungen B
   • B1 Umsetzungsprodukt eines Dodecenyl-Spirobislactons mit einer Mischung aus primärem und sekundärem Talgfettamin, hergestellt gemäß EP 0413279 .
   • B2 Umsetzungsprodukt eines Terpolymers aus C₁₄/₁₆-α-Olefin, Maleinsäureanhydrid und Allylpolyglykol mit 2 Equivalenten Ditalgfettamin, hergestellt gemäß EP 0606055 .
   • B3 Umsetzungsprodukt aus Phthalsäureanhydrid und 2 Equivalenten Di(hydriertem Talgfett)amin, hergestellt gemäß EP 0 061 894 .
   • B4 Umsetzungsprodukt aus Ethylendiamintetraessigsäure mit 4 Equivalenten Ditalgfettamin zum Amid-Ammoniumsalz, hergestellt gemäß EP 0 398 101 .
   • B5 Umsetzungsprodukt aus Poly(isobutenyl)bernsteinsäureanhydrid und Tetraethylenpentanmin.

The following additives were used:

1. (A) Characterization of the alkylphenol resins used
   • A1 acid catalysed nonylphenol-formaldehyde resin (Mw 1,300 g / mol)
   • A2 acid-catalyzed nonylphenol-formaldehyde resin (Mw 2,200 g / mol)
   • A3 acid catalyzed dodecylphenol-formaldehyde resin (Mw 2,600 g / mol)
   • A4 Alkaline-Catalyzed Dodecylphenol-Formaldehyde Resin (Mw 2,450 g / mol)
   • A5 Alkylphenol-formaldehyde resin prepared from acidic catalysis from equimolar proportions of nonylphenol and butylphenol (Mw 2,900 g / mol)
   • A6 Nonylphenol resin alkoxylated with 5 mol of ethylene oxide per phenolic OH group in accordance with A2 (comparison).
2. (B) Characterization of the nitrogen compounds B used
   • B1 Reaction product of a dodecenyl spirobislactone with a mixture of primary and secondary tallow fatty amine prepared according to EP 0413279 ,
   • B2 reaction product of a terpolymer of C _14/16 -α-olefin, maleic anhydride and di-tallow Allylpolyglykol with 2 equivalents prepared according to EP 0606055 ,
   • B3 Reaction product of phthalic anhydride and 2 equivalents of di (hydrogenated tallow fat) amine, prepared according to EP 0 061 894 ,
   • B4 Reaction product of ethylenediaminetetraacetic acid with 4 equivalents of ditallow fatty amine to the amide ammonium salt, prepared according to EP 0 398 101 ,
   • B5 Reaction product of poly (isobutenyl) succinic anhydride and tetraethylene pentanmin.

The molecular weights were determined by means of gel permeation chromatography in THF against poly (ethylene glycol) standards. Additives A and B were used as 50% settings in Solvent Naphtha, a commercial blend of high boiling aromatic hydrocarbons.

Improvement of the electrical conductivity of middle distillates

For conductivity measurements, the additives were dissolved in the indicated concentration in 250 ml of test oil 1 with shaking. The electrical conductivity in accordance with DIN 51412-T02-79 was determined using an automatic conductivity meter Maihak SLA 900. The unit of electrical conductivity is picosiemens / m (pS / m). For jet fuel is generally a conductivity specified by at least 50 pS / m. The stated dosing rates relate to the amounts of active ingredient used. Table 2: Electrical conductivity in test oil 1 Example no. Dosing rate additive A Dosing rate additive B conductivity [pS / m] @ 25 ° C @ 10 ° C 1 (See) 25 ppm A1 - - 3 2 2 (Cf.) 50 ppm A1 - - 3 2 3 (Cf.) 10 ppm A2 - - 1 1 4 (Cf.) 25 ppm A2 - - 3 1 5 (Cf.) 50 ppm A2 - - 4 2 6 (see) 50 ppm A3 - - 4 3 7 (Cf.) 50 ppm A4 - - 5 3 8 (Cf.) 25 ppm A6 - - 3 1 9 (Cf.) - - 10 ppm B2 3 2 10 (Cf.) - - 25 ppm B2 3 2 11 (Cf.) - - 50 ppm B2 8th 5 12 (Cf.) - - 10 ppm B3 1 1 13 (comp.) - - 25 ppm B3 2 2 14 (Cf.) - - 50 ppm B3 4 4 15 (Cf.) - - 10 ppm B4 3 2 16 (comp.) - - 25 ppm B4 5 4 17 (Cf.) - - 50 ppm B4 7 5 18 (Cf.) - - 25 ppm B5 4 3 19 7 ppm A2 3 ppm B2 44 57 20 3 ppm A2 7 ppm B2 57 68 21 16ppm A2 8 ppm B2 120 204 22 8 ppm A2 16 ppm B2 141 225 23 15 ppm A2 35 ppm B2 341 615 24 8 ppm A1 16 ppm B2 110 161 25 16 ppm A1 8 ppm B2 99 126 26 8 ppm A2 16 ppm B3 77 94 27 15 ppm A2 15 ppm B3 136 147 28 10 ppm A2 15 ppm B4 64 71 29 15 ppm A2 7 ppm B4 77 82 30 8 ppm A2 16 ppm B5 110 130 31 5 ppm A3 10 ppm B2 125 196 32 5 ppm A4 10 ppm B2 115 126 33 (Cf.) 8 ppm A6 16 ppm B2 24 18

Example 34: Upon further cooling of the composition according to Example 22 to 0 ° C., a conductivity of 353 pS / m was measured. Table 3: Electrical conductivity in test oil 2 Example no. Dosing rate additive A Dosing rate additive B Conductivity [pS / m] @ 25 ° C @ 10 ° C 35 (Cf.) 25 ppm A1 - - 1 0 36 (See) 10 ppm A2 - - 2 0 37 (Cf.) 25 ppm A2 - - 4 2 38 (Cf.) 25 ppm A5 - - 3 1 39 (Cf.) 25 ppm A6 - - 2 1 40 (Cf.) - - 25 ppm B1 3 1 41 (Cf.) - - 10 ppm B2 2 2 42 (Cf.) - - 25 ppm B2 6 3 43 (Cf.) - - 25 ppm B5 4 2 44 10 ppm A1 15 ppm B1 109 132 45 16 ppm A1 8 ppm B2 170 243 46 8 ppm A2 16 ppm B2 268 430 47 15 ppm A2 35 ppm B2 461 890 48 8 ppm A5 16 ppm B2 279 415 49 10 ppm A3 10 ppm B5 252 337 50 (Cf.) 10 ppm A6 5 ppm B2 24 16 51 (Cf.) 8 ppm A6 16 ppm B2 54 38 Example no. Dosing rate additive A Dosing rate additive B conductivity [pS / m] @ 25 ° C @ 10 ° C 52 10 ppm A2 - - 19 12 54 10 ppm A4 - - 26 17 55 10 ppm A6 - - 25 18 57 - - 3 ppm B2 41 24 59 10 ppm A2 3 ppm B2 105 73 60 10 ppm A4 3 ppm B2 97 66 61 10 ppm A6 3 ppm B2 160 102

The examples show that the compositions according to the invention have a pronounced synergistic effect on the individual components. Moreover, they show that the compositions according to the invention increase the electrical conductivity, in particular of aromatics-poor fuel oils with a low water content, more than the known additives of the prior art. The conductivity of the inventive mineral oil distillates increases with decreasing temperature. Since the additives used are also known to cause an improved paraffin dispersion, a comparable conductivity can be achieved with lower additive dosing of conventional additives. Another advantage of the invention is that with the additives of the invention in addition to the improvement of the conductivity at the same time the cold properties are improved, which allows the manufacturer of the fuel oil to process a higher proportion of paraffin-rich, cold problematic distillation cuts.

Claims (17)

Use of compositions containing at least one alkylphenol-aldehyde resin (component I) which is a structural element 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, and containing, based on the alkylphenol-aldehyde resin or the alkylphenol-aldehyde resins, 0.1 to 10 parts by weight of at least one polar oil-soluble nitrogen compound (component II), to improve the electrical conductivity of mineral oil distillates a water content of less than 150 ppm, in an amount such that the mineral oil distillates have a conductivity of at least 50 pS / m. Use according to claim 1 wherein the aldehyde used to condense the alkylphenol-aldehyde resin comprises 1 to 12 carbon atoms. Use according to claim 1 and / or 2, wherein the alkyl group of the alkylphenol-aldehyde resin comprises 1 to 200 carbon atoms. Use according to one or more of claims 1 to 3, wherein the molecular weight of the alkylphenol-aldehyde resins is 400 to 20,000 g / mol. Use according to one or more of claims 1 to 4, wherein the alkylphenol-aldehyde resin is a repeating structural unit of the formula

wherein R ^{5 is} C ₁ -C ₂₀₀ alkyl or C ₂ -C ₂₀₀ alkenyl and n is a number from 2 to 100. Use according to one or more of claims 1 to 5, wherein the polar oil-soluble nitrogen compound reaction products of compounds of formula NR ⁶ R ⁷ R ⁸ , wherein R ⁶ , R ⁷ and R ^{8 may be the} same or different, and at least one of these groups for C 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 , with compounds having a functional group of the formula

> C = O

include. Use according to claim 6, wherein the compounds of the formula NR ⁶ R ⁷ R ⁸ are reacted with carbonyl compounds which are copolymers of acrylic acid, methacrylic acid, maleic acid, fumaric acid and / or itaconic acid with olefins, alkyl esters of acrylic acid and methacrylic acid, alkyl vinyl esters, alkyl vinyl ethers with 2 bis In the case of olefins, the alkyl radical attached to the double bond has 2 to 75 carbon atoms and their molecular weights are between 400 and 20,000. Use according to claim 6, wherein the polar nitrogen compound is a reaction product of at least one mono- and / or polycarboxylic acid and at least one amine bearing at least one acidic hydrogen atom. Use according to one or more of claims 1 to 8, wherein additionally copolymers of ethylene and 6 to 21 mol% of vinyl esters, acrylic esters, methacrylic esters, alkyl vinyl ethers and / or alkenes are used. Use according to one or more of claims 1 to 9, wherein in addition comb polymers of the formula

to be used in which A R ', COOR', OCOR ', R "-COOR', OR '; DH, CH _3, A or R "; EH, A; GH, R ", R" -COOR ', an aryl radical or a heterocyclic radical; MH, COOR ", OCOR", OR ", COOH; NH, R ", COOR", OCOR, an aryl radical; R 'is a hydrocarbon chain of 8 to 50 carbon atoms; R "is a hydrocarbon chain of 1 to 10 carbon atoms; m is a number between 0.4 and 1.0; and n is a number between 0 and 0.6 mean. Use according to one or more of claims 1 to 10, wherein additionally polyoxyalkylene compounds are used which are esters, ethers and ether / esters which carry at least one alkyl radical having 12 to 30 carbon atoms. Use according to one or more of claims 1 to 11, wherein copolymers are additionally used which, in addition to structural units of ethylene, contain structural units derived from α-olefins having 3 to 24 carbon atoms and have molecular weights of up to 120,000 g / have mol. Use according to one or more of claims 1 to 12, wherein in addition polysulfones derived from olefins having 6 to 20 carbon atoms are used. A method for improving the electrical conductivity of mineral oil distillates having a water content of less than 150 ppm by adding to the mineral oil distillates compositions comprising at least one alkylphenol-aldehyde resin (component I) which is a structural element 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, and containing, based on the alkylphenol-aldehyde resin or the alkylphenol-aldehyde resins, 0.1 to 10 parts by weight of at least one polar, oil-soluble nitrogen compound (component II), added, so that the mineral oil distillates Conductivity of at least 50 pS / m reach. A method for improving the electrical conductivity of mineral oil distillates having a water content of less than 150 ppm, containing 0.1 to 200 ppm of at least one polar, oil-soluble nitrogen compound, by adding to the mineral oil distillates 0.1 to 200 ppm of at least one alkylphenol-aldehyde resin containing Structural element of the formula

in which 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, added, so that the mineral oil distillates have a conductivity of at least 50 pS / m. Use of at least one alkylphenol-aldehyde resin (constituent I) which is a structural element of the formula

in which 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, for improving the electrical conductivity of mineral oil distillates having a water content of less than 150 ppm, containing 0.1 to 200 ppm of at least one polar oil-soluble nitrogen compound (component II) in an amount such that the mineral oil distillates have a conductivity of at least 50 pS / m. Mineral oil distillates having an aromatic content of less than 21% by weight, a water content of less than 150 ppm and a conductivity of at least 50 pS / m, the 0.1 to 200 ppm of at least one alkylphenol-aldehyde resin (component I) which is a structural element 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 from 2 to 100, and contains from 0.1 to 200 ppm of at least one polar oil-soluble nitrogen compound (Ingredient II).