EP1801187A2 - Mineral oils containing detergent additives with improved cold flowability - Google Patents

Abstract

Use of at least an oil-soluble polyoxy alkylene compound comprising an oil soluble, amphiphilic compound containing at least a 10-500C- alkyl or alkenyl and a polar group with two or more nitrogen atoms for improving the cold flow characteristic of mineral oil in a distillating agent containing at least an ash free, a detergent additive containing nitrogen, where the oil-soluble polyoxy alkylene compound is e.g. an oil soluble ester, ether, ether/ester of alkoxylated polyol. Use of at least an oil-soluble polyoxy alkylene compound comprising an oil soluble, amphiphilic compound containing at least a 10-500C- alkyl or alkenyl and a polar group with two or more nitrogen atoms for improving the cold flow characteristic of mineral oil in a distillating agent containing at least an ash free, a detergent additive containing nitrogen, where the oil-soluble polyoxy alkylene compound is an oil soluble ester, ether, ether/ester of alkoxylated polyol with at least three 2-5C-alkylene oxide and polyol containing repetitive alkoxy per hydroxy group or at least two aliphatic 12-30C-hydrocarbon. Independent claims are included for: (1) a composition comprising at least an ash free, detergent additive containing nitrogen, which is an oil soluble, amphiphilic compound containing at least a 10-500C- alkyl- or alkenyl with two or more nitrogen atoms bonded to a polar group, and at least an oil soluble polyoxy alkylene compound, which is an oil soluble ester, ether or ether/ester of alkoxylated polyol with at least three 2-5C-alkylene oxide, and repetitive alkoxy per hydroxyl group; and (2) a distillative agent with a sulfur content of less than 100 ppm and 20-90 vol.% of agent exhibits a distillative boiling range of less than 120[deg]C, comprising the composition (10-10000 ppm) and at least a mineral oil cold flow improver.

Description

The present invention relates to the use of polyoxyalkylene compounds for improving the cold flowability of mineral oil distillates containing detergent additives, as well as to the additive mineral oil distillates.

Increasingly stringent environmental legislation requires ever more sophisticated engine technology to comply with established emission limits. However, occupying engine parts such as the combustion residue valves changes the characteristics of the engine and results in increased emissions as well as increased consumption. Therefore, motor fuels are added to detergent additives which remove such deposits or prevent their formation. These are generally oil-soluble amphiphiles which contain a polar head group in addition to an oil-soluble, temperature-stable hydrophobic radical.

On the other hand, in the course of decreasing world oil reserves, increasingly heavier and thus paraffin-rich crude oils are extracted and processed, which consequently also lead to paraffin-rich fuel oils. The paraffins contained in particular in middle distillates can crystallize on lowering the temperature of the oil and partially agglomerate with the inclusion of oil. This crystallization and agglomeration can cause blockages of the filters in engines and firing systems, especially in winter, which prevents safe metering of the fuels and may possibly lead to a complete interruption of the fuel supply. The paraffin problem is further exacerbated by the environmental reasons to reduce the sulfur content to be carried out hydrogenating desulfurization of fuel oils, which leads to an increased proportion of cold-critical paraffins in the fuel oil.

To improve the cold flow properties middle distillates are often added chemical additives, so-called cold flow improvers or flow improvers, modify the crystal structure and Agglomerationsneigung the precipitated paraffins, so that the so-additive oils still pump or use at temperatures, often more than 20 ° C. lower than non-additized oils. As the cold flow improver, oil-soluble copolymers of ethylene and unsaturated esters, oil-soluble polar nitrogen compounds and / or comb polymers are usually used. In addition, however, more specific additives have been proposed.

WO 03/042 336 discloses additives for low sulfur mineral oil distillates comprising an ester of an alkoxylated polyol and a polar nitrogen containing paraffin dispersant. The additives can be used together with detergent additives.

WO 03/042 337 discloses low sulfur mineral oil distillates having improved cold properties, comprising an ester of an alkoxylated polyol and a copolymer of ethylene and unsaturated esters. The mineral oil distillates may further contain detergent additives.

WO 03/042 338 discloses combinations of polyoxyalkylene compounds and alkylphenol resins as cold additives for middle distillates having a sulfur content of less than 0.05% by weight. The additives can be used together with detergent additives.

EP-A-0 973 848 discloses mixtures of esters of C ₁₀ -C ₄₀ carboxylic acids and alkoxylated monohydric alcohols having more than 10 C atoms with at least one further cold flow improver. These blends are used to improve the cold flow properties of fuel oils. The additives may also contain unspecified detergent additives.

US 5 522 906 discloses gasoline containing a nitrogen-containing detergent additive, a carrier oil based on alkylene oxide adducts of alcohols and esters of polyhydric alcohols or their alkylene oxide adducts.

WO 03/078 553 discloses detergent additives for gasoline containing a nitrogen-containing detergent and optionally a polyether as a solvent.

WO 96/23855 discloses additive mixtures of ashless dispersant additives and carboxylic acids or their esters for improving the lubricity of low-sulfur middle distillates. There is no indication of the common use with flow improvers this font.

As engine technology becomes ever more demanding, as well as increasing demands on the environmental performance of fuel oils and their combustion products, detergent additives are being developed with ever increasing effectiveness. In addition, they are often used in very high dosage rates. It is reported that this reduces, for example, in diesel fuels, the specific consumption and the performance of the engines is increased. However, these additives often have negative effects on the cold flowability of middle distillates and in particular on the efficacy of known cold flow improvers. Especially with middle distillates with low boiling point and simultaneously low aromatic content, it is often difficult or even impossible to adjust in the presence of modern detergent additives using conventional flow improvers a satisfactory cold flow behavior. Thus, in the presence of detergent additives, the paraffin dispersion set by paraffin dispersants is often impaired, without being able to be reconstituted by increased dosage of paraffin dispersant. Often the CFPP measured filterability with cold flow improvers additive oils is significantly reduced in the cold and can be compensated only by greatly increased dosage of the flow improver.

In particular, those detergent additives which are derived from higher polyamines and have, for example, very high molecular weights due to multiple alkylation and / or acylation of these polyamines are particularly problematical. Often problems in the cold additization are also caused by the presence of nitrogen-containing detergent additives derived either from higher polyamines or carrying on their hydrophobic moiety several polyamine groups and thus carrying a comparatively large polar headgroup.

It was therefore an object of the present invention to improve the response of cold flow improvers in middle distillates containing detergent additives. Another object of the invention was to provide a prior art improved detergent additive which does not interfere with the response of cold flow improvers.

Surprisingly, it has now been found that certain oil-soluble polyoxyalkylene compounds counteract or impair this impairment of the effectiveness of conventional cold flow improvers by nitrogen-containing detergent additives.

The invention thus relates to the use of at least one oil-soluble polyoxyalkylene compound,
wherein this polyoxyalkylene compound is an oil-soluble ester, ether or ether / ester of alkoxylated polyols having at least three, derived from alkylene oxides having 2 to 5 carbon atoms, repetitive alkoxy per OH group of the polyol, the at least two aliphatic hydrocarbon radicals having 12 to 30 Bears C atoms,
for improving the response of mineral oil flow improvers in middle distillates containing at least one ashless, nitrogen-containing detergent additive,
which is an oil-soluble, amphiphilic compound comprising at least one alkyl or alkenyl radical attached to a polar group, wherein the alkyl or alkenyl radical comprises 10 to 500 carbon atoms and the polar group comprises 2 or more nitrogen atoms.

Another object of the invention is a process for improving the response of mineral oil flow improvers in middle distillates containing ashless nitrogen-containing detergent additives.
and wherein the ashless nitrogen-containing detergent additives are oil-soluble, amphiphilic compounds comprising at least one alkyl or alkenyl radical attached to a polar group is bonded, where the alkyl or alkenyl radical comprises 10 to 500 C atoms and the polar group comprises 2 or more nitrogen atoms,
by adding to the oil at least one polyoxyalkylene compound which is an oil-soluble ester, ether or ether / ester of alkoxylated polyols having at least three repetitive alkoxy units derived from alkylene oxides having 2 to 5 carbon atoms per OH group of the polyol which is at least carries two aliphatic hydrocarbon radicals having 12 to 30 carbon atoms.

1. a) mindestens ein aschefreies, stickstoffhaltiges Detergenzadditiv, welches eine öllösliche, amphiphile Verbindung ist, die mindestens einen Alkyl- oder Alkenylrest umfasst, der an eine polare Gruppe gebunden ist, wobei der Alkyl- oder Alkenylrest 10 bis 500 C-Atome und die polare Gruppe 2 oder mehr Stickstoffatome umfasst,
   und
2. b) mindestens eine öllösliche Polyoxyalkylenverbindung, welche ein öllöslicher Ester, Ether oder Ether/Ester von alkoxylierten Polyolen mit mindestens drei, sich von Alkylenoxiden mit 2 bis 5 C-Atomen ableitenden, repetitiven Alkoxyeinheiten pro OH-Gruppe des Polyols ist, der mindestens zwei aliphatische Kohlenwasserstoffreste mit 12 bis 30 C-Atomen trägt.

Another object of the invention are additives containing

1. a) at least one ashless nitrogen-containing detergent additive which is an oil-soluble, amphiphilic compound comprising at least one alkyl or alkenyl radical attached to a polar group, wherein the alkyl or alkenyl radical is from 10 to 500 carbon atoms and the polar group Comprises 2 or more nitrogen atoms,
   and
2. b) at least one oil-soluble polyoxyalkylene compound, which is an oil-soluble ester, ether or ether / ester of alkoxylated polyols having at least three, derived from alkylene oxides having 2 to 5 carbon atoms, repetitive alkoxy per OH group of the polyol, the at least two aliphatic Hydrocarbon radicals having 12 to 30 carbon atoms contributes.

The combination of a) and b) is also referred to below as "inventive additive".

1. a) mindestens ein aschefreies, stickstoffhaltiges Detergenzadditiv, welches eine öllösliche, amphiphile Verbindung ist, die mindestens einen Alkyl- oder Alkenylrest umfasst, der an eine polare Gruppe gebunden ist, wobei der Alkyl- oder Alkenylrest 10 bis 500 C-Atome und die polare Gruppe 2 oder mehr Stickstoffatome umfasst,
2. b) mindestens eine öllösliche Polyoxyalkylenverbindung, welche ein öllöslicher Ester, Ether oder Ether/Ester von alkoxylierten Polyolen mit mindestens drei, sich von Alkylenoxiden mit 2 bis 5 C-Atomen ableitenden, repetitiven Alkoxyeinheiten pro OH-Gruppe des Polyols ist, der mindestens zwei aliphatische Kohlenwasserstoffreste mit 12 bis 30 C-Atomen trägt, sowie
3. c) mindestens einen Mineralölkaltfließverbesserer.

Another object of the invention are middle distillates having a sulfur content of less than 100 ppm and a 90% distillation point of below 360 ° C, containing

1. a) at least one ashless, nitrogen-containing detergent additive which is an oil-soluble, amphiphilic compound containing at least one alkyl or alkenyl radical which is bonded to a polar group, wherein the alkyl or alkenyl radical comprises 10 to 500 C atoms and the polar group comprises 2 or more nitrogen atoms,
2. b) at least one oil-soluble polyoxyalkylene compound, which is an oil-soluble ester, ether or ether / ester of alkoxylated polyols having at least three, derived from alkylene oxides having 2 to 5 carbon atoms, repetitive alkoxy per OH group of the polyol, the at least two aliphatic Hydrocarbon radicals having 12 to 30 carbon atoms contributes, as well
3. c) at least one mineral oil flow improver.

Especially affected is the response of flow improvers in middle distillates containing more than 10 ppm of a nitrogen containing detergent additive, especially more than 20 ppm and especially more than 40 ppm such as 50 to 2000 ppm of nitrogen containing detergent additive.

Preferably, the additives of the invention contain from 0.01 to 10 parts by weight, and especially from 0.1 to 5 parts by weight, for example 0.3 to 3 parts by weight of the oil-soluble polyoxyalkylene compound, relative to one part by weight of the nitrogen-containing detergent additive.

Ashless means that the additives in question essentially consist only of elements which form gaseous reaction products during combustion. Preferably, the additives consist essentially only of the elements carbon, hydrogen, oxygen and nitrogen. In particular, ashless additives are substantially free of metals and metal salts.

Preferably, middle distillates 10 to 10,000 ppm and in particular 100 to 3000 ppm of the nitrogen-containing detergent additives are added.

Preferably, the alkyl or alkenyl group imparts oil-solubility to the detergent additives.

Particularly problematic are those detergent additives whose alkyl radical has 15 to 500 carbon atoms and in particular 20 to 350 carbon atoms, for example 50 to 200 carbon atoms. This alkyl radical can be linear or branched, in particular it is branched. In a preferred embodiment, the alkyl radical is derived from oligomers of lower olefins having 3 to 6 C atoms such as propene, butene, pentene or hexene and mixtures thereof. Preferred isomers of these olefins are isobutene, 2-butene, 1-butene, 2-methyl-2-butene, 2,3-dimethyl-2-butene, 1-pentene, 2-pentene and iso-pentene and mixtures thereof. Particular preference is given to propene, isobutene, 2-butene, 2,3-dimethyl-2-butene and mixtures thereof. Preferred mixtures of polyolefins contain more than 50 mol%, in particular more than 70%, for example more than 90 mol% of isobutene. Particularly suitable for the preparation of such detergent additives are highly reactive low molecular weight polyolefins having a proportion of terminal double bonds of at least 75%, especially at least 85% and in particular at least 90% such as at least 95%. Particularly preferred low molecular weight polyolefins are poly (isobutylene), poly (2-butene), poly (2-methyl-2-butene), poly (2,3-dimethyl-2-butene), poly (ethylene-co-isobutylene) and atactic poly (propylene). The molecular weight of particularly preferred polyolefins is between 500 and 3000 g / mol. Such oligomers of lower olefins are accessible for example by polymerization by means of Lewis acids such as BF ₃ and AlCl ₃ , by means of Ziegler catalysts and in particular by means of metallocene catalysts.

The polar component of the detergent additives which are particularly problematic for the response of known cold additives is derived from polyamines having 2 to 20 N atoms. Such polyamines correspond for example to the formula

(R ⁹ ) ₂ N- [AN (R ⁹ )] _q - (R ⁹ )

wherein each R ^{9 is} independently hydrogen, an alkyl or hydroxyalkyl radical of up to 24 carbon atoms, a polyoxyalkylene radical - (AO) _r - or polyiminoalkylene radical - [AN (R ⁹ )] _s - (R ⁹ ) but wherein at least one R ^{9 is} hydrogen, q is an integer from 1 to 19, A is an alkylene radical having 1 to 6 C atoms, r and s independently of one another are from 1 to 50. Usually these are mixtures of polyamines and in particular mixtures of poly (ethylene amines) and / or poly (propyleneamines). Examples which may be mentioned: ethylenediamine, 1,2-propylenediamine, dimethylaminopropylamine, diethylenetriamine (DETA), dipropylenetriamine, triethylenetetramine (TETA), tripropylenetetramine, tetraethylenepentamine (TEPA), tetrapropylenepentamine, pentaethylenehexamine (PEHA) pentapropylenehexamine and heavy polyamines. Heavy polyamines are generally understood as meaning mixtures of polyalkylenepolyamines which, in addition to small amounts of TEPA and PEHA, mainly contain oligomers having 7 or more nitrogen atoms, of which two or more are in the form of primary amino groups. These polyamines often also contain branched structural elements via tertiary amino groups.

Other suitable amines include those which comprise cyclic structural units derived from piperazine. The piperazine units may preferably carry hydrogen at one or both nitrogen atoms, an alkyl or hydroxyalkyl radical having up to 24 carbon atoms or a polyiminoalkylene radical - [AN (R ⁹ )] _s - (R ⁹ ), where A, R ⁹ and s have the meanings given above.

Other suitable amines include alicyclic diamines such as 1,4-di (aminomethyl) cyclohexane and heterocyclic nitrogen compounds such as imidazolines and N-aminoalkylpiperazines such as N- (2-aminoethyl) piperazine.

Also, detergent additives whose polar portion is derived from hydroxyl-bearing polyamines, heterocycle-substituted polyamines, and aromatic polyamines are problematic. Examples which may be mentioned are: N- (2-hydroxyethyl) ethylenediamine, N, N ¹ -bis- (2-hydroxyethyl) ethylene diamine, 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, various isomers of phenylenediamine and naphthalenediamine and mixtures of these amines.

Especially critical for the cold additization of middle distillates are detergent additives based on heavy polyamines, in which in the above formula R ^{9 is} hydrogen and q has values of at least 3, in particular at least 4 such as 5, 6, 7 or higher. Particularly problematic are mixtures of polyamines containing at least 40 wt .-% and in particular at least 60 wt .-%, such as at least 80 wt .-% of higher polyamines having 5 or more nitrogen atoms. Among the particularly effective for the dispersing behavior, for the refrigeration but particularly problematic heavy polyamines are generally understood mixtures of polyalkylenepolyamines which in addition to TEPA and PEHA larger amounts, ie at least 10 wt .-% and in particular at least 30 wt .-%, especially at least 50 wt .-% such as more than 70 wt .-% of oligomers having 7 or more nitrogen atoms.

The oil-soluble alkyl moiety and the polar head group of the detergent additives may be linked together either directly via a C-N or through an ester, amide or imide bond. Accordingly, preferred detergent additives are alkylpolyamines, Mannich reaction products, hydrocarbyl-substituted succinic acid amides and imides, and mixtures of these classes of substances.

The detergent additives linked via C-N bonds are preferably alkylpoly (amines) which are obtainable, for example, by reacting polyisobutylenes with polyamines, for example by hydroformylation and subsequent reductive amination with the abovementioned polyamines. In this case, one or more alkyl radicals may be bound to the polyamine. Detergent additives based on higher polyamines having more than 4 N atoms, for example those having 5, 6, 7 or more N atoms, are particularly critical for the cold addition.

Detergent additives containing amide or imide bonds are obtainable, for example, by reaction of alkenylsuccinic anhydrides with polyamines. Alkenylsuccinic anhydride and polyamine are preferably reacted in a molar ratio of about 1: 0.5 to about 1: 1. The preparation of the underlying Alkenylbernsteinsäureanhydride is usually carried out by addition of ethylenically unsaturated polyolefins or chlorinated polyolefins to ethylenically unsaturated dicarboxylic acids.

For example, alkenyl succinic anhydrides can be prepared by reaction of chlorinated polyolefins with maleic anhydride. Alternatively, the preparation also succeeds by thermal addition of polyolefins to maleic anhydride in an "ene reaction". In this case, highly reactive olefins with a high content of, for example, more than 75% and especially more than 85 mol%, based on the total number of polyolefin molecules, of isomers having a terminal double bond are particularly suitable. The terminal double bonds can be both vinylidene double bonds [-CH ₂ -C (= CH ₂ ) -CH _3] and vinyl double bonds [-CH = C (CH ₃ ) _2] .

For the preparation of alkenylsuccinic anhydrides, the molar ratio of the two reactants in the reaction between maleic anhydride and polyolefin can vary within wide limits. Preferably, it may be between 10: 1 and 1: 5, with molar ratios of 6: 1 to 1: 1 being particularly preferred. Maleic anhydride is preferably used in stoichiometric excess, for example 1.1 to 3 moles of maleic anhydride per mole of polyolefin. Excess maleic anhydride can be removed from the reaction by, for example, distillation.

Since the adducts which are primarily formed by the ene reaction, in turn, contain an olefinic double bond, suitable addition of unsaturated dicarboxylic acids to form so-called bis-maleinates is possible with a suitable reaction procedure. The accessible reaction products have, based on the reacted with unsaturated carboxylic acids fractions of the poly (olefins) on average a Maleinierungsgrad of more than 1, preferably about 1.01 to 2.0 and in particular 1.1 to 1.8 dicarboxylic acid per alkyl radical. Reaction with the abovementioned amines results in products with markedly increased effectiveness as detergent additives. On the other hand, as the degree of maleation increases, so does the impairment of the efficacy of cold flow improvers. When such highly maleated alkenylsuccinic anhydrides are used, shorter-chain polyamines with, for example, 3, 4 or 5 N atoms also lead to said problems in the case of cold additization.

The reaction of alkenyl succinic anhydrides with polyamines leads to products which can carry one or more amide and / or imide bonds per polyamine and depending on the Maleinierungsgrad one or two polyamines per alkyl radical. Alkenylsuccinic anhydride per mole of polyamine is preferably used for the reaction of 1.0 to 1.7 and in particular 1.1 to 1.5, so that free primary amino groups remain in the product. In a further preferred embodiment, alkenyl succinic anhydride and polyamine are reacted equimolarly. In the reaction of polyamines with Alkenylbernsteinsäureanhydriden with a high degree of acylation of 1.1 or more anhydride groups per alkyl radical such as 1.3 or more anhydride groups per alkyl radical also arise polymers that are particularly problematic for the response of cold additives.

Typical and particularly preferred acylated nitrogen compounds are obtained by reacting poly (isobutylene), poly (2-butenyl), poly (2-methyl-2-butenyl) -, poly (2,3-dimethyl-2-butenyl) - or Poly (propenyl) succinic anhydrides having an average of about 1.2 to 1.5 anhydride groups per alkyl radical whose alkylene radicals carry between 50 and 400 carbon atoms, with a mixture of poly (ethylene amines) having at least 3 and preferably about 4 to 12 such as for example, 5 to 7 nitrogen atoms and at least 2 and preferably about 3 to 11 such as 4 to 6 ethylene units available.

Oil-soluble Mannich reaction products based on polyolefin-substituted phenols and polyamines also impair the effectiveness of conventional cold flow improvers. Mannich bases of this kind are prepared by known processes, for example by alkylating phenol and / or salicylic acid with the polyolefins described above, such as, for example, poly (isobutylene), poly (2-butene), poly (2-methyl-2-butene), poly ( 2,3-dimethyl-2-butene) or atactic poly (propylene) and subsequent condensation of the alkylphenol with aldehydes having 1 to 6 carbon atoms such as formaldehyde or its reactive equivalents such as formalin or paraformaldehyde and the above-described polyamines such as TEPA, PEHA or heavy polyamines produced.

The average molecular weight determined by means of vapor pressure osmometry is particularly efficient, but at the same time for the cold additization of middle distillates of particularly critical detergent additives is above 800 g / mol and especially between 2,000 and 20,000 g / mol such as between 3,000 and 15,000 g / mol (measured by GPC against poly (styrene) standards in THF). The average molecular weight of the above-described detergent additives can also be increased via crosslinking reagents and adapted to the intended use. Suitable crosslinking reagents are, for example, dialdehydes such as glutaric dialdehyde, bisepoxides derived, for example, from bisphenol A, dicarboxylic acids and their reactive derivatives such as maleic anhydride and alkenylsuccinic anhydrides, and higher polybasic carboxylic acids and their derivatives such as trimellitic acid, trimellitic anhydride and pyromellitic dianhydride.

In a preferred embodiment, the oil-soluble polyoxyalkylene compounds have at least 3, such as 4, 5 or more aliphatic hydrocarbon radicals. Preferably, these radicals independently of one another have 16 to 26 C atoms, for example 17 to 24 C atoms. The aliphatic hydrocarbon radicals can be linear or branched, preferably they are linear. Further preferably, they are largely saturated; in particular, these are alkyl radicals. Esters are especially preferred.

Particularly suitable polyols according to the invention are polyethylene glycols, polypropylene glycols, polybutylene glycols and their copolymers having a molecular weight of about 100 to about 5,000 g / mol, preferably 200 to 2,000 g / mol. In a particularly preferred embodiment, the oil-soluble polyoxyalkylene compounds are derived from polyols having 3 or more OH groups, preferably from polyols having 3 to about 50 OH groups, for example 4 to 10 OH groups, in particular neopentyl glycol, glycerol, trimethylolethane, trimethylolpropane , Sorbitan, pentaerythritol, and the oligomers having from 2 to 10 monomer units, such as polyglycerol, obtainable therefrom by condensation. Even higher polyols such as sorbitol, sucrose, glucose, fructose and their oligomers such as cyclodextrin are suitable as polyols, provided that their esterified or etherified alkoxylates at least in application-relevant Quantities are oil-soluble. Preferred polyoxyalkylene compounds thus have a branched polyoxyalkylene core to which are attached multiple alkyl-solubilizing alkyl radicals. The polyols are generally reacted with from 3 to 70 mol of alkylene oxide, preferably from 4 to 50, in particular from 5 to 20, mol of alkylene oxide per hydroxyl group of the polyol. Preferred alkylene oxides are ethylene oxide, propylene oxide and / or butylene oxide. The alkoxylation is carried out by known methods.

The fatty acids which are suitable for the esterification of the alkoxylated polyols preferably have 12 to 30 and in particular 16 to 26 C atoms. The alkyl radicals of the fatty acids may be branched or linear; preferred fatty acids carry linear alkyl radicals. Suitable fatty acids are, for example, lauric, tridecane, myristic, pentadecane, palmitic, margarine, stearic, isostearic, arachic and behenic, oleic and erucic acid, palmitoleic, myristoleic, ricinoleic acid and natural fats and oils derived fatty acid mixtures. Preferred fatty acid mixtures contain more than 50 mol% of fatty acids having at least 20 carbon atoms. Preferably, less than 50 mol% of the fatty acids used for the esterification contain double bonds, in particular less than 10 mol%; specifically, they are largely saturated. Esterification may also be carried out starting from reactive derivatives of the fatty acids such as esters with lower alcohols (e.g., methyl or ethyl esters) or anhydrides.

For the purposes of the present invention, the term "iodine value" of the fatty acid or of the fatty alcohol used is understood to be largely saturated by up to 5 g of I per 100 g of fatty acid or fatty alcohol.

For the esterification of the alkoxylated polyols, it is also possible to use mixtures of fatty acids with fat-soluble, polybasic carboxylic acids. Examples of suitable polybasic carboxylic acids are dimer fatty acids, alkenylsuccinic acids and aromatic polycarboxylic acids and derivatives thereof such as anhydrides and C ₁ - to C ₅ -esters. Alkenylsuccinic acid and its derivatives with alkyl radicals having 8 to 200, in particular 10 to 50, carbon atoms are preferred. Examples are dodecenyl, octadecenyl and poly (isobutenyl) succinic anhydride. The polybasic carboxylic acids are preferably used here to lower levels of up to 30 mol%, preferably 1 to 20 mol%, in particular 2 to 10 mol%.

Ester and fatty acid are used for the esterification based on the content of hydroxyl groups on the one hand and carboxyl groups on the other hand in the ratio of 1.5: 1 to 1: 1.5, preferably in the ratio of 1.1: 1 to 1: 1.1 and in particular equimolar.

In a preferred embodiment, after the alkoxylation of the polyol, the terminal hydroxyl groups are converted, for example, by oxidation or by reaction with dicarboxylic acids into terminal carboxyl groups. By reaction with fatty alcohols having 8 to 50, in particular 12 to 30, especially 16 to 26 carbon atoms, polyoxyalkylene esters according to the invention are likewise obtained. Preferred fatty alcohols or fatty alcohol mixtures contain more than 50 mol% of fatty alcohols having at least 20 carbon atoms. Preferably, less than 50 mol% of the fatty alcohols used for the esterification contain double bonds, in particular less than 10 mol%; specifically, they are largely saturated. Also, esters of alkoxylated fatty alcohols with fatty acids which contain the abovementioned proportions of poly (alkylene oxides) and whose fatty alcohol and fatty acid have the abovementioned alkyl chain lengths and degrees of saturation are suitable according to the invention.

The esterification is carried out by conventional methods. Has proven particularly useful the reaction of polyol with fatty acid, optionally in the presence of catalysts such as para-toluenesulfonic acid, C ₂ - to C ₅₀ -alkylbenzenesulfonic acids, methanesulfonic acid or acidic ion exchangers. The separation of the water of reaction can be carried out by distillation by direct condensation or preferably by azeotropic distillation in the presence of organic solvents, in particular aromatic solvents such as toluene, xylene or higher boiling mixtures such as ^® Shellsol A, ^® Shellsol B, ^® Shellsol AB or Solvent Naphtha. The esterification is preferably carried out essentially completely, ie for the esterification 1.0 to 1.5 moles of fatty acid per mole of hydroxyl groups are used. The acid number of the esters is generally below 15 mg KOH / g, preferably below 10 mg KOH / g, especially below 5 mg KOH / g. The OH number of the esters is preferably below 20 mg KOH / g and especially below 10 mg KOH / g. As complete esterification as possible has proven to be advantageous for efficient effectiveness in conjunction with detergent additives. Furthermore, this prevents the additized middle distillate unwanted emulsions with optionally in storage containers forms present water.

Furthermore, the alkoxylated polyols described above can be converted by etherification with fatty alcohols having 8 to 50, in particular 12 to 30, especially 16 to 26 C-atoms in accordance with the invention suitable polyoxyalkylene compounds. The preferred fatty alcohols are linear and largely saturated. Preferably, the etherification takes place completely or at least largely completely. The etherification is carried out by known methods.

Particularly preferred polyoxyalkylene compounds are derived from polyols having 3, 4 and 5 OH groups, which carry about 5 to 10 mol of structural units derived from ethylene oxide per hydroxyl group of the polyol and are largely completely esterified with largely saturated C ₁₇ -C ₂₄ fatty acids. Further particularly preferred polyoxyalkylene compounds are polyethylene glycols which have been esterified with largely saturated C ₁₇ -C ₂₄ -fatty acids and have molecular weights of about 350 to 1,000 g / mol. Examples of particularly suitable polyoxyalkylene compounds are stearic and especially behenic acid esterified polyethylene glycols having molecular weights between 350 and 800 g / mol; Neopentyl glycol 14-ethylene oxide distearate (neopentyl glycol alkoxylated with 14 moles of ethylene oxide and then esterified with 2 moles of stearic acid), and especially neopentyl glycol 14-ethylene oxide dibehenate; Glycerol 20-ethylene oxide tristearate, glycerol 20-ethylene oxide dibehenate, and especially glycerol 20-ethylene oxide tribehenate; Trimethylolpropane tribehenate 22-ethylene oxide; Sorbitan 25-ethylene oxide tristearate, sorbitan 25-ethylene oxide tetrastearate, sorbitan 25-ethylene oxide tribehenate, and especially sorbitan 25-ethylene oxide tetrabehenate; Pentaerythritol-30-ethylene oxide tribehenate, pentaerythritol-30-ethylene oxide tetrastearate, and especially pentaerythritol-30-ethylene oxide tetrabehenate and pentaerythritol-20-ethylene oxide-10-propylene oxide tetrabehenate.

The quantitative ratio between the detergent additive and the polyoxyalkylene compound in the additized oil can vary within wide limits. An insert of 0.01 to 10 parts by weight, in particular 0.1 to 5 parts by weight, has proven particularly useful For example, 0.3 to 3 parts by weight of polyoxyalkylene compound per part by weight of detergent additive, each based on the active ingredient.

Suitable flow improvers used in the middle distillates according to the invention are, in particular, one or more of the following substance classes III to VII, preference being given to using ethylene copolymers (constituent III) or mixtures thereof with one or more of constituents IV to VII. Mixtures of ethylene copolymers (constituent III) and alkylphenol-aldehyde resins (constituent V), of ethylene copolymers (constituent III) and comb polymers (constituent VI) and of ethylene copolymers (constituent III) and olefin (co ) polymers (component VII). Mixtures of ethylene copolymers (constituent III) with constituents IV and V or constituents IV and VI have proven particularly suitable for the paraffin dispersion.

Preferred cold flow improvers as constituent III are copolymers of ethylene and olefinically unsaturated compounds. Suitable ethylene copolymers are, in particular, those which contain, in addition to ethylene, from 8 to 21 mol%, in particular from 10 to 18 mol%, of olefinically unsaturated comonomer compounds.

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 and oil mixtures preferably contain 0.1 to 25, preferably 0.5 to 10 parts by weight of ethylene copolymers per part by weight of the additive combination according to the invention.

Other cold flow improvers which are suitable are oil-soluble polar nitrogen compounds (constituent IV). These are preferably reaction products of fatty amines with compounds containing an acyl group. The preferred amines are compounds of the formula NR ⁶ R ⁷ R ⁸ , in which R ⁶ , R ⁷ and R ^{8 may be} identical or different, and at least one of these groups is C ₈ -C ₃₆ -alkyl, C ₆ - C ₃₆ -cycloalkyl, C ₈ -C ₃₆ -alkenyl, in particular C ₁₂ -C ₂₄ -alkyl, C ₁₂ -C ₂₄ -alkenyl or cyclohexyl, and the other groups are either hydrogen, C ₁ -C ₃₆ -alkyl, C ₂ -C ₃₆ alkenyl, cyclohexyl, or a group of the formulas - (AO) _x -E or - (CH ₂ ) _n -NYZ, where A is an ethyl or propyl group, x is a number from 1 to 50, E = H, C ₁ -C ₃₀ -alkyl, C ₅ -C ₁₂ -cycloalkyl or C ₆ -C ₃₀ -aryl, and n = 2, 3 or 4, and Y and Z independently of one another are H, C ₁ -C ₃₀ Alkyl or - (AO) _x . The alkyl and alkenyl radicals can be linear or branched and contain up to two double bonds. They are preferably linear and substantially saturated, ie they have iodine numbers of less than 75 gl ₂ / g, preferably less than 60 gl ₂ / g and in particular between 1 and 10 gl ₂ / g. Particularly preferred are secondary fatty amines in which two of the groups R ⁶ , R ⁷ and R ^{8 are} C ₈ -C ₃₆ -alkyl, C ₆ -C ₃₆ -cycloalkyl, C ₈ -C ₃₆ -alkenyl, in particular C ₁₂ -C ₂₄ alkyl, C ₁₂ -C ₂₄ alkenyl or cyclohexyl. Suitable fatty amines are, for example, octylamine, decylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, eicosylamine, behenylamine, didecylamine, didodecylamine, ditetradecylamine, dihexadecylamine, dioctadecylamine, dieicosylamine, dibehenylamine and mixtures thereof. Specifically, the amines contain chain cuts based on natural raw materials such as coco fatty amine, tallow fatty amine, hydrogenated tallow fatty amine, dicocosfettamine, ditallow fatty amine and di (hydrogenated tallow fatty amine). Particularly preferred amine derivatives are amine salts, imides and / or amides such as, for example, amide ammonium salts of secondary fatty amines, in particular dicocosfettamine, ditallow fatty amine and distearylamine.

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, ltaconic, 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 middle distillate to be additive 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. The molecular weights of the polymeric carbonyl compounds are preferably between 400 and 20,000, more preferably between 500 and 10,000, for example between 1,000 and 5,000.

Oil-soluble polar nitrogen compounds which have been obtained by reaction of aliphatic or aromatic amines, preferably long-chain aliphatic amines, with aliphatic or aromatic mono-, di-, tri- or tetracarboxylic acids or their anhydrides have proven particularly suitable (cf. US 4 211 534 ). Similarly, amides and ammonium salts of aminoalkylene polycarboxylic acids such as nitrilotriacetic acid or ethylenediaminetetraacetic acid with secondary amines are suitable as oil-soluble polar nitrogen compounds (cf. EP 0 398 101 ). Other Oil-soluble polar nitrogen compounds are copolymers of maleic anhydride with 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 inventive ethylene copolymers III and oil-soluble polar nitrogen compounds as constituent IV may vary depending on the application. Such additive mixtures preferably contain 0.1 to 10 parts by weight, preferably 0.2 to 5 parts by weight, based on the active compounds, of at least one oil-soluble polar nitrogen compound per part by weight of the additive combination according to the invention.

Also suitable as flow improvers are alkylphenol-aldehyde resins as constituent V. These are, in particular, those alkylphenol-aldehyde resins which are derived from alkylphenols having one or two alkyl radicals in 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 generally understood to mean hydrocarbon radicals as defined below for the constituent V) may be identical or different in the alkylphenol-aldehyde resins which can be used in the process according to the invention, they may be saturated or unsaturated and have 1 to 200, preferably 1 to 20, in particular 4-16, such as 6-12 carbon atoms; it is preferably n-, iso- and tert-butyl, n- and isoPentyl-, n- and iso-hexyl, n- and iso-octyl, n- and iso-nonyl, n- and iso-decyl, n- and iso-dodecyl, tetradecyl, hexadecyl, octadecyl, tripropenyl, tetrapropenyl, poly (propenyl) - and poly (isobutenyl) radicals. In a preferred embodiment, mixtures of alkylphenols having different alkyl radicals are used for the preparation of the alkylphenol resins. For example, resins are on Basis of butyphenol on the one hand and octyl, nonyl and / or dodecylphenol in a molar ratio of 1:10 to 10: 1 on the other hand particularly proven.

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

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

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

worin R¹¹ für C₁-C₂₀₀-Alkyl oder -Alkenyl, O-R¹⁰ oder O-C(O)-R¹⁰, R¹⁰ für C₁-C₂₀₀-Alkyl oder -Alkenyl und n für eine Zahl von 2 bis 100 steht, enthalten. R¹⁰ steht bevorzugt für C₁-C₂₀-Alkyl oder -Alkenyl und insbesondere für C₄-C₁₆-Alkyl oder -Alkenyl wie beispielsweise für C₆-C₁₂-Alkyl oder -Alkenyl. Besonders bevorzugt steht R¹¹ 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 ^{11 is} C ₁ -C ₂₀₀ alkyl or alkenyl, OR ¹⁰ or OC (O) -R ¹⁰ , R ^{10 is} C ₁ -C ₂₀₀ alkyl or alkenyl and n is a number from 2 to 100, contain. R ¹⁰ stands preferably 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. With particular preference R ^{11 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.

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. Also, fatty acids and their derivatives such as esters with lower alcohols having 1 to 5 carbon atoms such as ethanol and especially methanol are suitable as solvents. 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. For neutralization, amines and / or aromatic bases are preferably used, since they can remain in the product; Metal ions containing and thus ash-forming salts are usually separated.

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.

Likewise suitable as flow improvers comb polymers (component VI), 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, for example 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and mixtures thereof. Also, 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-decan-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 ,

Also suitable as flow improvers are homo- and copolymers of olefins having 2 to 30 carbon atoms (constituent VII). These 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 olefins is preferably between 15 and 50 mol%, more preferably between 20 and 35 mol% and especially between 30 and 45 mol%. These copolymers can also be minor amounts, e.g. up to 10 mol% of other comonomers such as e.g. contain non-terminal olefins or non-conjugated olefins. Particularly preferred are ethylene-propylene copolymers. Further preferred are copolymers of various olefins having 5 to 30 carbon atoms such as poly (hexene-co-decene). The olefin homo- and copolymers can be prepared by known methods, e.g. 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 mixing ratio between the additives according to the invention 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.

For ease of handling, the additives according to the invention are preferably used as concentrates which contain from 10 to 95% by weight and preferably from 20 to 80% by weight, for example from 25 to 60% by weight, of solvent. Preferred solvents are higher-boiling, low-viscosity aliphatic, aromatic and alkylaromatic hydrocarbons, alcohols, esters, ethers and mixtures thereof. Such concentrates preferably contain from 0.01 to 10 parts by weight, preferably from 0.1 to 5 parts by weight, for example from 0.3 to 3 parts by weight of the polyoxyalkylene compound per part by weight of detergent additive.

The polyoxyalkylene compounds of the present invention improve the response of detergent-containing middle distillates such as kerosene, jet-fuel, diesel, and fuel oil to conventional flow improvers for lowering pour point and CFPP and improving paraffin dispersion.

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, boiling in the range of about 150 to 450 ° C and in particular in the range of about 170 to 390 ° C, for example kerosene, jet fuel, diesel and fuel oil. Typically, middle distillates contain about 5 to 50 wt .-%, such as about 10 to 35 wt .-% n-paraffins, of which the longer-chain crystallize on cooling and can affect the flowability of the middle distillate. Particularly advantageous are the compositions of the invention in middle aromatics with low aromatic content of less than 21 wt .-%, such as less than 19 wt .-%. The compositions according to the invention are furthermore particularly advantageous in low boiling end middle distillates, ie in middle distillates which have 90% distillation points below 360 ° C., in particular 350 ° C. and in special cases below 340 ° C. and further in such middle distillates, the boiling ranges between 20 and 90%. Distillation volume of less than 120 ° C and in particular less than 110 ° C have. 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, for example up to 40% by volume, preferably 1 to 20% by volume, especially 2 to 15, for example 3 to 10% by volume of the oils of animal and / or vegetable origin described in more detail below such as fatty acid methyl esters.

The compositions according to the invention are also suitable for improving the cold properties of detergent additives containing 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, palm and soybeans and their mixtures with rapeseed oil are preferred.

Particularly suitable as biofuels are lower alkyl esters of fatty acids. For example, commercially available mixtures of the ethyl, propyl, butyl and especially methyl esters of fatty acids having 14 to 22 carbon atoms, for example of lauric acid, myristic acid, palmitic acid, palmitoleic acid, Stearic acid, oleic acid, elaidic acid, petroselinic acid, ricinoleic acid, elaeostearic acid, linoleic acid, linolenic acid, 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 contain mainly, ie at least 50% by weight of methyl esters of fatty acids having 16 to 22 carbon atoms and 1, 2 or 3 double bonds contain. The preferred lower alkyl esters of fatty acids are the methyl esters of oleic, linoleic, linolenic and erucic acids.

The additives can be used alone or together with other additives, eg with other pour point depressants or dewaxing aids, with other detergents, with antioxidants, cetane number improvers, dehazers, demulsifiers, dispersing agents, defoamers, colorants, corrosion inhibitors, lubricity additives, sludge inhibitors, odorants and / or additions to the cloud point.

Examples Improvement of the cold flowability of middle distillates

To evaluate the effect of the additives of the present invention on the cold flow properties of middle distillates, detergent additives (A) having various polyoxyalkylene compounds (B) and ethylene copolymers (C) and paraffin dispersants (D) having the characteristics given below were used.

The suppression of the negative effect of the detergent additives on known cold flow improvers for mineral oils and mineral oil distillates by polyoxyalkylene compounds is firstly described by means of the CFPP test (Cold Filter Plugging Test according to EN 116).

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

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

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

In addition, immediately after cold storage, the lower 20% by volume is isolated and the cloud point determined according to IP 3015. Only a small deviation of the cloud point of the lower phase (CP _KS ) from the blank value of the oil shows a good paraffin dispersion. Table 1: Characterization of the test oils: The test oils used were current middle distillates from European refineries. The CFPP value was 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 was carried out in accordance with DIN EN 12916 (November 2001 edition) Test oil 1 Test oil 2 Test oil 3 Test oil 4 distillation IBP [° C] 192 186 165 184 20% [° C] 250 222 228 225 90% [° C] 322 324 335 338 (90-20)% [° C] 72 102 107 113 FBP [° C] 347 352 359 363 Cloud Point [° C] -8.0 -8.9 -4.4 -6.7 CFPP [° C] -10 -10 -5 -9 Density @ 15 ° C [g / cm ³ ] 0.835 .8307 .8273 .8340 Sulfur content [ppm] <10 <10 15 31 Aromatic content [% by weight] 19.6 18.8 22.8 22.7 of which mono [% by weight] 18.0 18.2 20.6 20.7 di [% by weight] 1.6 0.6 2.1 2.0 poly [% by weight] <0.1 <0.1 0.1 <0.1

The following additives were used: (A) Characterization of the detergent additives used

As detergent additives A, various reaction products of alkenyl succinic anhydrides listed in Table 2 (degree of maleation about 1.2 to 1.3) based on highly reactive polyolefins (molecular weight see Table 2, proportion of terminal double bonds> 90%) with polyamines were used. Alkenyl succinic anhydride and polyamine were reacted thereto in a molar ratio of 1.0 to 1.5 moles of acid anhydride groups (SA) per mole of polyamine (see Table 2). For better meterability, the detergent additives were used as 33% solutions in higher boiling aromatic solvent; in the However, Tables 2 to 4 for the detergent additives indicated dosage rates refer to the active ingredient used.

(B) Characterization of the polyoxyalkylene compounds used

• B1) Glycerol 20-ethylene oxide tribehenate, 50% in solvent naphtha.
• B2) Glycerol-28-ethylene oxide tristearate, 50% in solvent naphtha
• B3) Pentaerythritol 30-ethylene oxide tetrabehenate, 50% in Solvent Naphtha
• B4) Polyethylene glycol 600 dibehenate, 50% in solvent naphtha

In Examples B1) to B3), the numbers -20-, -28- and -30- indicate the number of moles of alkylene oxide per mole of glycerol. In Example B4), the number -600- indicates the molecular weight of the polyethylene glycol used for the esterification.

Characterization of the further flow improvers

• C1) Terpolymer of ethylene, 30% by weight of vinyl acetate and 8% by weight of vinyl neodecanoate with a melt viscosity V ₁₄₀ of 95 mPas, measured at 140 ° C., 65% in kerosene
• C2) mixture of identical parts of C1) and a copolymer of ethylene and 32 wt .-% vinyl acetate with a measured at 140 ° C melt viscosity V ₁₄₀ of 125 mPas, 56% in kerosene.

• D1) Mixture of 2 parts of reaction product of a copolymer of C ₁₄ / C ₁₆ -α-olefin and maleic anhydride with 2 equivalents of hydrogenated Ditalgfettamin with one part of nonylphenol-formaldehyde resin, 50% in Solvent Naphtha.
• D2) Reaction product of ethylenediaminetetraacetic acid with 4 equivalents of ditallow fatty amine to the amide ammonium salt prepared according to EP 0 398 101 , 50% in solvent naphtha.
• D3) Mixture of equal parts of a reaction product of phthalic anhydride and 2 equivalents of di (hydrogenated tallow fat) amine with a copolymer of fumaric acid ditetradecylester, 50% in Solvent Naphtha.

The determination of the CFPP values in test oil 1 was carried out after addition of the oil with 200 ppm C2 and 150 ppm D1. Table 2: Cold flow improvement in test oil 1 example Detergent additive (DA) CFPP in test oil 1 / ° C polyolefin Mw polyolefin polyamine mol of SA / mol of polyamine Dosing rate DA / ppm without DA with DA with DA +50 ppm B1 1 PIB 700 TEPA 1.0 150 -29 -25 -28 2 PIB 700 TEPA 1.4 150 -29 -26 -28 3 PIB 1000 PEHA 1.0 150 -29 -22 -29 4 PIB 1000 PEHA 1.5 150 -29 -21 -28 5 PIB 1000 PAM 1.0 150 -29 -18 -30 6 PIB 1000 PAM 1.3 150 -29 -15 -28 7 APP 1150 TEPA 1.0 150 -29 -25 -28 8th APP 1150 TEPA 1.5 150 -29 -25 -30 9 APP 1150 PEHA 1.1 150 -29 -24 -30 10 APP 1150 PEHA 1.5 150 -29 -26 -28 11 APP 1150 PAM 1.0 150 -29 -20 -28 12 APP 1150 PAM 1.5 150 -29 -20 -28 13 P2B 1000 TEPA 1.0 150 -29 -21 -29 14 P2B 1000 TEPA 1.3 150 -29 -20 -27 15 P2B 1200 PEHA 1.0 150 -29 -20 -28 16 P2B 1200 PEHA 1.4 150 -29 -18 -28 17 P2B 1000 PAM 1.1 150 -29 -11 -29 18 P2B 1000 PAM 1.4 150 -29 -14 -30 DA = detergent additive; PIB = poly (isobutylene); APP = atactic poly (propylene); P2B = poly (butene) from a mixture of different butene isomers with a proportion of 2-butene of about 80%; TEPA = tetraethylenepentamine; PEHA = pentaethylenehexamine; PAM = heavy polyamine

In the examples of the following Tables 3 to 5 as detergent additive A1, the reaction product of poly (isobutenyl) succinic anhydride and pentaethylenehexamine according to Table 2, Example 3, as detergent additive A2, the reaction product of poly (isobutenyl) succinic anhydride and pentaethylenehexamine according to Table 2, Example 4 and used as detergent additive A3, the reaction product of poly (butenyl) succinic anhydride and heavy polyamines according to Table 2, Example 18. Table 3: Cold Flow Improvement in Test Oil 2 example additives Test oil 2 A B C D CFPP [° C] 19 (See) - - 75 ppm C2 - -14 20 (Cf.) - - 100 ppm C2 - -19 21 (Cf.) - - 150 ppm C1 - -20 22 (See) - - 75 ppm C1 150 D1 -21 23 (Cf.) - - 100 ppm C1 150 D1 -29 24 (Cf.) - - 150 ppm C1 150 D1 -31 25 (Cf.) 50 A1 - 75 ppm C1 150 D1 -14 26 (Cf.) 50 A1 - 100 ppm C1 150 D1 -19 27 (Cf.) 50 A1 - 150 ppm C1 150 D1 -20 28 (Cf.) 50 A1 - 150 ppm C1 250 D1 -20 29 50 A1 25 B1 75 ppm C1 150 D1 -23 30 50 A1 25 B1 100 ppm C1 150 D1 -30 31 50 A1 25 B1 150 ppm C1 150 D1 -32 32 50 A1 25 B4 75 ppm C1 150 D1 -19 33 50 A1 25 B4 100 ppm C1 150 D1 -27 34 50 A1 25 B4 150 ppm C1 150 D1 -30 35 (Cf.) 50 A2 - 75 ppm C1 150 D1 -15 36 (See) 50 A2 - 100 ppm C1 150 D1 -12 37 (Cf.) 50 A2 - 150 ppm C1 150 D1 -20 38 (Cf.) 50 A2 - 150 ppm C1 250 D1 -21 39 50 A2 25 B1 75 ppm C1 150 D1 -22 40 50 A2 25 B1 100 ppm C1 150 D1 -28 41 50 A1 25 B1 150 ppm C1 150 D1 -30 example Additives [ppm] Test oil 3 (CP -4.4 ° C) A B C D CFPP [° C] Sediment [vol.%] Appearance oil phase CP _KS [° C] 42 (Cf.) - - 400 C2 200 D1 -20 2 cloudy -3.1 43 (Cf.) - - 535 C2 265 D1 -22 2 cloudy -3.2 44 (Cf.) 40 A2 - 400 C2 200 D1 -17 20 cloudy 0.2 45 (Cf.) 40 A2 - 535 C2 265 D1 -18 10 cloudy -1.2 46 40 A2 25 B1 400 C2 200 D1 -21 2 cloudy -3.3 47 40 A2 25 B1 535 C2 265 D1 -24 2 cloudy -2.9 48 40 A2 50 B1 400 C2 200 D1 -22 2 cloudy -3.0 49 40 A2 50 B1 535 C2 265 D1 -24 2 cloudy -2.9 50 40 A2 50 B2 400 C2 200 D1 -21 0 cloudy -1.4 51 40 A2 50 B2 535 C2 265 D1 -22 0 cloudy -2.3 52 40 A2 50 B4 400 C2 200 D1 -19 4 cloudy -2.4 53 40 A2 50 B4 535 C2 265 D1 -21 3 cloudy -3.2 54 (Cf.) 50 A3 - 400 C2 200 D1 -15 46 clear +2.4 55 (Cf.) 50 A3 - 535 C2 265 D1 -19 48 clear +1.6 56 50 A3 100 B1 400 C2 200 D1 -30 0 cloudy -2.4 57 50 A3 100 B1 535 C2 265 D1 -21 0 cloudy -3.1 58 50 A3 200 B1 400 C2 200 D1 -22 0 cloudy -3.1 59 50 A3 200 B4 400 C2 200 D1 -19 4 cloudy -0.1 60 50 A3 200 B4 535 C2 365 D1 -20 2 cloudy -1.6 example additives Test oil 4 A B C D CFPP [° C] 61 (Cf.) - - 50 ppm C1 - -12 62 (Cf.) - - 100 ppm C1 - -14 63 (Cf.) - - 200 ppm C1 - -20 64 (Cf.) 75 ppm A3 - 50 ppm C1 - -9 65 (Cf.) 75 ppm A3 - 100 ppm C1 - -10 66 (Cf.) 75 ppm A3 - 200 ppm C1 - -12 67 75 ppm A3 50 ppm B1 50 ppm C1 - -13 68 75 ppm A3 50 ppm B1 100 ppm C1 - -15 69 75 ppm A3 40 ppm B3 50 ppm C1 - -12 70 75 ppm A3 40 ppm B3 100 ppm C1 - -14 71 (Cf.) - - 50 ppm C1 150 ppm D1 -22 72 (Cf.) - - 100 ppm C1 150 ppm D1 -28 73 (Cf.) - - 200 ppm C1 150 ppm D1 -30 74 (Cf.) 100 ppm A2 - 50 ppm C1 150 ppm D1 -16 75 (Cf.) 100 ppm A2 - 100 ppm C1 150 ppm D1 -18. 76 (Cf.). 100 ppm A2 - 200 ppm C1 150 ppm D1 -19 77 100 ppm A2 50 ppm B1 50 ppm C1 150 ppm D1 -23 78 100 ppm A2 50 ppm B1 100 ppm C1 150 ppm D1 -27 79 100 ppm A2 50 ppm B3 50 ppm C1 150 ppm D1 -24 80 100 ppm A2 50 ppm B3 100 ppm C1 150 ppm D1 -30 81 (Cf.) - - 50 ppm C1 150 ppm D2 -21 82 (Cf.) - - 100 ppm C1 150 ppm D2 -26 83 (Cf.) - - 200 ppm C1 150 ppm D2 -27 84 (Cf.) 100 ppm A2 - 50 ppm C1 150 ppm D2 -14 85 (Cf.) 100 ppm A2 - 100 ppm C1 150 ppm D2 -15 86 (Cf.) 100 ppm A2 - 200 ppm C1 150 ppm D2 -17 87 100 ppm A2 40 ppm B1 50 ppm C1 150 ppm D2 -22 88 100 ppm A2 40 ppm B1 100 ppm C1 150 ppm D2 -26 89 100 ppm A2 50 ppm B4 50 ppm C1 150 ppm D3 -20 90 100 ppm A2 50 ppm B4 100 ppm C1 150 ppm D3 -24

The experiments show that the impairment of cold flow properties such as, for example, the CFPP value and the paraffin dispersion of middle distillates additized with flow improvers can only be compensated by adding the polyoxyalkylene compounds according to the invention. By higher dosage of the flow improver alone, this result can not be achieved.

Claims (33)

Use of at least one oil-soluble polyoxyalkylene compound,
wherein this polyoxyalkylene compound is an oil-soluble ester, ether or ether / ester of alkoxylated polyols having at least three, derived from alkylene oxides having 2 to 5 carbon atoms, repetitive alkoxy per OH group des_ polyol, the at least two aliphatic hydrocarbon radicals having 12 to 30 Bears C atoms,
for improving the response of mineral oil flow improvers in middle distillates containing at least one ashless, nitrogen-containing detergent additive,
which is an oil-soluble, amphiphilic compound comprising at least one alkyl or alkenyl radical attached to a polar group, wherein the alkyl or alkenyl radical comprises 10 to 500 carbon atoms and the polar group comprises 2 or more nitrogen atoms. Use according to claim 1, wherein the middle distillates contain more than 10 ppm of at least one ashless, nitrogen-containing detergent additive. Use according to claim 1 and / or 2, wherein based on one part by weight of the ashless nitrogen-containing detergent additive 0.01 to 10 parts by weight of at least one oil-soluble polyoxyalkylene compound are used. Use according to one or more of claims 1 to 3, wherein the alkyl or alkenyl radical of the detergent additive is derived from oligomers of lower olefins having 3 to 6 C atoms. Use according to one or more of claims 1 to 4, wherein the alkyl or alkenyl radical of the detergent additive comprises 15 to 500 carbon atoms. Use according to one or more of claims 1 to 5, wherein the detergent additive is derived from an alkenyl succinic anhydride having a Maleinierungsgrad, based on the reacted with unsaturated carboxylic acids portions of the poly (olefins), of the average more than 1 dicarboxylic acid per alkyl moiety. Use according to one or more of claims 1 to 6, wherein the polar group of the detergent additives of polyamines of the formula

(R ⁹ ) ₂ N- [AN (R ⁹ )] _q - (R ⁹ )

wherein each R ⁹ independently of one another represents hydrogen, an alkyl or hydroxyalkyl radical having up to 24 C atoms, a polyoxyalkylene radical - (AO) _r - or polyiminoalkylene radical - [AN (R ⁹ )] _s - (R ⁹ ) but wherein at least one R ^{9 is} hydrogen, q is an integer from 1 to 19, A is an alkylene radical having 1 to 6 C atoms, r and s independently of one another are an integer from 1 to 50. Use according to one or more of claims 1 to 7, wherein the polyamine from which the detergent additive is derived contains piperazine-derived structural elements. Use according to one or more of claims 1 to 8, wherein the polyamine from which the detergent additive is derived contains at least one primary amino group. Use according to claim 7 wherein the polyamine from which the detergent additive is derived contains greater than 10% by weight of amines in which q is 4 or greater than 4. Use according to one or more of claims 1 to 10, wherein the oil-soluble polyoxyalkylene compounds have at least 3 aliphatic hydrocarbon radicals. Use according to one or more of claims 1 to 11, wherein the oil-soluble polyoxyalkylene compounds are derived from polyols having 3 or more OH groups. Use according to one or more of claims 1 to 12, wherein the oil-soluble polyoxyalkylene compounds are esters, ethers and / or ether / esters in which less than 50 mol% of the fatty acids used for the esterification have double bonds. Use according to one or more of claims 1 to 13, wherein the cold flow improver comprises copolymers of ethylene and 8 to 21 mol% olefinically unsaturated compounds, wherein the olefinically unsaturated compounds are selected from one or more vinyl esters, acrylic esters, methacrylic esters, alkyl vinyl ethers and / or Alkenes which may be substituted with hydroxyl groups. Use according to one or more of claims 1 to 14, wherein the cold flow improver comprises oil-soluble polar nitrogen compounds which are reaction products of amines 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 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 a 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 containing an acyl group. Use according to one or more of claims 1 to 15, wherein the cold flow improver comprises alkylphenol-formaldehyde resins which are oligomers or polymers having a repeating structural unit of the formula

in which R ^{11 is} C ₁ -C ₂₀₀ -alkyl or -alkenyl, OR ¹⁰ or OC (O) -R ¹⁰ , R ^{10 is} C ₁ -C ₂₀₀ -alkyl or -alkenyl and n is a number from 2 to 100 is included. Use according to one or more of claims 1 to 16, wherein the cold flow improver comb polymers of the formula

which comprises 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. Use according to one or more of claims 1 to 17, wherein the cold flow improver comprises homo and copolymers of olefins having 2 to 30 carbon atoms, which have molecular weights of up to 120,000 g / mol. Use according to one or more of claims 1 to 18, which takes place in middle distillates with a sulfur content of less than 100 ppm and a distillation boiling width of between 20 and 90% by volume of less than 120 ° C. Compositions containing a) at least one ashless nitrogen-containing detergent additive which is an oil-soluble, amphiphilic compound comprising at least one alkyl or alkenyl radical attached to a polar group, wherein the alkyl or alkenyl radical is from 10 to 500 carbon atoms and the polar group Comprises 2 or more nitrogen atoms,
and b) at least one oil-soluble polyoxyalkylene compound, which is an oil-soluble ester, ether or ether / ester of alkoxylated polyols having at least three, derived from alkylene oxides having 2 to 5 carbon atoms, repetitive alkoxy per OH group of the polyol, the at least two aliphatic Hydrocarbon radicals having 12 to 30 carbon atoms contributes. Compositions according to claim 20 containing from 0.01 to 10 parts by weight of at least one oil-soluble polyoxyalkylene compound per part by weight of the ashless nitrogen-containing detergent additive. Compositions according to claim 20 and / or 21, containing 5 to 90 wt .-% of the components a) and b) and 10 to 95 wt .-% of solvent. Compositions according to one or more of claims 20 to 22, wherein, based on one part by weight of the ashless nitrogen-containing detergent additive, 0.01 to 10 parts by weight of at least one oil-soluble polyoxyalkylene compound are contained. Compositions according to one or more of claims 20 to 23, wherein the alkyl or alkenyl radical of the detergent additive is derived from oligomers of lower olefins having 3 to 6 carbon atoms. Compositions according to one or more of claims 20 to 24, wherein the alkyl or alkenyl radical of the detergent additive comprises 15 to 500 carbon atoms. Compositions according to one or more of claims 20 to 25, wherein the detergent additive is derived from an alkenylsuccinic anhydride having a Maleinierungsgrad, based on the reacted with unsaturated carboxylic acids portions of the poly (olefins), of the average more than 1 dicarboxylic acid per alkyl group. Compositions according to one or more of claims 20 to 26, wherein the polar group of the detergent additives of polyamines of the formula

(R ⁹ ) ₂ N- [AN (R ⁹ )] _q - (R ⁹ )

wherein each R ⁹ independently of one another represents hydrogen, an alkyl or hydroxyalkyl radical having up to 24 C atoms, a polyoxyalkylene radical - (AO) _r - or polyiminoalkylene radical - [AN (R ⁹ )] _s - (R ⁹ ) but wherein at least one R ^{9 is} hydrogen, q is an integer from 1 to 19, A is an alkylene radical having 1 to 6 C atoms, r and s independently of one another are an integer from 1 to 50. Compositions according to one or more of claims 20 to 27, wherein the polyamine from which the detergent additive is derived contains piperazine-derived structural elements. Middle distillates having a sulfur content of less than 100 ppm and a distillation boiling range between 20 and 90% by volume of less than 120 ° C, containing 10 to 10,000 ppm of a composition according to one or more of claims 20 to 28, and at least one mineral oil flow improver , A middle distillate according to claim 29, containing more than 10 ppm of at least one ashless nitrogen-containing detergent additive and, based on one part by weight of the ashless nitrogen-containing detergent additive, from 0.01 to 10 parts by weight of at least one oil-soluble polyoxyalkylene compound. Middle distillates according to claim 29 and / or 30, wherein the mineral oil flow improver is selected from III) copolymers of ethylene and 8 to 21 mol% of olefinically unsaturated compounds, wherein the olefinically unsaturated compounds are selected from one or more vinyl esters, acrylic esters, methacrylic esters, alkyl vinyl ethers and / or alkenes which may be substituted by hydroxyl groups; IV) oil-soluble polar nitrogen compounds which are reaction products of amines 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 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 an integer 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 containing an acyl group; V) Alkylphenol-formaldehyde resins, the oligo- or polymers having a repetitive structural unit of the formula

in which R ^{11 is} C ₁ -C ₂₀₀ -alkyl or -alkenyl, OR ¹⁰ or OC (O) -R ¹⁰ , R ^{10 is} C ₁ -C ₂₀₀ -alkyl or -alkenyl and n is a number from 2 to 100 stands; VI) comb polymers of the formula

wherein 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; VII) homo- and copolymers of olefins having 2 to 30 carbon atoms, which have molecular weights of up to 120,000 g / mol. Middle distillates according to claim 31, wherein the mineral oil flow improver is a mixture of 0.1 to 10 parts by weight of III) per part by weight of IV). Middle distillates according to one or more of claims 29 to 32, wherein the weight ratio between the total content of ashless nitrogen-containing detergent additive and oil-soluble polyoxyalkylene compound on the one hand and the total content of the Mineralölaltfließverbesserern according to claim 31 on the other hand between 10: 1 and 1:10.