EP1380633A1 - Vegetable or animal oils based oily liquids stabilised against oxidation. - Google Patents

Abstract

Oily liquids comprise: (a) an ester of a C1-C5 monohydric alcohol with fatty acids containing 8-30 carbon atoms, at least 50% 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 with a sulfur content of no more than 0.035 wt.% containing 0.001-0.5 wt.% of a composition as above.

Description

The present invention relates to oils with improved oxidation stability Fatty acid esters and alkylphenol resins, and their use as fuel oils and to improve the lubricating effect of desulfurized middle distillates.

In the course of decreasing world oil reserves and the discussion about the environment adverse consequences of fossil and mineral consumption Fuels are becoming more and more interested in alternative, renewable raw materials based energy sources. These include, in particular, native oils and fats of vegetable or animal origin. These are usually triglycerides from Fatty acids with 10 to 24 carbon atoms, which are the same as conventional fuels have a comparable calorific value, but at the same time as biodegradable and be classified as environmentally friendly.

entsprechen, in der R ein aliphatischer Rest mit 10 bis 25 Kohlenstoffatomen ist, der gesättigt oder ungesättigt sein kann.Oils obtained from animal or vegetable material are mainly metabolites which include triglycerides of monocarboxylic acids, e.g. B. acids with 10 to 25 carbon atoms, and the formula

correspond in which R is an aliphatic radical having 10 to 25 carbon atoms, which may be saturated or unsaturated.

Generally, such oils contain glycerides from a number of acids, the Number and variety varies with the source of the oil and they can be added Contain phosphoglycerides. Such oils can be found in the prior art known methods can be obtained.

Due to the partially unsatisfactory physical properties of the Triglyceride has become the technique of naturally occurring Triglycerides in fatty acid esters of lower alcohols such as methanol or ethanol convict.

In addition to being used directly as a fuel, fatty acid alkyl esters are also used as Additives used for example for mineral oils and mineral oil distillates: In particular, fuel oils with a reduced to less than 500 ppm Sulfur content has such poor friction and wear-reducing properties Properties that so-called lubricity additives must be added to them. These are based among other things on esters of unsaturated fatty acids with lower ones Alcohols (biodiesel).

The oily liquids used technically as fuel oils and additives are mainly based on oils from natural sources such as rapeseed, sunflowers, Soya and similar oil seeds. These have a high proportion of unsaturated Fatty acids of more than 50% and preferably of more than 80% on what gives them gives acceptable rheological properties, especially in the cold.

For example, EP-A-0635558 discloses the use of biodiesel based on C ₁ -C ₅ alkyl esters of saturated and unsaturated, straight-chain C ₁₂ -C ₂₂ fatty acids as lubrication improvers for gas oils with a low sulfur and aromatic content.

EP-A-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.

DE-A-10111857 discloses esters of predominantly saturated unbranched mono-fatty acids with mixtures of C ₁ -C ₄ monoalcohols with methylated monound / or dihydroxybenzenes as an additive to sulfur-free mineral diesel fuel. The hydroxybenzenes improve, among other things, the oxidation stability of the additives.

The oily liquids based on unsaturated fatty acids based on Because of their rheological properties compared to those on saturated fatty acids based esters may be preferred, in particular with longer storage Resin under elevated temperature to only partially oil-soluble products. This can lead to the formation of viscous deposits and deposits in the Guide the storage container and the additive fuel oil. This can also happen in the engine lead to deposits, particularly on the valves and injectors.

In addition, the effectiveness of agricultural production is great Amounts and inexpensive available fatty acid esters based on Oilseeds as lubricity additives are comparatively low. To achieve one in the High dosage rates of 1,000 ppm and are consequently sufficient in practice more is required, which requires a high logistical effort.

The object of the present invention was therefore to base fuel oils and additives to find unsaturated vegetable and animal oils that are one versus the other State of the art improved oxidation stability and at the same time improved Efficacy as a lubricity additive for sulfur-reduced mineral oils and Have mineral oil distillates.

Surprisingly, it was found that combinations of esters unsaturated fatty acids with alkylphenol-aldehyde resins a significantly improved Have oxidation stability. Furthermore they show in low sulfur Fuel oils have a superior lubricating effect to the individual components.

A) mindestens einen Ester aus Fettsäuren, deren Kohlenstoffkettenlängen zwischen 8 und 30 Kohlenstoffatomen liegen, und einem einwertigen C₁-C₅-Alkohol, wobei mindestens 50% 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 oily liquids

A) at least one ester of fatty acids, the carbon chain lengths of which are between 8 and 30 carbon atoms, and a monohydric C ₁ -C ₅ alcohol, at least 50% 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.

The oily liquids defined above are also used in the following as additives designated.

Another object of the invention is the use of those defined above oily liquids as fuel oil.

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 have the predominant hydrocarbon character do not interfere. 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 75% by weight, especially at least 90 % By weight of the fatty acids one or more double bonds. The iodine numbers of the Fatty acids or fatty acid mixtures on which the esters according to the invention are based are preferably above 50 g J / 100 g, particularly preferably between 100 and 190 g J / 100 g, in particular between 110 and 180 g J / 100 g and especially between 120 and 180 g I / 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 components of the fatty acid mixtures are dicarboxylic acids, such as dimer fatty acids and alkyl and alkenyl succinic acids with C ₈ -C ₅₀ alk (en) yl radicals, preferably with C ₈ -C ₄₀ -, in particular with C ₁₂ -C ₂₂ alk (en) ylresten. The alkyl radicals can be linear or branched (oligomerized alkenes, polyisobutylene) and saturated or unsaturated. Contents of up to 10% by weight, in particular less than 5% by weight, based on component A) are preferred.

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 contain 1-40% by weight, especially 1-25% by weight, in particular 1-5% by weight, of resin acids.
Suitable alcohols contain 1 to 5 carbon atoms. Particularly suitable alcohols are methanol and ethanol, especially methanol.

The esters are made from alcohols and fatty acids in a known manner by esterification produced. The transesterification of naturally occurring fats and oils is preferred lower alcohols and especially with methanol, being a by-product Glycerin is created. Preferred esters are those which consist of a fatty acid mixture are producible.

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 structural elements. 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 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 having 6 to 24, preferably 8 to 22, in particular 9 to 18 carbon atoms per alkyl group, or mixtures thereof and at least one aldehyde are reacted with one another, about 0.5 2 mol, 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 carry one or more 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. In particular, the alkylphenols ortho to the hydroxyl group are not included 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). In order to stabilize the fatty acid esters, smaller portions of the Components B from 0.001 to 20% by weight, preferably 0.005 to 10% by weight B) used, whereas to optimize the lubricity larger portions B of for example 5 to 90% by weight, preferably 10 to 80% by weight and in particular 15 up to 75% by weight can be 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 paraffin dispersants are preferably low molecular weight or polymeric, oil-soluble compounds with ionic or polar groups such as amine salts, imides and / or amides. Particularly preferred paraffin dispersants contain reaction products of secondary fatty amines with 8 to 36 carbon atoms, in particular dicocos fatty amine, ditallow fatty amine and distearyl amine. Paraffin dispersants which are obtained by reaction of aliphatic or aromatic amines, preferably long-chain aliphatic amines, with aliphatic or aromatic mono-, di-, tri- or tetracarboxylic acids or their anhydrides (cf. US Pat. No. 4,211,534) have proven particularly useful. Other paraffin dispersants are copolymers of maleic anhydride and α, β-unsaturated compounds which can optionally be reacted with primary monoalkylamines and / or aliphatic alcohols (cf. EP-A-0 154 177), the reaction products of alkenyl spirobis lactones with amines (cf. EP- A-0 413 279 B1) and after
EP-A-0 606 055 A2 reaction products of terpolymers based on α, β-unsaturated dicarboxylic acid anhydrides, α, β-unsaturated compounds and polyoxylalkylene ethers of lower unsaturated alcohols.
Particularly preferred paraffin dispersants are prepared by reacting compounds containing 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

The paraffin dispersants can be added to the additives according to the invention or added separately to the middle distillate to be added. The Quantity ratio between paraffin dispersants and those according to the invention Additives is 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 fluidity and Lubricating effect of mineral oils or mineral oil distillates. The terpolymers the 2-ethylhexanoic acid vinyl ester, neononanoic acid vinyl ester or the 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 -a olefin and an NC ₆ -C ₂₂ alkylmaleimide (cf. EP-A-0 320 766), furthermore 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 oily liquids according to the invention are particularly suitable for use as Suitable for fuel oil in diesel engines.

The oily liquids according to the invention are oils as additives in quantities from 0.001 to 10% by weight, preferably 0.01 to 5% by weight and especially 0.02 to 2 wt .-% added. They can be used as such or dissolved in solvents, such as. 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 can be used. Preferably contain the Additives according to the invention up to 70%, especially 5-60%, in particular 10-40 % By weight of solvent. They are particularly preferred without the addition of others Solvent used.

The oily liquids according to the invention can be stored at elevated temperature for a long time without aging effects, without there being any signs of aging such as resinification and the formation of insoluble structures or deposits in storage containers and / or engine parts. They also improve the oxidation stability of the oils they contain. This is particularly advantageous for oils that contain large amounts of oils from cracking processes.
Furthermore, they show an improvement in the lubricity of middle distillates that is superior to the individual components. The dosing rate required for setting the specification can thus be reduced.

Another advantage of the oily liquids according to the invention is their advantage those used according to the prior art as lubricity additives Fatty acid esters reduced crystallization temperature. So you can also at low temperatures of, for example, 0 ° C to -20 ° C and sometimes also lower can be used easily.

The oily liquids according to the invention are additives for use in Middle distillates are particularly suitable. Middle distillates are called especially those mineral oils that are obtained by distilling crude oil and boil in the range of 120 to 450 ° C, for example kerosene, jet fuel, diesel and heating oil. The oils can also contain alcohols such as methanol and / or ethanol or consist of these. The additives according to the invention are preferred used in middle distillates containing less than 350 ppm sulfur, in particular less than 200 ppm sulfur and in special cases less than 50 ppm or less than 10 ppm sulfur. It is in the general to those middle distillates that are hydrogenated refining were subjected, and therefore only small proportions of polyaromatic and contain polar compounds that give them a natural lubricating effect to lend. The additives of the invention are also preferably in such middle distillates used, the 95% distillation points below 370 ° C, in particular 350 ° C and in special cases below 330 ° C. Are the same the additives according to the invention for use in synthetic fuels with also low lubricity, as z. B. in the Fischer-Tropsch process 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 oily according to the invention Liquids can also be used as components in lubricating oils.

The oily liquids 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 oily liquids according to the invention are due to the following examples explained in more detail.

Examples

The following are the components used in the oily liquids characterized.

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 fatty acid esters used example Chemical name Iodine number [gJ / 100g] A1 Rapeseed oleic acid methyl ester containing 45% oleic acid, 39% linoleic acid, 4.5% linolenic acid as main components 123 A2 Soybean oil methyl ester containing 25% oleic acid, 51% linoleic acid, 7% linolenic acid as main components 134 A3 Tallow fatty acid methyl ester containing as main components, 65% oleic acid, 18% linoleic acid 102 Characterization of the alkylphenol resins used B1 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 B2 Dodecylphenol formaldehyde resin, prepared by condensing a mixture of dodecylphenol with 1.3 mol% didodecylphenol, with formaldehyde, Mw 2200 g / mol; 50% in solvent naphtha B3 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

Oxidation stability of the additives

10 g of the test sample are placed in a 500 ml Erlenmeyer flask Weighed fatty acid mixture and the amount of resin given in Table 3. The Flask is stored in a drying cabinet at a temperature of 90 ° C for three days, whereby the atmosphere above the additive is passed daily by passing a Airflow is exchanged.

After conditioning, the mixture is allowed to cool for one hour at room temperature. Then 500 ml of diesel fuel (test oil 1) is added and mixed well. After two hours of standing, the mixture is visually assessed for possible excretions, turbidity, 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 (see) 10 g A1 - cloudy + insoluble resin 120 s / 210 ml 3 (see) 10 g A2 - cloudy + insoluble resin 120 s / 330 ml 4 (see) 10 g A3 - cloudy + insoluble resin 120 s / 470 ml 5 10 g A1 0.5 g B3 homogeneously cloudy 79 s 6 10 g A1 1 g B3 almost clear 52 s 7 10 g A1 2g B3 clear 46 s 8th 10 g A1 0.5 g B1 clear 45 s 9 10 g A1 2 g B1 clear 43 s 10 10 g A1 1 g B2 clear 47 s 11 10 g A1 2g B2 clear 43 s 12 10 g A2 1g B1 clear 39 s 13 10 g A2 1g B3 clear 37 s 14 10 g A2 0.1 g B3 clear 42 s 15 10 g A3 1 g B3 clear 40 s na = not applicable because not completely soluble

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 is considered 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. Characterization of the test oils used Test oil 1 Test oil 2 distillation IBP [° C] 171 164 20% [° C] 218 214 90% [° C] 323 342 FBP [° C] 352 367 Cloud Point [° C] -8.2 -7.7 CFPP [° C] -12 -13 Density @ 15 ° C [g / cm ³ ] .8262 0.8293 Sulfur [ppm] 15 195 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-A-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-A-0606055) C3 Reaction product of phthalic anhydride and 2 equivalents of di (hydrogenated tallow fat) amine, 50% in solvent naphtha (produced according to EP-A-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-A-0398101) Wear Scar in Test Oil 1 example Dosing rate A Dosing rate B Dosing rate C Wear scar Friction 16 (see) - - - 575 0,329 17 0.2% A1 - - 537 0.260 18 0.5% A1 - - 498 0,205 19 0.75% A1 - - 423 0,180 20 1.0% A1 - - 373 0.171 21 (See) - 0.025% B1 - 555 0.312 22 (See) - 0.05% B1 - 467 0.201 23 0.5% A1 0.05% B1 387 0,178 24 0.4% A1 0.02% B1 - 448 0.195 25 0.3% A1 0.03% B1 - 408 0,178 26 (see) - 0.05% B3 - 565 0,320 27 (see) - 0.1% B3 - 510 0.243 28 0.5% A1 0.05% B3 - 382 0,180 29 0.5% A1 0.1% B3 - 303 0.174 30 0.3% A1 0.075% B3 - 432 0,181 31 0.3% A2 - - 523 0,248 32 0.3% A2 0.03% B1 - 376 0.182 33 0.3% A2 0.03% B2 - 391 0.185 34 0.25% A2 0.02% B1 0.01% C1 371 0,178 35 0.25% A2 0.02% B1 0.01% C2 343 0.176 36 0.25% A2 0.02% B1 0.01% C3 365 0.177 37 0.25% A2 0.02% B1 0.01% C4 358 0,178 Wear Scar in Test Oil 2 example Dosing rate A Dosing rate B Dosing rate C Wear scar Friction 38 (See) - - - 540 0.266 39 (see) 0.2% A2 - - 502 0.240 40 (see) 0.4% A2 - - 435 0.207 41 (see) 0.6% A2 - - 386 0.177 42 (See) - 200 ppm B2 - 535 0,255 43 (see) - 400 ppm B2 - 502 0,235 44 0.5% A2 200 ppm B2 - 275 0.166 45 0.4% A2 300 ppm B2 - 375 0.174 46 0.3% A2 150 ppm B2 100 ppm C1 398 0,187 47 0.25% A2 150 ppm B2 100 ppm C2 403 0.188

Claims (12)

Containing oily liquids A) at least one ester of fatty acids, the carbon chain lengths of which are between 8 and 30 carbon atoms, and a monohydric C ₁ -C ₅ alcohol, at least 50% 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. A composition according to claim 1, wherein the iodine number of component A) is more than 50 g I / 100 g ester. Composition according to one or more of claims 1 to 2, wherein the fatty acids, which are part of component A), 10 to 26 carbon atoms contain. Composition according to one or more of claims 1 to 3, wherein the fatty acid ester A) at least 75 wt .-% fatty acids with one or contain several double bonds. Composition according to one or more of claims 1 to 4, wherein the fatty acid mixtures contain one or more dicarboxylic acids. Composition according to one or more of claims 1 to 5, wherein the alcohols from which component A) is derived, methanol or ethanol are. Composition according to one or more of claims 1 to 6, wherein component A) is derived from fatty acid mixtures which contain up to 20% by weight contain saturated fatty acids. A composition according to one or more of claims 1 to 7, which further contains at least one nitrogen-containing paraffin dispersant. A composition according to one or more of claims 1 to 8, which further contains at least one ethylene copolymer. A composition according to one or more of claims 1 to 9, which further contains at least one comb polymer. Fuel oils with a maximum sulfur content of 0.035% by weight containing one Composition according to one or more of claims 1 to 10 in quantities from 0.001 to 0.5% by weight based on the fuel oil. Use of a composition according to one or more of the Claims 1 to 10 in amounts of 0.001 to 0.5 wt .-% based on the Fuel oil, to improve the lubricating effect of fuel oils with at most 0.035% by weight sulfur content.