EP1749873A2 - Mineral oils with improved conductivity and cold flowability. - Google Patents

Abstract

A mineral oil distillate having a water content of less than 150 ppm and a conductivity of at least 50 pS/m, comprises 0.1-200 ppm at least one alkylphenolaldehyde resin and 0.1-200 ppm at least one nitrogen-containing polymer. Independent claims are also included for the following: (1) improving the electrical conductivity of mineral oil distillates having a water content of less than 150 ppm and comprising 0.1-200 ppm nitrogen-containing polymer(s), by adding to the mineral oil distillates compositions comprising 0.1-200 ppm alkylphenol-aldehyde resin(s) and, based on the alkylphenol-aldehyde resin, 0.1-10 pbw nitrogen-containing polymer(s) so that the mineral oil distillates have a conductivity of at least 50 pS/m; and (2) an additive for mineral oil distillates comprising alkylphenol-aldehyde resin(s) and nitrogen-containing polymer (s) from a comb polymer containing units derived from esters of ethylenically unsaturated carboxylic acids, vinyl esters, and/or vinyl ethers, and nitrogen-containing comonomer(s); a copolymer of ethylene with an ethylenically unsaturated nitrogen-containing comonomer; and a polymeric polyamine, prepared by condensation of an aliphatic primary monoamine or of an N-alkylalkylene-diamine with epichlorohydrin or glycidol.

Description

The present invention relates to the use of alkylphenol-aldehyde resins and nitrogen-containing polymers to improve the conductivity of low-water mineral oil distillates, and 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, lubricity improvers, oxidation inhibitors, corrosion inhibitors, as well as 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 polymers which contain structural elements derived from nitrogen-containing monomers and for example can be added to fuel oils to improve various properties such as cold flowability, lubricity and also to improve electrical conductivity.

EP-A-1 088 045 discloses that alkylphenol resins can be used together with oil soluble polar nitrogen compounds to improve the cold properties of middle distillates and the lubricity of low sulfur fuel oils.

EP-A-1 502 938 discloses fuel oils of improved conductivity comprising mixtures of polymeric esters of acrylic acid, methacrylic acid and fumaric acid which may optionally contain nitrogen-containing comonomers with either a polysulfone and a polymeric reaction product of epichlorohydrin and an aliphatic primary monoamine or N-alkyl-alkylenediamine or alternatively with an oil-soluble copolymer of alkyl vinyl monomer and cationic vinyl monomer. According to paragraphs 17 to 19, these oils may additionally contain antioxidants such as BHT.

EP-A-1 274 819 discloses fuel oils with improved conductivity, the blends of an oil-soluble copolymer of alkyl vinyl monomer and cationic vinyl monomer, a polysulfone and optionally a polyamine or its sulfonic acid salt.

EP-A-0 964 052 discloses copolymers of ethylene with nitrogen-containing comonomers as lubricity improvers for low sulfur 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. The latter 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 oil-soluble nitrogen compounds known as further additive components as conductivity improvers alone is inadequate and, as well as the combinations of these polar oil-soluble nitrogen compounds with alkoxylated alkylphenol resins 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 in the oil, which does not contribute to improving the electrical conductivity but rather leads to increased corrosion problems and in the cold the risk of ice formation and consequent obstruction 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 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 contain neither halides nor sulfur-containing compounds.

Surprisingly, it has now been found that aromatic mineral oils can be significantly improved in their electrical conductivity by adding small amounts of phenolic resins (component I) and nitrogen-containing polymers (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 bzw. die Alkylphenol-Aldehydharze 0,1 bis 10 Gewichtsteile mindestens eines stickstoffhaltigen Polymers enthalten, zur Verbesserung der elektrischen Leitfähigkeit von Mineralöldestillaten mit einem Wassergehalt von weniger als 150 ppm.The invention thus relates to the use of compositions containing at least one alkylphenol-aldehyde resin, 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, containing, based on the alkylphenol-aldehyde resin or the alkylphenol-aldehyde resins 0.1 to 10 parts by weight of at least one nitrogen-containing polymer, to improve the electrical conductivity of mineral oil distillates having a water content of less than 150 ppm.

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 aromatenarmer Mineralöldestillate mit einem Wassergehalt von weniger als 150 ppm, die 0,1 bis 200 ppm mindestens eines stickstoffhaltigen Polymers (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, for improving the electrical conductivity of low-aromatic mineral oil distillates having a water content of less than 150 ppm, containing 0.1 to 200 ppm of at least one nitrogen-containing polymer (component 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 bezogen auf das Alkylphenol-Aldehydharz 0,1 bis 10 Gewichtsteile mindestens eines stickstoffhaltigen Polymers enthalten, zusetzt, so dass die Mineralöldestillate eine Leitfähigkeit vom 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, by the mineral oil distillates compositions containing at least one alkylphenol-aldehyde resin, 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, based on the alkylphenol-aldehyde resin, 0.1 to 10 parts by weight of at least one nitrogen-containing polymer, such 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, 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 nitrogen-containing polymer, by adding to the mineral oil distillates 0.1 to 200 ppm of at least one 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.

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 eines stickstoffhaltigen Polymers enthalten.Another object of the invention are mineral oil distillates having 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, 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 nitrogen-containing polymer.

Another object of the invention are additives for mineral oil distillates having a water content of less than 150 ppm, which contain at least one alkylphenol-aldehyde resin and at least one nitrogen-containing polymer in a mass ratio of 99: 1 to 1:99.

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.

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 especially 0.25 to 25 ppm such as 0.3 to 20 ppm of at least one nitrogen-containing polymer 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 nitrogen-containing polymer or nitrogen-containing polymers.

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 0.3 to 10 ppm of at least one alkylphenol-aldehyde resin and 0.2 to 50 ppm and especially 0.25 to 25 ppm such as 0 , 3 to 20 ppm of at least one nitrogen-containing polymer. The mineral oil distillates according to the invention particularly preferably contain 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 nitrogen-containing polymer or nitrogen-containing polymers.

It is preferred to use 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 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 nitrogen-containing polymer.

The mass ratio between constituent I and constituent II in the inventive additive for mineral oil distillates is preferably between 50: 1 and 1:50, particularly preferably between 10: 1 and 1:10, for example between 4: 1 and 1: 4.

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, such as, for example, 6 to 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, glyoxylic 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-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 ―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 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 -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 alkenyl. With particular preference R ^{5 is} C ₁ -C ₂₀ -alkyl or -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 g / mol, in particular between 1,000 and 10,000 g / mol, 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 are 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.

• a) Kammpolymere, enthaltend Einheiten abgeleitet von Monomeren mit einem C₄- bis C₄₀-Alkylrest und mindestens einem stickstoffhaltigen Comonomer,
• b) Copolymere des Ethylens mit ethylenisch ungesättigten stickstoffhaltigen Comonomeren, und
• c) polymere Polyamine, hergestellt durch Kondensation eines aliphatischen primären Monoamins oder eines N-Alkyl-alkylendiamins mit Epichlorhydrin oder Glycidol.

Particularly suitable nitrogen-containing polymers are

• a) comb polymers containing units derived from monomers having a C ₄ - to C ₄₀ -alkyl radical and at least one nitrogen-containing comonomer,
• b) copolymers of ethylene with ethylenically unsaturated nitrogen-containing comonomers, and
• c) polymeric polyamines prepared by condensation of an aliphatic primary monoamine or an N-alkyl-alkylenediamine with epichlorohydrin or glycidol.

As component IIa) suitable comb polymers are derived in particular from oil-soluble esters of ethylenically unsaturated carboxylic acids, oil-soluble vinyl esters and / or oil-soluble vinyl ethers, which carry a C ₄ - to C ₄₀ -alkyl radical. Particularly suitable polymers are poly (acrylates), poly (methacrylates), poly (maleate) and poly (fumarates), which are esters of acrylic, methacrylic, maleic and / or fumaric acid with C ₄ -C ₄₀ alcohols and in particular with C ₆ - to derive C ₂₂ alcohols. The alkyl radicals are preferably linear or branched, they are preferably saturated. Examples which may be mentioned are n-butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, stearyl acrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, stearyl methacrylate and the like.

Another group of suitable comb polymers IIa) is derived from olefins having 6 to 42 carbon atoms. Preferably, the olefins are linear. The double bond is preferably terminal such as, for example, 1-decane, 1-dodecane, 1-tetradecane, 1-hexadecane. Also preferred are mixtures of different olefins in the chain length range C ₂₀ -C ₂₄ , C ₂₂ -C ₂₈ and C ₂₄ -C ₃₀ .

The comb polymers IIa) contain at least one nitrogen-containing comonomer whose nitrogen is preferably present in the form of an amino, amido, imido or ammonium group and is bonded to the polymer backbone via a hydrocarbon radical. They are preferably amino or ammonium groups which are bonded to the polymer backbone via a C ₂ -C ₁₂ -alkylene radical, which may optionally be interrupted by ester or amide groups. Ammonium groups preferably include salts of primary, secondary and tertiary amines with mineral acids, organic sulfonic acids and preferably with carboxylic acids. Also comonomers carrying quaternary ammonium groups are suitable.

Examples of suitable comonomers are polymerizable unsaturated basic amines such as allylamine and diallylamine, amino-bearing olefins such as p- (2-diethylaminoethyl) styrene, nitrogen-containing heterocycles having exocyclic double bond such as vinylpyridine and vinylpyrrolidone, esters of ethylenically unsaturated carboxylic acids with amino alcohols such as N, N- (dimethylamino ) ethyl acrylate, N, N- (dimethylamino) ethyl methacrylate or N, N- (dimethylamino) propyl methacrylate, amides of diamines with ethylenically unsaturated carboxylic acids such as N, N- (dimethylamino) propylmethacrylamide, N- (aminopropyl) morpholine and their quaternized derivatives such as N , N, N- (trimethylammonium) ethyl methacrylate methosulfate, N, N, N- (trimethylammonium) propyl methacrylate methosulfate and imides of ethylenically unsaturated dicarboxylic acids with polyamines containing 2 to 5 nitrogen atoms, of which preferably only one is in the form of a primary amino group such as N, N -Dimethylaminopropylamin. Particular preference is given to polymers of C ₈ -C ₁₄ -alkyl methacrylate and N, N- (dimethylamino) propylmethacrylamide or N, N- (dimethylamino) propyl methacrylate and also copolymers of C ₈ -C ₁₄ -alkyl acrylate and N, N, N- (trimethylammonium ) propylmethacrylamidmethosulfat. Also suitable are nitrile-bearing monomers such as acrylonitrile and methacrylonitrile.

The molar ratio between the esters of ethylenically unsaturated carboxylic acids, vinyl esters, vinyl ethers and / or olefins on the one hand and the nitrogen-containing comonomers on the other hand is preferably between 20: 1 and 1: 1, for example between 10: 1 and 3: 1. Preferably, these copolymers have a nitrogen content of 0.3 to 5 wt .-%, such as 0.5 to 3 wt .-%.

The comb polymers IIa can also be up to 20 mol% such as 1 to 10 mol% of other comonomers such as α-olefins having 4 to 40 carbon atoms, acrylamide, methacrylamide, C ₁ -C ₂₀ alkylacrylamide and / or C ₁ - C ₂₀ alkyl methacrylamide included.

The comb polymers preferably have molecular weights (Mn) of from 1,000 to 100,000 g / mol, preferably from 5,000 to 50,000 g / mol, by means of gel permeation chromatography in THF against poly (styrene) standards.

The comb polymers IIa) are preferably prepared by direct copolymerization of the comonomers. Alternatively, however, they can also be obtained by polymer-analogous reaction of copolymers of esters of ethylenically unsaturated carboxylic acids, vinyl esters, vinyl ethers and / or olefins which carry a C ₁ - to C ₄₀ -alkyl radical and ethylenically unsaturated carboxylic acids or reactive derivatives thereof such as anhydrides, acid halides or esters lower alcohols having 1 to 4 carbon atoms with hydroxyamines or polyamines. Suitable hydroxyamines are, for example, N, N-dimethylaminoethanol and N-coconut fatty alkylaminoethanol. Suitable polyamines are, for example, N, N-dimethylaminopropylamine N-coconut fatty alkylpropylenediamine and N-tallow fatty alkylpropylenediamine. A further preparation variant is the grafting of the nitrogen-containing comonomers onto polymers of esters of ethylenically unsaturated carboxylic acids, vinyl esters, vinyl ethers and / or olefins which carry a C ₁ - to C ₄₀ -alkyl radical.

Quaternary ammonium group-bearing polymers can be prepared by copolymerization of the polymerizable quaternary ammonium compound or by polymer-analogous reaction of an amino group-bearing polymer with alkylating agents such as alkyl halides or sulfuric acid esters. Particularly preferred are halogen-free alkylating agents such as dimethyl sulfate.

Examples of particularly preferred nitrogen-containing polymers IIa) are copolymers of N, N, N, - (trimethylammonium) ethyl methacrylate methosulfate and 2-ethylhexyl acrylate, copolymers of dodecyl methacrylate and dimethylaminopropylmethacrylamide and alternating copolymers of tetradecene and acrylonitrile.

• i) Alkylaminoacrylate bzw. -methacrylate wie z.B. Aminoethylacrylat, Aminopropylacrylat, Amino-n-butylacrylat, N-Methylaminoethylacrylat, N,N-Dimethylaminoethylacrylat, N,N-(Dimethylamino)propylacrylat, N,N-(Diethylamino)propylacrylat, N,N,N-(Trimethylammonium)ethylacrylatmethosulfat sowie die entsprechenden Methacrylate,
• ii) Alkylacrylamide und -methacrylamide wie Ethylacrylamid, Butylacrylamid, N-Octylacrylamid, N-Propyl.N-methoxyacrylamid, N-Acryloylphthalimid, N-Acryloylsuccinimid, N-Methylolacrylamid sowie die entsprechenden Methacrylamide,
• iii) Vinylamide wie z.B. N-Vinyl-N-methylacetamid, N-Vinylsuccinimid,
• iv) Aminoalklyvinylether wie z. B. Aminopropylvinylether, Diethylaminoethylvinylether, Dimethylaminopropylvinylether,
• v) ethylenisch ungesättigte Amine wie Allylamin, Diallylamin, N-Allyl-N-methylamin, und N-Allyl-N-ethylamin
• vi) eine Vinylgruppe tragende Heterozyklen wie z.B. N-Vinylpyrrolidon, Methylvinylimidazol, 2-Vinylpyridin, 4-Vinylpyridin, 2-Methyl-5-vinylpyridin, Vinylcarbazol, Vinylimidazol, N-Vinyl-2-piperidon, N-Vinylcaprolactam.

The ethylenically unsaturated nitrogen-containing comonomers, which are constituents of the polymers IIb) according to the invention in addition to ethylene, are preferably those monomers which are also suitable for the preparation of the comb polymers IIa) and which have a nitrogen bound to the polymer backbone via a hydrocarbon radical in the form of an amino group. , Amido, imido or ammonium group. For example:

• i) Alkylaminoacrylates or methacrylates such as aminoethyl acrylate, aminopropyl acrylate, amino-n-butyl acrylate, N-methylaminoethyl acrylate, N, N-dimethylaminoethyl acrylate, N, N- (dimethylamino) propyl acrylate, N, N- (diethylamino) propyl acrylate, N, N , N- (trimethylammonium) ethyl acrylate methosulfate and the corresponding methacrylates,
• ii) alkylacrylamides and -methacrylamides such as ethylacrylamide, butylacrylamide, N-octylacrylamide, N-propyl.N-methoxyacrylamide, N-acryloylphthalimide, N-acryloylsuccinimide, N-methylolacrylamide and the corresponding methacrylamides,
• iii) vinylamides, for example N-vinyl-N-methylacetamide, N-vinylsuccinimide,
• iv) Aminoalklyvinylether such. Aminopropylvinylether, diethylaminoethylvinylether, dimethylaminopropylvinylether,
• v) ethylenically unsaturated amines such as allylamine, diallylamine, N-allyl-N-methylamine, and N-allyl-N-ethylamine
• vi) a vinyl group-bearing heterocycles such as N-vinylpyrrolidone, methylvinylimidazole, 2-vinylpyridine, 4-vinylpyridine, 2-methyl-5-vinylpyridine, vinylcarbazole, vinylimidazole, N-vinyl-2-piperidone, N-vinylcaprolactam.

Preferred copolymers IIb) contain, in addition to ethylene, from 0.1 to 15, in particular from 1 to 10, mol% of one or more of the nitrogen-containing comonomers. In addition, they may contain further, for example, one, two or three further ethylenically unsaturated comonomers. Suitable further comonomers are, for example Vinyl esters, acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters, vinyl ethers and olefins. Particularly preferred vinyl esters are vinyl acetate, vinyl propionate, vinyl butyrate, vinyl octanoate, vinyl 2-ethylhexanoate, vinyl laurate and vinyl esters of neocarboxylic acids having 8, 9, 10, 11 or 12 C atoms. Particularly preferred acrylic and methacrylic acid esters are derived from alcohols having 1 to 20 C atoms, in particular having 1 to 4 C atoms, such as methanol, ethanol and propanol. Particularly preferred olefins are those having 3 to 10 C atoms, especially propene, butene, isobutylene, diisobutylene, 4-methylpentene, hexene and norbornene. If the copolymers IIb) contain a further comonomer, its molar fraction is preferably up to 15 mol%, in particular from 1 to 12 mol%, for example from 2 to 10 mol%.

The melt viscosity of these copolymers, measured at 140 ° C., is preferably below 10,000 mPas, in particular between 10 and 1,000 mPas, for example between 20 and 500 mPas.

The copolymerization of the comonomers takes place by known processes (cf. Ullmanns Encyclopadie der Technischen Chemie, 4th Edition, Vol. 19, pages 169 to 178 ). The polymerization in solution, in suspension, in the gas phase and the high-pressure mass polymerization are suitable. Preference is given to the high-pressure mass polymerization, which at pressures of 50 to 400 MPa, preferably 100 to 300 MPa and temperatures of 50 to 350 ° C, preferably 100 to 300 ° C, is performed. The reaction of the comonomers is initiated by free radical initiators (free radical initiators). This class of substances includes, for example, oxygen, hydroperoxides, peroxides and azo compounds such as cumene hydroperoxide, t-butyl hydroperoxide, dilauroyl peroxide, dibenzoyl peroxide, bis (2-ethylhexyl) peroxydicarbonate, t-butyl permalate, t-butyl perbenzoate, dicumyl peroxide, t-butylcumyl peroxide, di ( t-butyl) peroxide, 2,2'-azobis (2-methylpropanonitrile), 2,2'-azobis (2-methylbutyronitrile). The initiators are used individually or as a mixture of two or more substances in amounts of 0.01 to 20 wt .-%, preferably 0.05 to 10 wt .-%, based on the comonomer mixture.

The desired melt viscosity and thus the molecular weight of the copolymers is adjusted for a given composition of the comonomer mixture by varying the reaction parameters pressure and temperature and optionally by adding moderators. As moderators have hydrogen, saturated or unsaturated hydrocarbons, e.g. Propane, propene, aldehydes, e.g. Propionaldehyde, n-butyraldehyde or isobutyraldehyde, ketones, e.g. Acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone or alcohols, e.g. Butanol, proven. Depending on the desired viscosity, the moderators are used in amounts of up to 20% by weight, preferably 0.05 to 10% by weight, based on the comonomer mixture.

The high-pressure mass polymerization is carried out batchwise or continuously in known high-pressure reactors, for example autoclaves or tubular reactors, tube reactors have proven particularly useful. Solvents such as aliphatic hydrocarbons or hydrocarbon mixtures, benzene or toluene may be included in the reaction mixture, although the solvent-free procedure has proven particularly useful. According to a preferred embodiment of the polymerization, the mixture of the comonomers, the initiator and, if used, the moderator, a tubular reactor via the reactor inlet and one or more side branches supplied. In this case, the comonomer streams can be composed differently ( EP-B-0 271 738 and EP-A-0 922 716 ).

Copolymers IIb) which are likewise suitable according to the invention can be prepared by reacting ethylene copolymers which contain acid groups with compounds carrying amino groups. Ethylene copolymers and ethylene terpolymers suitable for this purpose are, for example, those which comprise acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid or maleic anhydride. To prepare a copolymer IIb) according to the invention, these acid group-containing copolymers are present via the acid groups with alkanolamines such as ethanolamine, propanolamine, diethanolamine, N-ethylethanolamine, N, N-dimethylethanolamine, diglycolamine, 2-amino-2-methylpropanolamine and / or polyamines such as ethylenediamine and dimethylaminopropylamine and / or N-alkylalkylenepolyamines such as N-coconut fatty alkylpropylenediamine or the like Implemented ammonium-carrying compounds or mixtures thereof. From 0.1 to 1.2 moles, preferably equimolar amounts, of amine per mole of acid are used.

Both nitrogen-containing ethylene copolymers prepared by direct polymerization and by polymer-analogous reaction can be converted into quaternary ammonium salts by reaction with alkylating agents such as alkyl halides or sulfuric acid esters. Particularly preferred are halogen-free alkylating agents such as dimethyl sulfate.

The polymeric polyamines suitable as component IIc) according to the invention are in particular polyamines having 4 or more, preferably 6 or more, for example 8 or more nitrogen atoms in the molecule. The nitrogen atoms are part of the main chain. The polymer backbone preferably carries alkyl side chains of 8 or more carbon atoms.

The polymeric polyamines are preferably condensation products of amines and epichlorohydrin or glycidol in a molar ratio of 1: 1 to 1: 1.5. Preference is given to polymers based on primary monoamines, in particular alkylamines, and on the basis of N-alkyl-alkylenediamines whose alkyl radicals have 8 to 24 and in particular 8 to 12 C atoms and whose alkylene radical has 2 to 6 C atoms, for example N-alkyl -1,3-propylenediamine. The alkyl radicals are preferably linear. The condensation products IIc) preferably have degrees of polymerization of 2 to 20.

The nitrogen-containing polymers IIa), IIb) as well as IIc), in which the nitrogen is present as a basic amino group, are preferably used as salts and in particular as sulfonic acid salts. Preferred sulfonic acids for salt formation are oil-soluble sulfonic acids such as alkanesulfonic acids, arylsulfonic acids and alkylarylsulfonic acids such as dodecylbenzenesulfonic acid.

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 of solvent. Preferred solvents are higher-boiling aliphatic hydrocarbons, aromatic hydrocarbons, alcohols, esters, ethers and mixtures thereof. In the concentrates, the mixing ratio between the alkylphenol-aldehyde resins of the invention as component I and nitrogen compounds as component II may vary 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.

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 more preferably from 100,000 to 500,000, measured by GPC against poly (styrene) standards. The preparation of suitable polysulfones is for example US 3,917,466 known.

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

The additives according to the invention for mineral oil distillates contain in a preferred embodiment, 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, where the mentioned compounds may be substituted with 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, the alkyl groups mentioned with one or be substituted by several 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.

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 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 paraffin dispersants (constituent IV) which are suitable as further component according to the invention are preferably reaction products of fatty amines with compounds which contain at least one 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 . 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 as well as their mixtures. 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 II comprise 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 bonded to the double bond alkyl radical. 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.

Paraffin dispersants 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 ). Likewise, amides and ammonium salts of aminoalkylene polycarboxylic acids such as nitrilotriacetic acid or ethylenediaminetetraacetic acid with secondary amines are suitable as paraffin dispersants (cf. EP 0 398 101 ). Other paraffin dispersants 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 according to the invention and paraffin dispersants 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 paraffin dispersant.

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 V) may, for example, be represented 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. Particular preference is given to mixtures of n-tetradecan-1-ol and n-hexadecan-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 ,

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 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 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 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) _n A and (AB) _m , where n is a number between 1 and 10 and m is a number between 2 and 10.

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 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 additives of the invention increase the conductivity of mineral oil distillates such as gasoline, kerosene, jet fuel, diesel and heating oil, in particular in oils with 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 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 were 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 that could lead to ash during combustion and thus deposits in the combustion chamber or exhaust system and particle pollution of 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. 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 up to 40% by volume, preferably 1 to 20 vol .-%, especially 2 to 15 such as 3 to 10 vol .-% 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. 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 especially from 90 to 125. Mixtures with especially advantageous properties are those which contain mainly, ie at least 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 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: 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 from that mono [Wt .-%] 14.5 14.4 24.1 di [Wt .-%] 0.3 2.4 5.3 poly [Wt .-%] <0.1 0.1 0.5

The following additives were used:

• (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).
  The molecular weights were determined by means of gel permeation chromatography in THF against poly (ethylene glycol) standards. Resins A1) to A4) were used as 50% settings in Solvent Naphtha, a commercial blend of high boiling aromatic hydrocarbons.
• (B) Characterization of the nitrogen compounds B used
  • B1 copolymer of N, N, N- (trimethylammonium) ethyl methacrylate and 2-ethylhexyl acrylate in a molar ratio of 1: 4 according to EP 0909305 , 20% in higher boiling aromatic solvent.
  • B2 Terpolymer of ethylene, 17 wt .-% vinyl acetate and 8 wt .-% 1-vinyl-2-pyrrolidone having a melt viscosity of 170 mPas at 140 ° C, 50% in higher boiling aromatic solvent.
  • B3 Dimethyl sulfate quaternized terpolymer of ethylene, 14 wt .-% vinyl propionate and 10 wt .-% dimethylaminoethyl methacrylate having a melt viscosity of 220 mPas at 140 ° C, 50% in higher boiling aromatic solvent.
  • B4 Copolymer of N-tallow fatty alkyl-1,3-propylenediamine and epichlorohydrin, 30% in aromatic solvent.

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 of test oil 1 Example no. Dosing rate additive A Dosing rate additive B conductivity [pS / m] @ 22 ° 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 A5 - - 3 2 8 (Cf.) 25 ppm A6 - - 3 1 9 (Cf.) - - 10 ppm B1 9 7 10 (Cf.) - - 25 ppm B1 25 21 11 (Cf.) - - 10 ppm B2 5 3 12 (Cf.) - - 25 ppm B2 9 6 13 (Cf.) - - 10 ppm B3 7 6 14 (Cf.) - - 25 ppm B3 19 16 15 (Cf.) - - 10 ppm B4 8th 4 16 (Cf.) - - 25 ppm B4 22 18 17 (Cf.) - - 50 ppm B4 47 40 18 4 ppm A1 8 ppm B1 77 92 19 10 ppm A1 10 ppm B1 117 136 20 5 ppm A2 10 ppm B4 98 115 21 16 ppm A2 8 ppm B4 242 267 22 8 ppm A2 16 ppm B4 270 312 23 25 ppm A2 15 ppm B4 649 678 24 4 ppm A2 8 ppm B2 84 98 25 4 ppm A2 8 ppm B3 102 124 26 8 ppm A2 16 ppm B3 215 234 27 5 ppm A3 10 ppm B3 95 103 28 10 ppm A3 10 ppm B3 165 185 29 5 ppm A5 15 ppm B3 193 236 30 (Cf.) 10 ppm A6 10 ppm B3 44 38 31 (Cf.) 8 ppm A6 16 ppm B4 36 25 Example no. Dosing rate additive A Dosing rate additive B Conductivity [pS / m] @ 25 ° C @ 10 ° C 32 (Cf.) 25 ppm A1 - - 1 0 33 (Cf.) 10 ppm A2 - - 2 0 34 (Cf.) 25 ppm A2 - - 4 2 35 25 ppm A4 - - 5 3 36 (See) 25 ppm A6 - - 2 1 37 (Cf.) - - 10 ppm B1 5 3 38 (Cf.) - - 20 ppm B1 12 10 39 (Cf.) - - 10 ppm B2 4 2 40 (Cf.) - - 20 ppm B2 8th 7 41 (Cf.) - - 20 ppm B3 14 12 42 (Cf.) - - 20 ppm B4 16 13 43 8 ppm A1 8 ppm B1 94 106 44 8 ppm A1 8 ppm B2 114 128 45 4 ppm A2 8 ppm B2 122 136 46 8 ppm A2 4 ppm B3 118 128 47 4 ppm A4 12 ppm B3 187 205 48 3 ppm A4 7 ppm B4 167 178 49 10 ppm A4 3 ppm B4 102 110 50 (Cf.) 10 ppm A6 10 ppm B2 56 47 51 (Cf.) 5 A6 10 ppm B3 48 43 Example no. Dosing rate additive A Dosing rate additive B Conductivity [pS / m] @ 25 ° C @ 10 ° C 52 10 ppm A2 - - 19 12 53 10 ppm A6 - - 25 18 54 - - 5 ppm B1 60 35 55 - - 5 ppm B4 53 37 56 10 ppm A2 5 ppm B1 152 123 57 10 ppm A2 5 ppm B4 176 140 58 10 ppm A6 5 ppm B1 197 139 59 10 ppm A6 5 ppm B4 223 160

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. In addition, since the additives used also improve other properties of middle distillates, such as, for example, paraffin dispersion and lubricity, a comparable conductivity can be achieved with lower additive dosing with 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 (20)

Mineral oil distillates having a water content of less than 150 ppm and a conductivity of at least 50 pS / m, containing 0.1 to 200 ppm of at least one alkylphenol-aldehyde resin and 0.1 to 200 ppm of at least one nitrogen-containing polymer. The mineral oil distillates of claim 1, wherein the aldehyde used to condense the alkylphenol-aldehyde resin comprises 1 to 12 carbon atoms. Mineral oil distillates according to claim 1 and / or 2, wherein the alkyl group of the alkylphenol-aldehyde resin comprises 1 to 200 carbon atoms. Mineral oil distillates 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. Mineral oil distillates according to one or more of claims 1 to 4, wherein the alkylphenol-aldehyde resin is a repeating structural unit 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 stands. Mineral oil distillates according to one or more of claims 1 to 5, wherein the nitrogen-containing polymers are selected from a) comb polymers containing units derived from monomers having a C ₄ - to C ₄₀ -alkyl radical and at least one nitrogen-containing comonomer, b) copolymers of ethylene with ethylenically unsaturated comonomers containing nitrogen, and c) polymeric polyamines prepared by condensation of an aliphatic primary monoamine or an N-alkyl-alkylenediamine with epichlorohydrin or glycidol. Mineral oil distillates according to claim 6, wherein the nitrogen-containing polymers are derived from oil-soluble esters of ethylenically unsaturated carboxylic acids, oil-soluble vinyl esters and / or oil-soluble vinyl ethers carrying a C ₁ to C ₄₀ alkyl radical. Mineral oil distillates according to claim 6, wherein the nitrogen-containing polymers in addition to ethylene from 0.1 to 15 mol% of nitrogen-containing comonomers selected from i) alkylaminoacrylates or methacrylates, ii) alkylacrylamides and -methacrylamides, iii) vinyl amides, iv) aminoalklyvinyl ethers, v) ethylenically unsaturated amines and / or vi) contain a vinyl group-bearing heterocycles. Mineral oil distillates according to claim 6, wherein the nitrogen-containing polymers condensation products of primary alkylamines or N-alkyl-alkylenediamines whose alkyl radicals 8 to 24 and their alkylene radical has 2 to 6 carbon atoms, and epichlorohydrin or glycidol in a molar ratio of 1: 1 to 1 : 1.5 with degrees of condensation of 2 to 20 are. Mineral oil distillates according to one or more of claims 1 to 9, wherein additionally copolymers of ethylene and 6 to 21 mol% vinyl ester, acrylic esters, methacrylic esters, alkyl vinyl ethers and / or alkenes are included. Mineral oil distillates according to one or more of claims 1 to 10, wherein additionally comb polymers of the formula

contained 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. Mineral oil distillates according to one or more of claims 1 to 11, which additionally contain polyoxyalkylene compounds which are esters, ethers and ether / esters which carry at least one alkyl radical having 12 to 30 C atoms. Mineral oil distillates according to one or more of claims 1 to 12, wherein additionally copolymers are present, in addition to structural units of ethylene Structural units derived from α-olefins having 3 to 24 carbon atoms, containing, and having molecular weights of up to 120,000 g / mol. Mineral oil distillates according to one or more of claims 1 to 13, which additionally contain polysulfones derived from olefins having 6 to 20 carbon atoms. Mineral oil distillates as claimed in one or more of claims 1 to 14, which additionally contain paraffin dispersants which are reaction products of fatty amines with compounds containing at least one acyl group, the fatty amines being compounds of the formula NR ⁶ R ⁷ R ⁸ , where 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 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 - (A-O) _x . Use of compositions containing at least one alkylphenol-aldehyde resin and based on the alkylphenol-aldehyde resin, 0.1 to 10 parts by weight of at least one nitrogen-containing polymer for improving the conductivity of the mineral oil distillate having a water content of less than 150 ppm, so that the mineral oil distillates have a conductivity of at least 50 pS / m. Use of at least one alkylphenol-aldehyde resin for improving the electrical conductivity of mineral oil distillates having a water content of less than 150 ppm and containing 0.1 to 200 ppm of at least one nitrogen-containing polymer in an amount such that the mineral oil distillates have a conductivity of at least 50 pS / m have. A method for improving the electrical conductivity of mineral oil distillates having a water content of less than 150 ppm by containing the mineral oil distillates compositions comprising at least one alkylphenol-aldehyde resin and, based on the alkylphenol-aldehyde resin, 0.1 to 10 parts by weight of at least one nitrogen-containing polymer , so that the mineral oil distillates have a conductivity of at least 50 pS / m. 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 nitrogen-containing polymer by adding 0.1 to 200 ppm of at least one alkylphenol-aldehyde resin to the mineral oil distillates, so that the Mineral oil distillates have a conductivity of at least 50 pS / m. Mineral oil distillate additives having a water content of less than 150 ppm, containing at least one alkylphenol-aldehyde resin and at least one nitrogen-containing polymer selected from a) comb polymers containing units derived from esters of ethylenically unsaturated carboxylic acids, vinyl esters and / or vinyl ethers and at least one nitrogen-containing comonomer, b) copolymers of ethylene with ethylenically unsaturated comonomers containing nitrogen, and c) polymeric polyamines prepared by condensation of an aliphatic primary monoamine or an N-alkylalkylenediamine with epichlorohydrin or glycidol, in the mass ratio 9: 1 to 1: 9 included.