DE102005061465B4 - Detergent additives containing mineral oils with improved cold flowability - Google Patents

Abstract

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.

Description

The The present invention relates to the use of polyoxyalkylene compounds for improving the cold flowability mineral oil distillates containing detergent additives and the additized ones Petroleum distillates.

always sharply Environmental laws are becoming increasingly demanding Expected engine technology to comply with the specified emission limit values. An assignment of engine parts such as the valves with However, combustion residues change the characteristics of the engine and leads to increased emissions as well increased Consumption. Therefore, motor fuels are added to detergent additives, remove such deposits or prevent their formation. These are generally oil-soluble amphiphiles that are next to an oil-soluble, temperature-stable hydrophobic radical containing a polar head group.

on the other hand become ever heavier in the course of decreasing world oil reserves thus paraffin-rich crude oils promoted and processed, which consequently also lead to paraffin-rich fuel oils. The especially in middle distillates paraffins can in Lowering the temperature of the oil crystallize out and partially agglomerate with inclusion of oil. By this crystallization and agglomeration it can be especially in winter to blockages of filters in engines and combustion plants come, thereby preventing a safe metering of the fuels will and possibly a complete one Interruption of fuel supply may occur. The paraffin problem is also protected by environmental considerations in order to reduce the sulfur content Increasing hydrodesulfurization of fuel oils aggravates the to an increased Proportion of cold-critical Paraffins in the fuel oil leads.

to Improvement of cold flow properties middle distillates are often called chemical additives, so-called cold flow improvers or flow improver added, the crystal structure and agglomeration tendency of the precipitating Modify paraffins so that the oils so additized are still Pump or use at temperatures that often more than 20 ° C lower lie than non-additized oils. As a cold flow improver usually become oil-soluble copolymers of ethylene and unsaturated Esters, oil-soluble polar Nitrogen compounds and / or comb polymers used. Furthermore but more specific additives have also 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.

In the course of increasingly demanding engine technology and increasing demands To improve the environmental performance of fuel oils and their combustion products, detergent additives with ever increasing efficacy are being developed. 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.

Especially In particular, such detergent additives are problematic, differing from higher polyamines derive and, for example due to multiple alkylation and / or Acylation of these polyamines have very high molecular weights. Also particularly problematic are such detergent additives, whose hydrophobic residue is of higher molecular weight and / or multiple derived functionalized poly (olefins).

task Thus, it was the response of cold flow improvers to improve in detergent additives containing middle distillates. Another object of the invention was to provide a comparison with State of the art to provide improved detergent additive, which does not affect the response of cold flow improvers.

Surprisingly It has now been found that certain oil-soluble polyoxyalkylene compounds of impairment the effectiveness of the usual cold flow improvers Counteract by nitrogen-containing detergent additives or these impairment cancel.

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, wherein the alkyl or alkenyl radical comprises 10 to 500 carbon 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.

• 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
• 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

• 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 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 coals carries hydrogen radicals having 12 to 30 carbon atoms.

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

• 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,
• 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
• 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

• 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,
• 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
• c) at least one mineral oil flow improver.

Especially impaired is the response of flow improvers in middle distillates, more than 10 ppm of a nitrogen-containing detergent additive, in particular more than 20 ppm and especially more than 40 ppm such as Contains 50 to 2,000 ppm of nitrogen-containing detergent additive.

Prefers contain the additives of the invention based on one part by weight of the nitrogen-containing detergent additive 0.01 to 10 parts by weight, and especially 0.1 to 5 parts by weight such as 0.3 to 3 parts by weight of the oil-soluble polyoxyalkylene compound.

ash free means that the relevant additives are essentially just off Consist of elements that form gaseous reaction products during combustion. Preferably, the additives consist essentially only of the elements Carbon, hydrogen, oxygen and nitrogen. Especially are ashless additives essentially free of metals and metal salts.

Prefers For example, middle distillates will be 10 to 10,000 ppm and especially 100 to 3,000 ppm of the nitrogen-containing detergent additives added.

Preferably For example, 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. 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.

Further 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. For example:
N- (2-hydroxyethyl) ethylenediamine, N, N ¹ -bis (2-hydroxyethyl) ethylenediamine,
N- (3-hydroxybutyl) tetra (methylene) diamine, N-2-aminoethylpiperazine, N-2 and
N-3-aminopropylmorpholine, N-3- (dimethylamino) propylpiperazine,
2-heptyl-3- (2-aminopropyl) imidazoline, 1,4-bis (2-aminoethyl) piperazine,
1- (2-hydroxyethyl) piperazine, various isomers of phenylenediamine and naphthalenediamine and mixtures of these amines.

Detergent additives based on heavy polyamines, in which R ^{9 is} hydrogen in the above formula and q has values of at least 3, in particular at least 4, such as 5, 6 or 7, are particularly critical for the cold additization of middle distillates. For mixtures of various polyamines, a proportion of more than 10 wt .-%, in particular more than 20 wt .-% and especially of more than 50 wt .-% of amines having q-values of 4 or higher and especially with q Values of 5 or higher and in particular with q values of 6 or higher on the total amount of amines used have proven particularly critical.

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

at the over Linked C-N bonds Detergent additives are preferably alkylpolyamines, for example, by reacting polyisobutylenes with polyamines for example, by hydroformylation and subsequent reductive Amination with the above polyamines are accessible. It can am Polyamine be bound to one or more alkyl radicals. Especially critical for the cold additization are detergent additives based on higher polyamines with more than 4 N atoms such as those with 5, 6 or 7 N atoms.

amide or imide-containing detergent additives are, for example by reaction of alkenylsuccinic anhydrides with polyamines accessible. alkenylsuccinic and polyamine are preferably in the molar ratio of about 1: 0.5 to about 1: 1 reacted. The production of the basis lying alkenylsuccinic anhydrides usually takes place 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 can also be achieved by thermal addition of polyolefins to maleic anhydride in an "ene reaction." Highly reactive olefins having a high content of, for example, more than 75% and especially more than 85 mol%, based on the total number of polyolefin molecules, are present 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 ]. act.

For the production of alkenyl succinic anhydrides can the molar ratio the two reactants in the reaction between maleic anhydride and polyolefin vary within wide limits. Preferably it can between 10: 1 and 1: 5, with molar ratios of 6: 1 to 1: 1 being especially are preferred. maleic anhydride is preferred in stoichiometric excess used, such as 1.1 to 3 moles of maleic anhydride per mole of polyolefin. Excess maleic anhydride can be removed from the reaction mixture, for example by distillation become.

There the adducts primarily formed by ene reaction in turn contain an olefinic double bond is a suitable reaction further addition of unsaturated dicarboxylic acids forming so-called bis-maleinates possible. The accessible Reaction products have relative to those with unsaturated carboxylic acids converted amounts of 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 units per alkyl radical. By reaction with the above-mentioned amines arise from these products with significantly increased effectiveness as detergent additives. On the other hand, as the level of maleation increases, so does the impairment the effectiveness of cold flow improvers.

The Reaction of alkenyl succinic anhydrides with polyamines leads to products containing one or more amide and / or imide bonds per polyamine and depending of the degree of maleation carry one or two polyamines per alkyl radical can. Are preferred for the reaction of 1.0 to 1.7 and especially 1.1 to 1.5 mol alkenyl succinic anhydride used per mole of polyamine, leaving free primary amino groups in the product remain. In a further preferred embodiment, alkenyl succinic anhydride and reacted polyamine equimolar. In the implementation of polyamines with alkenyl succinic anhydrides 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 are.

typical and particularly preferred acylated nitrogen compounds are Reaction of poly (isobutylene) -, poly (2-butenyl) -, poly (2-methyl-2-butenyl) -, Poly (2,3-dimethyl-2-butenyl) - or poly (propenyl) succinic anhydrides with an average of about 1.2 to 1.5 anhydride groups per alkyl radical, whose Carry alkylene radicals between 50 and 400 carbon atoms, with a mixture of Poly (ethylene amines) having about 3 to 7 nitrogen atoms and about 1 up to 6 ethylene units available.

Also oil-soluble Mannich reaction products based on polyolefin-substituted phenols and polyamines impair the effectiveness of conventional Cold flow improvers. Such Mannich bases are by known methods, for example by alkylating phenol and / or salicylic acid with those described above Polyolefins such as 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 polyamines described above such as TEPA, PEHA or heavy polyamines.

The average molecular weight determined by vapor pressure osmometry particularly efficient, but at the same time for the cold additization of middle distillates particularly critical detergent additives are above 800 g / mol and in particular above 2,000 g / mol such as above 3,000 g / mol. The average molecular weight of those described above Detergent additives may also be over Increases crosslinking reagents and the purpose of use. Suitable crosslinking reagents For example, dialdehydes such as glutaric dialdehyde, bisepoxides Example derived from bisphenol A, dicarboxylic acids and their reactive derivatives such as maleic anhydride and alkenyl succinic anhydrides as well as higher polybasic carboxylic acids and their derivatives such as trimellitic acid, trimellitic anhydride and pyromellitic dianhydride.

In a preferred embodiment own the oil-soluble ones Polyoxyalkylenverbindungen at least 3, such as 4 or 5 aliphatic hydrocarbon radicals. Preferably, these possess Remainders independently each other 16 to 26 carbon atoms such as 17 to 24 carbon atoms. Preferably, these radicals are the oil-soluble Polyoxyalkylene compounds linear. Further preferred are they largely saturated, in particular, these are alkyl radicals. Esters are special prefers.

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 ones are derived Polyoxyalkylene compounds of polyols having 3 or more OH groups, preferably from polyols having from 3 to about 50 OH groups such as 4 to 10 OH groups, in particular neopentyl glycol, glycerol, trimethylolethane, trimethylolpropane, sorbitan, pentaerythritol, and the through Condensation accessible oligomers having 2 to 10 monomer units such. As polyglycerol. 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 are oil-soluble at least in application-relevant amounts. 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 for the Esterification of the alkoxylated polyols have suitable fatty acids preferably 12 to 30 and in particular 16 to 26 C-atoms. suitable fatty acids are, for example, lauric, tridecane, myristic, pentadecane, Palmitic, margarine, stearic, isostearic, arachinic and behenic acid, oleic and erucic acid, palmitoleein, Myristoleic, ricinoleic, as well as natural ones Fats and oils recovered fatty acid mixtures. preferred fatty acid mixtures contain more than 50 mol% fatty acids with at least 20 C atoms. Preferably, less than 50 mol% of those used for esterification fatty acids Double bonds, in particular less than 10 mol%; are special they are largely saturated. The esterification can also be based on reactive derivatives of fatty acids such as esters with lower alcohols (eg methyl or ethyl ester) or anhydrides.

Under largely saturated For the purposes of the present invention, an iodine value of the fatty acid used or of the fatty alcohol used of up to 5 g l per 100 g of fatty acid or Understood 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 be for the esterification based on the content of hydroxyl groups on the one hand and carboxyl groups in the ratio of 1.5: 1 to 1: 1.5, preferably in proportion 1.1: 1 to 1: 1.1 and in particular equimolar.

In a preferred embodiment become after the alkoxylation of the polyol, the terminal hydroxyl groups for example, by oxidation or by reaction with dicarboxylic acids in converted terminal carboxyl groups. By Reaction with fatty alcohols with 8 to 50, in particular 12 to 30, specifically 16 to 26 carbon atoms are also inventive polyoxyalkylene esters receive. Contain preferred fatty alcohols or fatty alcohol mixtures more than 50 mol% of fatty alcohols having at least 20 carbon atoms. Prefers contain less than 50 mol% of the fatty alcohols used for the esterification Double bonds, in particular less than 10 mol%; are special they are largely saturated. Also esters of alkoxylated fatty alcohols with fatty acids, the above-mentioned proportions containing poly (alkylene oxides) and their fatty alcohol and fatty acid above called alkyl chain lengths and saturation levels own, are suitable according to the invention.

The esterification is carried out by conventional methods. Has proven particularly useful the implementation 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. Complete esterification has been found to be most effective in synergy with detergent additives. Furthermore, this prevents the additized middle distillate from forming undesirable emulsions with water optionally present in storage containers.

Of others can the alkoxylated polyols described above by etherification with Fatty alcohols with 8 to 50, in particular 12 to 30, especially 16 to 26 carbon atoms in accordance with the invention suitable Polyoxyalkylenverbindungen be transferred. The one for this preferred fatty alcohols are linear and largely saturated. Prefers the etherification takes place completely or at least as far as possible completely. The etherification will 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 in particular, 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 ratio between detergent additive and polyoxyalkylene compound in the additized oil can in wide limits vary. Has proven particularly useful is the use of 0.01 to 10 parts by weight, especially 0.1 to 5 parts by weight such as 0.3 to 3 parts by weight of polyoxyalkylene compound per Weight part detergent additive, in each case based on the active ingredient.

When flow improvers, in the middle distillates according to the invention In particular, one or more of the following are used Substance classes III to VII into consideration, preference being given to ethylene copolymers (Component III) or mixtures thereof with one or more the ingredients IV to VII are used. Have proven especially mixtures of ethylene copolymers (component III) and alkylphenol-aldehyde resins (component V), of ethylene copolymers (component III) and comb polymers (constituent VI) and of ethylene copolymers (constituent III) and olefin (co) polymers (component VII). For the paraffin dispersion In particular, mixtures of ethylene copolymers (component III) with the constituents IV and V or the constituents IV and VI proven.

preferred cold flow improvers as constituent III are copolymers of ethylene and olefinically unsaturated Links. Suitable ethylene copolymers are, in particular, those in addition to ethylene 8 to 21 mol%, in particular 10 to 18 mol% olefinic unsaturated Contain compounds as comonomers.

at the olefinically unsaturated Compounds are preferably vinyl esters, acrylic esters, methacrylic esters, Alkyl vinyl ethers and / or alkenes, where the compounds mentioned may be substituted with hydroxyl groups. There may be one or more comonomers be contained 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. Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n- and iso-butyl (meth) acrylate, hexyl, octyl, 2-ethylhexyl, decyl, dodecyl, tetradecyl , Hexadecyl, octadecyl (meth) acrylate and mixtures of these comonomers. In a further embodiment, said alkyl groups may be substituted with one or more hydroxyl groups. An example of such an acrylic ester is hydroxyethyl methacrylate.

The alkyl vinyl ethers are preferably compounds of the formula 3 CH ₂ = CH-OR ₄ (3) wherein R ^{4 is} C ₁ - to C ₃₀ -alkyl, preferably C ₄ - to C ₁₆ -alkyl, especially C ₆ - to C ₁₂ -alkyl. Examples which may be mentioned are methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether. In a further embodiment, said alkyl groups may be substituted with one or more hydroxyl groups.

at 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 vinyl norbornene. In a further embodiment, the substituted alkyl groups substituted with one or more hydroxyl groups be.

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.

Prefers Mixtures of two or more of the above-mentioned ethylene copolymers are used. Particularly preferably, the mixtures differ based on the mixtures lying polymers in at least one characteristic. For example can contain different comonomers, different comonomer contents, Have molecular weights and / or degrees of branching.

The mixing ratio between the additives according to the invention and ethylene copolymers as component III may, depending on the application vary within wide limits, the ethylene copolymers III often the larger share represent. Preferably contain such additive and oil mixtures 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 For M is - (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. Cocosfettamine, 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, 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 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 proved particularly suitable (cf. US 4 211 534 ). Similarly, amides and ammonium salts of aminoalkylene polycarboxylic acids such as nitrilotriacetic acid or ethylenediaminetetraacetic acid with secondary amines are suitable as oil-soluble polar nitrogen compounds (cf. EP 0 398 101 ). Other oil-soluble polar nitrogen compounds are copolymers of maleic anhydride 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 understood for the component V generally hydrocarbon radicals as defined below) in the Ver in Ver They may be the same or different, they may be saturated or unsaturated and have 1-200, preferably 1-20, especially 4-16 such as 6-12 carbon atoms; it is preferably n-, iso- and tert-butyl, n- and iso-pentyl, n- and iso-hexyl, n- and iso-octyl, n- and iso-nonyl-, n - and iso-decyl, n- and iso-dodecyl, tetradecyl, hexadecyl, octadecyl, tripropenyl, tetrapropenyl, poly (propenyl) - and poly (isobutenyl) radicals. In a preferred embodiment, mixtures of alkylphenols having different alkyl radicals are used for the preparation of the alkylphenol resins. For example, resins based on butyphenol on the one hand and octyl, nonyl and / or dodecylphenol in a molar ratio of 1:10 to 10: 1 on the other hand have proven particularly useful.

suitable Alkylphenol resins can also structural units of other phenol analogues such as salicylic acid, hydroxybenzoic acid and their derivatives such as esters, amides and salts contain or from them consist.

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 by gel permeation chromatography against poly (styrene) standards in THF measured molecular weight of the alkylphenol-aldehyde resins is preferably 500-25,000 g / mol, more preferably 800-10,000 g / mol and especially 1,000-5,000 g / mol such as 1500-3000 g / mol. 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 is 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. B. 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 Mo no-sulfonic acids with one or more C ₁ -C ₂₈ -alkyl radicals and in particular those with 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 is H, CH _3, A or R '';
E H, 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.

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-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 ,

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.

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 small amounts, for. B. up to 10 mol% of other comonomers such. B. non-terminal olefins or non-conjugated olefins. Particularly preferred are ethylene-propylene copolymers. Further preferred are copoly mere different olefins having 5 to 30 carbon atoms such as polyhexene-co-decene). The olefin homo- and copolymers can be prepared by known methods, e.g. B. by Ziegler or metallocene catalysts.

Further Suitable olefin copolymers are block copolymers that block out olefinically unsaturated, aromatic Monomers A and blocks hydrogenated polyolefins B are included. 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 other components V, VI and VII is in general in each case between 1:10 and 10: 1, preferably between 1: 5 and 5: 1.

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

The Polyoxyalkylenverbindungen invention improve the response of detergent additive-containing Middle distillates such as kerosene, jet fuel, diesel and fuel oil for conventional flow improvers regarding the reduction of pour point and CFPP value as well as the Improvement of the paraffin dispersion.

Especially preferred mineral oil distillates are middle distillates. As middle distillate one calls in particular such mineral oils, by distillation of crude oil be recovered, in the range of about 150 to 450 ° C and in particular in the range from about 170 to 390 ° C boil, for example kerosene, jet fuel, diesel and heating oil. Usually For example, middle distillates contain about 5 to 50% by weight, for example about 10 to 35 wt .-% n-paraffins, of which the longer-chain on cooling crystallize and the fluidity of the middle distillate can.

Especially The compositions according to the invention are advantageous in middle distillates with a low aromatic content of less than 21 wt .-%, such as less than 19% by weight. Particularly advantageous are the compositions according to the invention continue in middle distillates with low boiling end, that is in such Middle distillates, the 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 exhibit. Among aromatic compounds, the sum of mono-, di- and polycyclic aromatic compounds understood as They by HPLC according to DIN EN 12916 (edition 2001) is determinable. The middle distillates can also minor amounts, such as up to 40% by volume, are preferred 1 to 20 vol.%, Especially 2 to 15 such as 3 to 10 vol.% the closer below described oils animal and / or vegetable origin such as fatty acid methyl esters contain.

The Compositions of the invention are also for improving the cold properties of detergent additives containing fuels based on renewable raw materials (biofuels) suitable. Biofuels are understood to be oils derived from animal and preferably obtained from vegetable matter or both and derivatives thereof, which are used as fuel and in particular as diesel or heating oil can be used. These are in particular triglycerides of fatty acids 10 to 24 carbon atoms and the accessible from them by transesterification fatty acid ester lower alcohols such as methanol or ethanol.

Examples for 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 oil, Beef tallow, bone oil, fish oils and used cooking oils. Other examples include oils which are derived from wheat, jute, sesame, shea nut, arachis oil and linseed oil. Also called biodiesel designated fatty acid alkyl esters can from these oils be derived by methods known in the art. Rapeseed oil, which is a mixture of glycerol-esterified fatty acids, is preferred because it is in large Quantities available is and is easily obtainable by squeezing rapeseed. Furthermore, the widely used oils of sunflowers, Palm and soybeans and their mixtures with rapeseed oil are preferred.

Especially suitable as biofuels are lower alkyl esters of fatty acids. Here come, for example, commercially available Mixtures of ethyl, propyl, butyl and especially methyl esters of fatty acids with 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 into consideration. Preferred esters have an iodine value of 50 to 150 and in particular from 90 to 125. Mixtures with particularly advantageous Properties are those that are mainly, i. H. at least 50% by weight of methyl esters of fatty acids with 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 acid.

The Additives can used alone or together with other additives, z. With other pour point depressants or dewaxing aids, with other detergents, with antioxidants, cetane improvers, Dehazers, demulsifiers, dispersants, defoamers, dyes, corrosion inhibitors, Lubricity additives, sludge inhibitors, odorants and / or additives to Humiliation of the cloud point.

Examples

Improvement of the calorific capacity of middle distillates

to Assessment of the effect of the additives of the invention on the cold flow properties of middle distillates were detergent additives (A) with different Polyoxyalkylene compounds (B) and ethylene copolymers (C) and Paraffin dispersants (D) having the characteristics given below used.

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

Furthermore, the paraffin dispersion in middle distillates is determined in the short sediment test as follows:
150 ml of the middle distillates mixed with the additive components indicated in the table were cooled to -13 ° C. in a cold cabinet at -2 ° C./hour in 200 ml graduated cylinders and stored at this temperature for 16 hours. Subsequently, the volume and appearance of both the sedimented paraffin phase and the oil phase above are visually determined and assessed. A 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 used detergent additives

When Detergent additives A were various reaction products listed in Table 2 from alkenyl succinic anhydrides (ASA) based on highly reactive polyolefins (proportion of terminal double bonds> 90%, degree of maleation about 1.2 to 1.3) with polyamines used.

alkenylsuccinic and polyamine were added thereto in a molar ratio of 1.0 to 1.5 moles of alkenyl succinic anhydride reacted per mole of polyamine (see Table 2). For better dosing were the detergent additives as 33% solutions in higher boiling aromatic solvent used; those given in Tables 2 to 4 for the detergent additives Dosing rates, however, relate to the active ingredient used.

(B) Characterization of the used polyoxyalkylene

• 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) give the numbers -20-, -28- and -30- the number of moles of alkylene oxide per mole of glycerol. In example B4) the number -600- gives the molecular weight of the esterification used polyethylene glycol.

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 for 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 from ditetradecyl fumarate, 50% in solvent naphtha.

The Determination of CFPP values in test oil 1 was carried out after addition of the oil with 200 ppm C2 and 150 ppm D1.

In the examples of the following Tables 3 to 5 were as Detergentsadditiv A1 the reaction Pro from 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 as detergent additive A3 the reaction product of poly (butenyl) succinic anhydride and heavy polyamines used according to Table 2, Example 18. Table 3: Cold Flow Improvement in Test Oil 2 example additives Test Oil 2 CFPP [° C] A B C D 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 Table 4: Cold flow improvement in test oil 3 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 200 200 D1 -19 4 cloudy -0.1 60 50 A3 200 B4 535 C2 365 D1 -20 2 cloudy -1.6 Table 5: Cold flow improvement in test oil 4 example additives Test Oil 4 CFPP [° C] A B C D 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.) 1.00 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 cold-flow properties such as the CFPP value and the paraffin dispersion of with flow improver additivated middle distillates only by adding the polyoxyalkylene compounds according to the invention can be compensated. 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, said polyoxyalkylene compound being an oil-soluble ester, ether or ether / ester of alkoxylated polyols having at least three repeating alkoxy units per OH group of the polyol derived from alkylene oxides having from 2 to 5 carbon atoms which is at least two carrying aliphatic hydrocarbon radicals having 12 to 30 carbon 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 more than 10 ppm of at least one ashless, nitrogen-containing Detergent additives included. Use according to claim 1 and / or 2, wherein based to 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 come into use. Use according to one or more of claims 1 to 3, wherein the alkyl or Alkenyl residue of the detergent additive of oligomers of lower olefins with 3 to 6 carbon atoms is derived. Use according to one or more of claims 1 to 4, wherein the alkyl or Alkenyl residue of the detergent additive comprises 15 to 500 C atoms. Use according to one or more of claims 1 to 5, wherein the detergent additive of an alkenyl succinic anhydride derives a Maleinierungsgrad, based on unsaturated with carboxylic acids converted amounts of poly (olefins), of on average more than 1 dicarboxylic acid per alkyl radical. 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 ) is derived; 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 a R ^{9 is} hydrogen, q is an integer from 1 to 19, A is an alkylene radical having 1 to 6 C atoms, around s are independently 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 containing 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, at least one primary Contains amino group. Use according to claim 7, wherein the polyamine, from which derives the detergent additive, more than 10 wt .-% of Contains amines, where q equals 4 or greater than 4 is. Use according to one or more of claims 1 to 10, being the oil-soluble Polyoxyalkylenverbindungen at least 3 aliphatic hydrocarbon radicals exhibit. Use according to one or more of claims 1 to 11, being the oil-soluble Polyoxyalkylene compounds of polyols having 3 or more OH groups are derived. Use according to one or more of claims 1 to 12, where the oil-soluble Polyoxyalkylene compounds are esters, ethers and / or ethers / esters, in which less than 50 mol% of the fatty acids used for the esterification double bonds exhibit. Use according to one or more of claims 1 to 13, wherein the cold flow improver 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 substituted with hydroxyl groups could be. 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 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 are independently 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

wherein A is R ', COOR', OCOR ', R''-COOR', OR '; D is H, CH _3, A or R ''; E H, 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 Homopolymers 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 in middle distillates with a sulfur content of less as 100 ppm and a distillation boiling width between 20 and 90 vol .-% of less than 120 ° C. he follows. Compositions comprising 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, said alkyl or alkenyl radical having 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 C atoms petitive alkoxy units per OH group of the polyol which carries at least two aliphatic hydrocarbon radicals having 12 to 30 carbon atoms. Compositions according to claim 20, containing 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 bis 95% by weight 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 Polyoxyalkylenverbindung are included. Compositions according to one or more of claims 20 to 23, wherein the alkyl or alkenyl radical of the detergent additive of Oligomeric lower olefins having 3 to 6 carbon atoms is derived. Compositions according to one or more of claims 20 to 24, wherein the alkyl or alkenyl radical of the detergent additive 15 bis Comprising 500 C atoms. Compositions according to one or more of claims 20 to 25 wherein the detergent additive is derived from an alkenyl succinic anhydride derives a Maleinierungsgrad, based on unsaturated with carboxylic acids converted amounts of poly (olefins), of on average more than 1 dicarboxylic acid per alkyl radical. 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 containing piperazine derived structural elements. Middle distillates with a sulfur content of less as 100 ppm and a distillation boiling width between 20 and 90% by volume less than 120 ° C, containing 10 to 10,000 ppm of a composition after one or more of the claims 20-28, and at least one mineral oil flow improver. Middle distillates 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, 0.01 to 10 parts by weight of at least one oil-soluble Polyoxyalkylene. 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 is R ', COOR', OCOR ', R''-COOR', OR '; D is H, CH _3, A or R ''; E H, 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 a mixture of 0.1 to 10 parts by weight III) per part by weight 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 Polyoxyalkylenverbindung on the one hand and the total content of the for mineral oils according to claim 31, on the other hand lies between 10: 1 and 1:10.