EP1526167A2 - Cold flow improver for fuel oils of animal or vegetable origin - Google Patents

Abstract

New additive comprises a copolymer (I) of ethylene and 8-21 mole% of an acrylic or vinyl ester with a C1-C18 alkyl group and a comb polymer (II) of an olefin (IIa) with a C8-C18 alkyl group attached to the double bond and an ethylenically unsaturated dicarboxylic acid amide or imide (IIb) with a C8-C16 alkyl group attached to the amide or imide group, where the sum Q of the molar average alkyl chain lengths in (IIa) and (IIb) is 23-27. An independent claim is also included for a fuel oil composition comprising a fuel oil of animal or vegetable origin and an additive as above.

Description

The present invention relates to an additive, its use as Cold flow improver for vegetable or animal fuel oils and accordingly additized fuel oils.

With decreasing world oil reserves and the environmental impact of fossil and mineral fuel consumption, there is a growing interest in alternative energy sources based on renewable raw materials. These include, in particular, natural oils and fats of plant or animal origin. These are typically triglycerides of fatty acids with 10 to 24 C atoms, which have a calorific value comparable to conventional fuels, but at the same time are considered less harmful to the environment. Biofuels, ie fuels derived from animal or plant material, are obtained from renewable sources and thus produce only as much CO ₂ as was previously converted into biomass. It has been reported that combustion produces less carbon dioxide than equivalent amount of petroleum distillate fuel, eg, diesel fuel, and that very little sulfur dioxide is produced. In addition, they are biodegradable.

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 comprising triglycerides of monocarboxylic acids, eg acids having 10 to 25 carbon atoms, and the formula

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

In general, such oils contain glycerides of a number of acids whose Number and variety varies with the source of the oil, and they may additionally Contain phosphoglycerides. Such oils can be used in the prior art known methods are obtained.

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

As an obstacle in the use of triglycerides as well as fatty acid esters lower monohydric alcohols as a diesel fuel substitute alone or in a mixture with Diesel fuel has proven the flow behavior at low temperatures. The reason for this is the high uniformity of these oils compared to Mineral oil middle distillates. Thus, e.g. Rapeseed acid methyl ester (RME) a cold Filter Plugging Point (CFPP) from -14 ° C to. With the additives of the state of Technology is not yet possible for use as a winter diesel in Central Europe demanded CFPP value of -20 ° C as well as for special applications from -22 ° C and below. This problem is exacerbated when Use of oils containing larger quantities of readily accessible oils Sunflowers and soy included.

EP-B-0 665 873 discloses a fuel oil composition comprising a A biofuel comprising a petroleum-based fuel oil and an additive which comprises (a) an oil-soluble ethylene copolymer or (b) a comb polymer or (c) a polar Nitrogen compound or (d) a compound in which at least one in the Substantially linear alkyl group having 10 to 30 carbon atoms with one not polymeric organic radical is connected to at least one linear chain of To provide atoms containing the carbon atoms of the alkyl groups and one or more includes non-terminal oxygen atoms, or (e) one or more of Components (a), (b), (c) and (d).

(I) Kammpolymer, das Copolymer von Maleinsäureanhydrid oder Fumarsäure und einem anderen ethylenisch ungesättigten Monomer, wobei das Copolymer verestert sein kann, oder Polymer oder Copolymer von α-Olefin, oder Fumarat- oder Itaconatpolymer oder -copolymer ist,

(II) Polyoxyalkylen-ester, -ester/ether oder eine Mischung derselben,

(III) Ethylen/ungesättigter Ester-Copolymer,

(IV) polarer, organischer, stickstoffhaltiger Paraffinkristallwachstumshemmstoff,

(V) Kohlenwasserstoffpolymer,

(VI) Schwefelcarboxyverbindungen und

(VII) mit Kohlenwasserstoffresten versehenes aromatisches Stockpunktsenkungsmittel

umfasst, mit der Maßgabe, dass die Zusammensetzung keine Mischungen von polymeren Estern oder Copolymeren von Estern von Acryl- und/oder Methacrylsäure umfasst, die von Alkoholen mit 1 bis 22 Kohlenstoffatomen abgeleitet sind.EP-B-0 629 231 discloses a composition comprising a major portion of oil consisting essentially of alkyl esters of fatty acids derived from vegetable or animal oils or both mixed with a minor proportion of mineral oil flow improver comprising one or more of the following:

(I) comb polymer, the copolymer of maleic anhydride or fumaric acid and another ethylenically unsaturated monomer, which copolymer may be esterified, or polymer or copolymer of α-olefin, or fumarate or itaconate polymer or copolymer,

(II) polyoxyalkylene ester, ester / ether or a mixture thereof,

(III) ethylene / unsaturated ester copolymer,

(IV) polar, organic, nitrogen-containing wax crystal growth inhibitor,

(V) hydrocarbon polymer,

(VI) sulfur carboxy compounds and

(VII) hydrocarbon residue-containing aromatic pour point depressant

with the proviso that the composition does not comprise mixtures of polymeric esters or copolymers of esters of acrylic and / or methacrylic acid derived from alcohols having from 1 to 22 carbon atoms.

a) an sich bekannte, zur Verbesserung des Tieftemperaturverhaltens von Mineralölen verwendete Additive PPD ("Pour Point Depressant") in Mengen von 0,0001 bis 10 Gew.-% bezogen auf die langkettigen Fettsäureester FAE zusetzt und

b) auf eine Temperatur unterhalb des Cold Filter Plugging Point der nichtadditivierten, langkettigen Fettsäureester FAE abkühlt und

c) die entstehenden Niederschläge (FAN) abtrennt.

EP-B-0 543 356 discloses a process for the preparation of compositions having improved low-temperature behavior for use as fuels or lubricants, starting from the esters of long-chain fatty acids obtained from natural sources with monohydric C ₁ -C ₆ -alcohols (FAE), characterized that he

a) known per se used to improve the low-temperature behavior of mineral oils additives PPD ("pour point depressant") in amounts of 0.0001 to 10 wt .-% based on the long-chain fatty acid esters FAE added and

b) to a temperature below the cold filter plugging point of the non-additive, long-chain fatty acid ester FAE cools and

c) the resulting precipitation (FAN) is separated.

a) 58 bis 95 Gew.-% mindestens eines Esters im lodzahlbereich 50 bis 150, der sich von Fettsäuren mit 12 bis 22 Kohlenstoffatomen und niederen aliphatischen Alkoholen mit 1 bis 4 Kohlenstoffatomen ableitet,

b) 4 bis 40 Gew.-% mindestens eines Esters von Fettsäuren mit 6 bis 14 Kohlenstoffatomen und niederen aliphatischen Alkoholen mit 1 bis 4 Kohlenstoffatomen und

c) 0,1 bis 2 Gew.-% mindestens eines polymeren Esters.

DE-A-40 40 317 discloses mixtures of fatty acid lower alkyl esters having improved low temperature stability

a) 58 to 95% by weight of at least one ester in the iodine value range 50 to 150, which is derived from fatty acids having 12 to 22 carbon atoms and lower aliphatic alcohols having 1 to 4 carbon atoms,

b) 4 to 40 wt .-% of at least one ester of fatty acids having 6 to 14 carbon atoms and lower aliphatic alcohols having 1 to 4 carbon atoms and

c) 0.1 to 2 wt .-% of at least one polymeric ester.

EP-B-0 153 176 discloses the use of polymers based on unsaturated C ₄ -C ₈ dicarboxylic acid di-alkyl esters having average alkyl chain lengths of 12 to 14 as cold flow improvers for certain petroleum distillate fuel oils. Suitable comonomers are unsaturated esters, in particular vinyl acetate, but also α-olefins.

I) einem Copolymer mit mindestens 25 Gew.-% eines n-Alkylesters einer monoethylenisch ungesättigten C₄-C₈-Mono- oder Dicarbonsäure, wobei die durchschnittliche Zahl der Kohlenstoffatome in den n-Alkylresten 12 - 14 ist und einem anderen ungesättigten Ester oder einem Olefin enthält, mit

II) einem anderen Niedertemperaturfließverbesserer für Destillatbrennstofföle umfasst.

EP-B-0 153 177 discloses an additive concentrate which is a combination of

I) a copolymer having at least 25% by weight of an n-alkyl ester of a monoethylenically unsaturated C ₄ -C ₈ mono- or dicarboxylic acid, wherein the average number of carbon atoms in the n-alkyl radicals is 12-14 and another unsaturated ester or an olefin, with

II) another low temperature flow improver for distillate fuel oils.

WO 95/22300 (= EP 0 746 598) discloses comb polymers in which the alkyl radicals have on average less than 12 C atoms. These additives are especially suitable for oils with cloud points of less than -10 ° C, where it is oils may also be native hydrocarbon oils (page 21, Line 16 ff.). However, native oils have cloud points from about -2 ° C upwards.

With the known additives, it is often not possible, fatty acid esters to a CFPP value required for use as winter diesel in Central Europe of -20 ° C as well as for special applications of -22 ° C and below safe adjust. Another problem with the known additives is one lack of cold resistance of the additized oils, that is the set CFPP value of the oils gradually increases when the oil is used for a long time changing temperatures in the cloud point or below becomes.

It was therefore the task of additives for improving the cold flow behavior of fatty acid esters, for example from rapeseed, sunflower and / or soybean oil to provide CFPP values of -20 ° C and below are set and the set CFPP value even with longer Storage of the oil in the area of its cloud point or below remains constant.

Surprisingly, it has now been found that an ethylene copolymer and Comb polymers containing additive an excellent flow improver for such fatty acid esters.

A) ein Copolymer aus Ethylen und 8-21 Mol-% mindestens eines Acryl- oder Vinylesters mit einem C₁-C₁₈-Alkylrest und

B) ein Kammpolymer, enthaltend Struktureinheiten aus

B1 ) mindestens einem Olefin als Monomer 1, welches an der olefinischen Doppelbindung wenigstens einen C₈-C₁₈-Alkylrest trägt, und

B2) mindestens einer ethylenisch ungesättigten Dicarbonsäure als Monomer 2, welche mindestens einen über eine Amid- und/oder Imidgruppierung gebundenen C₈-C₁₆-Alkylrest trägt,

wobei die Summe Q

der molaren Mittel der C-Kettenlängenverteilungen in den Alkylresten von Monomer 1 einerseits und den Alkylresten der Amid und/oder Imidgruppen von Monomer 2 andererseits von 23 bis 27 beträgt, worin

w₁

der molare Anteil der einzelnen Kettenlängen in den Alkylresten von Monomer 1,

w₂

der molare Anteil der einzelnen Kettenlängen in den Alkylresten der Amid- und/oder Imidgruppen von Monomer 2,

n₁

die einzelnen Kettenlängen in den Alkylresten von Monomer 1,

n₂

die einzelnen Kettenlängen in den Alkylresten der Amid und/oder Imidgruppen von Monomer 2,

i

die Laufvariable für die einzelnen Kettenlängen in den Alkylresten von Monomer 1, und

j

die Laufvariable für die einzelnen Kettenlängen in den Alkylresten der Amid und/oder Imidgruppen von Monomer 2 sind.

The invention relates to an additive containing

A) a copolymer of ethylene and 8-21 mol% of at least one acrylic or vinyl ester having a C ₁ -C ₁₈ alkyl radical and

B) a comb polymer comprising structural units

B1) at least one olefin as monomer 1, which carries at least one C ₈ -C ₁₈ -alkyl radical on the olefinic double bond, and

B2) at least one ethylenically unsaturated dicarboxylic acid as monomer 2 which carries at least one C ₈ -C ₁₆ -alkyl radical bound via an amide and / or imide group,

where the sum Q

the molar average of the C chain length distributions in the alkyl radicals of monomer 1 on the one hand and the alkyl radicals of the amide and / or imide groups of monomer 2 on the other hand from 23 to 27, wherein

w ₁

the molar fraction of the individual chain lengths in the alkyl radicals of monomer 1,

w ₂

the molar fraction of the individual chain lengths in the alkyl radicals of the amide and / or imide groups of monomer 2,

n ₁

the individual chain lengths in the alkyl radicals of monomer 1,

n ₂

the individual chain lengths in the alkyl radicals of the amide and / or imide groups of monomer 2,

i

the run variable for the individual chain lengths in the alkyl radicals of monomers 1, and

j

are the run variables for the individual chain lengths in the alkyl radicals of the amide and / or imide groups of monomer 2.

Another object of the invention is a fuel oil composition, containing a fuel oil of animal or vegetable origin and the above defined additive.

Another object of the invention is the use of the above defined Additive to improve the cold flow properties of animal fuel oil or of vegetable origin.

Another object of the invention is a method for improving the Cold flow properties of fuel oils of animal or vegetable origin, by giving fuel oils of animal or vegetable origin the above Adds defined additive.

In a preferred embodiment of the invention Q has values from 24 to 26.

Under side chain length of olefins here is the outgoing from the polymer backbone Understood alkyl radical, ie the chain length of the monomeric olefin minus the both olefinically bound C atoms. For olefins with non-terminal Double bonds, e.g. Olefins with vinylidene grouping is the corresponding Total chain length of the olefin minus the transition into the polymer backbone To consider double bond.

Suitable ethylene copolymers A) are those which contain from 8 to 21 mol% of one or more a plurality of vinyl and / or (meth) acrylic esters and 79 to 92 wt .-% ethylene. Particularly preferred are ethylene copolymers with 10 to 18 mol% and especially 12 to 16 mol% of at least one vinyl ester. Suitable vinyl esters are derived from Fatty acids with linear or branched alkyl groups having 1 to 18 C atoms and preferably from 1 to 12 carbon atoms. Examples include vinyl acetate, Vinyl propionate, vinyl butyrate, vinyl hexanoate, vinyl heptanoate, vinyl octanoate, Vinyl laurate and vinyl stearate and branched fatty acid based esters of Vinyl alcohol such as vinyl isobutyrate, vinyl pivalate, vinyl 2-ethylhexanoate, iso-nonanoic acid vinyl ester, Vinyl neononanoate, vinyl neodecanoate and Neoundecansäurevinylester. Particularly preferred is vinyl acetate. As comonomers also suitable are esters of acrylic and methacrylic acid having 1 to 20 carbon atoms in the alkyl radical such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n- and iso-butyl (meth) acrylate, hexyl, octyl, 2-ethylhexyl, decyl, dodecyl, tetradecyl, Hexadecyl, octadecyl (meth) acrylate and mixtures of two, three, four or also several of these comonomers.

Particularly preferred terpolymers of 2-Ethylhexansäurevinylesters, the Neononanoic or vinyl neodecanoate contain except Ethylene preferably 3.5 to 20 mol%, in particular 8 to 15 mol% of vinyl acetate and 0.1 to 12 mol%, in particular 0.2 to 5 mol% of at least one long-chain Vinylester, wherein the total comonomer content between 8 and 21 mol%, preferably between 12 and 18 mol%. Further preferred copolymers contain, in addition to ethylene and 8 to 18 mol% vinyl esters, 0.5 to 10 mol% Olefins such as propene, butene, isobutylene, hexene, 4-methylpentene, octene, diisobutylene and / or norbornene.

The copolymers A preferably have molecular weights which correspond to melt viscosities at 140 ° C. of from 20 to 10,000 mPas, in particular from 30 to 5,000 mPas and especially from 50 to 1,000 mPas. The determined by ¹ H NMR spectroscopy degrees of branching are preferably between 1 and 9 CH _3/100 CH ₂ groups, especially between 2 and 6 CH _3/100 CH ₂ groups, such as 2.5 to 5 CH _3/100 CH ₂ groups not derived from the comonomers.

The copolymers (A) are prepared by the usual copolymerization methods such as for example suspension polymerization, solvent polymerization, Gas phase polymerization or high-pressure mass polymerization produced. Preference is given to high pressure bulk polymerization at pressures of 50 to 400 MPa, preferably 100 to 300 MPa and temperatures of 100 to 300 ° C, preferably 150 to 220 ° C performed. In a particularly preferred production variant the polymerization takes place in a multizone reactor, wherein the Temperature difference between the Peroxiddosierungen along the tube reactor is kept as low as possible, i. <50 ° C, preferably <30 ° C, in particular <15 ° C. Preferably, the temperature maxima differ in the individual reaction zones less than 30 ° C, more preferably less than 20 ° C and especially around less than 10 ° C.

The reaction of the monomers is by free-radical initiators (Radical chain starter) initiated. This class of substance includes e.g. Oxygen, Hydroperoxides, peroxides and azo compounds such as cumene hydroperoxide, t-butyl hydroperoxide, dilauroyl peroxide, dibenzoyl peroxide, bis (2-ethylhexyl) peroxide carbonate, t-butyl perpivalate, t-butyl per-maleate, t-butyl perbenzoate, dicumyl peroxide, t-butyl cumyl peroxide, di- (t-butyl) peroxide, 2,2'-azobis (2-methylpropanonitrile), 2,2'-azobis (2-methylbutyronitrile). The initiators are used individually or as a mixture of two or more substances in amounts of 0.01 to 20 wt .-%, preferably 0.05 to 10 wt .-%, based on the monomer mixture used.

High pressure bulk polymerization is used in known high pressure reactors, e.g. Autoclaves or tube reactors, discontinuous or continuous, Tube reactors have proven particularly useful. Solvents such as aliphatic and / or aromatic hydrocarbons or hydrocarbon mixtures, benzene or toluene, may be included in the reaction mixture. Preferably, in the essential solvent-free operation. In a preferred embodiment the polymerization is the mixture of the monomers, the initiator and, if used, the moderator, a tubular reactor via the reactor inlet and above supplied to one or more side branches. Preferred moderators are for example, hydrogen, saturated and unsaturated hydrocarbons such as for example, propane or propene, aldehydes such as propionaldehyde, n-butyraldehyde or iso-butyraldehyde, ketones such as acetone, Methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and alcohols such for example, butanol. The comonomers as well as the moderators can do it both together with ethylene and separated via side streams in the reactor be dosed. Here, the monomer streams can be different be composed (EP-A-0 271 738 and EP-A-0 922 716).

Ethylen-Vinylacetat-Copolymere mit 10 - 40 Gew.-% Vinylacetat und 60 - 90 Gew.-% Ethylen;

die aus DE-A-34 43 475 bekannten Ethylen-Vinylacetat-Hexen-Terpolymere;

die in EP-B-0 203 554 beschriebenen Ethylen-Vinylacetat-Diisobutylen-Terpolymere;

die aus EP-B-0 254 284 bekannte Mischung aus einem Ethylen-Vinylacetat-Diisobutyten-Terpotymerisat und einem Ethylen/Vinylacetat-Copolymer;

die in EP-B-0 405 270 offenbarten Mischungen aus einem Ethylen-Vinylacetat-Copolymer und einem Ethylen-Vinylacetat-N-Vinylpyrrolidon-Terpolymerisat;

die in EP-B-0 463 518 beschriebenen Ethylen/Vinylacetat/iso-Butylvinylether-Terpolymere;

die aus EP-B-0 493 769 bekannten EthylenNinylacetat/Neononansäurevinylester bzw. Neodecansäurevinylester-Terpolymere, die außer Ethylen 10 - 35 Gew.-% Vinylacetat und 1 - 25 Gew.-% der jeweiligen Neoverbindung enthalten;

die in EP 0778875 beschriebenen Terpolymere aus Ethylen, einem ersten Vinylester mit bis zu 4 C-Atomen und einem zweiten Vinylester, der sich von einer verzweigten Carbonsäure mit bis zu 7 C-Atomen oder einer verzweigten aber nicht tertiären Carbonsäure mit 8 bis 15 C-Atomen ableitet;

die in DE-A-196 20 118 beschriebenen Terpolymere aus Ethylen, dem Vinylester einer oder mehrerer aliphatischer C₂- bis C₂₀-Monocarbonsäuren und 4-Methylpenten-1 ;

die in DE-A-196 20 119 offenbarten Terpolymere aus Ethylen, dem Vinylester einer oder mehrerer aliphatischer C₂- bis C₂₀-Monocarbonsäuren und Bicyclo[2.2.1]hept-2-en;

die in EP-A-0 926 168 beschriebenen Terpolymere aus Ethylen und wenigstens einem olefinisch ungesättigten Comonomer, das eine oder mehrere Hydroxylgruppen enthält.

Suitable copolymers or terpolymers include, for example:

Ethylene-vinyl acetate copolymers with 10-40% by weight of vinyl acetate and 60-90% by weight of ethylene;

the ethylene-vinyl acetate-hexene terpolymers known from DE-A-34 43 475;

the ethylene-vinyl acetate-diisobutylene terpolymers described in EP-B-0 203 554;

the mixture known from EP-B-0 254 284 comprising an ethylene-vinyl acetate-diisobutene terpolymer and an ethylene / vinyl acetate copolymer;

the blends disclosed in EP-B-0 405 270 of an ethylene-vinyl acetate copolymer and an ethylene-vinyl acetate-N-vinylpyrrolidone terpolymer;

the ethylene / vinyl acetate / iso-butyl vinyl ether terpolymers described in EP-B-0 463 518;

ethylene vinyl acetate / vinyl neononanoate or vinyl neodecanoate terpolymers known from EP-B-0 493 769, which contain, in addition to ethylene, 10-35% by weight of vinyl acetate and 1-25% by weight of the respective neo compound;

the terpolymers described in EP 0778875 of ethylene, a first vinyl ester having up to 4 C atoms and a second vinyl ester, which is derived from a branched carboxylic acid having up to 7 C atoms or a branched but not tertiary carboxylic acid having 8 to 15 C Deriving atoms;

the terpolymers of ethylene, the vinyl ester of one or more aliphatic C ₂ to C ₂₀ monocarboxylic acids and 4-methylpentene-1 described in DE-A-196 20 118;

the terpolymers disclosed in DE-A-196 20 119 of ethylene, the vinyl ester of one or more aliphatic C ₂ to C ₂₀ monocarboxylic acids and bicyclo [2.2.1] hept-2-ene;

the terpolymers of ethylene and at least one olefinically unsaturated comonomer containing one or more hydroxyl groups described in EP-A-0 926 168.

Preference is given to mixtures of identical or different ethylene copolymers used. Particularly preferably, the mixtures differ based on the mixtures lying polymers in at least one characteristic. For example, you can contain different comonomers, different comonomer contents, Have molecular weights and / or degrees of branching. The Mixing ratio of the different ethylene copolymers is preferred between 20: 1 and 1:20, preferably 10: 1 to 1:10, in particular 5: 1 to 1: 5.

The copolymers B are preferably derived from ethylenically unsaturated Dicarboxylic acids and their derivatives such as esters and anhydrides. Preferred are Maleic acid, fumaric acid, itaconic acid and their esters with lower alcohols with 1 to 6 carbon atoms and their anhydrides such as maleic anhydride. When Comonomers are monoolefins with 10 to 20, in particular with 12 to 18 C-atoms particularly suitable. These are preferably linear and the double bond is preferably terminal such as dodecene, tridecene, tetradecene, Pentadecene, hexadecene, heptadecene and octadecene. The ratio of Dicarboxylic acid or dicarboxylic acid derivative to olefin or olefins in the polymer preferably in the range 1: 1.5 to 1.5: 1, especially it is equimolar.

In minor amounts of up to 20 mol%, preferably <10 mol%, especially <5 mol%, other comonomers may also be present in copolymer B which are copolymerizable with ethylenically unsaturated dicarboxylic acids and the olefins mentioned, such as, for example, and longer-chain olefins, allyl polyglycol ethers, C ₁ -C ₃₀ -alkyl (meth) acrylates, vinylaromatics or C ₁ -C ₂₀ -alkyl vinyl ethers. In the same way, minor amounts of poly (isobutylene) having molecular weights of up to 5,000 g / mol are used, with highly reactive variants having a high proportion of terminal vinylidene groups being preferred. These other comonomers are not taken into account in the calculation of the factor Q which is decisive for the effectiveness.

worin

R¹

Wasserstoff oder Methyl,

R²

Wasserstoff oder C₁-C₄-Alkyl,

m

eine Zahl von 1 bis 100,

R³

C₁-C₂₄-Alkyl, C₅-C₂₀-Cycloalkyl, C₆-C₁₈-Aryl oder -C(O)-R⁴,

R⁴

C₁-C₄₀-Alkyl, C₅-C₁₀-Cycloalkyl oder C₆-C₁₈-Aryl, bedeuten.

Allyl polyglycol ethers correspond to the general formula

wherein

R ¹

Hydrogen or methyl,

R ²

Hydrogen or C ₁ -C ₄ -alkyl,

m

a number from 1 to 100,

R ³

C ₁ -C ₂₄ -alkyl, C ₅ -C ₂₀ -cycloalkyl, C ₆ -C ₁₈ -aryl or -C (O) -R ⁴ ,

R ⁴

C ₁ -C ₄₀ alkyl, C ₅ -C ₁₀ cycloalkyl or C ₆ -C ₁₈ aryl.

The preparation of the copolymers B) according to the invention is preferably carried out at Temperatures between 50 and 220 ° C, in particular 100 to 190 ° C, especially 130 to 170 ° C. The preferred manufacturing process is the solvent-free Bulk polymerization, but it is also possible, the polymerization in the presence aprotic solvents such as benzene, toluene, xylene or higher-boiling aromatic, aliphatic or isoaliphatic solvents or Solvent mixtures such as kerosene or solvent naphtha perform. Especially the polymerization is preferably in moderately moderating, aliphatic or isoaliphatic solvents. The solvent content in the polymerization mixture is generally between 10 and 90% by weight, preferably between 35 and 60% by weight. In the solution polymerization, the reaction temperature can be controlled by the Boiling point of the solvent or by working under low or high pressure be set particularly easy.

The average molecular weight of the copolymers B according to the invention is in the general between 1,200 and 200,000 g / mol, in particular between 2,000 and 100,000 g / mol, measured by gel permeation chromatography (GPC) against Polystyrene standards in THF. Inventive copolymers B must be in practice-relevant Dosiermengen be oil-soluble, that is, they must be in the zu dissolve additivating oil at 50 ° C residue-free.

The reaction of the monomers is by free-radical initiators (Radical chain starter) initiated. This class of substance includes e.g. Oxygen, Hydroperoxides and peroxides such as e.g. Cumene hydroperoxide, t-butyl hydroperoxide, Dilauroyl peroxide, dibenzoyl peroxide, bis (2-ethylhexyl) peroxide carbonate, t-butyl perpivalate, t-butyl per-maleate, t-butyl perbenzoate, dicumyl peroxide, t-butyl cumyl peroxide, di- (t-butyl) peroxide, and azo compounds such as e.g. 2,2'-azobis (2methylpropanonitril) or 2,2'-azobis (2-methylbutyronitrile). The initiators be used individually or as a mixture of two or more substances in quantities of 0.01 to 20 wt .-%, preferably 0.05 to 10 wt .-%, based on the Monomer mixture used.

The copolymers can be prepared either by reaction of maleic, fumaric and / or Itaconic acid or its derivatives with the corresponding amine and subsequent Copolymerization or by copolymerization of olefin or olefins with at least one unsaturated dicarboxylic acid or its derivative such as for example, itaconic and / or maleic anhydride and subsequent reaction be prepared with amines. Preference is given to copolymerization with Anhydrides performed and the resulting copolymer after preparation in converted an amide and / or an imide.

The reaction with amines takes place in both cases, for example by reaction with 0.8 to 2.5 moles of amine per mole of anhydride, preferably with 1.0 to 2.0 moles of amine per mol anhydride at 50 to 300 ° C. When using about 1 mol of amine per mole of anhydride arise at reaction temperatures of about 50 to 100 ° C preferably hemi-amides, which additionally carry one carboxyl group per amide group. At higher Reaction temperatures of about 100 to 250 ° C arise from primary amines below Dehydration prefers imides. When using larger amounts of amine, preferably 2 Mole of amine per mole of anhydride are formed at about 50 to 200 ° C amide ammonium salts and at higher temperatures of for example 100-300 ° C., preferably 120- 250 ° C diamonds. The water of reaction can by means of an inert gas stream distilled off or in the presence of an organic solvent by azeotropic Distillation be discharged. Preference is given to 20-80, in particular 30-70, especially 35-55 wt .-% of at least one organic solvent used. When Halbamides are here (50% in solvent-adjusted) with co-polymers Acid numbers of 30 - 70 mg KOH / g, preferably from 40 - 60 mg KOH / g considered. Corresponding copolymers with acid numbers of less than 40, especially less as 30 mg KOH / g are considered diamides or imides. Especially preferred are hemi-amides and imides.

Suitable amines are primary and secondary amines having one or two C ₈ -C ₁₆ alkyl radicals. They can carry one, two or three amino groups which are linked via alkylene radicals having two or three carbon atoms. Preference is given to monoamines. In particular, they carry linear alkyl radicals, but they can also minor amounts, eg. B. up to 30 wt .-%, preferably up to 20 wt .-% and especially up to 10 wt .-% (in 1- or 2-position) contain branched amines. Shorter as well as longer-chain amines can be used, but their proportion is preferably less than 20 mol% and especially less than 10 mol%, for example between 1 and 5 mol%, based on the total amount of amines used.

Particularly preferred as primary amines are octylamine, 2-ethylhexylamine, Decylamine, undecylamine, dodecylamine, n-tridecylamine, iso-tridecylamine, Tetradecylamine, pentadecylamine, hexadecylamine and mixtures thereof.

Preferred secondary amines are dioctylamine, dinonylamine, didecylamine, didodecylamine, ditetradecylamine, dihexadecylamine, and amines having different alkyl chain lengths such as N-octyl-N-decylamine, N-decyl-N-dodecylamine, N-decyl-N-tetradecylamine, N-decyl N-hexadecylamine, N-dodecyl-N-tetradecylamine, N-dodecyl-N-hexadecylamine, N-tetradecyl-N-hexadecylamine. Secondary amines which, in addition to a C ₈ -C ₁₆ -alkyl radical, bear shorter side chains having 1 to 5 C atoms, for example methyl or ethyl groups, are suitable according to the invention. In the case of secondary amines, the alkyl chain length n is taken into account as the mean value of the alkyl chain lengths of C ₈ to C ₁₆ for the calculation of the Q factor. Shorter and longer alkyl radicals, if present, are not included in the calculation because they do not contribute to the effectiveness of the additives.

Particularly preferred copolymers B are hemiamides and imides primary Monoamines.

By using mixtures of different olefins in the polymerization and Mixtures of different amines in the amidation or imidation, the Effectiveness further adapted to specific fatty acid ester compositions become.

In a preferred embodiment, in addition to components A and B, the additives may also contain polymers and copolymers based on C ₁₀ -C ₂₄ -alkyl acrylates or methacrylates (component C). These poly (alkyl acrylates) and methacrylates have molecular weights of 800 to 1,000,000 g / mol, and are preferably derived from caprylic, capric, undecyl, lauryl, myristyl, cetyl, palmitoleyl, stearyl alcohol or the like Mixtures such as coconut, palm, tallow or behenyl from.

In a preferred embodiment, mixtures of the invention Copolymers B are used, provided that the mean of the Q values of the Mixture components again have values from 23 to 27 and preferably values of 24 to 26.

The mixing ratio of the additives A and B according to the invention is (in Parts by weight) 20: 1 to 1:20, preferably 10: 1 to 1:10, in particular 5: 1 to 1: 2. The proportion of component C in the formulations of A, B and C can be up to 40 wt .-% amount; it is preferably less than 20% by weight, in particular between 1 and 10% by weight.

The additives according to the invention are oils in amounts of from 0.001 to 5% by weight, preferably 0.005 to 1 wt .-% and especially added 0.01 to 0.5 wt .-%. there they may be dissolved as such or dissolved in solvents, e.g. aliphatic and / or aromatic hydrocarbons or Hydrocarbon mixtures such. Toluene, xylene, ethylbenzene, decane, Pentadecane, gasoline fractions, kerosene, naphtha, diesel, fuel oil, isoparaffins or commercial solvent mixtures such as Solvent Naphtha, ®Shellsol AB, ® Solvesso 150, ®Solvesso 200, ®Exxsol, ®Isopar and ®Shellsol D types. Preferably, they are based on fuel oil of animal or vegetable origin dissolved by fatty acid alkyl esters. Preferably, the inventive Additives 1 - 80%, especially 10 - 70%, in particular 25 - 60% solvents.

In a preferred embodiment, the fuel oil is the often referred to as "biodiesel" or "biofuel" to Fatty acid alkyl esters of fatty acids having 12 to 24 carbon atoms and alcohols having 1 to 4 C-atoms. Usually a major part of the fatty acids contains one, two or three Double bonds.

Examples of oils derived from animal or vegetable material, and in where the additive according to the invention can be used are rapeseed oil, Coriander oil, soybean oil, cottonseed oil, sunflower oil, castor oil, olive oil, Peanut oil, corn oil, almond oil, palm kernel oil, coconut oil, mustard seed oil, beef tallow, Bone oil, fish oils and used cooking oils. Other examples include oils which are derived from wheat, jute, sesame, shea nut, arachis oil and linseed oil.

The fatty acid alkyl esters, also referred to as biodiesel, can be made from these oils be derived by methods known in the art. Rapeseed oil, that is a mixture of glycerol partially esterified fatty acids, is preferred because it is available in large quantities and in a simple manner by pressing out of Rapeseed is available. Furthermore, the also widely used oils of Sunflowers and soybeans and their mixtures with rapeseed oil preferred.

Particularly suitable as biofuels are lower alkyl esters of fatty acids. Here For example, commercial mixtures of ethyl, propyl, butyl and in particular methyl esters of fatty acids having 14 to 22 carbon atoms, for example, lauric acid, myristic acid, palmitic acid, palmitoleic acid, Stearic acid, oleic acid, elaidic acid, petroselinic acid, ricinoleic acid, Elaeostearic acid, linoleic acid, linolenic acid, eicosanoic acid, gadoleic acid, Docosanic acid or erucic acid, preferably having an iodine value of 50 to 150, especially 90 to 125 have. Mixtures with particularly advantageous Properties are those that are mainly, i. H. at least 50% by weight, Methyl esters of fatty acids having 16 to 22 carbon atoms and 1, 2 or 3 Double bonds included. The preferred lower alkyl esters of fatty acids are the methyl esters of oleic acid, linoleic acid, linolenic acid and erucic acid.

Commercial mixtures of the type mentioned are, for example, by Cleavage and esterification or by transesterification of animal and vegetable Greases and oils obtained with lower aliphatic alcohols. Are the same also used edible oils as starting materials suitable. For production of lower alkyl esters of fatty acids, it is advantageous from fats and oils with high iodine value, such as sunflower oil, rapeseed oil, Coriander oil, castor oil (castor oil), soybean oil, cottonseed oil, peanut oil or Beef tallow. Lower alkyl esters of fatty acids based on a new type of rapeseed oil, their fatty acid component to more than 80 wt .-% of unsaturated fatty acids derived with 18 carbon atoms are preferred.

Thus, a biofuel is an oil derived from vegetable or animal material or is obtained or a derivative thereof, which as fuel and especially as diesel or heating oil can be used. Although many of the The above oils can be used as biofuels are vegetable oil derivatives with particularly preferred biofuels alkyl ester derivatives of rapeseed oil, Cottonseed oil, soybean oil, sunflower oil, olive oil or palm oil are, being Rapsölsäuremethylester, sunflower oil and Sojaölsäuremethylester are very particularly preferred. Particularly preferred as In addition, biofuel or as a component in biofuel are also Altfettester such as Altfettmethylester.

The additive may be added to the oil to be treated according to art known in the art Procedures are introduced. If more than one additive component or Coadditive component should be used, such components be introduced together or separately in any combination in the oil.

With the additives according to the invention, the CFPP value of biodiesel can be determined Set values below -20 ° C and sometimes to values below -25 ° C, as they do be required for marketing for use especially in winter. Of the same is the pour point of biodiesel by the addition of the invention Additives are minimized. The additives of the invention are particularly advantageous in problematic oils containing a high proportion of esters of saturated fatty acids of more than 4% in particular more than 5% and especially with 7 to 25% like For example, with 8 to 20%, as for example in oils from sunflowers and Soy included. Such oils are characterized by cloud points of over -5 ° C and especially above -3 ° C. It succeeds with the additives according to the invention Thus, mixtures of Rapsölsäuremethylester and sunflower and / or Adjust soya oil fatty acid methyl ester to CFPP values of -20 ° C and below. In addition, the so-additive oils have a good resistance to cold, the means the CFPP value remains even when stored under wintry conditions constant.

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 already by themselves the cold flow properties of crude oils, lubricating oils or fuel oils. Examples of such co-additives are polar compounds that cause paraffin dispersion (Paraffin dispersants) and oil-soluble amphiphiles, with the proviso that they themselves differ from the comb polymers B.

The additives according to the invention can be mixed with paraffin dispersants be used. Paraffin dispersants reduce the size of the paraffin crystals and cause the paraffin particles do not settle, but colloid with significantly reduced tendency to sediment, remain dispersed. When Paraffin dispersants have both low molecular weight and polymeric, oil-soluble compounds having ionic or polar groups, e.g. amine salts and / or amides proven. Particularly preferred paraffin dispersants contain Reaction products of secondary fatty amines having 20 to 44 carbon atoms, in particular Dicocosamine, ditallow fatty amine, distearylamine and dibehenylamine with carboxylic acids and their derivatives. Paraffin dispersants which have proven particularly suitable are 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 are obtained (see US 4 211 534). Of are amides and ammonium salts of aminoalkylenepolycarboxylic such as Nitrilotriacetic acid or ethylenediaminetetraacetic acid with secondary amines as Paraffin dispersants are suitable (compare EP 0 398 101). Other paraffin dispersants are copolymers of maleic anhydride and α, β-unsaturated compounds, optionally with primary monoalkylamines and / or aliphatic alcohols can be implemented (see EP 0 154 177) and the reaction products of Alkenylspirobislactones with amines (see EP 0 413 279 B1) and after EP-A-0 606 055 A2 Reaction products of terpolymers based on α, β-unsaturated dicarboxylic anhydrides, α, β-unsaturated compounds and Polyoxyalkylene ethers of lower unsaturated alcohols.

The mixing ratio (in parts by weight) of the additives according to the invention Paraffin dispersants are 1:10 to 20: 1, preferably 1: 1 to 10: 1.

The additives can be used alone or together with other additives be, e.g. with other pour point depressants or dewaxing aids, with Antioxidants, cetane improvers, dehazers, demulsifiers, detergents, Dispersants, defoamers, dyes, corrosion inhibitors, Conductivity improvers, sludge inhibitors, odorants and / or additives to Humiliation of the cloud point.

Examples Characterization of the test oils:

The CFPP value is determined in accordance with EN 116 and the determination of the cloud point in accordance with ISO 3015. Characterization of the used test oils Oil no. CP CFPP E 1 Rapsölsäuremethylester -2.3 -14 ° C E 2 80% rapeseed oil methyl ester +
20% sunflower oil methyl ester -1.6 -10 ° C E 3 90% rapeseed oil methyl ester +
10% of soybean oil methyl ester -2.0 -8 ° C C chain distribution of the fatty acid methyl esters used for the preparation of the test oils (main constituents, FI .-% according to GC): C ₁₆ C ₁₆ ' C ₁₈ C ₁₈ ' C ₁₈ " C ₁₈ "' C ₂₀ C ₂₀ ' C ₂₂ Σ saturated RME 4.4 0.4 1.6 57.8 21.6 8.8 1.5 0.7 0.2 7.7 SBME 6.0 0.1 3.8 28.7 58.7 0.1 0.3 0.3 0.7 10.8 SojaME 10.4 0.1 4.1 24.8 51.3 6.9 0.5 0.4 0.4 15.4 RME = rapeseed oil acid methyl ester; SBME = sunflower oil methyl ester; SoyaME = soyaoic acid methyl ester

The following additives were used: Ethylene copolymers A

The ethylene copolymers used are commercial products having the characteristics given in Table 2. The products were used as 65% and 50% (A3) settings in kerosene, respectively. Characterization of the ethylene copolymers used example Comonomer (s) V140 CH ₃ / 100CH ₂ A1 13.6 mole% vinyl acetate 130 mPas 3.7 A2 13.7 mole percent vinyl acetate and 1.4 mole percent vinyl neodecanoate 105 mPas 5.3 A3 9.4 mol% vinyl acetate 220 mPas 6.2 A4 Mixture of EVA copolymer with 16 mol% vinyl acetate and EVA with 95 mPas 3.2 5 mol% vinyl acetate in the ratio 13: 1 350 mPas 5.7

Comb polymers B

The polymerization of maleic anhydride (MSA) with α-olefins takes place in one higher boiling aromatic hydrocarbon mixture at 160 ° C in the presence a mixture of equal parts of tert-butyl peroxybenzoate and tert-butyl peroxy-2-ethylhexanoate as a radical chain starter. Table 3 shows various examples Copolymers and the molar fractions used for their preparation Monomers and chain length (R) and molar amount (relative to MSA) of the Derivatization of amine used and the factor Q calculated therefrom. The amines used are, unless otherwise stated, to monoalkylamines.

The reactions with amines are carried out in the presence of solvent naphtha (50 wt .-%) at 50 to 100 ° C to the half-amide or amide ammonium salt and at 160 to 200 ° C with azeotropic culling of water of reaction to imide or diamide. The degree of amidation is inversely proportional to the acid number. Characterization of the comb polymers used example comonomers Amin Q acid number
[mg KOH / g] R mol B1 MSA-co-C _14/16 -α-olefin (1: 0.5: 0.5) C ₁₀ 1 23.0 60 B2 MSA-co-C _14/16 -α-olefin (1: 0.5: 0.5) C ₁₂ 1 25.0 58 B3 MSA-co-C _14/16 -α-olefin (1: 0.5: 0.5) C ₁₄ 1 27.0 56 B4 (V) MSA-co-C _14/16 -α-olefin (1: 0.5: 0.5) C ₁₆ 1 29.0 55 B5 MSA-co-C _12/14 -α-olefin (1: 0.5: 0.5) C ₁₄ 1 25.0 57 B6 MSA-co-C _12/14 -α-olefin (1: 0.5: 0.5) C ₁₂ 1 23.0 55 B7 MSA-co-C ₁₆ α-olefin (1: 1) C ₁₂ 1 26.0 56 B8 MSA-co-C ₁₄ -α-olefin (1: 1) C ₁₄ 1 26.0 58 B9 MSA-co-C ₁₀ -α-olefin (1: 1) C ₁₆ 0.5 25.0 59 C ₁₈ 0.5 B10 MSA-co-C _14/16 -α-olefin-co-Allylmethylpolyglykol (1: 0.45: 0.45: 0.1) C ₁₂ 1 25.0 56 B11 (V) MSA-co-C ₁₀ -α-olefin (1: 1) C ₁₂ 1 20.0 57 B12 MSA-co-C _14/16 -α-olefin (1: 0.5: 0.5) C ₁₂ 2 25.0 0.32 B13 MSA-co-C _14/16 -α-olefin (1: 0.5: 0.5) C ₁₂ 1 25.0 1.5 B14 MSA-co-C _14/16 -α-olefin (1: 0.5: 0.5) di-C ₁₂ 1 25.0 50 B15 (V) Fumarate vinyl acetate (1: 1) C ₁₄ 2 n / A 0.4 na = not applicable (V) = Comparative Example

Poly (alkyl (meth) acrylates) C

As poly (alkyl (meth) acrylate), the compounds listed in the table were used as 50% settings in higher-boiling solvent. The K values are determined according to Ubbelohde at 25 ° C. in 5% strength toluene solution. Characterization of the poly (acrylates) used C1 Poly (octadecyl acrylate), K value 32 C2 Poly (dodecyl acrylate), K value 35.6 C3 Poly (phenyl acrylate), K value 22.4

Effectiveness of the terpolymers

The CFPP value (according to EN 116, in ° C) of various biofuels according to the above table was determined after addition of 1200 ppm, 1500 ppm and 2000 ppm of additive mixture. Percentages refer to parts by weight in the respective mixtures. The results presented in Tables 5 to 7 show that comb polymers with the factor Q according to the invention achieve excellent CFPP reductions even at low dosing rates and offer additional potential at higher dosing rates. CFPP testing in test oil E1 Ex. comb polymer Ethylene copolymer polyacrylate CFPP in test oil 1 1200 ppm 1500 ppm 2000 ppm 1 20% B1 80% A2 - -19 -21 -23 2 20% B2 80% A2 - -24 -24 -24 3 20% B3 80% A2 - -19 -20 -23 4 (V) 20% B4 80% A2 - -15 -16 -17 5 20% B7 80% A2 - -21 -22 -24 6 20% B9 80% A2 - -23 -23 -24 7 20% B10 80% A2 - -23 -23 -25 8th 20% B10 80% A3 - -18 -20 -21 9 10% B10 90% A1 - -21 -22 -23 10 (V) 20% B11 80% A2 - -17 -19 -18 11 20% B12 80% A2 - -19 -22 -21 12 20% B13 80% A2 - -23 -24 -24 13 20% B14 80% A2 - -21 -23 -24 14 (V) 20% B15 80% A2 - -18 -17 -17 15 19% B2 76% A2 5% C1 -20 -24 -26 16 19% B2 76% A2 5% C2 -21 -23 -25 17 19% B2 76% A2 5% C3 -22 -23 -24 18 (V) - A2 - -15 -18 -17 19 (V) - - C1 -9 -11 -12 20 (V) - - C3 -18 -17 CFPP testing in test oil E2 Ex. comb polymer Ethylene copolymer CFPP in test oil 2 1500 ppm 2000 ppm 22 25% B2 75% A4 -20 -24 23 25% B3 75% A4 -21 -22 24 (V) 25% B4 75% A4 -13 -15 25 25% B5 75% A4 -21 -23 21 25% B6 75% A4 -19 -22 26 25% B7 75% A4 -21 -24 27 25% B8 75% A4 -20 -23 28 30% B9 70% A2 -21 -24 29 20% B10 80% A3 -20 -22 30 (V) 25% B11 75% A2 -15 -16 31 25% B12 75% A4 -20 -22 32 25% B13 75% A4 -22 -25 33 25% B14 75% A4 -18 -20 34 (V) 25% B15 75% A4 -15 -17 37 (V) - 100% A4 -12 -12 CFPP testing in test oil E3 Ex. comb polymer Ethylene copolymer polyacrylate CFPP in test oil 3 1200 ppm 1500 ppm 2000 ppm 21 20% B1 80% A1 - -18 -20 -21 22 20% B2 80% A1 - -20 -21 -23 23 20% B3 80% A1 - -20 -22 -21 24 (V) 20% B4 80% A1 - -11 -15 -16 25 20% B5 80% A1 - -20 -20 -22 26 20% B7 80% A1 - -20 -21 -23 27 20% B8 80% A1 - -19 -21 -22 28 25% B9 75% A2 - -20 -21 -23 29 15% B10 85% A3 - -18 -18 -20 30 (V) 20% B11 80% A2 - -15 -17 -17 31 20% B12 80% A1 - -19 -20 -20 32 20% B13 80% A1 - -21 -22 -23 33 20% B14 80% A1 - -19 -20 -20 34 (V) 20% B15 80% A1 - -15 -17 -18 35 19% B2 76% A1 5% C1 -19 -21 -22 36 19% B2 76% A1 5% C3 -20 -21 -23 37 (V) - A1 - -13 -13 -11 38 (V) - - C3 -14 -16 -16

Chilling resistance of fatty acid methyl esters

The CFPP value is used to determine the resistance to cold corrosion of an oil according to DIN EN 116 before and after a standardized cold change treatment compared.

500 ml of biodiesel (test oil E1) are treated with the appropriate cold additive, placed in a cylinder and stored in a programmable cold chamber for one week. During this time, a program is run through which repeatedly cools to -13 ° C and then warms up again to -3 ° C. 6 cycles are consecutively run through (Table 8). Cooling program for determining the resistance to cold chill: section begin The End duration description A → B + 5 ° C -3 ° C 8 h Pre-cooling to cycle start temperature B → C -3 ° C -3 ° C 2 h stationary temperature, start of cycle C → D -3 ° C -13 ° C. 14 h Temperature reduction, incipient crystal formation D → E -13 ° C - 13 ° C 2 h Stationary temperature, crystal growth E → F -13 ° C -3 ° C 6 h Temperature increase, melting of the crystals F → B Another 6 cycles B → F are carried out.

Subsequently, the additivierte oil sample is reheated to room temperature without shaking. From each of the upper, middle and lower sections of the cylinder a sample of 50 ml is drawn for CFPP measurements.
A difference between the mean values of the CFPP values after storage to the CFPP value before storage and between the individual phases of less than 3 K shows a good resistance to cold flashes.

Claims (19)

Additive containing A) a copolymer of ethylene and 8 to 21 mol% of at least one acrylic or vinyl ester having a C ₁ -C ₁₈ alkyl radical and B) a comb polymer comprising structural units B1) at least one olefin as monomer 1, which carries at least one C ₈ -C ₁₈ -alkyl radical on the olefinic double bond, and B2) at least one ethylenically unsaturated dicarboxylic acid as monomer 2 which carries at least one C ₈ -C ₁₆ -alkyl radical attached via an amide and / or imide moiety, the sum of Q.

the molar average of the C chain length distributions in the alkyl radicals of monomer 1 on the one hand and the alkyl radicals of the amide and / or imide groups of monomer 2 on the other hand from 23 to 27, wherein

W ₁

the molar fraction of the individual chain lengths in the alkyl radicals of monomer 1,

w ₂

the molar fraction of the individual chain lengths in the alkyl radicals of the amide and / or imide groups of monomer 2,

n ₁

the individual chain lengths in the alkyl radicals of monomer 1,

n ₂

the individual chain lengths in the alkyl radicals of the amide and / or imide groups of monomer 2,

i

the run variable for the individual chain lengths in the alkyl radicals of monomers 1, and

j

are the run variables for the individual chain lengths in the alkyl radicals of the amide and / or imide groups of monomer 2.

An additive according to claim 1, wherein Q is from 24 to 26. An additive according to claim 1 and / or 2, wherein in ingredient A except ethylene 3,5 to 20 mol% of vinyl acetate and 0.1 to 12 mol% of 2-ethylhexanoic acid vinyl ester, Vinyl neononanoate and / or vinyl neodecanoate are contained, wherein the total comonomer content is between 8 and 21 mol%. An additive according to one or more of claims 1 to 3, wherein in ingredient A in addition to ethylene and 8 to 18 mol% vinyl esters still 0.5 to 10 mol% olefins, selected from propene, butene, isobutylene, hexene, 4-methylpentene, octene, Diisobutylene or norbornene are included. An additive according to one or more of claims 1 to 4, wherein the Copolymers that make up component A have melt viscosities between 20 and 10,000 mPas. Additive according to one or more of claims 1 to 5, wherein the copolymers comprise component A, degrees of branching 1-9 CH _3/100 CH ₂ groups, which do not stem from the comonomers have. An additive according to one or more of claims 1 to 6, wherein the Copolymers constituting component B contain comonomers derived from Amides and / or imides of maleic acid, fumaric acid and / or itaconic acid are derived. An additive according to one or more of claims 1 to 7, wherein the amides and / or imides of component B are derived from primary amines. An additive according to one or more of claims 1 to 8, wherein the amides and / or imides of component B derived from amines with linear alkyl radicals are. An additive according to one or more of claims 1 to 9, wherein the amides and / or imides of component B are derived from monoamines. An additive according to one or more of claims 1 to 10, wherein the middle one Molecular weight of the copolymers B of the invention between 1,200 and 200,000 g / mol. An additive according to one or more of claims 1 to 11, wherein the Copolymers constituting component B contain comonomers derived from α-olefins are derived. An additive according to one or more of claims 1 to 12, wherein in addition to constituents A and B as constituent C, a polymer or copolymer comprising (C ₁₀ -C ₂₄ alkyl) acrylate units or methacrylate units having a molecular weight of 800 to 1,000. 000 g / mol in an amount of up to 40 wt .-% based on the total weight of A, B and C is contained. An additive according to any one of claims 1 to 13, containing polar nitrogen-containing Paraffin. A fuel oil composition containing an animal or a fuel oil of vegetable origin and an additive according to one or more of the claims 1 to 14. A fuel oil composition according to claim 15, characterized in that the fuel oil of animal or vegetable origin contains one or more esters of monocarboxylic acid having 14 to 24 carbon atoms and alcohol having 1 to 4 carbon atoms. A fuel oil composition according to claim 16, characterized in that the alcohol is methanol or ethanol. A fuel oil composition according to one or more of claims 15 to 17, characterized in that the fuel oil of animal or vegetable origin contains more than 5% by weight of esters of saturated fatty acids. Use of an additive according to one or more of claims 1 to 14 for improving the cold flow properties of fuel oil animal or of plant origin.