EP1209215A2 - Fuel oils with improved lubricating activity, containing blends of fatty acids with paraffin dispersants, and a lubricating activity improving additive - Google Patents

Abstract

Cold-stabilized fatty acid composition comprises: (a) 1-99 wt.% saturated mono- or di-carboxylic acids with 6-50 (C) carbon atoms; (b) 1-99 wt.% unsaturated mono- or di-carboxylic acids with 6-50 C atoms; and (c) 0.01-90 wt.% of a polar nitrogen-containing compound that is effective as a wax dispersant in middle distillates. Independent claims are also included for the following: (1) A solution comprising the fatty acid composition and 1-80 wt.% organic solvent. (2) Fuel oils comprising a middle distillate with a sulfur content of up to 0.05 wt.% and either the fatty acid composition or solution (1).

Description

The present invention relates to mixtures of fatty acids and Paraffin dispersants with improved low-temperature stability, and their use for Improvement of the lubricating effect of middle distillate fuel oils.

Mineral oils and mineral oil distillates used as fuel oils generally contain 0.5 wt .-% and more sulfur, when burning causes the formation of sulfur dioxide. To the resulting To reduce environmental pollution, the sulfur content of fuel oils lowered further and further. The diesel fuel standard EN 590 writes in Germany currently has a maximum sulfur content of 350 ppm. In Scandinavia already comes in with fuel oils with less than 50 ppm Exceptional cases with less than 10 ppm sulfur for use. This Fuel oils are usually made by taking those from petroleum Fractions obtained by distillation hydrogenated refined. In the Desulphurization also removes other substances that Give fuel oils a natural lubricating effect. About these substances include polyaromatic and polar compounds.

However, it has now been shown that the friction and wear reducing Properties of fuel oils with increasing desulfurization become worse. Often these properties are so poor that the materials lubricated by fuel, e.g. the distributor injection pumps from Diesel engines can be expected to eat after a short time got to. The maximum value for the 95% distillation point of maximum 360 ° C and now in Scandinavia further reduction of the 95% distillation point to below 350 ° C and sometimes below 330 ° C this problem is further exacerbated.

Approaches are therefore described in the prior art which provide a solution to this Problems (so-called lubricity additives).

EP-A-0 798 364 discloses salts and amides from mono- to tetracarboxylic acids 2 to 50 carbon atoms and aliphatic mono- / polyamines with 2 to 50 carbon atoms and 1 to 10 N atoms as lubricity additives for low-sulfur diesel fuel. Preferred amines have 8-20 C atoms, e.g. Coconut fatty amine, tallow fatty amine and Oleylamine.

WO-A-95/33805 discloses the use of cold flow improvers to improve the lubricating effect of low-sulfur middle distillates. Polar nitrogen-containing compounds which contain a group NR ¹³ , where R ^{13 is} a hydrocarbon radical having 8 to 40 carbon atoms and which can be in the form of a cation, are also mentioned as suitable substances.

WO-A-96/18706, in analogy to WO-A-95/33805, discloses the use of those therein mentioned nitrogenous compounds in combination with lubricity additives.

WO-A-96/23855, in analogy to WO-A-95/33805, discloses the use of those therein mentioned nitrogenous compounds in combination with detergent additives.

The fatty acids used according to the prior art have the disadvantage that when stored at low temperatures, i.e. often at room temperature, mostly solidify at temperatures of 0 ° C at the latest at -5 ° C, or that separate crystalline components and cause handling problems. This Problem is also only partially due to dilution with organic solvents solve, since portions crystallize from these solutions or the solution gelled and froze. So they have to be strong for use as lubricity additives diluted, or held in heated storage containers and over heated Lines are dosed.

The effectiveness of cold flow improvers as lubricity additives alone is not sufficient so that either very high dosing rates or synergists are used Need to become.

The object underlying the present invention was to provide lubricity additives find that reduced the lubricating effect of middle distillates Improve dosing rates, but homogeneous, clear and in particular even in the cold remain fluid.

It has been found that mixtures of fatty acids are used as paraffin dispersants polar nitrogen-containing compounds also active in middle distillates significantly lower temperatures, sometimes below -20 ° C, in special cases Flowable down to below -30 ° C and in special cases down to -40 ° C over a longer period and remain clear and the lubricating effect of middle distillates more efficient improve as pure fatty acids of the prior art.

A1) 1 bis 99 Gew.-% mindestens einer gesättigten Mono- oder Dicarbonsäure mit 6 bis 50 Kohlenstoffatomen,

A2) 1 bis 99 Gew.-% mindestens einer ungesättigten Mono- oder Dicarbonsäure mit 6 bis 50 Kohlenstoffatomen, sowie

B) mindestens einer als Paraffindispergator in Mitteldestillaten wirksamen polaren stickstoffhaltigen Verbindung in einer Menge von 0,01 bis 90 Gew.-% bezogen auf das Gesamtgewicht von A1), A2) und B).

The invention thus relates to cold-stabilized additives for fuel oils with a sulfur content of up to 0.05% by weight, containing fatty acid mixtures

A1) 1 to 99% by weight of at least one saturated mono- or dicarboxylic acid with 6 to 50 carbon atoms,

A2) 1 to 99% by weight of at least one unsaturated mono- or dicarboxylic acid with 6 to 50 carbon atoms, and

B) at least one polar nitrogen-containing compound effective as a paraffin dispersant in middle distillates in an amount of 0.01 to 90% by weight based on the total weight of A1), A2) and B).

Another object of the invention are cold stabilized solutions of Additives according to the invention in organic solvents, the solutions 1 to Contain 90 wt .-% solvent. Suitable solvents are aliphatic and / or aromatic hydrocarbons or hydrocarbon mixtures. Prefers the additives according to the invention contain 1-80%, especially 10-70%, in particular 25 - 60% solvent. The cold stabilized solutions according to the invention have an own pour point of below -40 ° C, preferably -45 ° C, especially -50 ° C.

A1) 1 bis 99 Gew.-% mindestens einer gesättigten Mono- oder Dicarbonsäure mit 6 bis 50 Kohlenstoffatomen,

A2) 1 bis 99 Gew.-% mindestens einer ungesättigten Mono- oder Dicarbonsäure mit 6 bis 50 Kohlenstoffatomen, sowie

B) mindestens einer als Paraffindispergator in Mitteldestillaten wirksamen polaren stickstoffhaltigen Verbindung in einer Menge von 0,01 bis 90 Gew.-% bezogen auf das Gesamtgewicht von A1), A2) und B).

The invention further relates to cold-stabilized fatty acid mixtures

A1) 1 to 99% by weight of at least one saturated mono- or dicarboxylic acid with 6 to 50 carbon atoms,

A2) 1 to 99% by weight of at least one unsaturated mono- or dicarboxylic acid with 6 to 50 carbon atoms, and

B) at least one polar nitrogen-containing compound effective as a paraffin dispersant in middle distillates in an amount of 0.01 to 90% by weight based on the total weight of A1), A2) and B).

A1) 1 bis 99 Gew.-% mindestens einer gesättigten Mono- oder Dicarbonsäure mit 6 bis 50 Kohlenstoffatomen,

A2) 1 bis 99 Gew.-% mindestens einer ungesättigten Mono- oder Dicarbonsäure mit 6 bis 50 Kohlenstoffatomen, sowie

B) mindestens einer als Paraffindispergator in Mitteldestillaten wirksamen polaren stickstoffhaltigen Verbindung in einer Menge von 0,01 bis 90 Gew.-% bezogen auf das Gesamtgewicht von A1), A2) und B).

The invention further relates to fuel oils which, in addition to a middle distillate with a sulfur content of up to 0.05% by weight, contain fatty acid mixtures

A1) 1 to 99% by weight of at least one saturated mono- or dicarboxylic acid with 6 to 50 carbon atoms,

A2) 1 to 99% by weight of at least one unsaturated mono- or dicarboxylic acid with 6 to 50 carbon atoms, and

B) at least one polar nitrogen-containing compound effective as a paraffin dispersant in middle distillates in an amount of 0.01 to 90% by weight based on the total weight of A1), A2) and B).

Another object of the invention is the use of the above Mixtures of components A and B to improve the Lubrication properties of low-sulfur middle distillates with up to 0.05% by weight Sulfur content.

Preferred fatty acids (component A) are those with 8-40 carbon atoms, especially 12 - 22 carbon atoms. The alkyl residues of the fatty acids consist of essentially from carbon and hydrogen. However, you can choose more Substituents such as Hydroxy, halogen, amino or nitro groups, provided these do not affect the predominant hydrocarbon character.

Component A2) can contain one or more double bonds and more natural or synthetic origin. With polyunsaturated carboxylic acids whose double bonds can be isolated or conjugated. The proportion of saturated Fatty acids A1) in the mixture of A1) and A2) is preferably below 20% by weight, in particular below 10% by weight, especially below 5% by weight. In preferred Fatty acid mixtures, which here means the combination of A1) and A2) contain at least 50% by weight, in particular at least 75% by weight, especially at least 90% by weight of the components one or more Double bonds. These preferred fatty acids (blends) have iodine numbers of at least 40 g I / 100 g, preferably at least 80 g I / 100 g, in particular at least 125 g I / 100 g.

Suitable fatty acids are, for example, lauric, tridecane, myristic, pentadecane, Palmitic, margarine, stearic, isostearic, arachic and behenic acid, oleic and Erucic acid, palmitoleic, myristoleic, linoleic, linolenic, elaeosteric and Arachidonic acid, ricinoleic acid and those obtained from natural fats and oils Fatty acid mixtures, e.g. Coconut oil, peanut oil, fish, linseed oil, palm oil, Rapeseed oil, castor oil, castor oil, rapeseed oil, soybean oil, sunflower oil and tall oil fatty acid.

Also suitable are dicarboxylic acids, such as dimer fatty acids and alkyl and alkenylsuccinic acids with C ₈ -C ₅₀ alk (en) yl radicals, preferably with C ₈ -C ₄₀ , in particular with C ₁₂ -C ₂₂ alkyl radicals. The alkyl radicals can be linear or branched (oligomerized alkenes, PIB).

The fatty acids may further contain 1-40, especially 1-25% by weight of resin acids, based on the weight of A1) and A2) together.

The additives according to the invention contain as component B at least one as Paraffin dispersant in middle distillates effective polar nitrogenous compound. Paraffin dispersants reduce the size of those that precipitate in the cold Paraffin crystals and cause the paraffin particles not to settle, but to colloidal with significantly reduced sedimentation efforts, remain dispersed. As Paraffin dispersants have become oil-soluble polar compounds with ionic or polar groups, e.g. Amine salts and / or amides proven by reaction aliphatic or aromatic amines, preferably long-chain aliphatic Amines, with aliphatic or aromatic mono-, di-, tri- or tetracarboxylic acids or their anhydrides are obtained. Particularly preferred Paraffin dispersants also contain reaction products of secondary fatty amines 8 to 36 carbon atoms, especially dicocos fatty amine, ditallow fatty amine and Distearyl. Other paraffin dispersants are copolymers of Maleic anhydride and α, β-unsaturated compounds, optionally with primary monoalkylamines and / or aliphatic alcohols are implemented can, the reaction products of alkenylspirobislactones with amines and Reaction products of terpolymers based on α, β-unsaturated Dicarboxylic anhydrides, α, β-unsaturated compounds and polyoxyalkylene ethers lower unsaturated alcohols. Alkylphenol-formaldehyde resins are also available Paraffin dispersants suitable. The following are some suitable ones Paraffin dispersants listed.

1. Umsetzungsprodukte von Alkenyl-spirobislactonen der Formel 4

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 (4) mit den Aminen Amide oder Amid-Ammoniumsalze.

2. Amide bzw. Ammoniumsalze von Aminoalkylenpolycarbonsäuren mit sekundären Aminen der Formeln 5 und 6

in denen
R¹⁰ einen geradkettigen oder verzweigten Alkylenrest mit 2 bis 6 Kohlenstoffatomen oder den Rest der Formel 7

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 8

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 9

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. Quartäre Ammoniumsalze der Formel 10 ⁺NR⁶R⁷R⁸R¹¹ X^- wobei R⁶, R⁷, R⁸ die oben gegebene Bedeutung haben und R¹¹ für C₁-C₃₀-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 = C₆-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-Methyltriethanolammoniumtristearylestermethosulfat und deren Mischungen.

4. Verbindungen der Formel 11

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 der Formel (11) 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- oder Ammoniumgruppe direkt an das Gerüst des Polymers gebunden enthalten, wobei die Amid- 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-C₄₀-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, 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. 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; Di-hexadecylfumarat, 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/C₁₄-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. 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, 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. 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. Vorzugsweise 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. 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 12 und/oder 14, sowie gegebenenfalls 13 enthalten, wobei die Struktureinheiten 13 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 15

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 16

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.The paraffin dispersants mentioned below are produced in part by reacting compounds which contain an acyl group 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 can be the} same or different, and at least one of these groups for C ₈ -C ₃₆ alkyl, C ₆ - C ₃₆ cycloalkyl, C ₈ -C ₃₆ alkenyl, in particular C ₁₂ -C ₂₄ alkyl, C ₁₂ -C ₂₄ alkenyl or cyclohexyl, and the other groups are either hydrogen, C ₁ -C ₃₆ alkyl, C ₂ -C ₃₆ -Alkenyl, cyclohexyl, or a group of the formulas - (AO) _x -E or - (CH ₂ ) _n -NYZ, in which A represents an ethylene or propylene group, x is a number from 1 to 50, E. = H, C ₁ -C ₃₀ alkyl, C ₅ -C ₁₂ cycloalkyl or C ₆ -C ₃₀ aryl, and n is 2, 3 or 4, and Y and Z independently of one another are H, C ₁ -C ₃₀ - Alkyl or - (AO) _x mean. Acyl group is understood here to mean a functional group of the following formula: > C = O

1. Reaction products of alkenyl spirobislactones of the formula 4

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 (4) with the amines.

2. Amides or ammonium salts of aminoalkylene polycarboxylic acids with secondary amines of the formulas 5 and 6

in which
R ^{10 is} a straight-chain or branched alkylene radical having 2 to 6 carbon atoms or the radical of the formula 7

in which R ⁶ and R ^{7 are} in particular alkyl radicals having 10 to 30, preferably 14 to 24, carbon atoms, the amide structures also partially or completely in the form of the ammonium salt structure of the formula 8

can be present. The amides or amide ammonium salts or ammonium salts, for example of nitrilotriacetic acid, ethylenediaminetetraacetic acid or propylene-1,2-diamine tetraacetic acid, are reacted with 0.5 to 1.5 mol of amine, preferably 0.8 to 1.2 mol, by reacting the acids Amine obtained per carboxyl group. The reaction temperatures are about 80 to 200 ° C., the water of reaction formed being continuously removed to produce the amides. However, the reaction does not have to be carried out completely to give the amide; on the contrary, 0 to 100 mol% of the amine used can be present in the form of the ammonium salt. The compounds mentioned under B1) can also be prepared under analogous conditions, as amines of the formula 9

Dialkylamines are particularly suitable in which R ⁶ , R ^{7 is} a straight-chain alkyl radical having 10 to 30 carbon atoms, preferably 14 to 24 carbon atoms. Dioleylamine, dipalmitinamine, dicoconut fatty amine and dibehenylamine and preferably ditallow fatty amine may be mentioned in particular.

3. Quaternary ammonium salts of formula 10 ⁺ NR ⁶ R ⁷ R ⁸ R ¹¹ X ^- where R ⁶ , R ⁷ , R ^{8 have} the meaning given above and R ¹¹ for 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 , with R ¹³ = C ₆ -C _40- alkenyl, n is a number from 1 to 30 and X represents halogen, preferably chlorine, or a methosulfate. Examples of such quaternary ammonium salts are: dihexadecyldimethylammonium chloride, distearyldimethylammonium chloride, quaternization products of esters of di- and triethanolamine with long-chain fatty acids (lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid and fatty acid fatty acid mixtures, such as tallow fatty acid fatty acids, such as tallow fatty acid fatty acids, such as tallow fatty acid fatty acids, such as tallow fatty acid fatty acids, such as tallow fatty acid fatty acids, such as tallow fatty acid fatty acids, such as tallow fatty acid fatty acids, such as coconut oil fatty acid fatty acids, such as coconut oil fatty acid fatty acids, such as coconut oil fatty acid fatty acids, such as coconut oil fatty acid fatty acids, such as coconut oil fatty acid fatty acids, such as coconut oil fatty acid fatty acids, such as coconut oil fatty acid fatty acids, such as coconut oil fatty acid fatty acids such as, such as N-methyltriethanolammonium distearyl ester chloride, N-methyltriethanolammonium distearyl ester methosulfate, N, N-dimethyldiethanolammonium distearyl ester chloride, N-methyltriethanolammonium dioleylester chloride, N-methyltriethanolammonium trilauryol ester methyl sulfonate methylsulfonate methylsulfonate methosulfonate methylsulfonate methylsulfonate methylsulfonate methylsulfonate methylsulfonate methylsulfonate methylsulfonate methylsulfonate methanesulfonate methylsulfonate methylsulfonate methylsulfonate methylsulfonate methylsulfonate methylsulfonate methylsulfonate methylsulfonate methylsulfonate methyl sulfate

4. Compounds of formula 11

in which R ^{14 stands} for CONR ⁶ R ⁷ or CO ₂ ^{- +} H ₂ NR ⁶ R ⁷ ,
R ¹⁵ and R ^{16 represent} 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), trimellite, pyromellitic acid (dianhydride), isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid (anhydride), maleic acid (anhydride), alkenylsuccinic acid (anhydride). The formulation (anhydride) means that the anhydrides of the acids mentioned are also preferred acid derivatives. If the compounds of the formula (11) are amides or amine salts, they are preferably of a secondary amine which contains a hydrogen and carbon-containing group with at least 10 carbon atoms It is preferred that R ^{17 contains} 10 to 30, in particular 10 to 22, for example 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 can be shorter, eg contain less than 6 carbon atoms, or, if desired, can have at least 10 carbon atoms. Suitable alkyl groups include methyl, ethyl, propyl, hexyl, decyl, dodecyl, tetradecyl, eicosyl and docosyl (behenyl). Also suitable are polymers which contain at least one amide or ammonium group directly attached to the backbone of the polymer, the amide - Or ammonium group carries at least one alkyl group of at least 8 carbon atoms on the nitrogen atom. Such polymers can be produced in various ways. One way is to use a polymer containing multiple carboxylic acid or anhydride groups and react that polymer with an amine of the formula NHR ⁶ R ⁷ to obtain the desired polymer. In general, copolymers of unsaturated esters such as C ₁ -C ₄₀ -alkyl (meth) acrylates, fumaric acid di (C ₁ -C ₄₀ -alkyl esters), C ₁ -C ₄₀ -alkyl vinyl ethers, C ₁ -C ₄₀ -alkyl vinyl esters or C. ₂ -C ₄₀ olefins (linear, branched, aromatic) with unsaturated carboxylic acids or their reactive derivatives, such as carboxylic acid anhydrides (acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, citraconic acid, preferably maleic anhydride). Carboxylic acids are preferably used with 0.1 up to 1.5 mol, in particular 0.5 to 1.2 mol, of amine per acid group, carboxylic anhydrides preferably reacted with 0.1 to 2.5, in particular 0.5 to 2.2 mol, of amine per acid anhydride group, amides depending on the reaction conditions, Ammonium salts, amide ammonium salts or imides are formed. Thus, copolymers containing unsaturated carboxylic anhydrides give half amide and half amine salts when reacted with a secondary amine due to the reaction with the anhydride group. Water can be split off by heating to form the diamond. Particularly suitable examples of amide group-containing polymers for use in accordance with the invention are:

5. Copolymers (a) of a dialkyl fumarate, maleate, citraconate or itaconate with maleic anhydride, or (b) of vinyl esters, for example vinyl acetate or vinyl stearate with maleic anhydride, or (c) of 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; Di-hexadecyl 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 if an ester amide is formed). If polymers containing an anhydride group are reacted, the resulting amino groups will be ammonium salts and amides. Such polymers can be used provided that they contain at least two amide groups. It is essential that the polymer containing at least two amide groups contain at least one alkyl group with at least 10 carbon atoms. This long-chain group, which can be a straight-chain or branched alkyl group, can be bound 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 are represented, wherein R ^{19 is} a divalent hydrocarbon group, preferably an alkylene or hydrocarbon-substituted alkylene group, and x is an integer, preferably between 1 and 30. Preferably one of the two or both R ⁶ and R ⁷ contain 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 which contain alkyl groups with at least 10 carbon atoms, for example didecylamine, didodecylamine, dicocosamine (ie mixed C ₁₂ -C ₁₄ amines), dioctadecylamine, hexadecyloctadecylamine, di- (hydrogenated tallow) amine (approximately 4 % By weight of nC ₁₄ -alkyl, 30% by weight of nC ₁₀ -alkyl, 60% by weight of nC ₁₈ -alkyl, the rest is unsaturated). Examples of suitable polyamines are N-octadecylpropane diamine, N, N'-dioctadecyl propane diamine, N-tetradecylbutanediamine and N, N'-dihexadecylhexanediamine. N-Cocospropylenediamine (C ₁₂ / C ₁₄ alkyl propylene diamine), N-tallow propylene diamine (C ₁₆ / C ₁₈ alkyl propylene diamine). The amide-containing polymers usually have an average molecular weight (number average) of 1000 to 500 000, for example 10,000 to 100,000.

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 particular, the structural units of the copolymers are derived from, for example, maleic acid, fumaric acid, tetrahydrophthalic acid, citraconic acid, preferably maleic anhydride. They can be used both in the form of their homopolymers and of 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 include: styrene, α-methylstyrene, dimethylstyrene, α-ethylstyrene, diethylstyrene, i-propylstyrene, tert-butylstyrene, ethylene, propylene, n-butylene, diisobutylene, decene, dodecene, tetradecene, hexadecene, octadecene. Styrene and isobutene are preferred, and styrene is particularly preferred. Examples of polymers are: polymaleic acid, a molar, alternating styrene / maleic acid copolymer, randomly constructed styrene / maleic acid copolymers in a ratio of 10:90 and an alternating copolymer of maleic acid and i-butene. The molar masses of the polymers are generally from 500 g / mol to 20,000 g / mol, preferably from 700 to 2000 g / mol. The reaction of the polymers or copolymers with the amines takes place at from 50 to 200 ° C. in the course of 0 3 to 30 hours. The amine is used in amounts of about one mole per mole of polymerized dicarboxylic anhydride, ie about 0.9 to 1.1 moles / mole. The use of larger or smaller amounts is possible, but has no advantage. If larger amounts than one mole are used, ammonium salts are obtained in part, since the formation of a second amide group requires higher temperatures, longer residence times and water separation. If less than one mole is used, there is no complete conversion to the monoamide 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 give the corresponding amides, it can sometimes be advantageous to use the monoamides of the monomers to produce and then copolymerize directly during the polymerization. In most cases, however, this is technically much more complex because the amines can attach to the double bond of the monomeric mono- and dicarboxylic acid and then copolymerization is no longer possible.

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 5 to 90 mol% of one or more ethylenically unsaturated dicarboxylic acids or their anhydrides, the copolymer being largely with a or more primary or secondary amines is converted to the monoamide or amide / ammonium salt of dicarboxylic acid. 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 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 particularly preferably 8 to 18 carbon atoms. They are preferably straight-chain and unbranched. However, up to 20% by weight of cyclic and / or branched portions can also be present. 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. Maleic anhydride is preferred. Compounds of the formula HNR ⁶ R ^{7 are} suitable as amines. It is generally 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 the anhydrides usually 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 used in amounts of about one to two moles per mole of polymerized dicarboxylic anhydride, ie about 0.9 to 2.1 moles / mole. The use of larger or smaller amounts is possible, but has no advantage. If more than two moles are used, free amine is present. If less than one mole is used, there is no complete conversion to the monoamide and the effect is reduced accordingly. In some cases it may be advantageous if the amide / ammonium salt structure is built up from two different amines. For example, a copolymer of lauryl acrylate and maleic anhydride can first be reacted with a secondary amine, such as hydrogenated ditallow fatty amine, to the amide, after which the free carboxyl group originating from the anhydride is neutralized with another amine, for example 2-ethylhexylamine, to give the ammonium salt. The reverse procedure is also conceivable: First the reaction with ethylhexylamine to form the monoamide, then with ditallow fatty amine to the ammonium salt. At least one amine is preferably used which has at least one straight-chain, unbranched alkyl group with more than 16 carbon atoms. It does not matter 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 the dicarboxylic acid anhydride with amines to give the corresponding amides or amide / ammonium salts, it can sometimes be advantageous to use the monoamides or to produce amide / ammonium salts of the monomers and then to copolymerize them directly during the polymerization. In most cases, however, this is technically much more complex, since the amines can attach to the double bond of the monomeric dicarboxylic acid and then copolymerization is no longer possible.

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 12 and / or 14 and optionally 13, the structural units 13 originating 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 stand for the groups -NHR ⁶ , N (R ⁶ ) ₂ and / or -OR ²⁷ , and R ²⁷ for a cation of the formula H ₂ N (R ⁶ ) ₂ or H ₃ NR ⁶ stands,
19-80 mol%, preferably 39-60 mol%, of bivalent structural units of the formula 15

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 to 30 mol%, preferably 1 to 20 mol% of bivalent structural units of the formula 16

wherein
R ^{30 is} hydrogen or methyl,
R ^{31 is} hydrogen or C ₁ -C ₄ alkyl,
R ³³ 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 , where
R ^{34 is} C ₁ -C ₄₀ alkyl, C ₅ -C ₁₀ cycloalkyl or C ₆ -C ₁₈ aryl,
contain.

The aforementioned alkyl, cycloalkyl and aryl radicals can 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. The following may be mentioned in detail: 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 with 5-20 Carbon atoms. Preferred cycloalkyl radicals are cyclopentyl and Cyclohexyl.

Aryl here stands for an optionally substituted aromatic Ring system with 6 to 18 carbon atoms.

The terpolymers consist of the bivalent structural units of the formulas 12 and 14 and 15 and 16 and possibly 13. They only contain in known in the polymerization by initiation, inhibition and chain termination end groups.

wie Maleinsäureanhydrid, Itaconsäureanhydrid, Citraconsäureanhydrid, bevorzugt Maleinsäureanhydrid, ab.
Die Struktureinheiten der Formel 15 leiten sich von den α,β-ungesättigten Verbindungen der Formel 19 ab.

Structural units of the formulas 12 to 14 are derived in particular from α, β-unsaturated dicarboxylic acid anhydrides of the formulas 17 and 18

such as maleic anhydride, itaconic anhydride, citraconic anhydride, preferably maleic anhydride.
The structural units of the formula 15 are derived from the α, β-unsaturated compounds of the formula 19.

The following α, β-unsaturated olefins may be mentioned by way of example: 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. Alpha-olefins having 10 to 24 carbon atoms and styrene are preferred, alpha-olefins having 12 to 20 carbon atoms are particularly preferred.

The structural units of the formula 16 are derived from polyoxyalkylene ethers of lower, unsaturated alcohols of the formula 20.

The monomers of the formula 20 are etherification products (R ³² = -C (O) R ³⁴ ) or esterification products (R ³² = -C (O) R ³⁴ ) of polyoxyalkylene ethers (R ³² = H).

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. The polyoxyalkylene ethers (R ³² = H) can be prepared by known processes by adding α-olefin oxides, such as ethylene oxide, propylene oxide and / or butylene oxide, to polymerizable lower, unsaturated alcohols of the formula 21

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 -buten-2-ol and 3-methyl-3-buten-1-ol. Addition products of ethylene oxide and / or propylene oxide onto allyl alcohol are preferred.

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-C₁₈Arylcarbonsäuren verwendet. Die Veresterung wird im allgemeinen bei Temperaturen von 0 bis 200°C, vorzugsweise 10 bis 100°C durchgeführt.Subsequent etherification of these polyoxyalkylene ethers to give compounds of the formula 20 with R ³² = C ₁ -C ₂₄ alkyl, cycloalkyl or aryl is carried out by processes known per se. Suitable processes are known, for example, from J. March, Advanced Organic Chemistry, 2nd edition, pp. 357f (1977). These etherification products of the polyoxyalkylene ethers can also be prepared by adding α-olefin oxides, preferably ethylene oxide, propylene oxide and / or butylene oxide, to alcohols of the formula 22 R ³² - OH wherein R ^{32 is} equal to C ₁ -C ₂₄ alkyl, C ₅ -C ₂₀ cycloalkyl or C ₆ -C ₁₈ aryl, by known methods and with polymerizable lower, unsaturated halides of the formula 23

implemented, where W stands for a halogen atom. The chlorides and bromides are preferably used as halides. Suitable production processes are mentioned, for example, in J. March, Advanced Organic Chemistry, 2nd edition, p.357f (1977). The esterification of the polyoxyalkylene ethers (R ³² = -C (O) -R ³⁴ ) takes place by reaction with common esterification agents, such as carboxylic acids, carboxylic acid halides, carboxylic acid 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 aryl carboxylic acids are preferably used. The esterification is generally carried out at temperatures from 0 to 200 ° C., preferably 10 to 100 ° C.

In the case of the monomers of the formula 20, the index m indicates the degree of alkoxylation, i.e. the number of moles of α-olefin, the per mole of formula 20 or 21 be attached.

Examples of suitable primary amines suitable for the preparation of the terpolymers are the following:
n-hexylamine, n-octylamine, n-tetradecylamine, n-hexadecylamine, n-stearylamine or also N, N-dimethylaminopropylenediamine, cyclohexylamine, dehydroabietylamine and mixtures thereof.

Secondary amines which are suitable for the preparation of the terpolymers are for example: didecylamine, ditetradecylamine, distearylamine, Dicocos fatty amine, ditallow fatty amine and mixtures thereof.

The terpolymers have K values (measured according to Ubbelohde in a 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 approximately 500 and 100,000. Suitable examples are listed in EP 606 055.

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 15 enthalten.Reaction products of alkanolamines and / or polyetheramines with polymers containing dicarboxylic acid anhydride groups, characterized in that they contain 20-80, preferably 40-60 mol% of bivalent structural units of the formulas 25 and 27 and optionally 26

in which

R ²² and R ²³

independently of one another 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

mean and
Contain 80 - 20 mol%, preferably 60 - 40 mol% of bivalent structural units of the formula 15.

The structural units of the formulas 25; 26 and 27 of α, β-unsaturated dicarboxylic anhydrides of the formulas 17 and / or 18 from.

The structural units of the formula 15 are derived from the α, β-unsaturated ones Olefins of the formula 19. The aforementioned alkyl, cycloalkyl and aryl radicals have the same meanings as under 8.

The radicals R ³⁷ and R ³⁸ in formula 25 and R ³⁹ in formula 27 are derived from polyetheramines or alkanolamines of the formulas 28 a) and b), amines of the formula NR ⁶ R ⁷ R ⁸ and, if appropriate, from alcohols having 1 to 30 carbon atoms from.

R⁵³

Wasserstoff, C₆-C₄₀-Alkyl oder

R⁵⁴

Wasserstoff, C₁-C₄-Alkyl

R⁵⁵

Wasserstoff, C₁- bis 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.

Mean in it

R ⁵³

Hydrogen, C ₆ -C ₄₀ alkyl or

R ⁵⁴

Hydrogen, C ₁ -C ₄ alkyl

R ⁵⁵

Hydrogen, C ₁ - to 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.

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 28 a) and b) were preferably used to derivatize the structural units of the formulas 17 and 18.

The preparation of the polyetheramines used is, for example, by reductive amination of polyglycols possible. Furthermore, it succeeds Production of polyetheramines with a primary amino group by Addition of polyglycols to acrylonitrile and subsequent catalytic Hydrogenation. In addition, polyetheramines are produced by the reaction of Polyethers with phosgene or thionyl chloride and subsequent amination accessible to polyetheramine. The used according to the invention Polyetheramines are (e.g.) under the name ® Jeffamine (Texaco) commercially available. Their molecular weight is up to 2000 g / mol and the ethylene oxide / propylene oxide ratio is from 1:10 to 6: 1. Another way to derivatize the structural units of the Formulas 17 and 18 is that instead of the polyether amines Alkanolamine of the formulas 28a) or 28b) used and subsequently one Oxalkylation is subjected.

0.01 to 2 mol, preferably 0.01 to 1 mol, are used per mole of anhydride Alkanolamine used. The reaction temperature is between 50 and 100 ° C (amide formation). In the case of primary amines, the conversion takes place at temperatures above 100 ° C (imide formation).

The oxyalkylation is usually carried out at temperatures between 70 and 170 ° C. with catalysis of bases, such as NaOH or NaOCH ₃ , by gassing up 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 are: Monoethanolamine, diethanolamine, N-methylethanolamine, 3-aminopropanol, Isopropanol, diglycolamine, 2-amino-2-methylpropanol and their mixtures.

The following may be mentioned as primary amines:
n-hexylamine, n-octylamine, n-tetradecylamine, n-hexadecylamine, n-stearylamine or also N, N-dimethylaminopropylenediamine, cyclohexylamine, dehydroabietylamine and mixtures thereof.

Examples of secondary amines are:
Didecylamine, Ditetradecylamine, Distearylamine, Dicocosfettamin, Ditalgfettamin and their mixtures.

Examples of alcohols include:
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.

Copolymers and terpolymers of NC ₆ -C ₂₄ alkyl maleimide with C ₁ -C ₃₀ vinyl esters, vinyl ethers and / or olefins with 1 to 30 C atoms, such as styrene or α-olefins. These are accessible on the one hand by reacting a polymer containing anhydride groups with amines of the formula H ₂ NR ⁶ or by imidation 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.

The mixing ratio between A and B can vary within wide limits. So even small amounts B of 100 ppm to 50,000 ppm, preferably 1,000 ppm, are effective up to 10,000 ppm, in fatty acid solutions as a cold additive for A. They can do that Prevent self-crystallization of the fatty acid, which leads to a lowering of the Cloud Points leads, or to prevent the sedimentation of formed crystals and enable easy handling at reduced temperatures. For special solutions to problems can also range from 5% to 50%, in particular Cases up to 90% of ingredient B based on the amount of ingredient A. to be present. In particular, the additive's own pour point lowered and the lubricity of the additive oil improved. As a result, the preferred mixing ratio of A: B is between 1:10 and 1: 0.0001, in particular between 1: 4 and 1: 0.0005, especially between 1: 1 and 1: 0.001.

The additives according to the invention are oils in amounts of 0.001 to 0.5% by weight, preferably 0.001 to 0.1 wt .-% added. They can be as such or also dissolved in solvents such as aliphatic and / or aromatic Hydrocarbons or hydrocarbon mixtures such as e.g. Toluene, xylene, Ethylbenzene, decane, pentadecane, gasoline fractions, kerosene or commercial Solvent mixtures such as Solvent Naphtha, ® Shellsol AB, ® Solvesso 150, ® Solvesso 200, ® Exxsol, ® Isopar and ® Shellsol D types can be used. Prefers contain the additives according to the invention 1-80%, especially 10-70%, especially 25 - 60% solvent. The additives, even at low Temperatures of, for example, -40 ° C and lower are easily used can improve the lubricity of the additive oils and their Cold and corrosion protection properties.

For the production of additive packages for special problem solutions the additives according to the invention also together with one or more oil-soluble Co-additives are used, which alone have the cold flow properties and / or improve the lubricating effect of crude oils, lubricating oils or fuel oils. Examples of such co-additives are copolymers containing vinyl acetate or Terpolymers of ethylene, comb polymers, alkylphenol-aldehyde resins and oil-soluble amphiphiles.

So have mixtures of the additives according to the invention with copolymers excellent proven, the 10 to 40 wt .-% vinyl acetate and 60 to 90 wt .-% Contain ethylene. According to a further embodiment of the invention, the additives according to the invention in a mixture with ethylene / vinyl acetate / Vinyl neononanoic acid terpolymers or ethylene vinyl acetate / Vinyl neodecanoate terpolymers to improve the flowability of Mineral oils or mineral oil distillates. The terpolymers of Besides contain neononanoic acid vinyl ester or the neodecanoic acid vinyl ester Ethylene 10 to 35 wt .-% vinyl acetate and 1 to 25 wt .-% of the respective Neo compound. In addition to ethylene and 10, other preferred copolymers contain up to 35% by weight vinyl esters still 0.5 to 20% by weight olefin such as diisobutylene, 4-methylpentene or norbornene. The mixing ratio of the invention Additives with the ethylene / vinyl acetate copolymers described above or the terpolymers of ethylene, vinyl acetate and the vinyl esters of Neononanoic or neodecanoic acid is (in parts by weight) 20: 1 to 1:20, preferably 10: 1 to 1:10.

worin R⁵⁰ für C₄-C₅₀-Alkyl oder -Alkenyl, R⁵¹ für Ethoxy- und/oder Propoxy, n für eine Zahl von 5 bis 100 und p für eine Zahl von 0 bis 50 steht.The additives according to the invention can thus be used together with alkylphenol-formaldehyde resins. In a preferred embodiment of the invention, these alkylphenol-formaldehyde resins are those of the formula

wherein R ^{50 is} C ₄ -C ₅₀ alkyl or alkenyl, R ^{51 is} ethoxy and / or propoxy, n is a number from 5 to 100 and p is a number from 0 to 50.

Finally, in a further embodiment of the invention, the additives according to the invention are used together with comb polymers. This is understood to mean polymers in which hydrocarbon radicals having at least 8, in particular at least 10, carbon atoms are bonded to a polymer backbone. They are preferably homopolymers whose alkyl side chains contain at least 8 and in particular at least 10 carbon atoms. In copolymers, at least 20%, preferably at least 30%, of the monomers have side chains (cf. Comb-like Polymers-Structure and Properties; NA Platé 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 -C ₂₄ -α-olefin and an NC ₆ -C ₂₂ -alkylmaleimide (cf. EP 0 320 766) , also 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.

Das Mischungsverhältnis (in Gewichtsteilen) der erfindungsgemäßen Additive mit Harzen bzw. Kammpolymeren beträgt jeweils 1:10 bis 20:1, vorzugsweise 1:1 bis 10:1.Comb polymers can, for example, 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 with 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 resins or comb polymers is in each case 1:10 to 20: 1, preferably 1: 1 to 10: 1.

The additives according to the invention are suitable for the lubricating properties of animal, vegetable, mineral or synthetic fuel oils with only to improve low dosing rates. Due to their improved cold properties Can be heated and / or thinned during storage and use to be dispensed with. In addition, they improve the cold and Corrosion protection properties of the additive oils. The The emulsifying properties of the additive oils are less impaired than with the State-of-the-art lubricating additives are the case. The invention Additives are particularly well suited for use in middle distillates. As Middle distillates are referred to as those mineral oils that pass through Distillation of crude oil and boiling in the range of 120 to 450 ° C, for example kerosene, jet fuel, diesel and heating oil. The oils can also contain alcohols contain or consist of such as methanol and / or ethanol. Preferably the additives of the invention are used in such middle distillates that 0.05% by weight of sulfur and less, particularly preferably less than 350 ppm Sulfur, especially less than 200 ppm sulfur and in special cases contain less than 50 ppm sulfur. It is generally about those middle distillates which have been subjected to hydrogenating refining, and which therefore only contains small amounts of polyaromatic and polar compounds contain, which give them a natural lubricating effect. The Additives according to the invention are also preferably used in such Middle distillates used, the 95% distillation points below 370 ° C, in particular 350 ° C and in special cases below 330 ° C. You can also use it as a Components are used in lubricating oils.

The mixtures can be used alone or together with other additives be used, e.g. with other pour point depressors or Dewaxing aids, with corrosion inhibitors, antioxidants, Sludge inhibitors, dehazers, conductivity improvers, lubricity additives, and Additions to lower the cloud point. Furthermore, they become successful used together with additive packages that include known ashless Contain dispersing additives, detergents, defoamers and corrosion inhibitors.

The improved low-temperature stability and the effectiveness of the additives according to the invention as lubricity additives is explained in more detail by the following examples.

Examples

A1) Tallölfettsäure, enthaltend als Hauptbestandteile 30 % Ölsäure, 60 % Linol- und andere mehrfach ungesättigte Fettsäuren und 4% gesättigte Fettsäuren. Jodzahl 155 gJ/100 g.

A2) Ölsäure (technisch) enthaltend als Hauptbestandteile 69 % Ölsäure, 12% Linolsäure, 5 % Hexadecensäure und 10 % gesättigte Fettsäuren. Jodzahl 90 gJ/100 g.

B1) Umsetzungsprodukt eines Terpolymers aus C₁₄/₁₆-α-Olefin, Maleinsäureanhydrid und Allylpolyglykol mit 2 Equivalenten Ditalgfettamin, 50 %ig in Solvent Naphtha

B2) Umsetzungsprodukt eines Dodecenyl-Spirobislactons mit einer Mischung aus primärem und sekundärem Talgfettamin 60 %ig in Solvent Naphtha

B3) Nonylphenol-Formaldehydharz, 50 %ig in Solvent Naphtha

B4) Mischung aus 2 Teilen B1 und 1 Teil B2

B5) Amid-Ammoniumsalz auf Basis Ethylendiamintetraessigsäure mit 3 Equivalenten Ditalgfettamin gemäß EP 0597278.

B6) Mischung aus Amid-Ammoniumsalz auf Basis Ethylendiamintetraessigsäure mit 4 Equivalenten Ditalgfettamin und Copolymer aus gleichen Teilen Maleinsäureanhydrid und C₂₀/₂₄-Olefin, imidiert mit N-Talgfettpropylendiamin gemäß EP-0 909 307

B7) Amid-Ammoniumsalz aus 1 mol Phthalsäureanhydrid und 2 mol einer Mischung gleicher Teile Ditalg- und Dicocosfettamin

B8) Mischung aus gleichen Teilen

a) Amid-Ammoniumsalz aus 1 mol Phthalsäureanhydrid und 2 mol Ditalgfettamin und

b) Copolymer aus Fumarsäuredi(tetradecylester), 50 %ig in Solvent Naphtha.

The following substances were used:

A1) Tall oil fatty acid, containing 30% oleic acid, 60% linoleic and other polyunsaturated fatty acids and 4% saturated fatty acids as main components. Iodine number 155 gJ / 100 g.

A2) Oleic acid (technical) containing 69% oleic acid, 12% linoleic acid, 5% hexadecenoic acid and 10% saturated fatty acids as main components. Iodine number 90 gJ / 100 g.

B1) Reaction product of a terpolymer of C _14/16 -α-olefin, maleic anhydride and di-tallow Allylpolyglykol with 2 equivalents, 50% in Solvent Naphtha

B2) reaction product of a dodecenyl spirobislactone with a mixture of primary and secondary tallow fatty amine 60% in solvent naphtha

B3) Nonylphenol-formaldehyde resin, 50% in solvent naphtha

B4) Mixture of 2 parts B1 and 1 part B2

B5) Amide ammonium salt based on ethylenediaminetetraacetic acid with 3 equivalents of ditallow fatty amine according to EP 0597278.

B6) mixture of amide-ammonium salt based on ethylenediaminetetraacetic acid with 4 equivalents of ditallow fatty amine and copolymer of equal parts of maleic anhydride and C _20- / _24-olefin, imidized with N-tallowpropylenediamine according to EP-0909307

B7) Amide ammonium salt from 1 mol of phthalic anhydride and 2 mol of a mixture of equal parts of ditalg and dicocos fatty amine

B8) Mixture of equal parts

a) Amide ammonium salt from 1 mol of phthalic anhydride and 2 mol of ditallow fatty amine and

b) copolymer of fumaric acid di (tetradecyl ester), 50% in solvent naphtha.

To assess the cold properties, the pour point was measured according to ISO 3016 (Table 1) and the cloud point according to ISO 3015 (Table 2) of the mixtures according to the invention. The additive mixtures according to the invention were then stored at various temperatures for several days and then assessed visually (Tables 3 to 5). V denotes comparative examples. Pour point of the additives according to the invention Composition (parts by weight) Pour point example A1 A2 B1 B2 B3 B4 1 80 20 -9 2 50 50 -24 3 20 80 0 4 80 20 -9 5 50 50 -24 6 20 80 -6 7 80 20 0 8th 50 50 -15 9 20 80 -48 10 80 20 -9 11 50 50 -18 12 20 80 -15 13 80 20 -27 14 50 50 -27 15 20 80 -6 16 80 20 -27 17 50 50 -54 18 20 80 -45 19 80 20 -21 20 50 50 -30 21 20 80 -21 22 80 20 -21 23 50 50 -21 24 20 80 -9 25 99.95 0.05 -36 26 99.95 0.05 -36 27 99.95 0.05 -15 V1 100 -9 V2 100 6 V3 100 9 V4 100 -12 V5 100 0 V6 100 -6 V7 100 -36 Cloud points of the additives according to the invention Composition (parts by weight) Cloud point example A1 A2 B1 B2 B3 B4 V8 100 -27.0 28 99.9995 0.0005 -33.0 29 99.9995 0.0005 -30.5 30 99,998 0,002 -33.5 31 99,998 0,002 -33.5 32 99.995 0.005 -31.0 33 99.995 0.005 -32.2 34 (B5) 99,998 0,002 -29.0 35 (B6) 99,998 0,002 -31.0 36 (B7) 99,998 0,002 -35.5 37 (B8) 99,998 0,002 -37.0 Storage stability of the additives (3 days storage at -20 ° C) example Composition (parts by weight) evaluation A2 B1 B2 B3 38 50 50 viscous 39 80 20 liquid 40 20 80 liquid 41 50 50 liquid 42 20 80 liquid V9 100 firm, waxy V10 100 firmly V11 100 firmly V12 100 viscous

MS is a mixture of a number of aliphatic and cyclic, non-aromatic hydrocarbons. The main components of MS can be found in the following table: Table 6: Components of MS component Concentration range (% by weight) Di-2-ethylhexyl 10 - 25 2-ethylhexyl acid-2-ethylhexyl 10 - 25 C ₁₆ lactones 4 - 20 2-Ethylhexylbutyrat 3 - 10 2-ethylhexanediol- (1,3) glycol mono-n-butyrate 5 - 15 2-ethylhexanol 4 - 10 C ₄ to C ₈ acetates 2 - 10 2-ethylhexanediol- (1,3) 2 - 5 Ethers and esters ≥ C ₂₀ 0 - 20

Lubricating effect in middle distillates

The lubricating effect of the additives was carried out using an HFRR device from PCS Instruments on additive oils at 60 ° C. The High Frequency Reciprocating Rig Test (HFRR) is described in D. Wei, H. Spikes, Wear, Vol. 111, No.2, p.217, 1986. The results are given as the coefficient of friction and wear scar (WS1.4) , A low coefficient of friction and a low wear scar show a good lubricating effect. Characterization of the test oils: Test oils with the following characteristics were used to test the lubricating effect: Test oil 1 Test oil 2 boiling range: 170-344 ° C 182-304 ° C density 0.830 g / cm ³ 0.821 g / cm ³ Cloud point -9 ° C -33 ° C sulfur content 45 ppm 6 ppm

The boiling data are determined in accordance with ASTM D-86 and the cloud point in accordance with ISO 3015. Wear Scar in Test Oil 1 example additive Wear scar Friction V15 Without 555 µm 0.33 63 100 ppm according to Ex. 37 385 µm 0.18 64 100 ppm A1 + 150 ppm B4 381 µm 0.18 V16 100 ppm A1 421 µm 0.18 V17 150 ppm B4 549 µm 0.34 Wear Scar in Test Oil 2 example additive Wear scar Friction V18 without 637 µm 0.30 65 200 ppm according to Ex. 42 386 0.18 66 200 ppm according to Ex. 48 395 0.18 V19 200 ppm according to example V13 405 0.19

Claims (11)

Cold-stabilized additives for fuel oils with a sulfur content of up to 0.05% by weight, containing fatty acid mixtures A1) 1 to 99% by weight of at least one saturated mono- or dicarboxylic acid with 6 to 50 carbon atoms, A2) 1 to 99% by weight of at least one unsaturated mono- or dicarboxylic acid with 6 to 50 carbon atoms,
such as B) at least one polar nitrogen-containing compound effective as a paraffin dispersant in middle distillates in an amount of 0.01 to 90% by weight based on the total weight of A1), A2) and B). Additives according to claim 1, wherein component A has carboxylic acids with 12 to 22 Includes carbon atoms. Additives according to Claim 1 and / or 2, containing 1 to less than 20% by weight of A1) and over 80 to 99% by weight of A2). Additives according to one or more of claims 1 to 3, wherein the Mixture of A1) and A2) has an iodine number of at least 40 g I / 100 g. Additives according to one or more of claims 1 to 4, wherein the Mixture of A1) and A2) comprises 1 to 40 wt .-% resin acids. Additives according to one or more of claims 1 to 5, wherein oil-soluble polar amine salts or amides are contained as paraffin dispersants. Cold-stabilized solutions of the additives according to one or more of the Claims 1 to 6 in organic solvents, the solutions 1 to 80 wt .-% Contain solvents. Cold-stabilized solutions according to claim 7, wherein as a solvent aliphatic and / or aromatic and / or oxygen-containing hydrocarbons be used. Cold stabilized fatty acid mixtures containing A1) 1 to 99% by weight of at least one saturated mono- or dicarboxylic acid with 6 to 50 carbon atoms, A2) 1 to 99% by weight of at least one unsaturated mono- or dicarboxylic acid with 6 to 50 carbon atoms,
such as B) at least one polar nitrogen-containing compound effective as a paraffin dispersant in middle distillates in an amount of 0.01 to 90% by weight based on the total weight of A1), A2) and B). Fuel oils containing a middle distillate with up to 0.05% by weight Sulfur content an additive according to one or more of claims 1 to 9. Use of additives according to one or more of claims 1 to 9 to improve the lubricating properties of low-sulfur middle distillates with up to to 0.05 wt .-% sulfur content.