EP1380634A1 - Lubricity additives stabilised against oxidation for highly desulphurised fuel oils. - Google Patents

Abstract

Additive for improving the lubricity of fuel oils having a sulfur content of no more than 0.035 wt.% comprises: (a) a partial ester of a di- or polyhydric alcohol with fatty acids containing 8-30 carbon atoms, at least 60 % of the fatty acids having at least one double bond; and (b) a resin produced by condensing an aldehyde or ketone with an alkylphenol having at least one alkyl or alkenyl group of 6-24 carbon atoms to give a product comprising 2-50 alkylphenol units. An Independent claim is also included for fuel oils having a sulfur content of no more than 0.035 wt.% containing 0.001-0.5 wt.% of the additive.

Description

The present invention relates to additives from esters between polyols and Fatty acid mixtures and alkylphenol resins with improved oxidation stability, and their use to improve the lubricating effect of highly desulfurized 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 Europe since November 1999 a maximum sulfur content of 350 ppm. Further reductions in the sulfur content are in preparation. In Scandinavia come with fuel oils with less than 50 ppm and in exceptional cases less than 10 ppm sulfur to use. These fuel oils are used in the Usually made by making those from the petroleum by distillation obtained fractions hydrogenated refined. During the desulfurization also removes other substances that give the fuel oils a natural Give lubrication. These substances include, among others polyaromatic and polar compounds.

However, it has now been shown that the friction and wear-reducing properties of fuel oils deteriorate as the level of desulfurization increases. Often these properties are so inadequate that the materials lubricated by the fuel, such as the distributor injection pumps of diesel engines, are likely to start seizing after a short time. The maximum value for the 95% distillation point of maximum 360 ° C, which has been set in accordance with EN 590 since 2000, and the further reduction of the 95% distillation point to below 350 ° C and sometimes below 330 ° C in Scandinavia further exacerbates this problem.
Approaches are therefore described in the prior art which are intended to represent a solution to this problem (so-called lubricity additives).

EP-A-0 680 506 discloses that esters of fatty acids are desulfurized Give fuel oils an improved lubricating effect. It will be particularly Called glycerol monooleate and diisodecyl adipate.

EP-A-0 739 970 discloses the suitability of glycerol ester mixtures for Improving the lubricity of low-sulfur fuel oils. It will Compositions of various degrees of esterification of the polyol and different degrees of saturation of the fatty acids disclosed.

EP-A-0 839 174 discloses in their lubricating effect improved fuel oils which are low in sulfur and a mixture of polyol esters with unsaturated fatty acids include.

DE 19614722 discloses mixtures of partial esters of highly unsaturated fatty acids with various polyols with improved cold stability. These can be found at low-sulfur diesel oils can also be added as lubricating additives.

EP 0743972 discloses fuel oils with improved lubricity, some Lubricity improvers and a nitrogen compound include.

EP 0935645 discloses the use of C ₁ -C ₃₀ -alkylphenol resins as lubricity additives for low-sulfur diesel. The examples show C ₁₈ and C ₂₄ alkylphenol resins.

WO-99/61562 discloses mixtures of alkylphenol resins, nitrogenous ones Compounds and ethylene copolymers as refrigeration and lubricity additives for low sulfur diesel.

WO 01/19941 discloses partial esters of polyhydric alcohols with unsaturated ones Fatty acids (pentaerythritol esterified with tall oil fatty acid) as lubricity additives improved cold stability.

Lubricity additives based on unsaturated fatty acids and their derivatives can with prolonged storage of the additive as well as the additive oils especially under elevated temperature to only partially oil-soluble products gum up. This can lead to the formation of viscous deposits and deposits in the additive storage container, in the fuel oil and in the engine. Stand like this z. B. the combustion and condensation products of glycerol suspected for Highly charged coke residues and deposits on the injection nozzles Diesel engines to be responsible.

The effectiveness of the lubricity additives currently used is often unsatisfactory, so that either very high dosing rates or synergists are used Need to become.

The fatty acid esters based on commercial fatty acid mixtures State of the art also show in the fuel oils additized with them pronounced tendency to emulsify. That means that when such a contact Fuel oil with water an emulsification of the water in the fuel oil takes place. These emulsions, particularly found at the oil / water phase boundary cannot be separated or only with great effort. As these emulsions as such can not be used as fuel oils, they reduce the value of Products. This problem is particularly pronounced when it comes to natural Fatty acid-based esters can be used.

The object of the present invention was therefore to provide lubrication-improving additives for to find desulfurized fuel oils, one compared to the prior art improved oxidation stability and at the same time an improved effectiveness than Have lubricity additive.

Surprisingly, it was found that combinations of partial esters unsaturated fatty acids and polyols with alkylphenol-aldehyde resins a clearly have improved oxidation stability and selected combinations Hydroxyl number and iodine number have a particularly low emulsifiability. Of they also show the individual components in low-sulfur fuel oils superior lubrication.

A) mindestens einen Partialester aus einem zwei- oder mehrwertigen Alkohol und ungesättigten sowie gegebenenfalls gesättigten Fettsäuren, deren Kohlenstoffkettenlängen zwischen 8 und 30 Kohlenstoffatomen liegen, wobei mindestens 60% der Fettsäurereste mindestens eine Doppelbindung enthalten, und

B) mindestens ein Alkylphenol-Aldehydharz, erhältlich durch die Kondensation von

(i) mindestens einem Alkylphenol mit mindestens einem C₆-C₂₄-Alkyl oder C₆-C₂₄-Alkenylrest und

(ii) mindestens einem Aldehyd oder Keton,

wobei der Kondensationsgrad zwischen 2 und 50 Alkylphenoleinheiten beträgt. The invention therefore relates to an additive for improving the lubricity of fuel oils having a sulfur content of at most 0.035% by weight

A) at least one partial ester of a dihydric or polyhydric alcohol and unsaturated and optionally saturated fatty acids, the carbon chain lengths of which are between 8 and 30 carbon atoms, at least 60% of the fatty acid residues containing at least one double bond, and

B) at least one alkylphenol-aldehyde resin, obtainable by the condensation of

(i) at least one alkylphenol with at least one C ₆ -C ₂₄ alkyl or C ₆ -C ₂₄ alkenyl radical and

(ii) at least one aldehyde or ketone,

the degree of condensation being between 2 and 50 alkylphenol units.

Another object of the invention are fuel oils with maximum 0.035 wt .-% sulfur content, which contain the additives according to the invention.

Another object of the invention is the use of the invention Additives to improve the lubricating effect of fuel oils with at most 0.035% by weight sulfur content.

Another object of the invention is a method for improving the Lubricating effect of fuel oils with a maximum sulfur content 0.035% by weight by adding the additive according to the invention to the fuel oils added.

Preferred fatty acids which are part of the ester A) are those with 10 to 26 C atoms, in particular 12 to 22 C atoms. The alkyl residues or alkenyl residues of Fatty acids consist essentially of carbon and hydrogen. You can however other substituents such as e.g. Hydroxy, halogen, amino or nitro groups if they do not have the predominant hydrocarbon character affect. The fatty acids preferably contain at least one Double bond. You can have several double bonds, for example 2 or 3 Double bonds, contained and be of natural or synthetic origin. at polyunsaturated carboxylic acids can isolate their double bonds or also be conjugated. Mixtures of two or more unsaturated are preferred Fatty acids with 10 to 26 carbon atoms. In particularly preferred fatty acid mixtures contain at least 50% by weight, in particular at least 75% by weight, specifically at least 90% by weight of the fatty acids contain one or more double bonds. The Iodine numbers of the fatty acids on which the esters according to the invention are based or Fatty acid mixtures are preferably above 100 g J / 100 g, particularly preferably between 105 and 190 g J / 100 g, in particular between 110 and 180 g J / 100 g and especially between 120 and 180 g l / 100 g fatty acid or fatty acid mixture.

Suitable unsaturated fatty acids are, for example, oleic, eruca, palmitoleic, Myristoleic, linoleic, linolenic, elaeosteric, arachidonic and / or ricinoleic acid. According to the invention, those obtained from natural fats and oils are preferred Fatty acid mixtures or fractions, e.g. Peanut oil, fish, linseed oil, palm oil, Rapeseed oil, ricin oil, castor oil, rapeseed oil, soybean oil, sunflower oil, safflower and Tall oil fatty acid used, which have corresponding iodine numbers.

Also suitable as fatty acids 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, polyisobutylene) and saturated or unsaturated. The dicarboxylic acids can be used as such or in mixtures with monocarboxylic acids, with mixtures of dicarboxylic acids of up to 10% by weight, in particular less than 5% by weight, being preferred in mixtures.

In addition, the fatty acid mixtures can have minor amounts, i.e. up to 20% by weight, preferably less than 10%, in particular less than 5% and especially less than 2% saturated fatty acids such as lauric, tridecane, Myristin, pentadecane, palmitin, margarine, stearin, isostearin, arachine and Contain beenic acid.

The fatty acids can further 1-40, especially 1-25 wt .-%, in particular Contain 1-5 wt .-% resin acids.

Suitable alcohols preferably contain 2 to 6, in particular 3 to 4 Carbon atoms, and 2 to 5, especially 3 to 4 hydroxyl groups, however a maximum of one hydroxyl group per carbon atom. Particularly suitable alcohols are ethylene glycol, diethylene glycol, propylene glycol, glycerin, trimethylolpropane, Neopentylglycol and pentaerythritol as well as the condensation accessible oligomers with 2 to 10 monomer units, such as Polyglycerol.

The partial esters are made from alcohols and fatty acids in a known manner Esterification can be produced. Alternatively, partial saponification is natural occurring fats and oils possible. Esters according to the invention are those which consist of a di- or polyhydric alcohol and a fatty acid or a mixture can be produced from fatty acids. Both mixtures are made of, for example Mono-, di- and / or triesters, or possibly higher esters, of an alcohol various fatty acids, from mono-, di- and / or triesters, or possibly higher Esters, different alcohols with different fatty acids, as well Mixtures of mono-, di- and / or triesters, or possibly higher esters, one or several alcohols with different fatty acids. Those are preferred Esters that can be produced from a fatty acid mixture.

The esters according to the invention preferably have iodine numbers of more than 50 g l / 100 g ester, particularly preferably between 90 and 200 g l / 100 g ester, in particular between 100 and 180 g l / 100 g ester and especially between 110 and 150 g l / 100 g ester. The iodine numbers result from the iodine number of the underlying fatty acid mixture and that used for the esterification Alcohol in a stoichiometric manner.

Also preferred are partial esters whose OH numbers between 10 and 200 mg KOH / g ester are, particularly preferably between 100 and 200, in particular between 110 and 195, especially between 130 and 190 mg KOH / g ester. Usually these are mixtures of different esters, e.g. B. mixtures from mono-, di- and triglycerides, mixtures such as those used in the esterification of Polyols are created.

Draw the partial esters with OH numbers between 110 and 200 mg KOH / g ester especially in combination with the alkylphenol resins B) through a very low tendency to emulsify. This is probably caused by the OH number limited HLB range of additives a reduced affinity of the amphiphilic Active substances to water; at the same time, the training becomes more surface active and micellar structures by the number characterized by iodine number Double bonds in the alkyl residues disturbed.

The alkylphenol-aldehyde resins (B) contained in the additive according to the invention are known in principle and are described, for example, in the Römpp Chemie Lexikon, 9th edition, Thieme Verlag 1988-92, Volume 4, pp. 3351ff. described. The alkyl or alkenyl radicals of the alkylphenol have 6-24, preferably 8-22, in particular 9-18, carbon atoms. They can be linear or preferably branched, the branching being able to contain secondary as well as tertiary structures. It is preferably n- and iso-hexyl, n- and iso-octyl, n- and iso-nonyl, n- and iso-decyl, n- and iso-dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl and tripropenyl, Tetrapropenyl, pentapropenyl and polyisobutenyl to C ₂₄ . The prefix iso here means that the alkyl chain contains one or more secondary branches. The alkylphenol-aldehyde resin can also contain up to 20 mol% phenol units and / or alkylphenols with short alkyl chains such as e.g. B. contain butylphenol. The same or different alkylphenols can be used for the alkylphenol-aldehyde resin.

The aldehyde in the alkylphenol-aldehyde resin has 1 to 10, preferably 1 to 4 Carbon atoms and can carry other functional groups. It is preferably a aliphatic aldehyde, particularly preferably it is formaldehyde.

The molecular weight of the alkylphenol-aldehyde resins is preferably 350- 10,000, in particular 400 - 5000 g / mol. This preferably corresponds to one Degree of condensation n from 3 to 40, in particular from 4 to 20. Prerequisite here that the resins are oil-soluble.

sind, worin R^A für C₆-C₂₄-Alkyl oder -Alkenyl und n für eine Zahl von 2 bis 50 steht.In a preferred embodiment of the invention, these alkylphenol-formaldehyde resins are those which contain oligomers or polymers with a repetitive structural unit of the formula

are where R ^{A is} C ₆ -C ₂₄ alkyl or alkenyl and n is a number from 2 to 50.

The alkylphenol-aldehyde resins are prepared in a known manner by basic catalysis, whereby condensation products of the resol type arise, or by acidic catalysis, producing condensation products of the novolak type.

The condensates obtained in both ways are for the inventive ones Suitable compositions. The condensation in the presence of acidic catalysts.

To prepare the alkylphenol-aldehyde resins, an alkylphenol with 6 - 24, preferably 8-22, in particular 9-18, carbon atoms per alkyl group, or mixtures thereof and at least one aldehyde reacted with one another, with per mol Alkylphenol compound about 0.5-2 moles, preferably 0.7-1.3 mol and in particular equimolar amounts of aldehyde can be used.

Suitable alkylphenols are, in particular, n- and iso-hexylphenol, n- and iso-octylphenol, n- and iso-nonylphenol, n- and iso-decylphenol, n- and iso-dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, eicosylphenol, tripropetraphenylphenol, tripropenylphenol (isobutenyl) phenol to C ₂₄ .

The alkylphenols are preferably para-substituted. The alkylphenols can be one or carry several alkyl radicals. They are preferably at most 5 mol%, especially at most 20 mol% and especially at most 40 mol% with more than an alkyl group. Preferably carry at most 40 mol%, in particular at most 20 mol% of the alkylphenols used in the ortho position an alkyl radical. Specifically, the alkylphenols ortho to the hydroxyl group are not tertiary Alkyl groups substituted.

The aldehyde can be a mono- or dialdehyde and other functional groups wear like -COOH. Particularly suitable aldehydes are formaldehyde, acetaldehyde, Butyraldehyde, glutardialdehyde and glyoxalic acid, formaldehyde is preferred. The Formaldehyde can be in the form of paraformaldehyde or in the form of a preferred 20 - 40 wt .-% aqueous formalin solution can be used. It can too appropriate amounts of trioxane can be used.

The reaction of alkylphenol and aldehyde usually takes place in the presence of alkaline catalysts, for example alkali 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. The condensation is preferably solvent-free at 90 to 200 ° C, preferably carried out at 100 to 160 ° C. In another preferred The embodiment is carried out in the presence of a water Azeotropic organic solvent, for example toluene, xylene, higher aromatics or mixtures thereof. The reaction mixture is on a Temperature of 90 to 200 ° C, preferably 100-160 ° C heated, the resulting Water of reaction is removed during the reaction by azeotropic distillation. Solvent that does not have protons under the conditions of condensation split off, can remain in the products after the condensation reaction. The Resins can 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 proportions by weight of components A) and B) in the additives according to the invention can vary widely depending on the application. they lay preferably between 10 and 99.999% by weight A) to 90 to 0.001% by weight B), in particular between 20 and 99.995% by weight A) to 80 to 0.005% by weight B). there to stabilize the fatty acids, smaller portions of the Components B from 0.001 to 10% by weight, preferably 0.005 to 5% by weight B) used, whereas to optimize the lubricity larger portions B of for example 5 to 90 wt .-%, preferably 10 to 80 wt .-% and in particular 25 to 75 wt .-% are used.

Surprisingly, it was also found that a further increase in Effectiveness as a lubricity additive is achieved if the inventive Mixtures used together with nitrogen-containing paraffin dispersants become. Paraffin dispersants are additives that increase the size when the oil cools reduce the precipitated paraffin crystals and also cause the Paraffin particles do not settle, but colloidally with significantly reduced Sedimentation efforts, remain dispersed.

The nitrogen-containing paraffin dispersants are preferably low molecular weight or polymeric, oil-soluble nitrogen compounds, e.g. Amine salts, Imides and / or amides obtained by reaction of aliphatic or aromatic amines, preferably long-chain aliphatic amines, with aliphatic or aromatic Obtain mono-, di-, tri-, tetra- and / or polycarboxylic acids or their anhydrides become. Contain particularly preferred paraffin dispersants Reaction products of secondary fatty amines with 8 to 36 carbon atoms, in particular Dicocos fatty amine, ditallow fatty amine and distearyl amine. Other paraffin dispersants are copolymers of maleic anhydride and α, β-unsaturated compounds, optionally with primary monoalkylamines and / or aliphatic alcohols can be implemented with the reaction products of alkenylspirobislactones Amines and reaction products of terpolymers based on α, β-unsaturated Dicarboxylic anhydrides, α, β-unsaturated compounds and polyoxyalkylene ethers lower unsaturated alcohols with amines and / or alcohols. Hereinafter some suitable paraffin dispersants are listed.

1. Umsetzungsprodukte von Alkenylspirobislactonen 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. 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, Dipalmitylamin, Dikokosfettamin und Dibehenylamin und vorzugsweise Ditalgfettamin genannt.

3. Quartäre Ammoniumsalze der Formel +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-Methyltriethanolammonium-distearylester-chlorid, N-Methyltriethanolammoniumdistearylester-methosulfat, N,N-Dimethyldiethanolammoniumdistearylesterchlorid, N-Methyltriethanolammonium-dioleylester-chlorid, N-Methyltriethanolammoniumtrilaurylestermethosulfat, N-Methyltriethanolammoniumtristearylestermethosulfat und deren Mischungen.

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- 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, Vinylpropionat, Vinyl-2-ethylhexanoat 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 ltaconat 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 equimolares, 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 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 z.B. durch Anlagerung von α-Olefinoxiden, wie Ethylenoxid, Propylenoxid und/oder Butylenoxid an polymerisierbare niedere, ungesättigte Alkohole der Formel 10

und anschließende Veresterung oder Veretherung 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.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.

9. 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 = R³⁷oderNR⁶R³⁹
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- 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.

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.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 (lmidbildung).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, lsopropanol, n-, sek.-, tert.-Butanol, Octanol,

Tetradecanol, Hexadecanol, Octadecanol, Talgfettalkohol, Behenylalkohol und deren Mischungen. Geeignete Beispiele sind in EP-A-688 796 aufgeführt.

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-C₂₂-Alkylmaleinsäureimid.

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 remaining groups are either hydrogen, C ₁ -C ₃₆ alkyl, C ₂ -C ₃₆ alkenyl, cyclohexyl, or a group of the formulas - (AO) _x -E or - (CH ₂ ) _n -NYZ, where A is an 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 alkenylspirobislactones 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. 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 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

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, with the amides being continuously removed from the water of reaction formed. 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 in the form of the ammonium salt. The compounds mentioned under B1) can also be prepared under analogous conditions. As amines of the formula

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, dipalmitylamine, dicoconut fatty amine and dibehenylamine and preferably ditallow fatty amine may be mentioned in particular.

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 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 is 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 coconut oil 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 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, , such as N-methyltriethanolammonium distearyl ester chloride, N-methyltriethanolammonium distearyl ester methosulfate, N, N-dimethyldiethanolammonium distearyl ester chloride, N-methyltriethanolammonium dioleylester chloride, N-methyltriethanolammoniumtrietulfate methyl ester mixtures, and methyltriethanolammoniumtrilaulfate methyl ester.

4. Compounds of the formula

in which R ^{14 stands} for CONR ⁶ R ⁷ or CO ₂ ⁺ H ₂ NR ⁶ R ⁷ , R ¹⁵ and R ¹⁶ for H, CONR ¹⁷ ₂ , CO ₂ R ¹⁷ or OCOR ¹⁷ , -OR ¹⁷ , -R ¹⁷ or - NCOR ¹⁷ are 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 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} 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 can have at least 10 carbon atoms if desired. 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 made 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. As polymers, copolymers of unsaturated esters such as C ₁ are generally used for this purpose -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 0.1 to 1.5 mol, in particular 0.5 to 1 , 2 mol amine per acid group, carboxylic anhydrides preferably reacted with 0.1 to 2.5, in particular 0.5 to 2.2 mol amine per acid anhydride group, amides, ammonium salts, amide-ammonium salt depending on the reaction conditions e or imides arise. 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 removed 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, vinyl propionate, vinyl 2-ethylhexanoate or vinyl stearate with maleic anhydride, or (c) a dialkyl fumarate, maleat, citraconate or itaconate with 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 ltaconate is used instead of the fumarate. In the above-mentioned 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 a Alcohol if an ester amide is formed). When 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 or both of the radicals 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 nC ₁₄ alkyl, 30% by weight nC ₁₀ - Alkyl, 60% by weight nC ₁₈ alkyl, the rest is unsaturated). Examples of suitable polyamines are N-octadecylpropanediamine, N, N'-dioctadecylpropanediamine, 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) from 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. Polymaleic acid, an equimolar, alternatingly constructed styrene / maleic acid copolymer, randomly constructed styrene / maleic acid copolymers in a ratio of 10:90 and an alternating copolymer of maleic acid are mentioned as examples of polymers 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 approximately 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 produce and then copolymerize 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 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. In general, 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 the anhydrides usually better copolymerize 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 approximately one to two. Mol per mole of copolymerized dicarboxylic acid anhydride, di about 0.9 to 2.1 mol / mol applied. 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 result is a correspondingly reduced effect. In some cases it can 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 give 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 is not important whether this amine is present in the structure of the amide structure or as the ammonium salt of 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 1 and / or 3, and optionally 2, the structural units 2 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 is 19-80 mol%, preferably 39-60 mol% of bivalent
Structural units of 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 to 30 mol%, preferably 1 to 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 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 contains} C ₁ -C ₄₀ alkyl, C ₅ -C ₁₀ cycloalkyl or C ₆ -C ₁₈ aryl. 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 residue. 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 coconut alkyll , 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 1 and 3 as well as 4 and 5 and optionally 2. They only contain in themselves The end groups formed during the polymerization by initiation, inhibition and chain termination are known. In particular, 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.

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. Preferred are α-olefins with 10 to 24 C atoms and styrene, particularly preferred are α-olefins with 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 using known processes, for example by adding α-olefin oxides, such as ethylene oxide, propylene oxide and / or butylene oxide, to polymerizable lower, unsaturated alcohols of the formula 10

and subsequent esterification or etherification. 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. Examples of primary amines suitable for the preparation of the terpolymers are:

n-hexylamine, n-octylamine, n-tetradecylamine, n-hexadecylamine,

n-stearylamine or also N, N-dimethylaminopropylenediamine, cyclohexylamine, dehydroabietylamine and mixtures thereof.

Examples of secondary amines suitable for the preparation of the terpolymers are: didecylamine, ditetradecylamine, distearylamine, dicocosfettamine, 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.) from 8 to 100, preferably 8 to 50, corresponding to average molecular weights (M _w ) between approximately 500 and 100,000. Suitable examples are listed in EP 606 055.

9. 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 80-20 mol%, preferably 60-40 mol%, of bivalent structural units of the formula 4 contain. In particular, the structural units of the formulas 13, 14 and 15 are derived from α, β-unsaturated dicarboxylic 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 R ³⁷ and R ³⁸ in formula 13 and R ³⁹ in formula 15 are derived from polyether amines 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

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 16 a) and b) are preferably used to derivatize the structural units of the formulas 6 and 7 It is possible to derivatize the structural units of the formulas 6 and 7 by using an alkanolamine of the formulas 16a) or 16b) instead of the polyetheramines and subsequently subjecting them to an alkoxylation. 0.01 to 2 mol, preferably 0.01 to 1 mol 1 mol of alkanolamine used. 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 oxalkylation 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.

10. copolymers and terpolymers of NC ₆ -C ₂₄ alkylmaleimide with C ₁ -C ₃₀ vinyl esters, vinyl ethers and / or olefins having 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 polar nitrogen-containing paraffin dispersants can be the inventive Additives are added or added separately to the middle distillate to be added become. The quantitative ratio between paraffin dispersants and Additives according to the invention are between 5: 1 and 1: 5 and preferably between 3: 1 and 1: 3.

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 lubricating effect and / or Improve the cold flow properties of crude oils, lubricating oils or fuel oils. Examples of such co-additives are copolymers containing vinyl acetate or Terpolymers of ethylene, comb polymers 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 2-ethylhexanoate terpolymers, Ethylene / vinyl acetate / neononanoic acid vinyl ester terpolymers and / or ethylene vinyl acetate / vinyl neodecanoate terpolymers to improve the flowability and lubrication of Mineral oils or mineral oil distillates. The terpolymers of vinyl 2-ethylhexanoate, Vinyl neononanoate or In addition to ethylene, neodecanoic acid vinyl esters contain 10 to 35% by weight of vinyl acetate and 1 to 25 wt .-% of the respective long-chain vinyl ester. More preferred In addition to ethylene and 10 to 35% by weight of vinyl esters, copolymers also contain 0.5 to 20 wt .-% olefin with 3 to 10 carbon atoms such. B. isobutylene, diisobutylene, 4-methylpentene or norbornene.

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 the case of 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) , 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 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 Ethylene copolymers or comb polymers are each 1:10 to 20: 1, preferably 1: 1 to 10: 1.

The additives of the invention are oiled in amounts from 0.0001 to 1% by weight, preferably 0.001 to 0.1% by weight and especially 0.002 to 0.05% by weight added. They can be used as such or dissolved in solvents such as e.g. aliphatic and / or aromatic hydrocarbons or Hydrocarbon mixtures such as Toluene, xylene, ethylbenzene, decane, Pentadecane, gasoline fractions, diesel, kerosene or commercial Solvent mixtures such as Solvent Naphtha, ® Shellsol AB, ® Solvesso 150, ® Solvesso 200, ® Exxsol, ® Isopar and ® Shellsol D types, as well as polar solvents such as Alcohols, glycols and esters such as fatty acid alkyl esters and in particular rapeseed oleic acid methyl ester (RME). Prefers contain the additives according to the invention up to 70%, especially 5-60%, in particular 10 - 40 wt .-% solvent.

The additives according to the invention can be used at elevated temperature for a long time stored without aging effects, without causing signs of aging such as resinification and the formation of insoluble structures or deposits in Storage containers and / or engine parts comes. They also improve the Oxidation stability of the additive oils with reduced at the same time Emulsify. This is especially true with oils that are made up of larger proportions of oils Crack processes included, beneficial.

Furthermore, they show an improvement in the superiority of the individual components Lubricity of middle distillates. This can be used for setting the specification required dosage rate can be reduced.

Another advantage of the additives according to the invention is that of the additives according to state of the art fatty acid esters used as lubricity additives reduced crystallization temperature. So you can even at low Temperatures of, for example, 0 ° C to -20 ° C and sometimes also lower can be used without any problems.

The additives of the invention are for use in middle distillates particularly suitable. Middle distillates are especially those Mineral oils obtained from crude oil distillation and in the range of Boil 120 to 450 ° C, for example kerosene, jet fuel, diesel and heating oil. The oils may also contain or from alcohols such as methanol and / or ethanol consist. The additives according to the invention are preferably used in such Middle distillates used that contain less than 350 ppm sulfur, in particular less than 200 ppm sulfur and in special cases less than 50 ppm or contain less than 10 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. They are the same additives according to the invention for use in synthetic fuels also low lubricity, as z. B. in Fischer-Tropsch erosion can be produced, suitable. The oils with improved lubricity have a wear scar diameter of preferred measured in the HFRR test less than 460 µm, especially less than 450 µm. The additives according to the invention can also be used as components in lubricating oils.

The mixtures can be used alone or together with other additives be used, e.g. with pour point depressants, corrosion inhibitors, Antioxidants, sludge inhibitors, dehazers, conductivity improvers, lubricity additives, and additives to lower the cloud point. Be further successfully used together with additive packages that include known ashless dispersion additives, detergents, defoamers, antioxidants, dehazers, Demulsifiers and corrosion inhibitors included.

The advantages of the additives according to the invention are shown by the following Examples explained in more detail.

Examples

Characterization of the test oils used Test oil 1 Test oil 2 Test oil 3 distillation IBP [° C] 202 182 164 20% [° C] 237 221 214 90% [° C] 321 280 342 FBP [° C] 348 304 367 Cloud Point [° C] -5.9 -29.7 -7.7 CFPP [° C] -8th -33 -13 Density 15 ° C [g / cm ³ ] .8348 .8210 0.8293 Sulfur [ppm] 32 6 195

The additives used are characterized below. The OH numbers were in accordance with DIN 53240 by implementation with a defined amount excess acetic anhydride and subsequent titration of the formed Acetic acid determined.

Iodine numbers are determined according to Kaufmann. For this purpose, a defined amount of a methanolic bromine solution is added to the sample, an amount of bromine which is equivalent to the content of double bonds being deposited. The excess bromine is back-titrated with sodium thiosulfate. Characterization of the lubricity additives used example Chemical name OH number [mg KOH / g] Iodine number [gJ / 100g] A1 Partial esters of glycerin and soybean oil fatty acid 158 103 A2 Partial esters of glycerin and tall oil fatty acid 88 116 A3 Partial esters of glycerin and tall oil fatty acid 193 122 A4 Partial esters from glycerin and tallow fatty acid 181 52 A5 Partial esters of glycerin and olein 278 77 A6 Partial esters of glycerin and olein 153 76 A7 Glycerol monooleate, technical 197 83 A8 dioleate 68 86 A9 pentaerythritol monooleate 111 85 Characterization of the alkylphenol resins used B1 Nonylphenol formaldehyde resin, produced by condensation of a mixture of nonylphenol with 0.5 mol% dinonylphenol, with formaldehyde, Mw 2000 g / mol; 50% in solvent naphtha B2 Dodecylphenol formaldehyde resin made by condensing a mixture of dodecylphenol with 1.3 mol% didodecylphenol with formaldehyde, Mw 2200 g / mol; 50% in solvent naphtha B3 C ₂₀ -C ₂₄ alkylphenol formaldehyde resin, prepared by condensing a mixture of C ₂₀ -C ₂₄ alkylphenol with 35 mol% di- (C ₂₀ -C ₂₄ alkyl) phenol, with formaldehyde, Mw 2500 g / mol; 50% in solvent naphtha Characterization of the polar nitrogen-containing compounds used C1 Reaction product of a dodecenyl spirobislactone with a mixture of primary and secondary tallow fatty amine, 60% in solvent naphtha (produced according to EP 0413279) C2 Reaction product of a terpolymer from a C14 / 16-α-olefin, maleic anhydride and allyl polyglycol with 2 equivalents of ditallow fatty amine, 50% in solvent naphtha (produced according to EP 0606055) C3 Reaction product of phthalic anhydride and 2 equivalents of di (hydrogenated tallow fat) amine, 50% in solvent naphtha (produced according to EP 0061894) C4 Reaction product from ethylenediaminetetraacetic acid with 4 equivalents of ditallow fatty amine to give the amide ammonium salt (prepared in accordance with EP 0398101)

Oxidation stability of the additives

10 g of the additive (mixture) to be checked are weighed into a 500 ml Erlenmeyer flask. The flask is stored in a drying cabinet at a temperature of 90 ° C for three days, with the atmosphere above the additive being replaced daily by passing an air stream over it.
After conditioning, the mixture is allowed to cool for one hour at room temperature. Then 500 ml of diesel fuel (test oil 3) is added and mixed well. After standing for two hours, the mixture is visually assessed for possible excretions, cloudiness, insoluble components, etc., which give indications of oxidative changes (visual assessment). Then it is filtered through a 0.8 µm filter at a pressure difference of 800 mbar. The total amount must be filterable within 2 minutes, otherwise the volume filtered after 2 minutes is noted. oxidation stability example A B visual assessment filtration 1 (see) - - clear 34 s 2 10 g A1 - cloudy; insoluble shares n / A 3 (see) 9.9 g A1 0.1 g B1 clear 62 s 4 9.9 g A1 0.1 g B2 clear 57 s 5 (see) 10 g A2 - cloudy; insoluble shares n / A 6 9.9 g A2 0.1 g B1 clear 53s 7 (See) 10 g A4 - cloudy 120 s / 260 ml 8th 9.9 g A4 0.1 g B1 clear 49 s 9 9 g A4 1 g B2 clear 52 s 10 (see) 10 g A5 - cloudy; insoluble shares n / A 11 9.9 g A5 0.1 g B1 clear 57s 12 (See) 10 g A3 - cloudy; insoluble shares n / A 13 5 g A3 5gB1 clear 68s 14 9.9 g A3 0.1 g B2 clear 63s 15 9.99 g A3 0.01 g B3 clear 76s 16 (see) 10 g A8 - cloudy; insoluble shares n / A 17 5gA8 5gB1 clear 84s 18 9.9 g A8 0.1 g B1 clear 60s 19 9.99 g A8 0.01 g B1 clear 72s 20 9.9 g A8 0.1 g B3 clear 62 s na = not applicable because not completely soluble

Example 21

A mixture of 9 g A 7, 1 g B1 and 2 g C2 gave after three days of storage 90 ° C and then diluted with 500 ml test oil 3 a clear solution and a filtration time of 65 s.

Cold stability of the additives

+

fließfähig und klar

O

fließfähig aber trüb bzw. mit Ausscheidungen

―

fest

Kältestabilität der Additive Beispiel Additiv 15°C +5°C -5°C Anteil A Anteil B 3 Tage 5 Tage 3 Tage 5 Tage 3 Tage 5 Tage 22 (Vgl.) A5 ― O ― ― 23 2 Teile A5 1 Teil B1 + O O ― ― 24' 1 Teil A5 1 Teil B1 + + + O ― 25 1 Teil A5 2 Teile B1 + + + + ― 26(Vgl.) A6 ― + + O - 27 2 Teile A6 1 Teil B2 + + + + O O 28 1 Teil.A6 1 Teil B2 + + + + + + 29 1 Teil A6 2 Teile B2 + + + + + + 30(Vgl.) A7 ― O ― ― 31 2 Teile A7 1 Teil B1 + + + + ― 32 1 Teil A7 1 Teil B1 + + + + ― 33 1 Teil A7 2 Teile B1 + + + + + + 34(Vgl.) A3 ― + + + + O ― 35 2 Teile A3 1 Teil B1 + + + + + 36 1 Teil A3 1 Teil B1 + + + + + + 37 1 Teil A3 2 Teile B1 + + + + + + 38(Vgl.) A8 ― + + + O 39 2-Teile-A8 1 Teil B1 + + + + O O 40 1 Teil A8 1 Teil B1 + + + + + + 41 1 Teil A8 2 Teile B1 + + + + + + 42(Vgl.) A9 ― + + + O O -- 43 2 Teile A9 1 Teil B1 + + + + + + 44 1 Teil A9 1 Teil B1 + + + + + + 45 1 Teil A9 2 Teile B1 + + + + + + Different esters were stored for 5 days at 15 ° C, + 5 ° C and -5 ° C and after 3 or 5 days visually assessed for flowability and possible excretions or turbidity. The ratings have the following meaning:

+

flowable and clear

O

flowable but cloudy or with excretions

-

firmly

Cold stability of the additives example additive 15 ° C + 5 ° C -5 ° C Share A Share B 3 days 5 days 3 days 5 days 3 days 5 days 22 (See) A5 - O - - 23 2 parts A5 1 part B1 + O O - - 24 ' 1 part A5 1 part B1 + + + O - 25 1 part A5 2 parts B1 + + + + - 26 (comp.) A6 - + + O - 27 2 parts A6 1 part B2 + + + + O O 28 1 part.A6 1 part B2 + + + + + + 29 1 part A6 2 parts B2 + + + + + + 30 (comp.) A7 - O - - 31 2 parts A7 1 part B1 + + + + - 32 1 part A7 1 part B1 + + + + - 33 1 part A7 2 parts B1 + + + + + + 34 (comp.) A3 - + + + + O - 35 2 parts A3 1 part B1 + + + + + 36 1 part A3 1 part B1 + + + + + + 37 1 part A3 2 parts B1 + + + + + + 38 (comp.) A8 - + + + O 39 2-Part A8 1 part B1 + + + + O O 40 1 part A8 1 part B1 + + + + + + 41 1 part A8 2 parts B1 + + + + + + 42 (comp.) A9 - + + + O O - 43 2 parts A9 1 part B1 + + + + + + 44 1 part A9 1 part B1 + + + + + + 45 1 part A9 2 parts B1 + + + + + +

Lubricating effect in middle distillates

The lubricating effect of the additives was tested 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 (WS 1.4). A low wear scar and a low coefficient of friction (friction) show a good lubricating effect. Wear scar values of less than 460 µm are regarded as an indication of a sufficient lubricating effect, although in practice values of less than 400 µm are aimed for. The dosing rates in Table 6 relate to the amount of active ingredient dosed. Wear Scar in Test Oil 1 example Dosing rate A Dosing rate B Dosing rate C Wear scar Friction 46 (see) - - - 575 0.38 47 (see) 80 ppm A1 - - 536 0.32 48 (see) 100 ppm A1 - - 427 0.22 49 80 ppm A1 20 ppm B2 - 380 0.21 50 70 ppm A1 20 ppm B2 10 ppm 364 0.18 51 (See) 50 ppm A3 - - 566 0.37 52 (See) 75 ppm A3 - - 523 0.25 53 (see) 100 ppm A3 - - 395 0.23 54 (see) - 50 ppm B1 - 570 0.38 55 (See) - - 40 ppm C2 566 0.34 56 (see) 75 ppm A3 - 40 ppm C2 412 0.23 57 (See) - 20 ppm B1 40 ppm C2 550 0.34 58 75 ppm A3 20 ppm B1 - 366 0.20 59 75 ppm A3 20 ppm B1 40 ppm C2 276 0.18 60 50 ppm A3 50 ppm B1 - 425 0.22 61 50 ppm A3 20 ppm B1 - 458 0.24 62 50 ppm A3 20 ppm B1 30 ppm C2 378 0.20 Wear Scar in Test Oil 2 example Dosing rate A Dosing rate B Dosing rate C Wear scar Friction 63 (See) - - - 611 0.41 64 (See) 100 ppm A2 - - 551 0.25 65 (See) 120 ppm A2 - - 352 0.19 66 (see) - 10 ppm B1 - 613 0.41 67 (See) - - 10 ppm C1 603 0.41 68 90 ppm A2 10 ppm B1 - 457 0.23 69 100 ppm A2 10 ppm B2 - 322 0.17 70 80 ppm A2 10 ppm B1 10 ppm C1 384 0.20 71 70 ppm A2 10 ppm B2 10 ppm C1 436 0.22 72 80 ppm A2 10 ppm B1 10 ppm C3 413 0.21 73 80 ppm A2 10 ppm B1 10 ppm C4 407 0.21

Claims (13)

Additive to improve the lubricity of fuel oils with a maximum sulfur content of 0.035% by weight A) at least one partial ester of a dihydric or polyhydric alcohol and unsaturated and optionally saturated fatty acids, the carbon chain lengths of which are between 8 and 30 carbon atoms, at least 60% of the fatty acid residues containing at least one double bond, and B) at least one alkylphenol-aldehyde resin, obtainable by the condensation of (i) at least one alkylphenol with at least one C ₆ -C ₂₄ alkyl or C ₆ -C ₂₄ alkenyl radical and (ii) at least one aldehyde or ketone, the degree of condensation being between 2 and 50 alkylphenol units. Additive according to claim 1, wherein the iodine number of component A) more than 50 g l / 100 g ester. Additive according to claim 1 and / or 2, wherein the OH number of component A) is between 10 and 200 mg KOH / g ester. Additive according to one or more of claims 1 to 3, wherein the Fatty acids that are part of the fatty acid mixture, 10 to 26 carbon atoms contain. Additive according to one or more of claims 1 to 4, wherein the Fatty acid mixtures contain up to 20% by weight of saturated fatty acids. Additive according to one or more of claims 1 to 5, wherein the Fatty acid mixtures contain one or more dicarboxylic acids. Additive according to one or more of claims 1 to 6, wherein the Alcohols contain 2 to 6 carbon atoms. Additive according to one or more of claims 1 to 7, wherein the Alcohols 2 to 5 hydroxyl groups, but a maximum of one hydroxyl group per Carbon atom. The additive according to one or more of claims 1 to 8, which further contains at least one nitrogen-containing paraffin dispersant. The additive according to one or more of claims 1 to 9, which further contains at least one ethylene copolymer. The additive according to one or more of claims 1 to 10, which further contains at least one comb polymer. Fuel oils with a maximum of 0.035 wt .-% sulfur content, containing one Additive according to one or more of claims 1 to 11 in amounts of 0.001 to 0.5% by weight based on the fuel oil. Use of an additive according to one or more of claims 1 to 11 in amounts of 0.001 to 0.5 wt .-% based on the fuel oil for Improve the lubricating effect of fuel oils with at most 0.035% by weight sulfur content.