EP1451271B1 - Additives for low-sulphur mineral oil distillates, containing an ester of an alkoxylated polyol and a polar nitrogenous paraffin dispersant - Google Patents

Description

The invention relates to additives for low sulfur mineral oil distillates having improved cold flowability and paraffin dispersion comprising an ester of an alkoxylated polyol and a polar nitrogen containing paraffin dispersant, additive fuel oils and the use of the additive.

In the course of the decreasing oil reserves ever more problematic crude oils are produced and processed with constantly increasing energy demand. In addition, the requirements for the fuel oils derived from them, such as diesel and heating oil, are becoming ever more demanding, not least due to legislative requirements. Examples are the reduction of sulfur content, the limitation of the boiling point and the aromatics content of middle distillates, which force the refineries to constantly adapt the processing technology. In many cases, this leads to an increased proportion of paraffins in middle distillates, especially in the chain length range from C ₁₈ to C ₂₄ , which in turn has a negative influence on the cold flow properties of these fuel oils.

Depending on the origin of the crude oils, crude oils and middle distillates obtained by distillation of crude oils, such as gas oil, diesel oil or fuel oil, contain different amounts of n-paraffins which crystallize out as platelet-shaped crystals when the temperature is lowered and partly agglomerate with the inclusion of oil. As a result of this crystallization and agglomeration, the flow properties of the oils or distillates deteriorate, which can lead to disruptions in the extraction, transport, storage and / or use of the mineral oils and mineral oil distillates. When transporting mineral oils through pipelines, the crystallization phenomenon, especially in winter, can lead to deposits on the pipe walls, in individual cases, for example when a pipeline is at a standstill, even to its complete blockage. In the storage and processing of mineral oils, it may also be necessary in winter, the Store mineral oils in heated tanks. In the case of mineral oil distillates, as a result of the crystallization, blockages of the filters in diesel engines and firing systems may occur, as a result of which reliable metering of the fuels is prevented and, under certain circumstances, a complete interruption of the fuel or heating agent supply occurs.

In addition to the classical methods for removing the crystallized paraffins (thermal, mechanical or with solvents), which relate only to the removal of already formed precipitates, chemical additives (so-called flow improvers) have been developed in recent years. These cause physical interaction with the precipitated paraffin crystals that their shape, size and adhesion properties are modified. The additives act as additional nuclei and partially crystallize out with the paraffins, resulting in a larger number of smaller paraffin crystals with altered crystal form. The modified paraffin crystals are less prone to agglomeration, so that the oils added with these additives can still be pumped or processed at temperatures which are often more than 20 ° C. lower than for non-additized oils.

Typical flow improvers for crude oils and middle distillates are copolymers and terpolymers of ethylene with carboxylic acid esters of vinyl alcohol.

Another object of flow improver additives is the dispersion of paraffin crystals, i. the delay or prevention of the sedimentation of paraffin crystals and thus the formation of a paraffin-rich layer at the bottom of storage containers.

In the prior art, certain poly (oxyalkylene) compounds and alkylphenol resins are known, which are added as additives to middle distillates.

EP-A-0 061 895 discloses cold flow improvers for mineral oil distillates containing esters, ethers or mixtures thereof. The esters / ethers contain two linear saturated C ₁₀ to C ₃₀ alkyl groups and a polyoxyalkylene group having 200 to 5000 g / mol.

EP 0 973 848 and EP 0 973 850 disclose mixtures of esters of alkoxylated alcohols having more than 10 carbon atoms and fatty acids having 10 to 40 carbon atoms in combination with ethylene copolymers as flow improvers.

EP-A-0 935 645 discloses alkylphenol-aldehyde resins as an oil-improving additive in low-sulfur middle distillates.

EP-A-0857776 and EP-A-1 088 045 disclose processes for improving the flowability of paraffin-containing mineral oils and mineral oil distillates by adding ethylene copolymers and alkylphenol-aldehyde resins and optionally further, nitrogen-containing paraffin dispersants.

Finally, JP-A-61 181892 discloses fatty acids partially esterified alkoxylated polyols used as cold flow improvers for a variety of fuel oils.

The above-described flow-improving and / or paraffin-dispersing effect of the known paraffin dispersants is not always sufficient, so that on cooling the oils sometimes form large paraffin crystals, which lead to filter blockages and sediment due to their higher density over time and thus to the formation lead a paraffin-rich layer at the bottom of storage containers. Problems occur especially in the case of the addition of paraffin-rich and narrow-cut distillation sections having boiling ranges of 20-90% by volume, less than 120 ° C., in particular less than 100 ° C. The situation is particularly problematic for low-sulfur winter qualities with cloud points below -5 ° C; In many cases, sufficient paraffin dispersion can not be achieved here by the addition of known additives.

It was therefore an object to improve the flowability, and in particular the paraffin dispersion in mineral oils or mineral oil distillates by the addition of suitable additives.

Surprisingly, it has now been found that an additive which, in addition to polar nitrogen-containing paraffin dispersants, also contains certain esters of alkoxylated polyols contains a particularly good cold flow improver for low-sulfur fuel oils.

The invention thus relates to additives for middle distillates with a maximum of 0.05% by weight of sulfur content, comprising at least one fatty acid ester of alkoxylated polyols having at least 3 OH groups (A) and at least one polar nitrogen-containing paraffin dispersant (D), where the fatty acid ester is an OH Number of less than 15 mg KOH / g.

Another object of the invention are middle distillates with a maximum of 0.05 wt .-% sulfur content containing an additive containing at least one fatty acid ester of alkoxylated polyols having at least 3 OH groups (A) and at least one polar nitrogen-containing paraffin dispersant (D), wherein the fatty acid ester has an OH number of less than 15 mg KOH / g.

The invention further provides for the use of an additive comprising at least one fatty acid ester of alkoxylated polyols having at least 3 OH groups (A) and at least one polar nitrogen-containing paraffin dispersant (D), the fatty acid ester having an OH number of less than 15 mg KOH / g has to improve the cold flow properties and paraffin dispersion of middle distillates with a maximum of 0.05 wt .-% sulfur content.

Another object of the invention is a method for improving the cold flow properties of middle distillates with a maximum of 0.05 wt .-% sulfur content by the middle distillates an additive containing at least one fatty acid ester of alkoxylated polyols having at least 3 OH groups (A) and at least one polar nitrogen-containing paraffin dispersant (D), wherein the fatty acid ester has an OH number of less than 15 mg KOH / g added.

The esters (A) are derived from polyols having 3 or more OH groups, in particular glycerol, trimethylolpropane, pentaerythritol and the oligomers having 2 to 10 monomer units, such as polyglycerol, obtainable therefrom by condensation. The polyols are generally reacted with 1 to 100 mol of alkylene oxide, preferably 3 to 70, in particular 5 to 50 mol of alkylene oxide per mole of polyol. Preferred alkylene oxides are ethylene oxide, propylene oxide and Butylene oxide. The alkoxylation is carried out by known methods.

The fatty acids suitable for the esterification of the alkoxylated polyols preferably have 8 to 50, in particular 12 to 30, especially 16 to 26 C-atoms. Suitable fatty acids are, for example, lauric, tridecane, myristic, pentadecane, palmitic, margarine, stearic, isostearic, arachic and behenic, oleic and erucic acid, palmitoleic, myristolein, ricinoleic acid, as well as natural fats and Oils derived fatty acid mixtures. Preferred fatty acid mixtures contain more than 50% fatty acids with at least 20 C atoms. Preferably, less than 50% of the fatty acids used for esterification contain double bonds, in particular less than 10%; specifically, they are largely saturated. Under largely saturated here is an iodine value of the fatty acid used of up to 5 g I per 100 g fatty acid are understood. 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 esterification of the alkoxylated polyols, it is also possible to use mixtures of the above 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 acids and their 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 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 1.1: 1 to 1: 1.1, in particular equimolar. The paraffin-dispersing effect is particularly pronounced when with an acid excess of up to 20 mol%, especially up to 10 mol%, especially up to to 5 mol% is worked.

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- alkylbenzene sulfonic 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 completely, ie for the esterification 1.0 to 1.5 moles of fatty acid are used per mole of hydroxyl groups. The acid number of the esters is below 15 mg KOH / g, preferably below 10 mg KOH / g especially below 5 mg KOH / g.

The polar nitrogen-containing paraffin dispersants (D) contained in the additive according to the invention are low molecular weight or polymeric, oil-soluble nitrogen compounds, e.g. Amine salts, amides and / or imides, which are 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. Particularly preferred paraffin dispersants contain reaction products of secondary fatty amines having 8 to 36 carbon atoms, in particular dicoco fatty amine, ditallow fatty amine and distearylamine. Other paraffin dispersants are copolymers of maleic anhydride and α, β-unsaturated compounds which can optionally be reacted with primary monoalkylamines and / or aliphatic alcohols, the reaction products of alkenyl spiro-bis-lactones with amines and reaction products of terpolymers based on α, β-unsaturated dicarboxylic acid anhydrides, α, β -unsaturated compounds and polyoxyalkylene ethers of lower unsaturated alcohols. In the following, some suitable paraffin dispersants (D) are listed.

1. 1. Umsetzungsprodukte von Alkenyl-spirobislactonen der Formel
   
   wobei R jeweils C₈-C₂₀₀-Alkenyl bedeutet, mit Aminen der Formel NR⁶R⁷R⁸. Geeignete Umsetzungsprodukte sind in EP-A-0 413 279 aufgeführt. Je nach Reaktionsbedingung erhält man bei der Umsetzung von Verbindungen der Formel mit den Aminen Amide oder Amid-Ammoniumsalze.
2. 2. Amide bzw. Ammoniumsalze von Aminoalkylenpolycarbonsäuren mit sekundären Aminen der Formeln
   
   
   in denen
   R¹⁰ einen geradkettigen oder verzweigten Alkylenrest mit 2 bis 6 Kohlenstoffatomen oder den Rest der Formel
   
   in der R⁶ und R⁷ insbesondere Alkylreste mit 10 bis 30, bevorzugt 14 bis 24 C-Atomen bedeuten, wobei die Amidstrukturen auch zum Teil oder vollständig in Form der Ammoniumsalzstruktur der Formel
   
   vorliegen können.
   Die Amide bzw. Amid-Ammoniumsalze bzw. Ammoniumsalze z.B. der Nitrilotriessigsäure, der Ethylendiamintetraessigsäure oder der Propylen-1,2-diamintetraessigsäure werden durch Umsetzung der Säuren mit 0,5 bis 1,5 Mol Amin, bevorzugt 0,8 bis 1,2 Mol Amin pro Carboxylgruppe erhalten. Die Umsetzungstemperaturen betragen etwa 80 bis 200°C, wobei zur Herstellung der Amide eine kontinuierliche Entfernung des entstandenen Reaktionswasser erfolgt. Die Umsetzung muß jedoch nicht vollständig zum Amid geführt werden, vielmehr können 0 bis 100 Mol-% des eingesetzten Amins in Form des Ammoniumsalzes vorliegen. Unter analogen Bedingungen können auch die unter B1) genannten Verbindungen hergestellt werden.
   Als Amine der Formel
   
   kommen insbesondere Dialkylamine in Betracht, in denen R⁶, R⁷ einen geradkettigen Alkylrest mit 10 bis 30 Kohlenstoffatomen, vorzugsweise 14 bis 24 Kohlenstoffatomen, bedeutet. Im einzelnen seien Dioleylamin, Dipalmitinamin, Dikokosfettamin und Dibehenylamin und vorzugsweise Ditalgfettamin genannt.
3. 3. Quartäre Ammoniumsalze der Formel
   
           ⁺NR⁶R⁷R⁸R¹¹ X^-
   
   wobei R⁶, R⁷, R⁸ die oben gegebene Bedeutung haben und R¹¹ für C₁-C_30-Alkyl, bevorzugt C₁-C₂₂-Alkyl, C₁-C₃₀-Alkenyl, bevorzugt C₁-C₂₂-Alkenyl, Benzyl oder einen Rest der Formel -(CH₂-CH₂-O)_n-R¹² steht, wobei R¹² Wasserstoff oder ein Fettsäurerest der Formel C(O)-R¹³ ist, mit R¹³ = C_6-C₄₀-Alkenyl, n eine Zahl von 1 bis 30 und X für Halogen, bevorzugt Chlor, oder ein Methosulfat steht.
   Beispielhaft für derartige quartäre Ammoniumsalze seien genannt:
   • Dihexadecyl-dimethylammoniumchlorid, Distearyldimethylammoniumchlorid, Quaternisierungsprodukte von Estern des Di- und Triethanolamins mit langkettigen Fettsäuren (Laurinsäure, Myristinsäure, Palmitinsäure, Stearinsäure, Behensäure, Ölsäure und Fettsäuremischungen, wie Cocosfettsäure, Talgfettsäure, hydrierte Talgfettsäure, Tallölfettsäure), wie N-Methyltriethanolammoniumdistearylester-chlorid, N-Methyltriethanolammoniumdistearylestermethosulfat, N,N-Dimethyldiethanolammoniumdistearylesterchlorid, N-Methyltriethanolammoniumdioleylester-chlorid, N-Methyltriethanolammoniumtrilaurylestermethosulfat, N-Methyltriethanolamrrioniumtristearylestermethosulfat und deren Mischungen.
4. 4. Verbindungen der Formel
   
   in denen
   R¹⁴ für CONR⁶R⁷ oder CO₂ ^{- +}H₂NR⁶R⁷ steht,
   R¹⁵ und R¹⁶ für H, CONR¹⁷ ₂, CO₂R¹⁷ oder OCOR¹⁷, -OR¹⁷, -R¹⁷ oder -NCOR¹⁷ stehen, und
   R¹⁷ Alkyl, Alkoxyalkyl oder Polyalkoxyalkyl ist und mindestens 10 Kohlenstoffatome aufweist.
   Bevorzugte Carbonsäuren bzw. Säurederivate sind Phthalsäure(anhydrid), Trimellit, Pyromellitsäure(dianhydrid), Isophthalsäure, Terephthalsäure, Cyclohexan-dicarbonsäure(anhydrid), Maleinsäure(anhydrid), Alkenylbernsteinsäure(anhydrid). Die Formulierung (anhydrid) bedeutet, dass auch die Anhydride der genannten Säuren bevorzugte Säurederivate sind.
   Wenn die Verbindungen obiger Formel Amide oder Aminsalze sind, sind sie vorzugsweise von einem sekundären Amin, das eine Wasserstoff und Kohlenstoff enthaltende Gruppe mit mindestens 10 Kohlenstoffatomen enthält, erhalten.
   Es ist bevorzugt, dass R¹⁷ 10 bis 30, insbesondere 10 bis 22, z.B. 14 bis 20 Kohlenstoffatome enthält und vorzugsweise geradkettig oder an der 1- oder 2-Position verzweigt ist. Die anderen Wasserstoff und Kohlenstoff enthaltenden Gruppen können kürzer sein, z.B. weniger als 6 Kohlenstoffatome enthalten, oder können, falls gewünscht, mindestens 10 Kohlenstoffatome aufweisen. Geeignete Alkylgruppen schließen Methyl, Ethyl, Propyl, Hexyl, Decyl, Dodecyl, Tetradecyl, Eicosyl und Docosyl (Behenyl) ein.
   Des weiteren sind Polymere geeignet, die mindestens eine Amid-, Imid- oder Ammoniumgruppe direkt an das Gerüst des Polymers gebunden enthalten, wobei die Amid-, Imid- oder Ammoniumgruppe mindestens eine Alkylgruppe von mindestens 8 C-Atomen am Stickstoffatom trägt. Derartige Polymere können auf verschiedene Arten hergestellt werden. Eine Art ist, ein Polymer zu verwenden, das mehrere Carbonsäure oder - Anhydridgruppen enthält, und dieses Polymer mit einem Amin der Formel NHR⁶R⁷ umzusetzen, um das gewünschte Polymer zu erhalten.
   Als Polymere sind dazu allgemein Copolymere aus ungesättigten Estern wie C₁-C₄₀-Alkyl(meth)acrylaten, Fumarsäuredi(C₁-C₄₀-alkylestern), C₁-C_40-Alkylvinylethern, C₁-C₄₀-Alkylvinylestern oder C₂-C₄₀-Olefinen (linear, verzweigt, aromatisch) mit ungesättigten Carbonsäuren bzw. deren reaktiven Derivaten, wie z.B. Carbonsäureanhydriden (Acrylsäure, Methacrylsäure, Maleinsäure, Fumarsäure, Itaconsäure, Tetrahydrophthalsäure, Citraconsäure, bevorzugt Maleinsäureanhydrid) geeignet.
   Carbonsäuren werden vorzugsweise mit 0,1 bis 1,5 mol, insbesondere 0,5 bis 1,2 mol Amin pro Säuregruppe, Carbonsäureanhydride vorzugsweise mit 0,1 bis 2,5, insbesondere 0,5 bis 2,2 mol Amin pro Säureanhydridgruppe umgesetzt, wobei je nach Reaktionsbedingungen Amide, Ammoniumsalze, Amid-Ammoniumsalze oder Imide entstehen. So ergeben Copolymere, die ungesättigte Carbonsäureanhydride enthalten, bei der Umsetzung mit einem sekundären Amin auf Grund der Reaktion mit der Anhydridgruppe zur Hälfte Amid und zur Hälfte Aminsalze. Durch Erhitzen kann unter Bildung des Diamids Wasser abgespalten werden.
   Besonders geeignete Beispiele amidgruppenhaltiger Polymere zur erfindungsgemäßen Verwendung sind:
5. 5. Copolymere (a) eines Dialkylfumarats, -maleats, -citraconats oder -itaconats mit Maleinsäureanhydrid, oder (b) von Vinylestern, z.B. Vinylacetat oder Vinylstearat mit Maleinsäureanhydrid, oder (c) eines Dialkylfumarats, -maleats, -citraconats oder -itaconats mit Maleinsäureanhydrid und Vinylacetat.
   Besonders geeignete Beispiele für diese Polymere sind Copolymere von Didodecylfumarat, Vinylacetat und Maleinsäureanhydrid; Ditetradecylfumarat, Vinylacetat und Maleinsäureanhydrid; Dihexadecylfumarat, Vinylacetat und Maleinsäureanhydrid; oder den entsprechenden Copolymeren, bei denen anstelle des Fumarats das Itaconat verwendet wird.
   In den oben genannten Beispielen geeigneter Polymere wird das gewünschte Amid durch Umsetzung des Polymers, das Anhydridgruppen enthält, mit einem sekundären Amin der Formel HNR⁶R⁷ (gegebenenfalls außerdem mit einem Alkohol, wenn ein Esteramid gebildet wird) erhalten. Wenn Polymere, die eine Anhydridgruppe enthalten, umgesetzt werden, werden die resultierenden Aminogruppen Ammoniumsalze und Amide sein. Solche Polymere können verwendet werden, mit der Maßgabe, dass sie mindestens zwei Amidgruppen enthalten.
   Es ist wesentlich, dass das Polymer, das mindestens zwei Amidgruppen enthält, mindestens eine Alkylgruppe mit mindestens 10 Kohlenstoffatomen enthält. Diese langkettige Gruppe, die eine geradkettige oder verzweigte Alkylgruppe sein kann, kann über das Stickstoffatom der Amidgruppe gebunden vorliegen.
   Die dafür geeigneten Amine können durch die Formel R⁶R⁷NH und die Polyamine durch R⁶NH[R¹⁹NH]_xR⁷ wiedergegeben werden, wobei R¹⁹ eine zweiwertige Kohlenwasserstoffgruppe, vorzugsweise eine Alkylen- oder kohlenwasserstoffsubstituierte Alkylengruppe, und x eine ganze Zahl, vorzugsweise zwischen 1 und 30 ist. Vorzugsweise enthalten einer der beiden oder beide Reste R⁶ und R⁷ mindestens 10 Kohlenstoffatome, beispielsweise 10 bis 20 Kohlenstoffatome, zum Beispiel Dodecyl, Tetradecyl, Hexadecyl oder Octadecyl.
   Beispiele geeigneter sekundärer Amine sind Dioctylamin und solche, die Alkylgruppen mit mindestens 10 Kohlenstoffatomen enthalten, beispielsweise Didecylamin, Didodecylamin, Dicocosamin (d.h. gemischte C₁₂-C₁₄-Amine), Dioctadecylamin, Hexadecyloctadecylamin, Di-(hydriertes Talg)-Amin (annähernd 4 Gew.-% n-C₁₄-Alkyl, 30 Gew.-% n-C₁₀-Alkyl, 60 Gew.-% n-C₁₈-Alkyl, der Rest ist ungesättigt). Beispiele geeigneter Polyamine sind N-Octadecylpropandiamin, N,N'-Dioctadecylpropandiamin, N-Tetradecylbutandiamin und N,N'-Dihexadecylhexandiamin. N-Cocospropylendiamin (C₁₂/C_14-Alkylpropylen-diamin), N-Talgpropylendiamin (C₁₆/C₁₈-Alkylpropylendiamin).
   Die amidhaltigen Polymere haben üblicherweise ein durchschnittliches Molekulargewicht (Zahlenmittel) von 1000 bis 500 000, zum Beispiel 10 000 bis 100 000.
6. 6. Copolymere des Styrols, seiner Derivate oder aliphatischer Olefine mit 2 bis 40 C-Atomen, bevorzugt mit 6 bis 20 C-Atomen und olefinisch ungesättigten Carbonsäuren oder Carbonsäureanhydriden, die mit Aminen der Formel HNR⁶R⁷ umgesetzt sind. Die Umsetzung kann vor oder nach der Polymerisation vorgenommen werden.
   Im einzelnen leiten sich die Struktureinheiten der Copolymere von z.B. Maleinsäure, Fumarsäure, Itaconsäure, Tetrahydrophthalsäure, Citraconsäure, bevorzugt Maleinsäureanhydrid ab. Sie können sowohl in Form ihrer Homopolymeren als auch der Copolymeren eingesetzt werden. Als Comonomere sind geeignet: Styrol und Alkylstyrole, geradkettige und verzweigte Olefine mit 2 bis 40 Kohlenstoffatomen, sowie deren Mischungen untereinander. Beispielsweise seien genannt: Styrol, α-Methylstyrol, Dimethylstyrol, α-Ethylstyrol, Diethylstyrol, i-Propylstyrol, tert.-Butylstyrol, Ethylen, Propylen, n-Butylen, Diisobutylen, Decen, Dodecen, Tetradecen, Hexadecen, Octadecen. Bevorzugt sind Styrol und Isobuten, besonders bevorzugt ist Styrol.
   Als Polymere seien beispielsweise im einzelnen genannt: Polymaleinsäure, ein molares, alternierend aufgebautes Styrol/Maleinsäure-Copolymer, statistisch aufgebaute Styrol/Maleinsäure-Copolymere im Verhältnis 10:90 und ein alternierendes Copolymer aus Maleinsäure und i-Buten. Die molaren Massen der Polymeren betragen im allgemeinen 500 g/mol bis 20 000 g/mol, bevorzugt 700 bis 2000 g/mol.
   Die Umsetzung der Polymeren oder Copolymeren mit den Aminen erfolgt bei Temperaturen von 50 bis 200°C im Verlauf von 0,3 bis 30 Stunden. Das Amin wird dabei in Mengen von ungefähr einem Mol pro Mol einpolymerisiertem Dicarbonsäureanhydrid, d.i. ca.0,9 bis 1,1 Mol/Mol, angewandt. Die Verwendung größerer oder geringerer Mengen ist möglich, bringt aber keinen Vorteil. Werden größere Mengen als ein Mol angewandt, erhält man zum Teil Ammoniumsalze, da die Bildung einer zweiten Amidgruppierung höhere Temperaturen, längere Verweilzeiten und Wasserauskreisen erfordert. Werden geringere Mengen als ein Mol angewandt, findet keine vollständige Umsetzung zum Monoamid statt und man erhält eine dementsprechend verringerte Wirkung.
   Anstelle der nachträglichen Umsetzung der Carboxylgruppen in Form des Dicarbonsäureanhydrids mit Aminen zu den entsprechenden Amiden kann es manchmal von Vorteil sein, die Monoamide der Monomeren herzustellen und dann bei der Polymerisation direkt einzupolymerisieren. Meist ist das jedoch technisch viel aufwendiger, da sich die Amine an die Doppelbindung der monomeren Mono- und Dicarbonsäure anlagern können und dann keine Copolymerisation mehr möglich ist.
7. 7. Copolymere, bestehend aus 10 bis 95 Mol-% eines oder mehrerer Alkylacrylate oder Alkylmethacrylate mit C₁-C₂₆-Alkylketten und aus 5 bis 90 Mol-% einer oder mehrerer ethylenisch ungesättigter Dicarbonsäuren oder deren Anhydriden, wobei das Copolymere weitgehend mit einem oder mehreren primären oder sekundären Aminen zum Monoamid oder Amid/Ammoniumsalz der Dicarbonsäure umgesetzt ist.
   Die Copolymeren bestehen zu 10 bis 95 Mol-%, bevorzugt zu 40 bis 95 Mol-% und besonders bevorzugt zu 60 bis 90 Mol-% aus Alkyl(meth)acrylaten und zu 5 bis 90 Mol-%, bevorzugt zu 5 bis 60 Mol-% und besonders bevorzugt zu 10 bis 40 Mol-% aus den olefinisch ungesättigten Dicarbonsäurederivaten. Die Alkylgruppen der Alkyl(meth)acrylate enthalten aus 1 bis 26, bevorzugt 4 bis 22 und besonders bevorzugt 8 bis 18 Kohlenstoffatome. Sie sind bevorzugt geradkettig und unverzweigt. Es können jedoch auch bis zu 20 Gew.-% cyclische und/oder verzweigte Anteile enthalten sein.
   Beispiele für besonders bevorzugte Alkyl(meth)acrylate sind n-Octyl(meth)acrylat, n-Decyl(meth)acrylat, n-Dodecyl(meth)acrylat, n-Tetradecyl(meth)acrylat, n-Hexadecyl(meth)acrylat und n-Octadecyl(meth)acrylat sowie Mischungen davon.
   Beispiele ethylenisch ungesättigter Dicarbonsäuren sind Maleinsäure, Tetrahydrophthalsäure, Citraconsäure und Itaconsäure bzw. deren Anhydride sowie Fumarsäure. Bevorzugt ist Maleinsäureanhydrid.
   Als Amine kommen Verbindungen der Formel HNR⁶R⁷ in Betracht.
   In der Regel ist es von Vorteil, die Dicarbonsäuren in Form der Anhydride, soweit verfügbar, bei der Copolymerisation einzusetzen, z.B. Maleinsäureanhydrid, Itaconsäureanhydrid, Citraconsäureanhydrid und Tetrahydrophthalsäureanhydrid, da die Anhydride in der Regel besser mit den (Meth)acrylaten copolymerisieren. Die Anhydridgruppen der Copolymeren können dann direkt mit den Aminen umgesetzt werden.
   Die Umsetzung der Polymeren mit den Aminen erfolgt bei Temperaturen von 50 bis 200°C im Verlauf von 0,3 bis 30 Stunden. Das Amin wird dabei in Mengen von ungefähr einem bis zwei Mol pro Mol einpolymerisiertem Dicarbonsäureanhydrid, d.i. ca. 0,9 bis 2,1 Mol/Mol angewandt. Die Verwendung größerer oder geringerer Mengen ist möglich, bringt aber keinen Vorteil. Werden größere Mengen als zwei Mol angewandt, liegt freies Amin vor. Werden geringere Mengen als ein Mol angewandt, findet keine vollständige Umsetzung zum Monoamid statt und man erhält eine dementsprechend verringerte Wirkung.
   In einigen Fällen kann es von Vorteil sein, wenn die Amid/Ammoniumsalzstruktur aus zwei unterschiedlichen Aminen aufgebaut wird. So kann beispielsweise ein Copolymer aus Laurylacrylat und Maleinsäureanhydrid zuerst mit einem sekundären Amin, wie hydriertem Ditalgfettamin zum Amid umgesetzt werden, wonach die aus dem Anhydrid stammende freie Carboxylgruppe mit einem anderen Amin, z.B. 2-Ethylhexylamin zum Ammoniumsalz neutralisiert wird. Genauso ist die umgekehrte Vorgehensweise denkbar: Zuerst wird mit Ethylhexylamin zum Monoamid, dann mit Ditalgfettamin zum Ammoniumsalz umgesetzt. 0Vorzugsweise wird dabei mindestens ein Amin verwendet, welches mindestens eine geradkettige, unverzweigte Alkylgruppe mit mehr als 16 Kohlenstoffatomen besitzt. Es ist dabei nicht erheblich, ob dieses Amin am Aufbau der Amidstruktur oder als Ammoniumsalz der Dicarbonsäure vorliegt.
   Anstelle der nachträglichen Umsetzung der Carboxylgruppen bzw. des Dicarbonsäureanhydrids mit Aminen zu den entsprechenden Amiden oder Amid/Ammoniumsalzen, kann es manchmal von Vorteil sein, die Monoamide bzw. Amid/Ammoniumsalze der Monomeren herzustellen und dann bei der Polymerisation direkt einzupolymerisieren. Meist ist das jedoch technisch viel aufwendiger, da sich die Amine an die Doppelbindung der monomeren Dicarbonsäure anlagern können und dann keine Copolymerisation mehr möglich ist.
8. 8. Terpolymere auf Basis von α,β-ungesättigten Dicarbonsäureanhydriden, α,β-ungesättigten Verbindungen und Polyoxyalkylenethern von niederen, ungesättigten Alkoholen, die dadurch gekennzeichnet sind, dass sie 20 - 80, bevorzugt 40 - 60 Mol-% an bivalenten Struktureinheiten der Formeln 1 und/oder 3, sowie gegebenenfalls 2 enthalten, wobei die Struktureinheiten 2 von nicht umgesetzten Anhydridresten stammen,
   
   
   
   wobei
   R²² und R²³ unabhängig voneinander Wasserstoff oder Methyl,
   a, b gleich Null oder Eins und a + b gleich Eins,
   R²⁴ und R²⁵ gleich oder verschieden sind und für die Gruppen -NHR⁶,
   N(R⁶)₂ und/oder -OR²⁷ stehen, und R²⁷ für ein Kation der Formel H₂N(R⁶)₂ oder H₃NR⁶ steht,
   19 - 80 Mol-%, bevorzugt 39-60 Mol-% an bivalenten Struktureinheiten der Formel 4
   
   worin
   R²⁸ Wasserstoff oder C₁-C₄-Alkyl und
   R²⁹ C₆-C₆₀-Alkyl oder C₆-C₁₈-Aryl bedeuten und
   1 - 30 Mol-%, bevorzugt 1 - 20 Mol-% an bivalenten Struktureinheiten der Formel 5
   
   worin
   R³⁰ Wasserstoff oder Methyl,
   R³¹ Wasserstoff oder C₁-C₄-Alkyl,
   R³³ C₁-C₄-Alkylen,
   m eine Zahl von 1 bis 100,
   R³² C₁-C₂₄-Alkyl, C₅-C₂₀-Cycloalkyl, C₆-C₁₈-Aryl oder -C(O)-R³⁴, wobei
   R³⁴ C₁-C₄₀-Alkyl, C₅-C₁₀-Cycloalkyl oder C₆-C₁₈-Aryl,
   enthalten.
   Die vorgenannten Alkyl-, Cycloalkyl- und Arylreste können gegebenenfalls substituiert sein. Geeignete Substituenten der Alkyl- und Arylreste sind beispielsweise (C₁-C₆)-Alkyl, Halogene, wie Fluor, Chlor, Brom und Jod, bevorzugt Chlor und (C₁-C₆)-Alkoxy.
   Alkyl steht hier für einen geradkettigen oder verzweigten Kohlenwasserstoffrest. Im einzelnen seien genannt: n-Butyl, tert.-Butyl, n-Hexyl, n-Octyl, Decyl, Dodecyl, Tetradecyl, Hexadecyl, Octadecyl, Dodecenyl, Tetrapropenyl, Tetradecenyl, Pentapropenyl, Hexadecenyl, Octadecenyl und Eicosanyl oder Mischungen, wie Cocosalkyl, Talgfettalkyl und Behenyl.
   Cycloalkyl steht hier für einen cyclischen aliphatischen Rest mit 5 - 20 Kohlenstoffatomen. Bevorzugte Cycloalkylreste sind Cyclopentyl und Cyclohexyl.
   Aryl steht hier für einen gegebenenfalls substituiertes aromatisches Ringsystem mit 6 bis 18 Kohlenstoffatomen.
   Die Terpolymere bestehen aus den bivalenten Struktureinheiten der Formeln 1 und 3 sowie 4 und 5 und ggf. 2. Sie enthalten lediglich noch in an sich bekannter Weise die bei der Polymerisation durch Initiierung, Inhibierung und Kettenabbruch entstandenen Endgruppen.
   Im einzelnen leiten sich Struktureinheiten der Formeln 1 bis 3 von α,β-ungesättigten Dicarbonsäureanhydriden der Formeln 6 und 7
   
   
   wie Maleinsäureanhydrid, Itaconsäureanhydrid, Citraconsäureanhydrid, bevorzugt Maleinsäureanhydrid, ab.
   Die Struktureinheiten der Formel 4 leiten sich von den α,β-ungesättigten Verbindungen der Formel 8 ab.
   
   
   Beispielhaft seien die folgenden α,β-ungesättigten Olefine genannt: Styrol, α-Methylstyrol, Dimethylstyrol, α-Ethylstyrol, Diethylstyrol, i-Propylstyrol, tert.-Butylstyrol, Diisobutylen und α-Olefine, wie Decen, Dodecen, Tetradecen, Pentadecen, Hexadecen, Octadecen, C₂₀-α-Olefin, C₂₄-α-Olefin, C₃₀-α-Olefin, Tripropenyl, Tetrapropenyl, Pentapropenyl sowie deren Mischungen. Bevorzugt sind α-Olefine mit 10 bis 24 C-Atomen und Styrol, besonders bevorzugt sind α-Olefine mit 12 bis 20 C-Atomen.
   Die Struktureinheiten der Formel 5 leiten sich von Polyoxyalkylenethern niederer, ungesättigter Alkohole der Formel 9 ab.
   
   
   Bei den Monomeren der Formel 9 handelt es sich um Veretherungsprodukte (R³² = -C(O)R³⁴) oder Veresterungsprodukte (R³² = -C(O)R³⁴) von Polyoxyalkylenethern (R³² = H).
   Die Polyoxyalkylenether (R³² = H) lassen sich nach bekannten Verfahren durch Anlagerung von α-Olefinoxiden, wie Ethylenoxid, Propylenoxid und/oder Butylenoxid an polymerisierbare niedere, ungesättigte Alkohole der Formel 10
   
   herstellen. Solche polymerisierbaren niederen ungesättigten Alkohole sind z.B. Allylalkohol, Methallylalkohol, Butenole, wie 3-Buten-1-ol und 1-Buten-3-ol oder Methylbutenole, wie 2-Methyl-3-buten-1-ol, 2-Methyl-3-buten-2-ol und 3-Methyl-3-buten-1-ol. Bevorzugt sind Anlagerungsprodukte von Ethylenoxid und/oder Propylenoxid an Allylalkohol.
   Eine nachfolgende Veretherung dieser Polyoxyalkylenether zu Verbindungen der Formel 9 mit R³² = C₁-C₂₄-Alkyl, Cycloalkyl oder Aryl erfolgt nach an sich bekannten Verfahren. Geeignete Verfahren sind z.B. aus J. March, Advanced Organic Chemistry, 2. Auflage, S. 357f (1977) bekannt. Diese Veretherungsprodukte der Polyoxyalkylenether lassen sich auch herstellen, indem man α-Olefinoxide, bevorzugt Ethylenoxid, Propylenoxid und/oder Butylenoxid an Alkohole der Formel 11
   
           R³² - OH     (11)
   
   worin R³² gleich C₁-C₂₄-Alkyl, C₅-C₂₀-Cycloalkyl oder C₆-C₁₈-Aryl, nach bekannten Verfahren anlagert und mit polymerisierbaren niederen, ungesättigten Halogeniden der Formel 12
   
   umsetzt, wobei W für ein Halogenatom steht. Als Halogenide werden bevorzugt die Chloride und Bromide eingesetzt. Geeignete Herstellungsverfahren werden z.B. in J. March, Advanced Organic Chemistry, 2.Auflage, S.357f (1977) genannt.
   Die Veresterung der Polyoxyalkylenether (R³² = -C(O)-R³⁴) erfolgt durch Umsetzung mit gängigen Veresterungsmitteln, wie Carbonsäuren, Carbonsäurehalogeniden, Carbonsäureanhydriden oder Carbonsäureestern mit C₁-C₄-Alkoholen. Bevorzugt werden die Halogenide und Anhydride von C₁-C₄₀-Alkyl-, C₅-C₁₀-Cycloalkyl- oder C₆-C_18-Arylcarbonsäuren verwendet. Die Veresterung wird im allgemeinen bei Temperaturen von 0 bis 200°C, vorzugsweise 10 bis 100°C durchgeführt.
   Bei den Monomeren der Formel 9 gibt der Index m den Alkoxylierungsgrad, d.h. die Anzahl der Mole an α-Olefin an, die pro Mol der Formel 20 oder 21 angelagert werden.
   Als zur Herstellung der Terpolymere geeignete primäre Amine seien beispielsweise die folgenden genannt:
   • n-Hexylamin, n-Octylamin, n-Tetradecylamin, n-Hexadecylamin, n-Stearylamin oder auch N,N-Dimethylaminopropylendiamin, Cyclohexylamin, Dehydroabietylamin sowie deren Mischungen.
   
   Als zur Herstellung der Terpolymere geeignete sekundäre Amine seien beispielsweise genannt: Didecylamin, Ditetradecylamin, Distearylamin, Dicocosfettamin, Ditalgfettamin und deren Mischungen.
   Die Terpolymeren besitzen K-Werte (gemessen nach Ubbelohde in 5 gew.-%iger Lösung in Toluol bei 25°C) von 8 bis 100, bevorzugt 8 bis 50, entsprechend mittleren Molekulargewichten (M_w) zwischen ca. 500 und 100.000. Geeignete Beispiele sind in EP 606 055 aufgeführt.
   Umsetzungsprodukte von Alkanolaminen und/oder Polyetheraminen mit Polymeren enthaltend Dicarbonsäureanhydridgruppen, dadurch gekennzeichnet, dass sie 20 - 80, bevorzugt 40 - 60 Mol-% an bivalenten Struktureinheiten der Formeln 13 und 15 und gegebenenfalls 14
   
   
   
   wobei
   R²² und R²³ unabhängig voneinander Wasserstoff oder Methyl,
   a, b gleich Null oder 1 und a + b gleich 1,
   R³⁷ = -OH, -O-[C₁-C₃₀-Alkyl], -NR⁶R⁷, -O^sN^rR⁶R⁷H₂
   R³⁸ = R³⁷ oder NR⁶R³⁹
   R³⁹ = -(A-O)_x-E
   mit
   A = Ethylen- oder Propylengruppe
   x = 1 bis 50
   E = H, C₁-C₃₀-Alkyl, C₅-C₁₂-Cycloalkyl oder C₆-C₃₀-Aryl
   bedeuten, und 80 - 20 Mol-%, bevorzugt 60 - 40 Mol-% an bivalenten Struktureinheiten der Formel 4 enthalten.
   Im einzelnen leiten sich die Struktureinheiten der Formeln 13, 14 und 15 von α,β-ungesättigten Dicarbonsäureanhydriden der Formeln 6 und/oder 7 ab.
   Die Struktureinheiten der Formel 4 leiten sich von den α,β-ungesättigten Olefinen der Formel 8 ab. Die vorgenannte Alkyl-, Cycloalkyl- und Arylreste haben die gleichen Bedeutungen wie unter 8.
   Die Reste R37 und R38 in Formel 13 bzw. R39 in Formel 15 leiten sich von Polyetheraminen oder Alkanolaminen der Formeln 16 a) und b), Aminen der Formel NR6R7R8 sowie gegebenenfalls von Alkoholen mit 1 bis 30 Kohlenstoffatomen ab.
   
   
   
   Darin bedeuten

   R⁵³

   Wasserstoff, C₆-C₄₀-Alkyl oder

   

   R⁵⁴

   Wasserstoff, C₁-C₄-Alkyl

   R⁵⁵

   Wasserstoff, C₁-C₄-Alkyl, C₅- bis C₁₂-Cycloalkyl oder C₆- bis C₃₀-Aryl

   R⁵⁶, R⁵⁷

   unabhängig voneinander Wasserstoff, C₁- bis C₂₂-Alkyl, C₂- bis C₂₂-Alkenyl oder Z - OH

   Z

   C₂- bis C₄-Alkylen

   n

   eine Zahl zwischen 1 und 1000.

   
   Zur Derivatisierung der Struktureinheiten der Formeln 6 und 7 werden vorzugsweise Gemische aus mindestens 50 Gew.-% Alkylaminen der Formel HNR⁶R⁷R⁸ und höchstens 50 Gew.-% Polyetheraminen, Alkanolaminen der Formeln 16 a) und b) verwendet.
   Die Herstellung der eingesetzten Polyetheramine ist beispielsweise durch reduktive Aminierung von Polyglykolen möglich. Des weiteren gelingt die Herstellung von Polyetheraminen mit einer primären Aminogruppe durch Addition von Polyglykolen an Acrylnitril und anschließende katalytische Hydrierung. Darüber hinaus sind Polyetheramine durch Umsetzung von Polyethern mit Phosgen bzw. Thionylchlorid und anschließende Aminierung zum Polyetheramin zugänglich. Die erfindungsgemäß eingesetzten Polyetheramine sind (z.B.) unter der Bezeichnung ® Jeffamine (Texaco) kommerziell erhältlich. Ihr Molekulargewicht beträgt bis zu 2000 g/mol und das Ethylenoxid-/Propylenoxid-Verhältnis beträgt von 1:10 bis 6:1.
   Eine weitere Möglichkeit zur Derivatisierung der Struktureinheiten der Formeln 6 und 7 besteht darin, dass anstelle der Polyetheramine ein Alkanolamin der Formeln 16a) oder 16b) eingesetzt und nachfolgend einer Oxalkylierung unterworfen wird.
   Pro Mol Anhydrid werden 0,01 bis 2 Mol, bevorzugt 0,01 bis 1 Mol Alkanolamin eingesetzt. Die Reaktionstemperatur beträgt zwischen 50 und 100°C (Amidbildung). Im Falle von primären Aminen erfolgt die Umsetzung bei Temperaturen oberhalb 100°C (Imidbildung).
   Die Oxalkylierung erfolgt üblicherweise bei Temperaturen zwischen 70 und 170°C unter Katalyse von Basen, wie NaOH oder NaOCH3, durch Aufgasen von Alkylenoxiden, wie Ethylenoxid (EO) und/oder Propylenoxid (PO). Üblicherweise werden pro Mol Hydroxylgruppen 1 bis 500, bevorzugt 1 bis 100 Mol Alkylenoxid zugegeben.
   Als geeignete Alkanolamine seien beispielsweise genannt:
   • Monoethanolamin, Diethanolamin, N-Methylethanolamin, 3-Aminopropanol, Isopropanol, Diglykolamin, 2-Amino-2-methylpropanol und deren Mischungen.
   
   Als primäre Amine seien beispielsweise die folgenden genannt:
   • n-Hexylamin, n-Octylamin, n-Tetradecylamin, n-Hexadecylamin, n-Stearylamin oder auch N,N-Dimethylaminopropylendiamin, Cyclohexylamin, Dehydroabietylamin sowie deren Mischungen.
   
   Als sekundäre Amine seien beispielsweise genannt:
   • Didecylamin, Ditetradecylamin, Distearylamin, Dicocosfettamin,
   • Ditalgfettamin und deren Mischungen.
   
   Als Alkohole seien beispielsweise genannt:
   • Methanol, Ethanol, Propanol, Isopropanol, n-, sek.-, tert.-Butanol, Octanol, Tetradecanol, Hexadecanol, Octadecanol, Talgfettalkohol, Behenylalkohol und deren Mischungen. Geeignete Beispiele sind in EP-A-688 796 aufgeführt.
9. 10. Co- und Terpolymere von N-C₆-C₂₄-Alkylmaleinimid mit C₁-C₃₀-Vinylestern, Vinylethern und/oder Olefinen mit 1 bis 30 C-Atomen, wie z.B. Styrol oder α-Olefinen. Diese sind zum einen durch Umsetzung eines Anhydridgruppen enthaltenden Polymers mit Aminen der Formel H2NR6 oder durch Imidierung der Dicarbonsäure und anschließende Copolymerisation zugänglich. Bevorzugte Dicarbonsäure ist dabei Maleinsäure bzw. Maleinsäureanhydrid. Bevorzugt sind dabei Copolymere aus 10 bis 90 Gew.-% C₆-C₂₄-α-Olefinen und 90 bis 10 Gew.-% N-C₆-C_22-Alkylmaleinsäureimid.

The following Paraffindispergatoren (D) are partially by Reaction of compounds containing an acyl group made with an amine. This amine is a compound 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 remaining groups are either hydrogen, C ₁ -C ₃₆ alkyl, C ₂ -C ₃₆ alkenyl, Cyciohexyi, or a group of formulas - (AO) _x -E or - (CH ₂ ) _n -NYZ where A is an ethylene or propylene group, x is a number from 1 to 50, E Is H, C ₁ -C ₃₀ -alkyl, C ₅ -C ₁₂ -cycloalkyl or C ₆ -C ₃₀ -aryl, and n is 2, 3 or 4, and Y and Z are each independently H, C ₁ -C ₃₀ - Alkyl or - (AO) _x . By acyl group is meant here a functional group of the following formula:

> C = O

1. 1. Reaction products of alkenyl-spirobislactones of the formula
   
   where R is in each case C ₈ -C ₂₀₀ -alkenyl, with amines of the formula NR ⁶ R ⁷ R ⁸ . Suitable reaction products are listed in EP-A-0 413 279. Depending on the reaction condition, amides or amide-ammonium salts are obtained in the reaction of compounds of the formula with the amines.
2. 2. Amides or ammonium salts of aminoalkylene polycarboxylic acids with secondary amines of the formulas
   
   
   in which
   R ^{10 is} a straight-chain or branched alkylene radical having 2 to 6 carbon atoms or the radical of the formula
   
   in which R ⁶ and R ⁷ denote in particular alkyl radicals having 10 to 30, preferably 14 to 24 C atoms, wherein the amide structures also partly or completely in the form of the ammonium salt structure of the formula
   
   may be present.
   The amides or amide ammonium salts or ammonium salts of, for example, nitrilotriacetic acid, ethylenediaminetetraacetic acid or propylene-1,2-diaminetetraacetic acid are obtained by reacting the acids with from 0.5 to 1.5 mol of amine, preferably from 0.8 to 1.2 mol Amine per carboxyl group. The reaction temperatures are about 80 to 200 ° C, wherein for the preparation of the amides a continuous removal of the resulting water of reaction takes place. However, the reaction does not have to be completely led to the amide, but may be 0 to 100 mol% of the amine used in the form of the ammonium salt. Under analogous conditions, the compounds mentioned under B1) can also be prepared.
   As amines of the formula
   
   Particularly suitable dialkylamines are contemplated in which R ⁶ , R ^{7 is} a straight-chain alkyl radical having 10 to 30 carbon atoms, preferably 14 to 24 carbon atoms. Specifically, dioleylamine, dipalmitinamine, dicoco fatty amine and dibehenylamine and preferably ditallow fatty amine may be mentioned.
3. 3. Quaternary ammonium salts of the formula
   
   ⁺ NR ⁶ R ⁷ R ⁸ R ¹¹ X ^-
   
   wherein R ^6, R ^7, R ⁸ have the meaning given above and R ¹¹ is C ₁ -C ₃₀ alkyl, preferably C ₁ -C ₂₂ alkyl, C ₁ -C ₃₀ -alkenyl, preferably C ₁ -C ₂₂ - Alkenyl, benzyl or a radical of the formula - (CH ₂ -CH ₂ -O) _n -R ¹² , where R ^{12 is} hydrogen or a fatty acid radical of the formula C (O) -R ¹³ , where R ¹³ = C _{6 -C 40} alkenyl, n is a number from 1 to 30 and X is halogen, preferably chlorine, or a methosulfate.
   Examples of such quaternary ammonium salts include:
   • Dihexadecyldimethylammonium chloride, distearyldimethylammonium chloride, quaternization products of esters of di- and triethanolamine with long-chain fatty acids (lauric, myristic, palmitic, stearic, behenic, oleic and fatty acid mixtures such as coconut fatty acid, tallow fatty acid, hydrogenated tallow fatty acid, tall oil fatty acid) such as N-methyltriethanolammonium distearyl ester chloride; N-methyltriethanolammonium distearyl ester methosulfate, N, N-dimethyldiethanolammonium distearyl ester chloride, N-methyltriethanolammonium dioleyl ester chloride, N-methyltriethanolammonium trilauryl ester methosulfate, N-methyltriethanolammonium tristearyl ester methosulfate, and mixtures thereof.
4. 4. Compounds of the formula
   
   in which
   R ^{14 is} CONR ⁶ R ⁷ or CO ₂ ^{- +} H ₂ NR ⁶ R ⁷ ,
   R ¹⁵ and R ^{16 are} H, CONR ¹⁷ ₂ , CO ₂ R ¹⁷ or OCOR ¹⁷ , -OR ¹⁷ , -R ¹⁷ or -NCOR ¹⁷ , and
   R ^{17 is} alkyl, alkoxyalkyl or polyalkoxyalkyl and has at least 10 carbon atoms.
   Preferred carboxylic acids or acid derivatives are phthalic acid (anhydride), trimellit, pyromellitic acid (dianhydride), isophthalic acid, terephthalic acid, cyclohexane-dicarboxylic acid (anhydride), maleic acid (anhydride), alkenylsuccinic acid (anhydride). The formulation (anhydride) means that the anhydrides of said acids are preferred acid derivatives.
   When the compounds of the above formula are amides or amine salts, they are preferably obtained from a secondary amine containing a hydrogen and carbon containing group having at least 10 carbon atoms.
   It is preferred that R ^{17 contains from} 10 to 30, in particular from 10 to 22, for example from 14 to 20 carbon atoms and is preferably straight-chain or branched at the 1- or 2-position. The other hydrogen and carbon containing groups may be shorter, eg containing less than 6 carbon atoms, or may have at least 10 carbon atoms if desired. Suitable alkyl groups include methyl, ethyl, propyl, hexyl, decyl, dodecyl, tetradecyl, eicosyl and docosyl (behenyl).
   Furthermore, polymers are suitable which contain at least one amide, imide or ammonium group bound directly to the skeleton of the polymer, wherein the amide, imide or ammonium group carries at least one alkyl group of at least 8 C atoms on the nitrogen atom. Such polymers can be prepared in various ways. One way is to use a polymer containing several carboxylic acid or anhydride groups and react this polymer with an amine of the formula NHR ⁶ R ⁷ to obtain the desired polymer.
   As polymers are generally copolymers of unsaturated esters such as C ₁ -C ₄₀ alkyl (meth) acrylates, fumaric di (C ₁ -C ₄₀ alkyl esters), C ₁ -C ₄₀ alkyl vinyl ethers, C ₁ -C ₄₀ alkyl vinyl esters or C. C ₂ -C ₄₀ -olefins (linear, branched, aromatic) with unsaturated carboxylic acids or their reactive derivatives, such as, for example, carboxylic anhydrides (acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, tetrahydrophthalic acid, citraconic acid, preferably maleic anhydride) suitable.
   Carboxylic acids are preferably reacted with from 0.1 to 1.5 mol, in particular from 0.5 to 1.2 mol of amine per acid group, carboxylic anhydrides, preferably with from 0.1 to 2.5, in particular from 0.5 to 2.2, mol of amine per acid anhydride group Depending on the reaction conditions, amides, ammonium salts, amide-ammonium salts or imides are formed. Thus, copolymers containing unsaturated carboxylic acid anhydrides, upon reaction with a secondary amine, yield half amide and half amine salts by reaction with the anhydride group. By heating, water can be split off to form the diamide.
   Particularly suitable examples of amide group-containing polymers for use according to the invention are:
5. 5. Copolymers of (a) a dialkyl fumarate, maleate, citraconate or itaconate with maleic anhydride, or (b) vinyl esters, for example vinyl acetate or vinyl stearate with maleic anhydride, or (c) a dialkyl fumarate, maleate, citraconate or itaconate Maleic anhydride and vinyl acetate.
   Particularly suitable examples of these polymers are copolymers of didodecyl fumarate, vinyl acetate and maleic anhydride; Ditetradecyl fumarate, vinyl acetate and maleic anhydride; Dihexadecyl fumarate, vinyl acetate and maleic anhydride; or the corresponding copolymers in which the itaconate is used instead of the fumarate.
   In the above examples of suitable polymers, the desired amide is obtained by reacting the polymer containing anhydride groups with a secondary amine of the formula HNR ⁶ R ⁷ (optionally also with an alcohol when forming an ester amide). When polymers containing an anhydride group are reacted, For example, the resulting amino groups will be ammonium salts and amides. Such polymers may be used provided that they contain at least two amide groups.
   It is essential that the polymer containing at least two amide groups contains at least one alkyl group having at least 10 carbon atoms. This long-chain group, which may be a straight-chain or branched alkyl group, may be bonded via the nitrogen atom of the amide group.
   The suitable amines can be represented by the formula R ⁶ R ⁷ NH and the polyamines by R ⁶ NH [R ¹⁹ NH] _x R ⁷ , wherein R ^{19 is} a divalent hydrocarbon group, preferably an alkylene or hydrocarbyl-substituted alkylene group, and x is a whole Number, preferably between 1 and 30. Preferably, one of the two or both R ⁶ and R ^{7 contains} at least 10 carbon atoms, for example 10 to 20 carbon atoms, for example dodecyl, tetradecyl, hexadecyl or octadecyl.
   Examples of suitable secondary amines are dioctylamine and those containing alkyl groups of at least 10 carbon atoms, for example, didecylamine, didodecylamine, dicocosamine (ie, mixed C ₁₂ -C ₁₄ amines), dioctadecylamine, hexadecyloctadecylamine, di (hydrogenated tallow) amine (approx Wt% nC ₁₄ alkyl, 30 wt% nC ₁₀ alkyl, 60 wt% nC ₁₈ alkyl, the remainder is unsaturated). Examples of suitable polyamines are N-octadecylpropanediamine, N, N'-dioctadecylpropanediamine, N-tetradecylbutanediamine and N, N'-dihexadecylhexanediamine. N-Cocospropylenediamine (C ₁₂ / C _14- alkylpropylene-diamine), N-tallowpropylenediamine (C ₁₆ / C ₁₈ -alkylpropylenediamine).
   The amide-containing polymers usually have a number average molecular weight of from 1,000 to 500,000, for example 10,000 to 100,000.
6. 6. Copolymers of styrene, its derivatives or aliphatic olefins having 2 to 40 carbon atoms, preferably having 6 to 20 carbon atoms and olefinically unsaturated carboxylic acids or carboxylic anhydrides, which are reacted with amines of the formula HNR ⁶ R ⁷ . The reaction can be carried out before or after the polymerization.
   In detail, the structural units of the copolymers are derived from, for example, maleic acid, fumaric acid, itaconic acid, tetrahydrophthalic acid, citraconic acid, preferably maleic anhydride. They can be used both in the form of their homopolymers and the copolymers. Suitable comonomers are: styrene and alkylstyrenes, straight-chain and branched olefins having 2 to 40 carbon atoms, and mixtures thereof with one another. Examples which may be mentioned: styrene, α-methylstyrene, dimethylstyrene, α-ethylstyrene, diethylstyrene, i-propylstyrene, tert-butylstyrene, ethylene, propylene, n-butylene, diisobutylene, decene, dodecene, tetradecene, hexadecene, octadecene. Preference is given to styrene and isobutene, particular preference to styrene.
   Examples of polymers which may be mentioned are: polymaleic acid, a molar styrene / maleic acid copolymer of alternating design, random copolymers of styrene / maleic acid in a ratio of 10:90 and an alternating copolymer of maleic acid and i-butene. The molar masses of the polymers are generally 500 g / mol to 20,000 g / mol, preferably 700 to 2000 g / mol.
   The reaction of the polymers or copolymers with the amines is carried out at temperatures of 50 to 200 ° C in the course of 0.3 to 30 hours. The amine is applied in amounts of about one mole per mole of copolymerized dicarboxylic anhydride, ie about 0.9 to 1.1 mol / mol. The use of larger or smaller amounts is possible, but brings no advantage. If larger amounts are used than one mole, ammonium salts are sometimes obtained, since the formation of a second amide grouping higher temperatures, longer residence times and Water recirculation requires. If amounts smaller than one mole are used, complete conversion to the monoamide does not take place and a correspondingly reduced effect is obtained.
   Instead of the subsequent reaction of the carboxyl groups in the form of the dicarboxylic anhydride with amines to the corresponding amides, it may sometimes be advantageous to prepare the monoamides of the monomers and then to copolymerize them directly in the polymerization. In most cases, however, this is technically much more complicated because the amines can attach to the double bond of the monomeric mono- and dicarboxylic acid and then no copolymerization is possible.
7. 7. Copolymers consisting of 10 to 95 mol% of one or more alkyl acrylates or alkyl methacrylates with C ₁ -C ₂₆ alkyl chains and from 5 to 90 mol% of one or more ethylenically unsaturated dicarboxylic acids or their anhydrides, wherein the copolymer is largely with a or more primary or secondary amines to the monoamide or amide / ammonium salt of the dicarboxylic acid is reacted.
   The copolymers consist of 10 to 95 mol%, preferably 40 to 95 mol% and particularly preferably 60 to 90 mol% of alkyl (meth) acrylates and 5 to 90 mol%, preferably 5 to 60 mol -% and particularly preferably from 10 to 40 mol% of the olefinically unsaturated dicarboxylic acid derivatives. The alkyl groups of the alkyl (meth) acrylates contain from 1 to 26, preferably 4 to 22 and more preferably 8 to 18 carbon atoms. They are preferably straight-chain and unbranched. However, it may also contain up to 20 wt .-% cyclic and / or branched portions.
   Examples of particularly preferred alkyl (meth) acrylates are n-octyl (meth) acrylate, n-decyl (meth) acrylate, n-dodecyl (meth) acrylate, n-tetradecyl (meth) acrylate, n-hexadecyl (meth) acrylate and n-octadecyl (meth) acrylate and mixtures thereof.
   Examples of ethylenically unsaturated dicarboxylic acids are maleic acid, tetrahydrophthalic acid, citraconic acid and itaconic acid or their anhydrides and fumaric acid. Preference is given to maleic anhydride.
   Suitable amines are compounds of the formula HNR ⁶ R ⁷ .
   As a rule, it is advantageous to use the dicarboxylic acids in the form of the anhydrides, if available, in the copolymerization, for example maleic anhydride, itaconic anhydride, citraconic anhydride and tetrahydrophthalic anhydride, since the anhydrides generally copolymerize better with the (meth) acrylates. The anhydride groups of the copolymers can then be reacted directly with the amines.
   The reaction of the polymers with the amines takes place at temperatures of 50 to 200 ° C in the course of 0.3 to 30 hours. The amine is employed in amounts of about one to two moles per mole of copolymerized dicarboxylic acid anhydride, ie, about 0.9 to 2.1 moles / mole. The use of larger or smaller amounts is possible, but brings no advantage. If amounts greater than two moles are used, free amine is present. If amounts smaller than one mole are used, complete conversion to the monoamide does not take place and a correspondingly reduced effect is obtained.
   In some cases, it may be advantageous for the amide / ammonium salt structure to be built up from two different amines. For example, a copolymer of lauryl acrylate and maleic anhydride may first be reacted with a secondary amine such as hydrogenated di-tallow fatty amine to form the amide, after which the free carboxyl group derived from the anhydride is neutralized with another amine, eg 2-ethylhexylamine, to the ammonium salt. Likewise, the reverse procedure is conceivable: first with ethylhexylamine to the monoamide, then reacted with Ditalgfettamin to the ammonium salt. Preferably, at least one amine is used, which has at least one straight-chain, unbranched alkyl group having more than 16 carbon atoms. It is not significant whether this amine is present in the structure of the amide structure or as the ammonium salt of the dicarboxylic acid.
   Instead of the subsequent reaction of the carboxyl groups or of the dicarboxylic anhydride with amines to the corresponding amides or amide / ammonium salts, it may sometimes be advantageous to prepare the monoamides or amide / ammonium salts of the monomers and then to copolymerize them directly in the polymerization. However, this is usually technically much more complicated because the amines can attach to the double bond of the monomeric dicarboxylic acid and then no copolymerization is possible.
8. 8. terpolymers based on α, β-unsaturated dicarboxylic anhydrides, α, β-unsaturated compounds and polyoxyalkylene ethers of lower, unsaturated alcohols, which are characterized in that they contain 20-80, preferably 40-60 mol% of bivalent structural units of the formulas 1 and / or 3, and optionally 2, wherein the structural units 2 originate from unreacted anhydride residues,
   
   
   
   in which
   R ²² and R ²³ independently of one another are hydrogen or methyl,
   a, b is zero or one and a + b is one,
   R ²⁴ and R ^{25 are the} same or different and for the groups -NHR ⁶ ,
   N (R ⁶ ) ₂ and / or -OR ²⁷ , and R ^{27 is} a cation of the formula H ₂ N (R ⁶ ) ₂ or H ₃ NR ⁶ ,
   19-80 mol%, preferably 39-60 mol% of bivalent structural units of the formula 4
   
   wherein
   R ^{28 is} hydrogen or C ₁ -C ₄ -alkyl and
   R ^{29 is} C ₆ -C ₆₀ -alkyl or C ₆ -C ₁₈ -aryl and
   1 - 30 mol%, preferably 1 - 20 mol% of bivalent structural units of the formula 5
   
   wherein
   R ^{30 is} hydrogen or methyl,
   R ^{31 is} hydrogen or C ₁ -C ₄ -alkyl,
   R ^{33 is} C ₁ -C ₄ -alkylene,
   m is a number from 1 to 100,
   R ^{32 is} C ₁ -C ₂₄ -alkyl, C ₅ -C ₂₀ -cycloalkyl, C ₆ -C ₁₈ -aryl or -C (O) -R ³⁴ , wherein
   R ^{34 is} C ₁ -C ₄₀ -alkyl, C ₅ -C ₁₀ -cycloalkyl or C ₆ -C ₁₈ -aryl,
   contain.
   The abovementioned alkyl, cycloalkyl and aryl radicals may optionally be substituted. Suitable substituents of the alkyl and aryl radicals are, for example, (C ₁ -C ₆ ) -alkyl, halogens, such as fluorine, chlorine, bromine and iodine, preferably chlorine and (C ₁ -C ₆ ) -alkoxy.
   Alkyl here stands for a straight-chain or branched hydrocarbon radical. Specific examples which may be mentioned are: n-butyl, tert-butyl, n-hexyl, n-octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, dodecenyl, tetrapropenyl, tetradecenyl, pentapropenyl, hexadecenyl, octadecenyl and eicosanyl or mixtures such as cocoalkyl , Tallow fatty alkyl and behenyl.
   Cycloalkyl here stands for a cyclic aliphatic radical having 5 to 20 carbon atoms. Preferred cycloalkyl radicals are cyclopentyl and cyclohexyl.
   Aryl here stands for an optionally substituted aromatic ring system having 6 to 18 carbon atoms.
   The terpolymers consist of the bivalent structural units of the formulas 1 and 3 and 4 and 5 and optionally 2. They contain only in a conventional manner the end groups formed in the polymerization by initiation, inhibition and chain termination.
   In detail, structural units of the formulas 1 to 3 are derived from α, β-unsaturated dicarboxylic acid anhydrides of the formulas 6 and 7
   
   
   such as maleic anhydride, itaconic anhydride, citraconic anhydride, preferably maleic anhydride.
   The structural units of the formula 4 are derived from the α, β-unsaturated compounds of the formula 8.
   
   
   Examples which may be mentioned are the following α, β-unsaturated olefins: styrene, α-methylstyrene, dimethylstyrene, α-ethylstyrene, diethylstyrene, i-propylstyrene, tert-butylstyrene, diisobutylene and α-olefins, such as decene, dodecene, tetradecene, pentadecene, Hexadecene, octadecene, C ₂₀ -α-olefin, C ₂₄ -α-olefin, C ₃₀ -α-olefin, tripropenyl, tetrapropenyl, pentapropenyl and mixtures thereof. Preference is given to α-olefins having 10 to 24 C atoms and styrene, particular preference being given to α-olefins having 12 to 20 C atoms.
   The structural units of the formula 5 are derived from polyoxyalkylene ethers of lower, unsaturated alcohols of the formula 9.
   
   
   The monomers of the formula 9 are etherification products (R ³² = -C (O) R ³⁴ ) or esterification products (R ³² = -C (O) R ³⁴ ) of polyoxyalkylene ethers (R ³² = H).
   The polyoxyalkylene ethers (R ³² = H) can be prepared by known processes by addition of α-olefin oxides, such as ethylene oxide, propylene oxide and / or butylene oxide to polymerizable lower, unsaturated alcohols of the formula 10
   
   produce. Such polymerizable lower unsaturated alcohols are, for example, allyl alcohol, methallyl alcohol, butenols, such as 3-buten-1-ol and 1-buten-3-ol or methylbutenols, such as 2-methyl-3-buten-1-ol, 2-methyl-3 -but-2-ol and 3-methyl-3-buten-1-ol. Preferred are addition products of ethylene oxide and / or propylene oxide with allyl alcohol.
   A subsequent etherification of these polyoxyalkylene ethers to give compounds of the formula 9 where R ³² = C ₁ -C ₂₄ -alkyl, cycloalkyl or aryl is carried out by processes known per se. Suitable methods are, for example, J. March, Advanced Organic Chemistry, 2nd edition, p. 357f (1977). known. These etherification products of the polyoxyalkylene ethers can also be prepared by reacting α-olefin oxides, preferably ethylene oxide, propylene oxide and / or butylene oxide, with alcohols of the formula II
   
   R ³² - OH (11)
   
   wherein R ³² is C ₁ -C ₂₄ -alkyl, C ₅ -C ₂₀ -cycloalkyl or C ₆ -C ₁₈ -aryl, deposited by known methods and with polymerizable lower, unsaturated halides of the formula 12th
   
   where W is a halogen atom. The halides used are preferably the chlorides and bromides. Suitable production methods are mentioned, for example, in J. March, Advanced Organic Chemistry, 2nd Edition, p. 377f (1977).
   The esterification of the polyoxyalkylene ethers (R ³² = -C (O) -R ³⁴ ) takes place by reaction with customary esterification agents, such as carboxylic acids, carboxylic acid halides, carboxylic anhydrides or carboxylic acid esters with C ₁ -C ₄ -alcohols. The halides and anhydrides of C ₁ -C ₄₀ -alkyl, C ₅ -C ₁₀ -cycloalkyl or C ₆ -C ₁₈ -arylcarboxylic acids are preferably used. The esterification is generally carried out at temperatures of 0 to 200 ° C, preferably 10 to 100 ° C.
   In the monomers of formula 9, the index m indicates the degree of alkoxylation, ie the number of moles of α-olefin, which are added per mole of formula 20 or 21.
   Examples of suitable primary amines for the preparation of the terpolymers are the following:
   • n-hexylamine, n-octylamine, n-tetradecylamine, n-hexadecylamine, n-stearylamine or else N, N-dimethylaminopropylenediamine, cyclohexylamine, dehydroabietylamine and mixtures thereof.
   
   Examples of suitable secondary amines for preparing the terpolymers are: didecylamine, ditetradecylamine, distearylamine, dicocosfettamine, ditallow fatty amine and mixtures thereof.
   The terpolymers have K values (measured according to Ubbelohde in 5% strength by weight solution in toluene at 25 ° C.) of 8 to 100, preferably 8 to 50, corresponding to average molecular weights (M _w ) of between about 500 and 100,000. Suitable examples are listed in EP 606,055.
   Reaction products of alkanolamines and / or polyetheramines with polymers containing dicarboxylic anhydride groups, characterized in that they contain 20-80, preferably 40-60, mol% of bivalent structural units of the formulas 13 and 15 and optionally 14
   
   
   
   in which
   R ²² and R ²³ independently of one another are hydrogen or methyl,
   a, b is zero or 1 and a + b is 1,
   R ³⁷ = -OH, -O- [C ₁ -C ₃₀ -alkyl], -NR ⁶ R ⁷ , -O ^s N ^r R ⁶ R ⁷ H ₂
   R ³⁸ = R ³⁷ or NR ⁶ R ³⁹
   R ³⁹ = - (AO) _x -E
   With
   A = ethylene or propylene group
   x = 1 to 50
   E = H, C ₁ -C ₃₀ -alkyl, C ₅ -C ₁₂ -cycloalkyl or C ₆ -C ₃₀ -aryl
   and 80 to 20 mol%, preferably 60 to 40 mol%, of bivalent structural units of the formula 4.
   In detail, the structural units of the formulas 13, 14 and 15 are derived from α, β-unsaturated dicarboxylic acid anhydrides of the formulas 6 and / or 7.
   The structural units of the formula 4 are derived from the α, β-unsaturated olefins of the formula 8. The abovementioned alkyl, cycloalkyl and aryl radicals have the same meanings as under 8.
   The radicals R37 and R38 in formula 13 or R39 in formula 15 are derived from polyetheramines or alkanolamines of the formulas 16 a) and b), amines of the formula NR 6 R 7 R 8 and optionally from alcohols having 1 to 30 carbon atoms.
   
   
   
   Mean in it

   R ⁵³

   Hydrogen, C ₆ -C ₄₀ -alkyl or

   

   R ⁵⁴

   Hydrogen, C ₁ -C ₄ -alkyl

   R ⁵⁵

   Is hydrogen, C ₁ -C ₄ -alkyl, C ₅ - to C ₁₂ -cycloalkyl or C ₆ - to C ₃₀ -aryl

   R ⁵⁶ , R ⁵⁷

   independently of one another hydrogen, C ₁ - to C ₂₂ -alkyl, C ₂ - to C ₂₂ -alkenyl or Z - OH

   Z

   C ₂ - to C ₄ -alkylene

   n

   a number between 1 and 1000.

   
   To derivatize the structural units of the formulas 6 and 7, preference is given to using mixtures of at least 50% by weight of alkylamines of the formula HNR ⁶ R ⁷ R ⁸ and at most 50% by weight of polyetheramines, alkanolamines of the formulas 16 a) and b).
   The preparation of the polyetheramines used is possible, for example, by reductive amination of polyglycols. Furthermore, it is possible to prepare polyetheramines having a primary amino group by addition of polyglycols to acrylonitrile and subsequent catalytic hydrogenation. In addition, polyetheramines are by reaction of Polyethers with phosgene or thionyl chloride and subsequent amination to the polyetheramine accessible. The polyetheramines used according to the invention are (for example) commercially available under the name ® Jeffamine (Texaco). Its molecular weight is up to 2000 g / mol and the ethylene oxide / propylene oxide ratio is from 1:10 to 6: 1.
   A further possibility for derivatizing the structural units of the formulas 6 and 7 is that, instead of the polyether amines, an alkanolamine of the formula 16a) or 16b) is used and subsequently subjected to alkoxylation.
   From 0.01 to 2 mol, preferably from 0.01 to 1 mol of alkanolamine are used per mole of anhydride. The reaction temperature is between 50 and 100 ° C (amide formation). In the case of primary amines, the reaction takes place at temperatures above 100 ° C (imide formation).
   The alkoxylation is usually carried out at temperatures between 70 and 170 ° C with catalysis of bases, such as NaOH or NaOCH3, by gassing of alkylene oxides, such as ethylene oxide (EO) and / or propylene oxide (PO). Usually, 1 to 500, preferably 1 to 100, moles of alkylene oxide are added per mole of hydroxyl groups.
   Examples of suitable alkanolamines include:
   • Monoethanolamine, diethanolamine, N-methylethanolamine, 3-aminopropanol, isopropanol, diglycolamine, 2-amino-2-methylpropanol and mixtures thereof.
   
   As primary amines, for example, the following may be mentioned:
   • n-hexylamine, n-octylamine, n-tetradecylamine, n-hexadecylamine, n-stearylamine or else N, N-dimethylaminopropylenediamine, cyclohexylamine, dehydroabietylamine and mixtures thereof.
   
   Examples of secondary amines are:
   • Didecylamine, ditetradecylamine, distearylamine, dicocosfettamine,
   • Ditalgfettamine and their mixtures.
   
   Examples of alcohols which may be mentioned are:
   • Methanol, ethanol, propanol, isopropanol, n-, sec-, tert-butanol, octanol, tetradecanol, hexadecanol, octadecanol, tallow fatty alcohol, behenyl alcohol and mixtures thereof. Suitable examples are listed in EP-A-688,796.
9. 10. Co- and terpolymers of NC ₆ -C ₂₄ -alkylmaleinimid with C ₁ -C ₃₀ vinyl esters, vinyl ethers and / or olefins having 1 to 30 carbon atoms, such as styrene or α-olefins. These are accessible on the one hand by reacting an anhydride-containing polymer with amines of the formula H2NR6 or by imidization of the dicarboxylic acid and subsequent copolymerization. Preferred dicarboxylic acid is maleic acid or maleic anhydride. Copolymers of 10 to 90% by weight of C ₆ -C ₂₄ -α-olefins and 90 to 10% by weight of NC ₆ -C ₂₂ -alkylmaleimide are preferred.

In a preferred embodiment of the invention, ethylene copolymers (B), alkylphenol-aldehyde resins (C) and / or comb polymers can also be added to the additives and fuel oils according to the invention which contain components (A) and (D). Accordingly, preferred embodiments are also fuel oils according to the invention which comprise ethylene copolymers (B), alkylphenol-aldehyde resins (C) and / or comb polymers and the use according to the invention of additives which comprise ethylene copolymers (B), alkylphenol-aldehyde resins (C) and / or comb polymers , and the corresponding procedure.

Copolymer B) is preferably an ethylene copolymer having an ethylene content of 60 to 90 mol% and a comonomer content of 10 to 40 mol%, preferably 12 to 18 mol%. Suitable comonomers are vinyl esters of aliphatic carboxylic acids having 2 to 15 carbon atoms. Preferred vinyl esters for copolymer B) are vinyl acetate, vinyl propionate, vinyl hexanoate, vinyl octanoate, Vinyl 2-ethylhexanoate, vinyl laurate and vinyl esters of neocarboxylic acids, in particular neononane, neodecane and neoundecanoic acid. Particularly preferred are an ethylene-vinyl acetate copolymer, an ethylene-vinyl propionate copolymer, an ethylene-vinyl acetate vinyl octanoate terpolymer, an ethylene-vinyl acetate-vinyl 2-ethylhexanoate terpolymer, an ethylene-vinyl acetate-neononanoic acid vinyl ester terpolymer, or an ethylene -Vinylacetat-neodecanoate terpolymer. Preferred acrylic acid esters are acrylic esters having alcohol radicals of from 1 to 20, in particular from 2 to 12 and especially from 4 to 8 carbon atoms, such as, for example, methyl acrylate, ethyl acrylate and 2-ethylhexyl acrylate. The copolymers may contain up to 5% by weight of other comonomers. Such comonomers may be, for example, vinyl esters, vinyl ethers, alkyl acrylates, alkyl methacrylates having C ₁ to C ₂₀ alkyl radicals, isobutylene and olefins. Preferred as higher olefins are hexene, isobutylene, octene and / or diisobutylene. Other suitable comonomers are olefins such as propene, hexene, butene, isobutene, diisobutylene, 4-methylpentene-1 and norbornene. Particularly preferred are ethylene-vinyl acetate-diisobutylene and ethylene-vinyl acetate-4-methylpentene-1 terpolymers.
Preferably, the copolymers have melt viscosities at 140 ° C of 20 to 10,000 mPas, especially from 30 to 5000 mPas, especially from 50 to 2000 mPas.

The copolymers (B) can be prepared by the usual copolymerization methods such as suspension polymerization, solvent polymerization, gas phase polymerization or high-pressure bulk polymerization. Preference is given to the high-pressure mass polymerization at pressures of preferably 50 to 400, in particular 100 to 300 MPa and temperatures of preferably 50 to 350, in particular 100 to 250 ° C. The reaction of the monomers is initiated by free radical initiators (free radical initiators). This class of substances includes, for example, oxygen, hydroperoxides, peroxides and azo compounds such as cumene hydroperoxide, t-butyl hydroperoxide, dilauroyl peroxide, dibenzoyl peroxide, bis (2-ethylhexyl) peroxide carbonate, t-butyl perpivalate, t-butyl permalate, t-butyl perbenzoate, dicumyl peroxide, t-butylcumyl peroxide , Di- (t-butyl) peroxide, 2,2'-azobis (2-methylpropanonitrile), 2,2'-azobis (2-methylbutyronitrile). The initiators are used individually or as a mixture of two or more substances in amounts of 0.01 to 20 wt .-%, preferably 0.05 to 10 wt .-%, based on the monomer mixture.

High pressure bulk polymerization is used in known high pressure reactors, e.g. Autoclaves or tubular reactors, discontinuous or continuous, have proven particularly useful tubular reactors. Solvents such as aliphatic and / or aromatic hydrocarbons or hydrocarbon mixtures, benzene or toluene may be present in the reaction mixture. The solvent-free mode of operation is preferred. In a preferred embodiment of the polymerization, the mixture of the monomers, the initiator and, if used, the moderator, a tubular reactor via the reactor inlet and via one or more side branches supplied. In this case, the monomer streams may be composed differently (EP-A-0 271 738).

• Ethylen-Vinylacetat-Copolymere mit 10 - 40 Gew.-% Vinylacetat und 60 - 90 Gew.-% Ethylen;
• die aus DE-A-34 43 475 bekannten Ethylen-Vinylacetat-Hexen-Terpolymere;
• die in EP-B-0 203 554 beschriebenen Ethylen-Vinylacetat-Diisobutylen-Terpolymere;
• die aus EP-B-0 254 284 bekannte Mischung aus einem Ethylen-Vinylacetat-Diisobutylen-Terpolymerisat und einem Ethylen/Vinylacetat-Copolymer;
• die in EP-B-0 405 270 offenbarten Mischungen aus einem Ethylen-Vinylacetat-Copolymer und einem Ethylen-Vinylacetat-N-Vinylpyrrolidon-Terpolymerisat;
• die in EP-B-0 463 518 beschriebenen Ethylen/Vinylacetat/iso-Butylvinylether-Terpolymere;
• die in EP-B-0 491 225 offenbarten Mischpolymerisate des Ethylens mit Alkylcarbonsäurevinylestern;
• die aus EP-B-0 493 769 bekannten Ethylen/Vinylacetat/ Neononansäurevinylester bzw. Neodecansäurevinylester-Terpolymere, die außer Ethylen 10 - 35 Gew.-% Vinylacetat und 1 - 25 Gew.-% der jeweiligen Neoverbindung enthalten;
• die in DE-A-196 20 118 beschriebenen Terpolymere aus Ethylen, dem Vinylester einer oder mehrerer aliphatischer C₂- bis C₂₀-Monocarbonsäuren und 4-Methylpenten-1 ;
• die in DE-A-196 20 119 offenbarten Terpolymere aus Ethylen, dem Vinylester einer oder mehrerer aliphatischer C₂- bis C₂₀-Monocarbonsäuren und Bicyclo[2.2.1]hept-2-en.

Suitable copolymers or terpolymers include, for example:

• Ethylene-vinyl acetate copolymers with 10-40% by weight of vinyl acetate and 60-90% by weight of ethylene;
• the ethylene-vinyl acetate-hexene terpolymers known from DE-A-34 43 475;
• the ethylene-vinyl acetate-diisobutylene terpolymers described in EP-B-0 203 554;
• the mixture known from EP-B-0 254 284 comprising an ethylene-vinyl acetate-diisobutylene terpolymer and an ethylene / vinyl acetate copolymer;
• the blends disclosed in EP-B-0 405 270 of an ethylene-vinyl acetate copolymer and an ethylene-vinyl acetate-N-vinylpyrrolidone terpolymer;
• the ethylene / vinyl acetate / iso-butyl vinyl ether terpolymers described in EP-B-0 463 518;
• the copolymers of ethylene with alkylcarboxylic acid vinyl esters disclosed in EP-B-0 491 225;
• the ethylene / vinyl acetate / vinyl neononanoate or vinyl neodecanoate terpolymers known from EP-B-0 493 769, which contain, in addition to ethylene, 10-35% by weight of vinyl acetate and 1-25% by weight of the respective neo compound;
• the terpolymers of ethylene, the vinyl ester of one or more aliphatic C ₂ to C ₂₀ monocarboxylic acids and 4-methylpentene-1 described in DE-A-196 20 118;
• the terpolymers disclosed in DE-A-196 20 119 of ethylene, the vinyl ester of one or more aliphatic C ₂ to C ₂₀ monocarboxylic acids and bicyclo [2.2.1] hept-2-ene.

The ethylene copolymers can be used individually or as a mixture of various polymers.

Alkylphenol-aldehyde resins (C) are known in principle and, for example, in Römpp Chemie Lexikon, 9th edition, Thieme Verlag 1988-92, Volume 4, p 3351ff. described. The alkyl radicals of the o- or p-alkylphenol have 1 to 50, preferably 4 to 20, in particular 6 to 12, carbon atoms; it is preferably n-, iso- and tert-butyl, n- and iso-pentyl, n- and iso-hexyl, n- and iso-octyl, n- and iso-nonyl, n- and iso-decyl , n- and iso-dodecyl as well as tetrapropenyl, pentapropenyl and polyisobutenyl. The alkylphenol-aldehyde resin may also contain up to 50 mole percent phenol units. For the alkylphenol-aldehyde resin, the same or different alkylphenols may be used. The aliphatic aldehyde in the alkylphenol-aldehyde resin has 1-10, preferably 1-4, carbon atoms and may carry other functional groups such as aldehyde or carboxyl groups. It is preferably formaldehyde. The molecular weight of the alkylphenol-aldehyde resins is 400-10,000, preferably 400-5,000, g / mol.

The prerequisite here is that the resins are oil-soluble.

The preparation of the alkylphenol-aldehyde resins is carried out in a known manner by basic catalysis, resulting in resol-type condensation products, or by acid catalysis to form novolac-type condensation products.

The condensates obtained according to both types are suitable for the compositions according to the invention. Preferably, the condensation is in the presence of acidic catalysts.

For the preparation of the alkylphenol-aldehyde resins are a bifunctional o- or p-alkylphenol having 1 to 50 carbon atoms, preferably 4 to 20, in particular 6 to 12 carbon atoms per alkyl group, or mixtures thereof and an aliphatic aldehyde with 1 to 10 C atoms reacted with each other, wherein per mole of alkylphenol about 0.5 to 2 mol, preferably 0.7 to 1.3 mol and in particular equimolar amounts of aldehyde are used.

Suitable alkylphenols are, in particular, C ₄ -C ₅₀ -alkylphenols, for example o- or p-cresol, n-, sec- and tert-butylphenol, n- and i-pentylphenol, n- and isohexylphenol, n- and - iso-octylphenol, n- and iso-nonylphenol, n- and iso-decylphenol, n- and iso-dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, eicosylphenol, tripropenylphenol, tetrapropenylphenol and polyis (isobutenyl) phenol. The alkylphenols are preferably para-substituted. They are preferably substituted at most 7 mol%, in particular at most 3 mol% with more than one alkyl group.

Particularly suitable aldehydes are formaldehyde, acetaldehyde, butyraldehyde and glutaraldehyde, with formaldehyde being preferred.

The formaldehyde can be used in the form of paraformaldehyde or in the form of a preferably 20-40% strength by weight aqueous formalin solution. Corresponding amounts of trioxane can also be used.

The reaction of alkylphenol and aldehyde is usually carried out in the presence of alkaline catalysts, for example alkali metal hydroxides or alkylamines, or of acidic catalysts, for example inorganic or organic acids, such as hydrochloric acid, sulfuric acid, phosphoric acid, sulfonic acid, sulfamido acids or haloacetic acids, and in the presence of one with water Azeotrope-forming organic solvent, such as toluene, xylene, higher aromatics or mixtures thereof. The reaction mixture is heated to a temperature of 90 to 200 ° C, preferably 100 to 160 ° C, wherein the resulting reaction water is removed during the reaction by azeotropic distillation. Solvents that do not release protons under condensation conditions may remain in the products after the condensation reaction. The resins may be used directly or after neutralization of the catalyst, optionally after further dilution of the solution with aliphatic and / or aromatic hydrocarbons or hydrocarbon mixtures, e.g. Gasoline fractions, kerosene, decane, pentadecane, toluene, xylene, ethylbenzene or solvents such as ® Solvent Naphtha, ® Shellsol AB, ® Solvesso 150, ® Solvesso 200, ® Exxsol, ® ISOPAR and ® Shellsol D types.

The alkylphenol resins can then optionally be alkoxylated by reaction with 1 to 10, especially 1 to 5 moles of alkylene oxide such as ethylene oxide, propylene oxide or butylene oxide per phenolic OH group.

Finally, in a further embodiment of the invention, the additives and middle distillates of the invention may comprise comb polymers. This term refers to polymers in which hydrocarbon radicals having at least 8, in particular at least 10, carbon atoms are bonded to a polymer backbone. Preferably, they are homopolymers whose alkyl side chains contain at least 8 and in particular at least 10 carbon atoms. In the case of copolymers, at least 20%, preferably at least 30% of the monomers have side chains (compare Comblike Polymers-Structure and Properties, NA Plate and VP Shibaev, J. Polym, Sci. Macromolecular Revs 1974, 8, 117 ff). Examples of suitable Comb polymers are, for example, fumarate / vinyl acetate copolymers (cf., EP 0 153 176 A1), copolymers of a C ₆ - to C ₂₄ -α-olefin and an NC ₆ - to C ₂₂ -alkylmaleimide (compare EP 0 320 766), further esterified olefin / maleic anhydride copolymers, polymers and copolymers of α-olefins and esterified copolymers of styrene and maleic anhydride.

beschrieben werden. Darin bedeuten

A

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

D

H, CH₃, A oder R;

E

H oder A;

G

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

M

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

N

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

R'

eine Kohlenwasserstoffkette mit 8-150 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.

Comb polymers may, for example, be represented by the formula

to be discribed. Mean in it

A

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

D

H, CH _3, A or R;

e

H or A;

G

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

M

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

N

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

R '

a hydrocarbon chain of 8-150 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.

The mixing ratio (in parts by weight) of the additives according to the invention with paraffin dispersants, resins or comb polymers is in each case 1:10 to 20: 1, preferably 1: 1 to 10: 1.
The additive components according to the invention can be separated or mixed in mineral oils or mineral oil distillates. In a preferred embodiment, the individual additive components or the corresponding mixture before addition to the middle distillates in a dissolved or dispersed organic solvent or dispersing agent. The solution or dispersion generally contains 5 to 90, preferably 5 to 75,% by weight of the additive or additive mixture.

Suitable solvents or dispersants are aliphatic and / or aromatic hydrocarbons or hydrocarbon mixtures, e.g. Benzine fractions, kerosene, decane, pentadecane, toluene, xylo !, ethylbenzene or commercial solvent mixtures such as Solvent Naphtha, ® Shellsol AB, ® Solvesso 150, ® Solvesso 200, ® Exxsol, ® ISOPAR and ® Shellsol D types. Optionally, polar solubilizers such as 2-ethylhexanol, decanol, iso-decanol or iso-tridecanol can be added.

Mineral oils or mineral oil distillates improved in their refrigeration properties by the additives according to the invention contain from 0.001 to 2, preferably from 0.005 to 0.5,% by weight of the additives, based on the mineral oil or mineral oil distillate.

The additives according to the invention are particularly suitable for improving the cold flow properties of animal, vegetable or mineral oils. At the same time they improve the dispersion of the precipitated paraffins below the cloud point. They are particularly well suited for use in middle distillates. As middle distillates are in particular those mineral oils which are obtained by distillation of crude oil and boil in the range of 120 to 450 ° C, for example kerosene, jet fuel, diesel and fuel oil. Preferably, the additives of the present invention are used in low sulfur middle distillates containing 350 ppm sulfur and less, more preferably less than 200 ppm sulfur, and more preferably less than 50 ppm sulfur. The additives according to the invention are furthermore preferably used in middle distillates which have 95% distillation points below 365 ° C., in particular 350 ° C. and in special cases below 330 ° C., and in addition to high contents of paraffins having 18 to 24 C atoms only small proportions Containing paraffins with chain lengths of 24 and more carbon atoms. They can also be used as components in lubricating oils.

The mineral oils or mineral oil distillates may also contain other conventional additives such as dewaxing aids, corrosion inhibitors, antioxidants, lubricity additives, sludge inhibitors, Cetanzahlverbesserer, detergent additives, dehazers, conductivity improvers or dyes.

Examples

The following esters A) were used as a 50% solution in aromatic solvent (EO stands for ethylene oxide, PO stands for propylene oxide): Table 1: Characterization of the esters used (constituent A) Main components of fatty acids acid number OH number additive polyol alkoxylation C ₁₈ C ₂₀ C ₂₂ [mg KOH / g] [mg KOH / g] A1 glycerin 22 mol EO 2 7 88 7 13 A2 glycerin 22 mol EO 95% 5 4 A3 glycerin 22 mol EO 37 10 48 1 2 A4 glycerin 16 mol PO 37 10 48 7 9 A5 glycerin 16 mol PO 2 7 88 5 7 A6 glycerin 24 mol PO 37 10 48 8th 11 A7 glycerin 10 mol EO 2 7 88 7 9 A8 glycerin 30 mol EO 2 7 88 2 4 A9 glycerin 40 mol EO 2 7 88 12 10 A10 glycerin 20 moles of EO 36 36 24 13 13 A11 glycerin 20 moles of EO 2 7 88 0.5 11 A12 glycerin 15 mol EO 2 7 88 5 7 A13 (V) ethylene glycol 13 mol EO 37 10 48 0.9 4 A14 (V) glycerin - 2 7 88 0.2 4 A15 With mixture of behenic acid (2% C ₁₈ , 7% C ₂₀ , 88% C ₂₂ ) and 10 mol% poly (isobutenyl succinic anhydride (MW 1000 g / mol) esterified glycerol ethoxylate (20 mol EO)

Characterization of the ethylene copolymers used as flow improvers (component B)).
The viscosity is determined according to ISO 3219 / B using a rotary viscometer (Haake RV20) with a plate-and-cone measuring system at 140 ° C. Additive no. Comonomers (besides ethylene) V ₁₄₀ B 1) 32% by weight of vinyl acetate 125 mPas B 2) 31% by weight of vinyl acetate + 8% by weight of vinyl neodecanoate 110 mPas B 3) Mixture of the copolymers B1) and B2) in the ratio 1: 5

The additives are used to improve the handling as 50% solutions in solvent naphtha or kerosene.

• C 1) Nonylphenol-Formaldehydharz
• C 2) Dodecylphenol-Formaldehydharz
• C 3) C_20/24-Alkylphenol-Formaldehydharz

Characterization of the alkylphenol-aldehyde resins used (ingredient C))

• C 1) nonylphenol-formaldehyde resin
• C 2) dodecylphenol-formaldehyde resin
• C 3) C _20/24 alkylphenol-formaldehyde resin

• D 1) Umsetzungsprodukt eines Dodecenyl-Spirobislactons mit einer Mischung aus primärem und sekundärem Talgfettamin
• D 2) Umsetzungsprodukt eines Terpolymers aus C₁₄/C₁₆-α-Olefin, Maleinsäureanhydrid und Allylpolyglykol mit 2 Equivalenten Ditalgfettamin.

Characterization of the Paraffin Dispersants Used (Ingredient D))

• D 1) Reaction product of a dodecenyl spirobislactone with a mixture of primary and secondary tallow fatty amine
• D 2) Reaction product of a terpolymer of C ₁₄ / C ₁₆ -α-olefin, maleic anhydride and allylpolyglycol with 2 equivalents of ditallow fatty amine.

Characterization of the test oils:

The boiling characteristics are determined according to ASTM D-86, the CFPP value according to EN 116 and the determination of the cloud point according to ISO 3015. Table 2: Characteristics of the test oils Test oil 1 Test oil 2 Test oil 3 Test oil 4 Start of boiling [° C] 169 200 174 241 20% [° C] 211 251 209 256 90% [° C] 327 342 327 321 95% [° C] 344 354 345 341 Cloud Point [° C] -9.0 -4.2 -6.7 -8.2 CFPP [° C] -10 -6 -8th -10 sulfur content 33 ppm 35 ppm 210 ppm 45 ppm

Effectiveness of the additives

• 150 ml der mit den in der Tabelle angegebenen Additivkomponenten versetzten Mitteldestillate wurden in 200 ml-Meßzylindem in einem Kälteschrank mit -2°C/Stunde auf -13°C abgekühlt und 16 Stunden bei dieser Temperatur gelagert. Anschließend wurden visuell Volumen und Aussehen sowohl der sedimentierten Paraffinphase wie auch der darüber stehenden Ölphase bestimmt und beurteilt. Eine geringe Sedimentmenge bei gleichzeitig homogen trüber Ölphase bzw. ein großes Sedimentvolumen bei klarer Ölphase zeigen eine gute Paraffindispergierung. Zusätzlich wurden die unteren 20 Vol.-% isoliert und der Cloud Point gemäß ISO 3015 bestimmt. Eine nur geringe Abweichung des Cloud Points der unteren Phase (CP_KS) vom Blindwert des Öls zeigt eine gute Paraffindispergierung.

Tabelle 3: CFPP-Wirksamkeit in Testöl 1 Die CFPP-Wirksamkeit der erfindungsgemäßen Ester A wurde in Kombination mit gleichen Mengen C und D in Testöl 1 wie folgt gemessen: A C D B3 in ppm 50 75 100 Beispiel 1 50 ppm A1 50 ppm C1 50 ppm D2 -29 -31 -30 Beispiel 2 50 ppm A11 50 ppm C2 50 ppm D1 -27 -30 -30 Beispiel 3 50 ppm A7 50 ppm C1 50 ppm D2 -17 -28 -29 Beispiel 4 50 ppm A12 50 ppm C1 50 ppm D2 -19 -31 -29 Beispiel 5 50 ppm A8 50 ppm C1 50 ppm D2 -21 -29 -29 Beispiel 6 50 ppm A9 50 ppm C1 50 ppm D2 -18 -24 -29 Beispiel 7 50 ppm A2 50 ppm C1 50 ppm D2 -26 -29 -28 Beispiel 8 50 ppm A3 50 ppm C1 50 ppm D2 -30 -27 -30 Beispiel 9 50 ppm A5 50 ppm C1 50 ppm D2 -22 -29 -30 Beispiel 10 50 ppm A10 50 ppm C1 50 ppm D2 -19 -30 -29 Beispiel 11 50 ppm A6 50 ppm C1 50 ppm D2 -16 -26 -29 Beispiel 12 50 ppm A15 50 ppm C1 50 ppm D2 -28 -30 -31 Beispiel 13 50 ppm A13 50 ppm C1 50 ppm D2 -14 -22 -28 Beispiel 14 (Vergleich) - 75 ppm C1 75 ppm D2 -12 -17 -21 Tabelle 4: CFPP-Wirksamkeit in Testöl 2 Die Additivbestandteile A wurden mit 5 Teilen B2) gemischt und auf ihre CFPP-Wirksamkeit in Testöl 2 geprüft. CFPP [°C] Bestandteil A 100 ppm 200 ppm 300 ppm Beispiel 15 (Vergleich) A1 -11 -20 -21 Beispiel 16 (Vergleich) A2 -11 -22 -23 Beispiel 17 (Vergleich) A3 -10 -20 -22 Beispiel 18(Vergleich) A4 -10 -18 -23 Beispiel 19 (Vergleich) A13 -8 -10 -17 Beispiel 20 (Vergleich) - -6 -8 -9 Tabelle 5: CFPP- und Dispergierwirkung in Testöl 3 Für die Dispergiertests in Testöl 3 wurden in allen Messungen zusätzlich 200 ppm des Additivs B1) zudosiert. Additive Testöl 3 (CP -6,7°C) A C Sediment [Vol.-%] Aussehen Ölphase CFPP [°C] CP_KS [°C] Beispiel 21 (V) 100 ppm A1 50 ppm C1 0 trüb -23 -5,9 Beispiel 22 (V) 100 ppm A1 50 ppm C2 7 trüb -24 -3,3 Beispiel 23 (V) 100 ppm A2 50 ppm C2 10 trüb -21 -2,4 Beispiel 24 (V) 100 ppm A1 50 ppm C3 20 wolkig -21 -0,8 Beispiel 25 (V) 50 ppm A2 100 ppm C1 20 wolkig -26 -1,4 Beispiel 26 (V) 100 ppm A3 50 ppm C1 10 trüb -28 -1,4 Beispiel 27 (V) 50 ppm A3 100 ppm C1 0 trüb -28 -5,3 Beispiel 28 (V) 100 ppm A4 100 ppm C1 7 trüb -21 -3,6 Beispiel 29 (V) 50 ppm A4 100 ppm C1 13 trüb -27 -2,0 Beispiel 30 (V) 100 ppm A5 50 ppm C1 3 trüb -22 -6,1 Beispiel 31 (V) 50 ppm A5 100 ppm C1 15 trüb -22 -2,0 Beispiel 32 (V) 100 ppm A6 50 ppm C1 20 wolkig -23 -1,6 Beispiel 33 (V) 50 ppm A6 100 ppm C1 3 trüb -21 -4,4 Beispiel 34 (V) 100 ppm A15 50 ppm C1 0 trüb -25 -6,2 Beispiel 35 (V) 100 ppm A14 50 ppm C1 16 klar -18 +3,0 Beispiel 36 (V) 150 ppm A1 ― 20 klar -20 +3,4 Beispiel 37 (V) 150 ppm A2 ― 20 klar -19 +3,2 Beispiel 38 (V) ― 150 ppm C1 10 wolkig -20 +0,1 Beispiel 39 (V) ― ― 25 klar -19 +3,6 Tabelle 6: CFPP- und Dispergierwirkung in Testöl 4 Für die Dispergiertests in Testöl 4 wurden in allen Messungen zusätzlich 200 ppm des Additivs B1 zudosiert. Additive Testöl 4 (CP -8,2°C) A C Sediment [Vol.-%] Aussehen Ölphase CFPP [°C] CP_KS [°C] Beispiel 40 (V) 100 ppm A1 100 ppm C1 0 trüb -24 -6,3 Beispiel 41 (V) 100 ppm A1 100 ppm C1 0 trüb -24 -7,5 Beispiel 42 (V) 50 ppm A3 100 ppm C1 0 trüb -24 -5,4 Beispiel 43 (V) 50 ppm A3 100 ppm C1 0 trüb -28 -5,3 Beispiel 44 (V) 100 ppm A5 50 ppm C1 50 wolkig -23 -3,3 Beispiel 45 (V) 100 ppm A5 100 ppm C1 0 trüb -23 -5,5 Beispiel 46 (V) 50 ppm A5 100 ppm C1 70 wolkig -24 -4,3 Beispiel 47 (V) 100 ppm A14 50 ppm C1 16 klar -18 -1,1 Beispiel 48 (V) 150 ppm A1 ― 20 klar -21 +2,4 Beispiel 49 (V) ― 150 ppm C1 35 wolkig -20 +1,2 Beispiel 50 (V) ― ― 20 klar -18 +2,6 Tabelle 7: CFPP- und Dispergierwirkung in Testöl 1 Für die Dispergiertests in Testöl 1 wurden in allen Messungen zusätzlich 75 ppm des Additivs B3 zudosiert Additive Testöl 1 (CP -9,0°C) A C D Sediment [Vol.-%] Aussehen Ölphase CFPP [°C] CP_KS [°C] Beispiel 51 50 ppm A1 50 ppm C1 50 ppm D2 0 trüb -29 -7,2 Beispiel 52 80 ppm A1 90 ppm C1 90 ppm D2 0 trüb -30 -8,0 Beispiel 53 50 ppm A2 50 ppm C1 50 ppm D2 0 trüb -27 -7,4 Beispiel 54 50 ppm A3 50 ppm C1 50 ppm D2 0 trüb -29 -6,7 Beispiel 55 50 ppm A4 50 ppm C1 50 ppm D2 0,5 trüb -28 -6,0 Beispiel 56 50 ppm A6 50 ppm C1 50 ppm D2 0,5 trüb -28 -6,7 Beispiel 57 (V) 100 ppm A1 50 ppm C1 ― 0,3 trüb -24 -6,7 Beispiel 58 150 ppm A2 ― 50 ppm D2 10 wolkig -24 -0,5 Beispiel 59 (V) ― 50 ppm C1 100 ppm D2 2 trüb -25 -4,5 Beispiel 60 (V) ― ― ― 25 klar -21 2,2 Table 4 describes the superior efficiency of the inventive additives in comparison with the prior art together with ethylene copolymers for mineral oils and mineral oil distillates by means of the CFPP test (Cold Filter Plugging Test according to EN 116).
The paraffin dispersion in middle distillates was 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 overlying oil phase were determined and assessed visually. A small amount of sediment with simultaneously homogeneously turbid oil phase or a large sediment volume with a clear oil phase show a good paraffin dispersion. In addition, the lower 20% by volume were isolated and the cloud point was determined according to ISO 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 3: CFPP activity in test oil 1 The CFPP activity of the esters A according to the invention was measured in combination with equal amounts of C and D in test oil 1 as follows: A C D B3 in ppm 50 75 100 example 1 50 ppm A1 50 ppm C1 50 ppm D2 -29 -31 -30 Example 2 50 ppm A11 50 ppm C2 50 ppm D1 -27 -30 -30 Example 3 50 ppm A7 50 ppm C1 50 ppm D2 -17 -28 -29 Example 4 50 ppm A12 50 ppm C1 50 ppm D2 -19 -31 -29 Example 5 50 ppm A8 50 ppm C1 50 ppm D2 -21 -29 -29 Example 6 50 ppm A9 50 ppm C1 50 ppm D2 -18 -24 -29 Example 7 50 ppm A2 50 ppm C1 50 ppm D2 -26 -29 -28 Example 8 50 ppm A3 50 ppm C1 50 ppm D2 -30 -27 -30 Example 9 50 ppm A5 50 ppm C1 50 ppm D2 -22 -29 -30 Example 10 50 ppm A10 50 ppm C1 50 ppm D2 -19 -30 -29 Example 11 50 ppm A6 50 ppm C1 50 ppm D2 -16 -26 -29 Example 12 50 ppm A15 50 ppm C1 50 ppm D2 -28 -30 -31 Example 13 50 ppm A13 50 ppm C1 50 ppm D2 -14 -22 -28 Example 14 (comparison) - 75 ppm C1 75 ppm D2 -12 -17 -21 The additive ingredients A were mixed with 5 parts B2) and tested for their CFPP activity in test oil 2. CFPP [° C] Component A 100 ppm 200 ppm 300 ppm Example 15 (comparison) A1 -11 -20 -21 Example 16 (comparison) A2 -11 -22 -23 Example 17 (comparison) A3 -10 -20 -22 Example 18 (comparison) A4 -10 -18 -23 Example 19 (comparison) A13 -8th -10 -17 Example 20 (comparison) - -6 -8th -9 For the dispersing tests in test oil 3, an additional 200 ppm of additive B1) was added in all measurements. additives Test oil 3 (CP -6.7 ° C) A C Sediment [vol.%] Appearance oil phase CFPP [° C] CP _KS [° C] Example 21 (V) 100 ppm A1 50 ppm C1 0 cloudy -23 -5.9 Example 22 (V) 100 ppm A1 50 ppm C2 7 cloudy -24 -3.3 Example 23 (V) 100 ppm A2 50 ppm C2 10 cloudy -21 -2.4 Example 24 (V) 100 ppm A1 50 ppm C3 20 cloudy -21 -0.8 Example 25 (V) 50 ppm A2 100 ppm C1 20 cloudy -26 -1.4 Example 26 (V) 100 ppm A3 50 ppm C1 10 cloudy -28 -1.4 Example 27 (V) 50 ppm A3 100 ppm C1 0 cloudy -28 -5.3 Example 28 (V) 100 ppm A4 100 ppm C1 7 cloudy -21 -3.6 Example 29 (V) 50 ppm A4 100 ppm C1 13 cloudy -27 -2.0 Example 30 (V) 100 ppm A5 50 ppm C1 3 cloudy -22 -6.1 Example 31 (V) 50 ppm A5 100 ppm C1 15 cloudy -22 -2.0 Example 32 (V) 100 ppm A6 50 ppm C1 20 cloudy -23 -1.6 Example 33 (V) 50 ppm A6 100 ppm C1 3 cloudy -21 -4.4 Example 34 (V) 100 ppm A15 50 ppm C1 0 cloudy -25 -6.2 Example 35 (V) 100 ppm A14 50 ppm C1 16 clear -18 +3.0 Example 36 (V) 150 ppm A1 - 20 clear -20 +3.4 Example 37 (V) 150 ppm A2 - 20 clear -19 +3.2 Example 38 (V) - 150 ppm C1 10 cloudy -20 +0.1 Example 39 (V) - - 25 clear -19 +3.6 For the dispersing tests in test oil 4, an additional 200 ppm of additive B1 was added in all measurements. additives Test oil 4 (CP -8,2 ° C) A C Sediment [vol.%] Appearance oil phase CFPP [° C] CP _KS [° C] Example 40 (V) 100 ppm A1 100 ppm C1 0 cloudy -24 -6.3 Example 41 (V) 100 ppm A1 100 ppm C1 0 cloudy -24 -7.5 Example 42 (V) 50 ppm A3 100 ppm C1 0 cloudy -24 -5.4 Example 43 (V) 50 ppm A3 100 ppm C1 0 cloudy -28 -5.3 Example 44 (V) 100 ppm A5 50 ppm C1 50 cloudy -23 -3.3 Example 45 (V) 100 ppm A5 100 ppm C1 0 cloudy -23 -5.5 Example 46 (V) 50 ppm A5 100 ppm C1 70 cloudy -24 -4.3 Example 47 (V) 100 ppm A14 50 ppm C1 16 clear -18 -1.1 Example 48 (V) 150 ppm A1 - 20 clear -21 +2.4 Example 49 (V) - 150 ppm C1 35 cloudy -20 +1.2 Example 50 (V) - - 20 clear -18 +2.6 For the dispersing tests in test oil 1, an additional 75 ppm of additive B3 was added in all measurements additives Test Oil 1 (CP -9.0 ° C) A C D Sediment [vol.%] Appearance oil phase CFPP [° C] CP _KS [° C] Example 51 50 ppm A1 50 ppm C1 50 ppm D2 0 cloudy -29 -7.2 Example 52 80 ppm A1 90 ppm C1 90 ppm D2 0 cloudy -30 -8.0 Example 53 50 ppm A2 50 ppm C1 50 ppm D2 0 cloudy -27 -7.4 Example 54 50 ppm A3 50 ppm C1 50 ppm D2 0 cloudy -29 -6.7 Example 55 50 ppm A4 50 ppm C1 50 ppm D2 0.5 cloudy -28 -6.0 Example 56 50 ppm A6 50 ppm C1 50 ppm D2 0.5 cloudy -28 -6.7 Example 57 (V) 100 ppm A1 50 ppm C1 - 0.3 cloudy -24 -6.7 Example 58 150 ppm A2 - 50 ppm D2 10 cloudy -24 -0.5 Example 59 (V) - 50 ppm C1 100 ppm D2 2 cloudy -25 -4.5 Example 60 (V) - - - 25 clear -21 2.2

Claims (16)

1. An additive for middle distillates having a maximum sulfur content of 0.05% by weight, comprising at least one fatty ester of alkoxylated polyols having at least 3 OH groups (A) and at least one polar nitrogen-containing paraffin dispersant (D), said fatty ester having an OH number of less than 15 mg KOH/g.
2. An additive as claimed in claim 1, wherein the alkoxylated polyol (A) is derived from a polyol having three or more OH groups which has been reacted with from 1 to 100 mol of alkylene oxide.
3. An additive as claimed in claim 1 and/or 2, wherein the alkoxylated polyol (A) has been esterified with a fatty acid having from 8 to 50 carbon atoms.
4. An additive as claimed in one or more of claims 1 to 3, wherein the alkoxylated polyol (A) has been esterified with a mixture of at least one fatty acid having from 8 to 50 carbon atoms and at least one fat-soluble, polybasic carboxylic acid.
5. An additive as claimed in one or more of claims 1 to 4, wherein the alkoxylated polyol (A) is derived from glycerol.
6. An additive as claimed in one or more of claims 1 to 5, wherein the polar nitrogen-containing paraffin dispersant present is a low molecular weight or polymeric, oil-soluble nitrogen compound which may be obtained by reacting aliphatic or aromatic amines with aliphatic or aromatic mono-, di-, tri- or tetracarboxylic acids or their anhydrides.
7. An additive as claimed in one or more of claims 1 to 6, wherein the polar nitrogen-containing paraffin dispersant present is an amino salt and/or amide of secondary fatty amines having from 8 to 36 carbon atoms.
8. An additive as claimed in one or more of claims 1 to 7, wherein at least one ethylene copolymer (B) is additionally present.
9. An additive as claimed in claim 8, wherein the ethylene copolymer (B) contains at least one unsaturated vinyl ester of an aliphatic carboxylic acid having from 2 to 15 carbon atoms.
10. An additive as claimed in claim 8 and/or 9, wherein the ethylene copolymer (B), in addition to ethylene, contains from 10 to 40 mol% of comonomers.
11. An additive as claimed in one or more of claims 1 to 10, wherein at least one alkylphenol-aldehyde resin (C) is additionally present.
12. An additive as claimed in claim 11, wherein the alkyl radicals of the alkylphenol-aldehyde resin (C) have from 1 to 50 carbon atoms.
13. An additive as claimed in claim 11 and/or 12, wherein the alkylphenol-aldehyde resin (C) is derived from at least one aldehyde having from 1 to 10 carbon atoms.
14. A dispersion of an additive as claimed in one or more of claims 1 to 13 in an organic solvent or dispersant, comprising from 5 to 90% by weight of the additive.
15. A middle distillate having a maximum sulfur content of 0.05% by weight, which comprises an additive as claimed in one or more of claims 1 to 13.
16. The use of an additive as claimed in one or more of claims 1 to 13 for improving the cold flow properties and paraffin dispersancy in middle distillates having a maximum sulfur content of 0.05% by weight.