EP1526168A2 - Cold flow improver for fuel oils of vegetable or animal 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) comprising (meth)acrylate, vinyl ester, vinyl ether, (meth)acrylamide, allyl ether or diketene units with C8-C16 alkyl groups, where the sum of the molar average alkyl chain lengths in (II) is 11-14. 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 proportion of oil consisting essentially of alkyl esters of fatty acids derived from vegetable or animal oils, or both, mixed with a small proportion of mineral oil flow improver comprising one or more of 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 Iodzahlbereich 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 wt .-% of at least one ester in the iodine number 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.

EP-A-0 626 442 and EP-A-0 694 125 disclose fatty acid esters which contain pour point depressants for the purpose of improving the low-temperature properties. The following are mentioned as PPDs: styrene-MSA copolymers esterified with a mixture of short-chain (butanol) and longer-chain C ₁₀ -C ₁₈ -alcohols neutralized with aminopropylmorpholine; Poly (C _4-24- alkyl (meth) acrylates and their copolymers with N-containing monomers; alkyl-bridged alkylaromatics.

EP-A-1 032 620 discloses poly (alkyl (meth) acrylates) having broad C chain distribution and hydroxy-functional comonomers as an additive for mineral oil and biodiesel.

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 resistance to cold oxidation of the additized oils, i. the set CFPP value of the oils gradually increases when the oil is changing for a long time Temperatures are stored in the area of the cloud point or below.

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 prolonged storage of the Oil stays constant around its cloud point or below.

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

B) mindestens ein Kammpolymer enthaltend Struktureinheiten mit C₈-C₁₆-Alkylresten, wobei die Struktureinheiten ausgewählt sind aus C₈-C₁₆-Alkyl(meth)acrylaten, C₈-C₁₆-Alkylvinylestern, C₈-C₁₆-Alkylvinylethern, C₈-C₁₆-Alkyl(meth)acrylamiden, C₈-C₁₆-Alkylallylethern und C₈-C₁₆-Diketenen,

wobei die Summe R

der molaren Mittel der C-Kettenlängenverteilungen in den Alkylresten der Monomere B) 11,0 bis 14,0 beträgt,
worin

m₁, m₂, ... m_g

die Molenbrüche der oben genannten Monomere B) im Polymer sind, wobei die Summe der Molenbrüche m₁ bis m_g = 1 ist,

w_1i, w_1j..w_2i, w_2j...w_gp

die Gewichtsanteile der einzelnen Kettenlängen i, j, .... p der Alkylreste der verschiedenen Monomeren B) 1 bis g sind, und

n_1i, n_1j..n_2i, n_2j...n_gp

die Kettenlängen der Alkylreste i, j, .... p der Monomere B) 1 bis g sind.

The invention relates to a fuel oil composition containing a fuel oil of animal or vegetable origin and an additive containing

A) at least one 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) at least one comb polymer containing structural units with C ₈ -C ₁₆ -alkyl radicals, the structural units being selected from C ₈ -C ₁₆ -alkyl (meth) acrylates, C ₈ -C ₁₆ -alkyl vinyl esters, C ₈ -C ₁₆ -alkyl vinyl ethers, C ₈ -C ₁₆ -alkyl (meth) acrylamides, C ₈ -C ₁₆ -alkyl allyl ethers and C ₈ -C ₁₆ -diketenes,

where the sum R

the molar average C chain length distribution in the alkyl radicals of monomers B) is 11.0 to 14.0,
wherein

m ₁ , m ₂ , ... m _g

the mole fractions of the abovementioned monomers B) in the polymer are, the sum of the mole fractions m ₁ to m _g = 1,

w _1i , w _1j ... w _2i , w _2j ... w _gp

the weight fractions of the individual chain lengths i, j,... p of the alkyl radicals of the different monomers B) are 1 to g, and

n _1i , n _1j ... n _2i , n _2j ... n _gp

the chain lengths of the alkyl radicals i, j,... p of the monomers B) are 1 to g.

Another object of the invention is an additive as defined above.

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 R has values of 11.5 to 13.5 and specifically 12.0 to 13.0.

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 30 carbon atoms and preferably 1 to 18, especially 1 to 12 C atoms, from. As examples may be mentioned Vinyl acetate, vinyl propionate, vinyl butyrate, vinyl hexanoate, vinyl heptanoate, Vinyloctanoate, vinyl laurate and vinyl stearate, as well as branched fatty acids based esters of vinyl alcohol such as vinyl isobutyrate, vinyl pivalate, Vinyl 2-ethylhexanoate, iso-nonanoic acid vinyl ester, vinyl neononanoate, Vinyl neodecanoate and vinyl neoundecanoate. Particularly preferred Vinyl acetate. Also suitable as comonomers are esters of acrylic and Methacrylic acid having 1 to 20 C 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 more 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 conventional 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 isobutyraldehyde, 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).

Suitable copolymers or terpolymers include, for example: ethylene-vinyl acetate copolymers with 10 to 40% by weight of vinyl acetate and 60 to 90% by weight of ethylene; the ethylene-vinyl acetate-hexene terpolymers known from DE-A-34 43 475; the ethylene-vinyl acetate-diisobutylene terpolymers described in EP-B-0 203 554; the mixture known from EP-B-0 254 284 comprising an ethylene-vinyl acetate-diisobutylene terpolymer and an ethylene-vinyl acetate copolymer; the blends disclosed in EP-B-0 405 270 of an ethylene-vinyl acetate copolymer and an ethylene-vinyl acetate-N-vinylpyrrolidone terpolymer; the ethylene / vinyl acetate / iso-butyl vinyl ether terpolymers described in EP-B-0 463 518; 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-0 778 875 of ethylene, a first vinyl ester having up to 4 C atoms and a second vinyl ester, which is a branched carboxylic acid having up to 7 carbon atoms or a branched but not tertiary carboxylic acid with 8 bis Derived 15 C 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 derived from alkyl acrylates, alkyl methacrylates, Alkylacrylamides, alkylmethacrylamides, alkylvinylesters, alkylvinylethers, Alkylallyl ethers and Alkyldiketenen having 8 to 16 carbon atoms in the alkyl radical. These Comonomers are referred to below as comonomers B1).

In a preferred embodiment, the copolymers which are Component B to those containing comonomers derived from Esters, amides and / or imides of ethylenically unsaturated monocarboxylic acids with 3 to 8 carbon atoms are derived with alcohols or amines, wherein the Alcohols or amines carry alkyl radicals having 8 to 16 carbon atoms.

Optionally, the copolymers B) may also contain comonomers B2) which comprise i) esters, amides and / or imides of ethylenically unsaturated dicarboxylic acids having 4 to 8 C atoms and alcohols or amines having 8 to 16 C atoms in the alkyl radicals and / or or ii) C ₁₀ to C ₂₀ olefins.

The alkyl radicals of the comonomers B1 and B2 are preferably linear, but may also be minor amounts of branched isomers of up to 30 mol%, preferably up to 20 mol% and especially 2 to 5 mol%.

The proportion of comonomers B1) and optionally B2) is preferably Polymer more than 50 mol%, especially more than 70 mol% and especially at least 80 mol%, such as 90 to 95 mol%. The proportion of monomers B2), if present, is preferably less than 80 mol%, in particular less than 50 mole% and especially less than 20 mole% such as 2 to 10 mol% of the total amount of monomers B1) and B2). Especially preferred the polymers B) consist only of the monomers B1) and optionally B2), the then add up to 100 mol%.

Preferred monomers of the copolymers B) are esters of acrylic acid, Methacrylic acid, maleic acid, fumaric acid and itaconic acid with octanol, nonanol, Decanol, undecanol, dodecanol, n-tridecanol, iso-tridecanol, tetradecanol, Pentadecanol, hexadecanol and mixtures thereof. Preferred monomers are furthermore amides and optionally imides of these acids with octylamine, nonylamine, Decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, Pentadecylamine, hexadecylamine and mixtures thereof.

In a preferred embodiment, the copolymers containing component B Comonomers which esters and / or ethers of ethylenic unsaturated alcohols having 2 to 10 carbon atoms, and carboxylic acids or Alcohols bearing alkyl radicals of 8 to 16 carbon atoms are.

Such preferred monomers of the copolymers B) are, for example, esters of Vinyl alcohol with octanoic acid, 2-ethylhexanoic acid, nonanoic acid, neononanoic acid, Decanoic acid, neodecanoic acid, undecanoic acid, neoundecanoic acid, dodecanoic acid, Tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid and their Mixtures.

Further preferred monomers of the copolymers B) are, for example, ethers of Allyl and especially the vinyl alcohol with octanol, nonanol, decanol, Undecanol, dodecanol, n-tridecanol, isotridecanol, tetradecanol, pentadecanol, Hexadecanol and mixtures thereof.

As comonomers B2 are also olefins having 10-20 carbon atoms, preferably with 12-18 C atoms and in particular with 10-16 C atoms suitable. This is it preferably linear α-olefins with terminal double bond. In a Another preferred embodiment is branched olefins such as in particular oligomers of isobutylene and of propylene having 10 to 20 C atoms.

Other monomers such as alkyl (meth) acrylates, alkyl vinyl esters, alkyl vinyl ethers with 1 to 5 C atoms in the alkyl radical and ethylenically unsaturated free carboxylic acids such as for example, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid and functional groups such as -OH, -SH, -N-, -CN-bearing Monomers may be present in minor amounts of <20 mol%, <10 mol%, <5 mol%, also be present in the copolymer B. In subordinate Quantities of up to 20 mol%, preferably <10 mol%, especially <5 mol% can also contain other comonomers containing those monomers copolymerizable, e.g. Allyl polyglycol ethers, vinyl aromatics and higher molecular weight olefins such as poly (isobutylene).

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.

All not covered by the above definitions of B1) and / or B2) Comonomers are not taken into account in the calculation of the factor R.

The polymers of the invention can be prepared by direct polymerization from the mentioned monomers in known polymerization processes such as mass, Solution, emulsion, suspension or precipitation polymerization.

They may also be obtained by derivatization of e.g. Acid or Hydroxyl-bearing base polymer with corresponding fatty acids, Fatty alcohols or fatty amines having 8 to 16 carbon atoms in the alkyl radical become. The esterifications, etherifications, amidations and / or imidations done by known condensation methods. In this case, the derivatization be complete or partial. Partially esterified or amidated, acid-based Polymers have (solvent-free) preferably acid numbers of 60-140 mg KOH / g and in particular from 80 to 120 mg KOH / g. Copolymers with acid numbers less than 80, especially less than 60 mg KOH / g are considered to be fully derivatized. Partially esterified or etherified hydroxyl-bearing polymers have OH numbers from 40 to 200 mg KOH / g, preferably 60 to 150 mg KOH / g; Copolymers with Hydroxyl numbers of less than 60 and in particular less than 40 mg KOH / g are considered fully derivatized. Particularly preferred are partial derivatized polymers.

For the derivatization with fatty alcohols and / or amines to esters and / or Amides suitable acid group-bearing polymers are homopolymers and copolymers ethylenically unsaturated carboxylic acids such as acrylic acid, Methacrylic acid, maleic acid, fumaric acid, itaconic acid or their reactive Equivalents such as lower esters or anhydrides such as Methacrylates and maleic anhydride with each other as well as with further monomers copolymerizable with these acids. Suitable examples are poly (acrylic acid), poly (methacrylic acid), poly (maleic acid), Poly (maleic anhydride), poly (acrylic acid-co-maleic acid).

Suitable fatty alcohols and fatty amines are especially linear, but they can also minor amounts, z. B. up to 30 wt .-%, preferably up to 20 wt .-% and especially up to 10 wt .-% of branched alkyl radicals. The branches are preferably in the 1- or 2-position. Shorter as well as longer-chained Fatty alcohols or fatty amines can be used, but their share preferably below 20 mol% and especially below 10 mol%, such as between 1 and 5 mol% based on the total amount of amines used.

Particularly preferred fatty alcohols are octanol, decanol, undecanol, dodecanol, Tridecanol, tetradecanol, pentadecanol and hexadecanol.

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. Especially 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. Therefore, the proportion of shorter and longer alkyl chains is preferably below 20 mol%, preferably below 10 mol%, based on the total amount of amine used. Particularly preferred are amides derived from primary monoamines and imides.

For the derivatization with fatty acids and / or fatty alcohols to esters and / or Ethern particularly suitable hydroxyl-bearing polymers are homo- and Copolymers of hydroxyl-bearing monomers such as vinyl alcohol, allyl alcohol or hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and Hydroxypropyl methacrylate. Suitable fatty acids have 8 to 16 carbon atoms in the alkyl radical. The alkyl radical is essentially linear but may also be secondary Quantities, e.g. B. up to 30 wt .-%, preferably up to 20 wt .-% and especially up to Contain 10 wt .-% of branched isomers. Particularly suitable Nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, Tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid and Octadecanoic and nonadecanoic acid and mixtures thereof.

By using mixtures of different fatty acids, alcohols and / or amines in the esterification, etherification, amidation or imidization, the effectiveness the additives of the invention further to special Fatty acid ester compositions are adjusted.

The molecular weights of the inventive copolymers B are in between 1,000 and 100,000, especially between 2,000 and 50,000 and in particular between 2,500 and 25,000 g / mol, measured by gel permeation chromatography (GPC) against poly (styrene). Copolymers of the invention B must be oil-soluble in practice-relevant dosage quantities, that means they have to be in the oil to be added at 50 ° C without residue.

In a preferred embodiment, mixtures of the invention Copolymers B, provided that the average of the R values of the In turn, mixture components have values from 11 to 14, preferably from 11.5 to 13.5 and in particular assumes values of 12.0 to 13.0.

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 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 as e.g. 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%, especially 25 - 60% (m / m) solvent.

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, Docosanoic 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 of the invention, the CFPP value of biodiesel can be on 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.

Paraffin dispersants reduce the size of the paraffin crystals and cause The paraffin particles do not settle, but colloidly with significantly reduced Sedimentation tendency, remain dispersed. As paraffin dispersants have become both low molecular weight and polymeric, oil-soluble compounds with ionic or polar groups, e.g. Amine salts and / or amides proven. Especially preferred paraffin dispersants contain reaction products of secondary Fatty amines containing 20 to 44 carbon atoms, in particular dicocosamine, ditallow fatty amine, Distearylamine and dibehenylamine with carboxylic acids and their derivatives. Paraffin dispersants which have proved particularly suitable by reaction aliphatic or aromatic amines, preferably long-chain aliphatic Amines, with aliphatic or aromatic mono-, di-, tri- or tetracarboxylic acids or their anhydrides are obtained (see US 4 211 534). Are the same Amides and ammonium salts of aminoalkylene polycarboxylic acids 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 according to EP 0 606 055 A2 Reaction products of terpolymers based on α, β-unsaturated Dicarboxylic acid anhydrides, α, β-unsaturated compounds and polyoxyalkylene ethers 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 _3/100 CH ₂ A1 13.6 mol% vinyl acetate 130 mPas 3.7 A2 13.7 mol% of vinyl acetate and 1.4 mol% of 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 5 mol% vinyl acetate in the ratio 13: 1 95 mPas / 350 mPas 3.2 / 5.7

Comb polymers B

Various copolymers and terpolymers with the molar ratios of the monomers given in Table 3 and the factors R calculated therefrom were investigated. The polymers were used as 50% settings in a higher boiling aromatic solvent. The calculated acid numbers refer to these 50% settings. Characterization of the comb polymers used example comonomers R acid number
[mg KOH / g] B1 Poly (decyl acrylate-co-tetradecyl acrylate) from 50% decyl acrylate and 50% tetradecyl acrylate, Mw 9,200 12.0 2.5 B2 Poly (dodecyl acrylate-co-tetradecyl acrylate) of 70% dodecyl acrylate and 30% tetradecyl acrylate with Mw 10,500 12.6 1.2 B3 Poly (dodecyl methacrylate) with Mw 22,000 12.0 1.7 B4 Poly (vinyl laurate-co-decyl acrylate) from 40% vinyl laurate and 60% decyl acrylate, Mw 7,500 11.6 3.0 B5 Poly (2-ethylhexanoate-co-tetradecyl acrylate) from 10% 2-ethylhexyl acrylate and 90% tetradeo-acrylate with Mw 6,400 13.4 10 B6 Poly (dodecyl vinyl ether-co-decyl methacrylate) of equal proportions dodecyl vinyl ether and Decylmethacryat with Mw 5,200 11.0 2.8 B7 Poly (acrylic acid) esterified with a mixture of 75% dodecanol and 25% hexadecanol, Mw 15,000 13.0 43 B8 Poly (acrylic acid) esterified with a mixture of 40% decanol, 30% dodecanol and 30% tetradecanol, Mw 24,000 11.8 51 B9 Poly (acrylic acid-co-maleic acid) esterified with a mixture of 55% decanol and 45% hexadecanol, Mw 19,000 12.7 34 B10 (Cf.) Poly (acrylic acid) esterified with a mixture of 30% octanol, 30% decanol and 40% dodecanol, Mw 23,000 10.2 42 B11 (Cf.) Poly (decyl acrylate) with Mw 19,000 10.0 2.3 B12 (Cf.) Poly (tetradecyl acrylate-co-hexadecyl acrylate) with equal proportions of tetradecyl and hexadecyl acrylate, Mw 24,000 15.0 1.6 B13 (Cf.) Alternating poly (ditetradecylfumarate-altvinylacetate) 14.0 0.4

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 additive mixtures. The results shown in Tables 5 to 7 show that comb polymers with the factor R 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. Ethylene copolymer A Comb polymer B CFPP in test oil 1 1200 ppm 1500 ppm 2000 ppm 1 80% A1 20% B1 -20 -23 -24 2 80% A1 20% B2 -21 -24 -27 3 80% A1 20% B3 -21 -24 -26 4 80% A1 20% B4 -20 -23 -25 5 80% A1 20% B5 -20 -21 -23 6 80% A1 20% B6 -19 -20 -22 7 80% A1 20% B7 -21 -24 -28 8th 80% A1 20% B8 -21 -25 -27 9 80% A1 20% B9 -21 -24 -28 10 (Cf.) 80% A3 20% B9 -19 -19 -21 11 (Cf.) 80% A1 20% B10 -17 -17 -18 12 (Cf.) 80% A1 20% B12 -18 -17 -19 13 (Cf.) 80% A1 20% B13 -18 -18 -17 14 (Cf.) 100% A1 --- -16 -18 -17 15 (V) 100% A2 -15 -18 -17 CFPP testing in test oil E2 Ex. Ethylene copolymer A Comb polymer B CFPP in test oil 2 1200 ppm 1500 ppm 2000 ppm 16 70% A2 30% B1 -21 -25 -27 17 70% A2 30% B2 -21 -24 -28 18 70% A2 30% B3 -21 -23 -26 19 70% A2 30% B4 -20 -23 -24 20 70% A2 30% B5 -20 -22 -23 21 70% A2 30% B6 -19 -21 -22 22 70% A2 30% B7 -20 -23 -25 23 70% A2 30% B8 -20 -23 -26 24 70% A2 30% B9 -21 -24 -27 25 50% A2 50% B9 -20 -23 -25 26 (Cf.) 70% A2 30% B11 -15 -17 -19 27 (Cf.) 70% A2 30% B12 -12 -14 -15 28 (Cf.) 70% A2 30% B13 -16 -18 -19 29 (Cf.) 100% A2 --- -12 -13 -12 CFPP testing in test oil E3 Ex. Ethylene copolymer A Comb polymer B CFPP in test oil E3 1500 ppm 2000 ppm 30 70% A2 30% B2 -20 -25 31 70% A2 30% B3 -19 -24 32 70% A2 30% B4 -20 -26 33 70% A2 30% B9 -20 -25 34 (Cf.) 70% A2 30% B11 -16 -17 35 (Cf.) 70% A2 30% B12 -16 -13 36 (See) 70% A2 30% B13 -15 -15 36 (See) 100% A2 --- -14 -13

Chilling resistance of fatty acid methyl esters

To determine the resistance to cold swelling of an oil, the CFPP value according to DIN EN 116 is compared before and after a standardized cold-change treatment.
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 (18)

A fuel oil composition containing a fuel oil of animal or vegetable origin and an additive containing A) at least one 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) at least one comb polymer containing structural units with C ₈ -C ₁₆ -alkyl radicals, the structural units being selected from C ₈ -C ₁₆ -alkyl (meth) acrylates, C ₈ -C ₁₆ -alkyl vinyl esters, C ₈ -C ₁₆ -alkyl vinyl ethers, C ₈ -C ₁₆ -alkyl (meth) acrylamides, C ₈ -C ₁₆ -alkyl allyl ethers and C ₈ -C ₁₆ -diketenes, where the sum R

the molar average C chain length distribution in the alkyl radicals of monomers B) is 11.0 to 14.0,
wherein

m _1, m ₂ , ... m _g

the mole fractions of the abovementioned monomers B) in the polymer are, the sum of the mole fractions m ₁ to m _g = 1,

w _1i , w _1j ... w _2i , w _2j ... w _gp

the weight fractions of the individual chain lengths i, j,... p of the alkyl radicals of the different monomers B) are 1 to g, and

n _1i , n _1j ... n _2i , n _2j ... n _gp

the chain lengths of the alkyl radicals i, j,... p of the monomers B) are 1 to g.

A fuel oil composition according to claim 1, wherein R is from 11.5 to 13.5 is. A fuel oil composition according to claim 1 and / or 2, wherein in Component A except ethylene 3.5 to 20 mol% vinyl acetate and 0.1 to 12 mol% Vinyl neononanoate, vinyl 2-ethylhexanoate and / or Neodecansäurevinylester are included, wherein the total comonomer content is between 8 and 21 mol%. A fuel oil composition according to one or more of claims 1 to 3, wherein in component A in addition to ethylene and 8 to 18 mol% vinyl esters still 0.5 to 10 mol% of olefins selected from propene, butene, isobutylene, hexene, 4-methylpentene, octene, diisobutylene or norbornene are included. A fuel oil composition according to one or more of claims 1 to 4, wherein the copolymers constituting ingredient A have melt viscosities between 20 and 10,000 mPas. A fuel oil composition according to one or more of claims 1 to 5, wherein the copolymers, constituting the component A, degrees of branching 1-9 CH _3/100 CH ₂ groups, which do not stem from the comonomers have. A fuel oil composition according to one or more of claims 1 to 6, wherein the copolymers constituting ingredient B contain comonomers, which of esters, amides and / or imides of ethylenically unsaturated Carboxylic acids having 3 to 8 carbon atoms and alcohols or amines having 8 to 16 carbon atoms are derived in the alkyl radicals. A fuel oil composition according to one or more of claims 1 to 7, wherein the copolymers constituting ingredient B contain comonomers, which of esters and / or ethers of ethylenically unsaturated alcohols having 2 to 10 C atoms and carboxylic acids or alcohols having 8 to 16 carbon atoms in the Alkyl radicals are derived. A fuel oil composition according to one or more of claims 1 to 8, wherein the copolymers constituting ingredient B contain comonomers, which of esters, amides and / or imides of ethylenically unsaturated Dicarboxylic acids with 4 to 8 carbon atoms and alcohols or amines with 8 to 16 C atoms are derived in the alkyl radicals. A fuel oil composition according to one or more of claims 1 to 9, wherein the copolymers constituting ingredient B contain comonomers, which are derived from α-olefins having 10 to 20 carbon atoms. A fuel oil composition according to one or more of claims 1 to 10, wherein the comonomers of which constituent B is composed in contain essential linear alkyl radicals. A fuel oil composition according to one or more of claims 1 to 11, wherein the average molecular weight of the copolymers B is between 1,000 and 100,000 g / mol. A fuel oil composition according to one or more of claims 1 to 12, containing polar nitrogen-containing paraffin dispersants. A fuel oil composition according to one or more of claims 1 to 13, 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 one or more of claims 1 to 14, characterized in that the alcohol is methanol or ethanol. A fuel oil composition according to one or more of claims 1 to 15, 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 13 for improving the cold flow properties of fuel oil animal or of plant origin. An additive as defined in one or more of claims 1 to 12.