DE10357877B4 - Fuel oils from middle distillates and oils of vegetable or animal origin with improved cold properties - Google Patents

Abstract

der molaren Mittel der C-Kettenlängenverteilungen in den Alkylresten von Monomer 1 einerseits und den Alkylresten der Estergruppen von Monomer 2 andererseits von 21,0 bis 28,0 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 Estergruppen...Fuel oil composition F) containing
F1) 89-50% by volume of a fuel oil of mineral origin and
F2) 11-50 vol .-% of a fuel oil of vegetable and / or animal origin, and as a cold additive, the ingredients
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 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 ₁₈ -alkyl radical bonded via an ester grouping,
where the sum Q

the molar average of C chain length distributions in the alkyl radicals of monomer 1 on the one hand and the alkyl radicals of the ester groups of monomer 2 on the other hand is from 21.0 to 28.0, wherein
w _{1 is} the molar fraction of the individual chain lengths in the alkyl radicals of monomer 1,
w _{2 is} the molar fraction of the individual chain lengths in the alkyl radicals of the ester groups ...

Description

The The present invention relates to mineral fuel oils containing Ingredients of plant or animal origin with improved cold properties and the use of an additive as a cold flow improver for such Fuel oils.

As world biodiesel reserves decline and the environmental consequences of fossil and mineral fuel consumption increase, so does the interest in alternative energy sources based on renewable raw materials (biofuels). 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 amounts 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 of 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 the Generally, such oils contain Glycerides of a range of acids, their number and variety varies with the source of the oil, and they may additionally contain phosphoglycerides contain. Such oils can obtained by methods known in the art.

On Reason for the partially unsatisfactory physical properties triglycerides, the technique has evolved to the naturally occurring ones Triglycerides in fatty acid esters lower alcohols such as methanol or ethanol to convert.

When Obstacle to the use of lower monovalent fatty acid esters Alcohols as diesel fuel substitutes alone have their behavior across from Engine parts, in particular various sealing materials proven again and again to failures with these from renewable Raw materials produced fuel-powered engines. to Bypassing these problems will be a use of these on renewable Raw materials based oils preferred as an admixture to conventional middle distillates.

Of Another has been in the use of triglycerides as well of fatty acid esters lower monohydric alcohols than diesel fuel substitute alone or mixed with diesel fuel, the flow behavior at low temperatures proved to be an obstacle. The reason for this is especially their salary more saturated with esters fatty acids as well as the high uniformity (less than 10 main components) these oils compared to mineral oil middle distillates. Thus, e.g. Rapsölsäuremethylester (RME) a cold filter plugging point (CFPP) of -14 ° C, soybean oil methyl ester a CFPP of -5 ° C, Altfettmethylester a CFPP of + 1 ° C, and animal fat a CFPP of + 9 ° C. With the additives of the prior art, it is often so far not possible, based on these esters or mineral diesel containing these esters one for the use as winter diesel in Central Europe demanded CFPP value from -20 ° C also for special applications of -22 ° C and sure to stop. This problem is exacerbated when Use of oils, the larger quantities of also easily accessible oils of sunflowers and soy included.

EP-B-0 665 873 discloses a fuel oil composition containing a biofuel, a fuel based on petroleum and an additive comprising (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 substantially linear alkyl group having 10 to 30 carbon atoms with a non-polymeric organic radical to provide at least one linear chain of atoms which includes the carbon atoms of the alkyl groups and one or more 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 nicht-additivierten, 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 in that

• 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.

• – C₃- bis C₁₈-α-Ölefinhomopolymere
• – Copolymere aus C₃- bis C₁₈-α-Olefine mit Estern ungesättigter Mono- und Dicarbonsäuren
• – Homopolymere von Vinylestern oder (Meth)Acrylsäureestern
• – Copolymere von Vinylestern oder (Meth)Acrylsäureestern und Dicarbonsäureester
• – stickstoffhaltige Copolymere

erhalten werden. Das Dokument offenbart dagegen keine Mischung aus den Bestandteilen A und B des vorliegenden Anspruchs 1. FR-A-1 561 581 discloses polymers obtained by grafting of ethylene

• C ₃ to C ₁₈ α-olefin homopolymers
• - Copolymers of C ₃ - to C ₁₈ -α-olefins with esters of unsaturated mono- and dicarboxylic acids
• Homopolymers of vinyl esters or (meth) acrylic acid esters
• - Copolymers of vinyl esters or (meth) acrylic acid esters and dicarboxylic acid esters
• - nitrogen-containing copolymers

to be obtained. In contrast, the document does not disclose a mixture of components A and B of present claim 1.

• – ein Ethylen/Vinylester-Copolymer, und
• – ein Pfropfprodukt aus einem Dicarbonsäureester und einem Ethylen/Vinylacetat-Copolymer

enthalten. Ein Pfropfprodukt aus einem Dicarbonsäureester und einem Ethylen/Vinylacetat-Copolymer ist jedoch nicht identisch zum Bestandteil B gemäß vorliegendem Hauptanspruch. Dieser verlangt ein Copolymer aus einem Dicarbonsäureester und einem C₈- bis C₁₈-Olefin. JP-A-11-181453 discloses fuel oils used as a cold additive

• An ethylene / vinyl ester copolymer, and
• A graft product of a dicarboxylic acid ester and an ethylene / vinyl acetate copolymer

contain. However, a graft product of a dicarboxylic acid ester and an ethylene / vinyl acetate copolymer is not identical to the component B according to the present main claim. This requires a copolymer of a dicarboxylic acid ester and a C ₈ to C ₁₈ olefin.

• – ein Pfropfprodukt aus einem Dicarbonsäureester und einem Ethylen/Vinylester-Copolymer, und
• – das Veresterungsprodukt aus alkoxyliertem Glycerin und einer gesättigten Fettsäure.

JP-A-10-245 574 discloses an effective as a cold additive additive composition comprising

• A graft product of a dicarboxylic acid ester and an ethylene / vinyl ester copolymer, and
• The esterification product of alkoxylated glycerine and a saturated fatty acid.

none these constituents are the additive constituents A according to the invention and B also chemically similar. The components A and B are neither grafted products nor alkoxylate ester.

JP-A-10-237469 discloses a cold-additive composition comprising

• - one A grafted product of a dicarboxylic acid ester and an ethylene / vinyl ester copolymer, and
• - one Partial ester of possibly alkoxylated triol and fatty acid.

Also here exists between the additive risers disclosed in this document and the components of the invention A and B no chemical similarity.

EP-A-0 214 786 discloses additive combinations which correspond to the features for components A and B of the present main claim. However, the main claim is not directed to an additive combination but to a fuel oil composition. In addition to the additive combination, this fuel oil composition must comprise a mixture of 50 to 89% by volume of one, mineral and 11 to 50% by volume of a vegetable / animal fuel oil. The disclosure of this document at least lacks the latter feature of a vegetable or animal fuel oil content.

EP-A-0 441 548 discloses copolymers which, in addition to structural elements of α-olefins, comprise those of monounsaturated dicarboxylic acids. However, the document lacks any disclosure to modify such copolymers to include ester groups of C ₈ to C ₁₆ alcohols. The document also fails to disclose the use of these copolymers with ethylene-vinyl ester copolymers.

With the known additives it is often not possible, fatty acid esters containing middle distillates to one for use as winter diesel in Central Europe demanded CFPP value of -20 ° C as well as for special applications of -22 ° C and sure to stop. Problematic with the known additives is about it In addition, a lack of sedimentation stability of the additized oils. The Paraffins and fatty acid esters precipitating below the cloud point sediment at prolonged Storage below the cloud point and lead to the bottom of the storage container Formation of a phase with worse cold properties. It consisted thus the task of fuel oils with improved cold properties available too provide middle distillates and fatty acid esters, wherein the CFPP values at -20 ° C and underneath. Furthermore, the sedimentation should be more unusual Paraffins and fatty acid esters at longer Storage of the fuel oil in the area of its cloud point or slowed down or prevented become.

Surprisingly It has now been found that fuel oils from middle distillates and vegetable oils and / or animal origin, which is an ethylene copolymer and certain Comb polymers containing additive, excellent cold properties demonstrate.

• F1) ein Brennstofföl mineralischen Ursprungs und
• F2) ein Brennstofföl pflanzlichen und/oder tierischen Ursprungs, und

als Kälteadditiv die Bestandteile

• 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 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 Estergruppen von Monomer 2 andererseits von 21,0 bis 28,0 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 Estergruppen von Monomer 2,

n₁

die einzelnen Kettenlängen in den Alkylresten von Monomer 1,

n₂

die einzelnen Kettenlängen in den Alkylresten der Estergruppen 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 Estergruppen von Monomer 2 sind.

The invention thus relates to a fuel oil composition F) containing

• F1) a fuel oil of mineral origin and
• F2) a fuel oil of vegetable and / or animal origin, and

as a cold additive, the ingredients

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

where the sum Q

the molar average of C chain length distributions in the alkyl radicals of monomer 1 on the one hand and the alkyl radicals of the ester groups of monomer 2 on the other hand is from 21.0 to 28.0, 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 ester 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 ester 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 ester groups of monomer 2.

One Another object of the invention is the use of the above defined Additive containing the components A) and B), for improvement the cold flow properties of fuel oil compositions F), containing fuel oils mineral (F1) and animal and / or vegetable (F2) origin.

One Another object of the invention is a process for the preparation of fuel oil compositions F) containing fuel oils mineral (F1) and animal and / or vegetable (F2) origin, with improved cold properties, by mixing the mixture of fuel oils mineral (F1) and animal and / or vegetable (F2) origin as defined above Additive containing the components A) and B), added.

Preferred oils mineral Origin are middle distillates. The mixing ratio between the fuel oils animal and / or vegetable origin (which is also hereafter as biofuel oils are designated) and middle distillates is preferably between 88 to 65 vol.% Middle distillate and 12 to 35 vol.% Biofuel oil. this Mixtures impart superior properties to the additives of the invention Cold properties.

In a preferred embodiment of the invention takes Q values between 22.0 and 27.0, in particular 23.0-26.0 and, for example, 23, 24, 24.5, 25 or 26.

Under Side chain length of olefins here is the outgoing from the polymer backbone alkyl radical understood, so the chain length of the monomeric olefin minus the two olefinically bound C atoms. For olefins with not terminal Double bonds, e.g. Olefins with vinylidene grouping is the corresponding Total chain length of 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 vinyl and / or (meth) acrylic esters and from 79 to 92% by weight of 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. Examples which may be mentioned are vinyl acetate, vinyl propionate, vinyl butyrate, vinyl hexanoate, Vinylheptanoat, 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-Nonansäurevinylester, Neononansäurevinylester, vinyl neodecanoate and Neoundecansäurevinylester. 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 isobutyl (meth) acrylate, Hexyl, octyl, 2-ethylhexyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl (meth) acrylate and mixtures of two, three, four or more of these Comono mers.

Especially preferred terpolymers of vinyl 2-ethylhexanoate, vinyl neononanoate or the Neodecansäurevinylesters included except Ethylene preferably 3.5 to 20 mol%, in particular 8 to 15 mol% Vinyl acetate and 0.1 to 12 mol%, in particular 0.2 to 5 mol% of respective long-chain vinyl ester, the total comonomer content is between 8 and 21 mol%, preferably between 12 and 18 mol%. Other preferred copolymers contain in addition to ethylene and 8 bis 18 mol% of vinyl esters or 0.5 to 10 mol% of 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 by the usual Copolymerization processes such as suspension polymerization, solution 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 up to 300 ° C, preferably 150 to 220 ° C carried out. In a particularly preferred production variant, the Polymerization in a multi-zone reactor, the temperature difference between the peroxide doses along the tubular reactor as possible is kept low, i. <50 ° C, preferably <30 ° C, in particular <15 ° C. Prefers the temperature maxima differ in the individual reaction zones less than 30 ° C, more preferably less than 20 ° C and especially less than 10 ° C.

The Reaction of the monomers is by radical-forming 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 singly 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.

The high-pressure mass polymerization is carried out batchwise or continuously in known high-pressure reactors, for example autoclaves or tubular reactors, tube reactors have proven particularly useful. Solvents such as aliphatic and / or aromatic hydrocarbons or hydrocarbon mixtures, benzene or toluene may be present in the reaction mixture. Preferred is the substantially solvent-free operation. In a preferred embodiment of the polymerization, the mixture of the monomers, the initiator and, if used, the moderator, a tubular reactor via the reactor inlet and via one or more side branches supplied. Preferred moderators are, for example, hydrogen, saturated and unsaturated hydrocarbons such as 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 as butanol. The comonomers as well as the moderators can be metered into the reactor both together with ethylene and separately via side streams. In this case, the monomer streams can be composed differently ( EP-A-0 271 738 and EP-A-0 922 716 ).

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;
from DE-A-34 43 475 known ethylene-vinyl acetate-hexene terpolymers;
in the EP-B-0 203 554 described ethylene-vinyl acetate-diisobutylene terpolymers;
from EP-B-0 254 284 known mixture of an ethylene-vinyl acetate-diisobutylene terpolymer and an ethylene / vinyl acetate copolymer;
in the EP-B-0 405 270 disclosed blends of an ethylene-vinyl acetate copolymer and an ethylene-vinyl acetate-N-vinylpyrrolidone terpolymer;
in the EP-B-0 463 518 described ethylene / vinyl acetate / iso-butyl vinyl ether terpolymers;
from EP-B-0 493 769 known ethylene / vinyl acetate / vinyl neononanoate or vinyl neodecanoate terpolymers containing, in addition to ethylene, 10-35% by weight of vinyl acetate and 1-25% by weight of the respective neo compound;
in the EP 0778875 described terpolymers 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 carbon atoms or a branched but not tertiary carboxylic acid having 8 to 15 carbon atoms;
in the DE-A-196 20 118 described terpolymers of ethylene, the vinyl ester of one or more aliphatic C ₂ - to C ₂₀ monocarboxylic acids and 4-methylpentene-1;
in the DE-A-196 20 119 disclosed terpolymers 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;
in the EP-A-0 926 168 described terpolymers of ethylene and at least one olefinically unsaturated comonomer containing one or more hydroxyl groups.

Prefers are mixtures of identical or different ethylene copolymers used. Particularly preferably, the mixtures differ underlying 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 are preferably 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 copolymers of ethylenically unsaturated Dicarboxylic acids and their derivatives such as lower esters and anhydrides. Prefers are maleic acid, fumaric acid, itaconic and especially maleic anhydride. As comonomers are monoolefins 10 to 20, in particular with 12-18 carbon atoms particularly suitable. These are preferably linear and the double bond is preferably terminal such as for example Dodecene, tridecene, tetradecene, pentadecene, hexadecene, heptadecene and octadecene. The relationship of maleic anhydride to olefin or olefins in the polymer is preferably in the range 1: 1.5 to 1.5: 1, especially equimolar.

In minor amounts of up to 20 mol%, preferably <10 mol%, especially <5 mol%, it is also possible to contain further comonomers which are copolymerizable with maleic anhydride and the olefins mentioned, for example shorter-chain 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.Alkyl polyglycol ethers correspond to the general formula

wherein
R ^{1 is} hydrogen or methyl,
R ^{2 is} hydrogen or C ₁ -C ₄ -alkyl,
m is a number from 1 to 100,
R ^{3 is} C ₁ -C ₂₄ -alkyl, C ₅ -C ₂₀ -cycloalkyl, C ₆ -C ₁₈ -aryl or -C (O) -R ⁴ ,
R ^{4 is} 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 method of preparation is solvent-free bulk polymerization, but it is also possible to carry out the polymerization in the presence of aprotic solvents such as benzene, toluene, xylene or higher-boiling aromatic, aliphatic or isoaliphatic solvents or solvent mixtures such as kerosene or solvent naphtha less moderating, aliphatic or isoaliphatic solvents. The proportion of solvent in the polymerization mixture is generally between 10 and 90 wt .-%, preferably between 35 and 60 wt .-%. 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 can be easily adjusted.

The mean molecular mass the copolymers of the invention B is generally 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. Copolymers of the invention B need be oil-soluble in practice-relevant dosing quantities, that means they have to be in the oil to be added residue-free at 50 ° C to solve.

The Reaction of the monomers is by radical-forming initiators (Radical chain starter) initiated. This class of substance includes e.g. Oxygen, hydroperoxides and peroxides such as. For example, 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. 2,2'-azo-bis (2methylpropanonitril) or 2,2'-azobis (2-methylbutyronitrile). The initiators are used singly 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.

The Copolymers can either by esterification of maleic, fumaric and / or itaconic acid with the corresponding alcohols and subsequent copolymerization or by copolymerization of olefin or olefins with itacon and / or maleic anhydride and subsequent Esterification can be produced. Preference is given to a copolymerization carried out with anhydrides and esterified the resulting copolymer after preparation.

These Esterification occurs in both cases for example, by reaction with 0.8 to 2.5 moles of alcohol per mole Anhydride, vorzut with 1.0 to 2.0 moles of alcohol per mole of anhydride at 50 to 300 ° C. When using about 1 mole of alcohol per mole of anhydride arise Halbester. Here, esterification temperatures of about 70 to 120 ° C are preferred. When using larger quantities Alcohol, preferably 2 moles of alcohol per mole of anhydride formed at 100-300 ° C, preferably 120-250 ° C Diester. The water of reaction can by means of an inert gas stream distilled off or in the presence of an organic solvent be discharged by azeotropic distillation. To be favoured to 20-80, especially 30-70, especially 35-55 wt .-% at least an organic solvent used. As half ester here are copolymers with acid numbers from 30-70 mg KOH / g, preferably from 40-60 mg KOH / g. copolymers with acid numbers less than 40, especially less than 30 mg KOH / g are considered Diester considered. Particularly preferred are half esters.

suitable Alcohols are particularly linear, but they may also be subordinate Quantities, e.g. up to 30% by weight, preferably up to 20% by weight and especially up to 10 wt .-% (in 1- or 2-position) branched alcohols. shorter- as well as longer-chained ones Alcohols can used, but their proportion is preferably below 20 mol% and especially below 10 mol% such as between 1 and 5 mol% based on the total amount of the alcohols used. at the calculation of the Q-factor these shorter and longer alcohols, if present, not considered, because they do not contribute to the effectiveness of the additives.

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

By Use of mixtures of different olefins in the polymerization and mixtures of different alcohols in the esterification, the Effectiveness further adapted to specific fatty acid ester compositions become.

In a preferred embodiment mixtures of the copolymers B of the invention are used, with the proviso that the mean of the Q values of the mixture components turn Values from 21.0 to 28.0, preferably values from 22.0 to 27.0 and especially Values from 23.0 to 26.0.

The mixing ratio the additives of the invention A and B 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 of the invention are added to oils in amounts of 0.001 to 5 wt .-%, preferably 0.005 to 1 wt .-% and especially 0.01 to 0.5 wt .-%. They may be dissolved as such or dissolved or dispersed in solvents, such as aliphatic and / or aromatic hydrocarbons or hydrocarbon mixtures such as toluene, xylene, ethylbenzene, decane, pentadecane, gasoline fractions, kerosene, Naphtha, diesel, heating 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 dissolved in fuel oil of animal or vegetable origin based on fatty acid alkyl esters. The additives according to the invention preferably contain 1-80%, especially 10-70%, in particular 25-60% of solvent.

In a preferred embodiment is the fuel oil F2, which is often referred to as "biodiesel", "biofuel" or "biofuel", to fatty acid alkyl esters from fatty acids with 12 to 24 C atoms and alcohols with 1 to 4 C atoms. Usually contains a larger part of fatty acids one, two or three double bonds.

Examples for oils F2, the derived from animal or vegetable material, and the used according to the invention can be 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 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. Also called biodiesel designated fatty acid alkyl esters can from these oils be derived by methods known in the art. Rapeseed oil, which is a mixture of glycerol partially esterified fatty acids, is preferred because it is in large Quantities available is and is easily obtainable by squeezing rapeseed. Furthermore, the also widespread oils of sunflowers and soy, as well as their mixtures with rapeseed oil.

Especially suitable as biofuels F2) are lower alkyl esters of fatty acids. Here come, for example, commercially available Mixtures of ethyl, propyl, butyl and especially methyl esters of fatty acids with 14 to 22 carbon atoms, for example of 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 into consideration, which preferably has an iodine value of 50 to 150, in particular 90 to 125 have. Mixtures with particularly advantageous properties are those that are mainly, i.e. at least 50 wt .-%, methyl esters of fatty acids with Contain 16 to 22 carbon atoms and 1, 2 or 3 double bonds. The preferred lower alkyl esters of fatty acids are the methyl esters of oleic, linoleic, linolenic and Erucic acid.

Commercially available mixtures of the type mentioned are, for example, by cleavage and esterification or by transesterification of animal and vegetable fats and oils with obtained lower aliphatic alcohols. The same are the same used cooking oils suitable as starting materials. For the preparation of lower alkyl esters of fatty acids it is advantageous to start with high iodine fats and oils, 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 Rapeseed oil, whose fatty acid component to more than 80% by weight of unsaturated fatty acids derived with 18 carbon atoms are preferred.

Consequently is a biofuel an oil, obtained from vegetable or animal material or both or a derivative thereof, which is used as fuel and in particular as diesel or heating oil can be used. Although many of the above oils are used as biofuels can be vegetable oil derivatives are preferred, particularly preferred biofuels alkyl ester derivatives of Rapeseed oil, cottonseed, Soybean oil, sunflower oil, olive oil or palm oil, wherein rapeseed methyl, Sonnenblumenölsäuremethylester and soybean oil methyl ester are very particularly preferred. Particularly preferred as biofuel or as component in the biofuel are also Altfettester such as used fat methyl ester.

When mineral component F1 are especially suitable middle distillates, by distillation of crude oil be recovered and boiling in the range of 120 to 450 ° C, for example kerosene, Jet-fuel, diesel and fuel oil. Preferably, such middle distillates are used, the 0.05 % By weight of sulfur and less, more preferably less than 350 ppm sulfur, especially less than 200 ppm sulfur and in special make less than 50 ppm sulfur, such as less than 10 ppm Containing sulfur. These are generally such Middle distillates subjected to hydrogenating refining were, and therefore only small proportions of polyaromatic and contain polar compounds. Preferably, it is such middle distillates, the 95% distillation points below 370 ° C, in particular 350 ° C and in special cases below 330 ° C exhibit. Also, synthetic fuels, as for example after The Fischer-Tropsch process are available as middle distillates suitable.

The additive may be added to the oil to be added according to methods known in the art be led. When more than one additive component or co-additive component is to be used, such components may be incorporated into the oil together or separately in any combination and order.

With the additives of the invention let yourself the CFPP value of blends of biodiesel and mineral oils far improve more efficiently than with the known additives of the state of the technique. The additives according to the invention are particularly advantageous in oil blends, their mineral oil component F1) has a boiling width between the 20 and 90% distillation point less than 120 ° C, in particular less than 110 ° C and especially less than 100 ° C having. About that In addition, they are particularly advantageous in oil mixtures, their mineral oil component F1) a cloud point of below -4 ° C, especially from -6 ° C to -20 ° C such as from -8 ° C to -20 ° C has, as for an insert can be used especially in winter. The same is the pour point of the mixtures according to the invention by the addition the additives of the invention reduced. The additives of the invention are particularly advantageous in oil blends, more than 11% by volume of biofuel F2, preferably more than 12% Vol .-% biofuel F2 and especially more than 15 vol .-% biofuel F2 such as 15 to 35% by volume of biofuel F2 included. The additives of the invention are beyond particularly advantageous in problematic oils whose biofuel component F2 has a high content of saturated fatty acid esters of more than 4%, in particular more than 5% and especially from 7 to Contains 25% such as from 8 to 20%, as for example in oils Sunflowers and soy are the case. Such biofuels have prefers a cloud point of about -5 ° C and especially from over -3 ° C. oil mixtures F), in which the additives according to the invention show particularly advantageous effect, preferably have cloud points from above -9 ° C and especially from above -6 ° C. It succeeds with the additives according to the invention thus, rapeseed oil methyl ester and sunflower and / or soybean oil fatty acid methyl esters containing oil mixtures to CFPP values of -22 ° C and adjust below.

to Production of additive packages for special problem solutions can the additives of the invention also be used together with one or more oil-soluble co-additives that already for themselves only the cold flow properties of crude oils, lubricating oils or fuel oils improve. Examples of such co-additives are polar compounds, which differ from the polymers of the invention B and which cause a paraffin dispersion (paraffin dispersants), Alkylphenol condensates, esters and ethers of polyoxyalkylene compounds, Olefin copolymers and oil-soluble amphiphiles.

Thus, the additives according to the invention can be used to further reduce the sedimentation in the cold precipitated paraffins and fatty acid esters in admixture with paraffin dispersants. Paraffin dispersants reduce the size of the paraffin and fatty acid ester crystals and cause the paraffin particles to not settle but remain colloidally dispersed with significantly reduced sedimentation effort. Suitable paraffin dispersants are both low molecular weight and polymeric, oil-soluble compounds having ionic or polar groups such as amine salts and / or amides have proven. Particularly preferred paraffin dispersants contain reaction products of secondary fatty amines having 20 to 44 carbon atoms, in particular dicocoamine, ditallow fatty amine, distearylamine and dibehenylamine with carboxylic acids and derivatives thereof. Paraffin dispersants which have been obtained by reaction of aliphatic or aromatic amines, preferably long-chain aliphatic amines, with aliphatic or aromatic mono-, di-, tri- or tetracarboxylic acids or their anhydrides have proven particularly suitable (cf. US 4 211 534 ). Likewise, amides and ammonium salts of aminoalkylene polycarboxylic acids such as nitrilotriacetic acid or ethylenediaminetetraacetic acid with secondary amines are suitable as paraffin dispersants (cf. EP 0 398 101 ). Other paraffin dispersants are copolymers of maleic anhydride and α, β-unsaturated compounds, which can optionally be reacted with primary monoalkylamines and / or aliphatic alcohols (cf. EP 0 154 177 ) and the reaction products of alkenyl spiro-bis-lactones with amines (cf. 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.

Alkylphenol-aldehyde resins are for example in Römpp Chemie Lexikon, 9th edition, Thieme Verlag 1988-92, Volume 4, p 3351 ff. described. The alkyl radicals of the o- or p-alkylphenol can in the with the inventive additives usable alkylphenol-aldehyde resins same or different be and have 1-50, preferably 1-20, especially 4-12 carbon atoms; it is preferably n-, iso- and tert-butyl, n- and isopentyl, n- and iso-hexyl, n- and iso-octyl, n- and iso-nonyl, n- and iso-decyl, n- and iso-dodecyl and octadecyl. The aliphatic aldehyde in the alkylphenol-aldehyde resin preferably has 1-4 carbon atoms. Especially preferred Aldehydes are formaldehyde, acetaldehyde and butyraldehyde, in particular Formaldehyde. The molecular weight of the alkylphenol-aldehyde resins is 400-10,000, preferably 400-5000 g / mol. Condition is that the resins are oil-soluble.

worin R⁵ für C₁-C₅₀-Alkyl oder -Alkenyl und n für eine Zahl von 2 bis 100 steht. Bevorzugt steht R⁵ für C₄-C₂₀-Alkyl oder -Alkenyl und insbesondere für C₆-C₁₆-Alkyl oder -Alkenyl. Bevorzugt steht n für eine Zahl von 4 bis 50 und speziell für eine Zahl von 5 bis 25.In a preferred embodiment of the invention, these alkylphenol-formaldehyde resins are those which are oligomers or polymers having a repeating structural unit of the formula

wherein R ^{5 is} C ₁ -C ₅₀ alkyl or alkenyl and n is a number from 2 to 100. R ⁵ is preferably C ₄ -C ₂₀ -alkyl or -alkenyl and in particular C ₆ -C ₁₆ -alkyl or -alkenyl. Preferably, n is a number from 4 to 50 and especially from 5 to 25.

Further suitable flow improvers are polyoxyalkylene compounds such as esters, ethers and Ether / ester, the at least one alkyl radical having 12 to 30 carbon atoms wear. When the alkyl groups are derived from one acid, the remainder comes from a polyhydric alcohol; the alkyl radicals come from a fatty alcohol, so the rest of the compound is from a polyacid.

suitable Polyols are polyethylene glycols, polypropylene glycols, polybutylene glycols and their copolymers having a molecular weight of about 100 to about 5000, preferably 200 to 2000. Further suitable Alkoxylates of polyols, such as glycerin, trimethylolpropane, Pentaerythritol, neopentyl glycol, as well as the resulting from condensation accessible Oligomers having 2 to 10 monomer units, such as e.g. Polyglycerol. Preferred alkoxylates are those having 1 to 100, in particular 5 to 50 moles of ethylene oxide, propylene oxide and / or butylene oxide per mole Polyol. Esters are especially preferred.

Fatty acids containing 12 to 26 carbon atoms are preferred for reaction with the polyols to form the ester additives, preferably using C ₁₈ to C ₂₄ fatty acids, especially stearic and behenic acid. The esters can also be prepared by esterification of polyoxyalkylated alcohols. Preference is given to completely esterified polyoxyalkylated polyols having molecular weights of 150 to 2,000, preferably 200 to 1,500. Particularly suitable are PEG-600 dibehenate and glycerol-ethylene glycol tribehenate.

When Component of the additive according to the invention suitable olefin polymers can derived directly from monoethylenically unsaturated monomers or indirectly by hydrogenation of polymers differing several times unsaturated Derive monomers such as isoprene or butadiene. Preferred copolymers contain, in addition to ethylene, structural units, derived from α-olefins with 3 to 24 carbon atoms and molecular weights of up to 120,000. Preferred α-olefins are propylene, butene, isobutene, n-hexene, isohexene, n-octene, isooctene, n-decene, isodecene. The comonomer content of olefins is preferably between 15 and 50 mol%, more preferably between 20 and 35 mol% and specifically between 30 and 45 mol%. These copolymers can also small quantities, e.g. up to 10 mol% of other comonomers such as e.g. not terminal Olefins or non-conjugated olefins contain. Preferred are Ethylene-propylene copolymers. The olefin copolymers can after prepared methods, e.g. using Ziegler or Metallocene catalysts.

Other suitable olefin copolymers are block copolymers containing blocks of olefinically unsaturated aromatic monomers A and blocks of hydrogenated polyolefins B. Particularly suitable are block copolymers of the structure (AB) _n A and (AB) _m , where n is a number between 1 and 10 and m is a number between 2 and 10.

The mixing ratio (in parts by weight) of the additives according to the invention with paraffin dispersants, comb polymers, Alkylphenol condensates, polyoxyalkylene derivatives or olefin copolymers is each 1:10 to 20: 1, preferably 1: 1 to 10: 1 such as 1: 1 to 4: 1.

The Additives can used alone or together with other additives, 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 additions to the Cloud Point.

Examples

Characterization of the test oils:

• RME = Rapsölsäuremethylester;
• SBME = Sonnenblumenölsäuremethylester;
• SojaME = Sojaölsäuremethylester

Tabelle 3: Charakterisierung der eingesetzten Mineralöle (F1) D 1 D 2 D 3 Siedebeginn 193°C 181°C 200°C 20 % Destillation 230°C 235°C 247°C 90 % Destillation 332°C 344°C 339°C 95 % Destillation 348°C 361°C 358°C (90-20) % Destillation 102°C 109°C 92°C Cloud Point -6,0°C -8,2°C -4,7°C CFPP -8°C -12°C -9°C S-Gehalt 20 ppm 32 ppm 9 ppm The CFPP value is determined according to EN 116 and the determination of the cloud point according to ISO 3015. Both properties are determined in ° C. Table 1: Characterization of the biofuel oils used (F2) 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% soybean oil methyl ester -2.0 -8 ° C Table 2: C chain distribution of the fatty acid methyl esters used for the preparation of the test oils (main constituents,% by volume according to GC): C ₁₆ C ₁₆ ' C ₁₈ C ₁₈ ' C ₁₈ '' C ₁₈ ''' C ₂₀ C ₂₀ ' C ₂₂ Σ saturated RME 4.5 0.5 1.7 61.6 18.4 8.7 0.7 1.5 0.4 7.3 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

Table 3: Characterization of the mineral oils used (F1) D 1 D 2 D 3 Initial boiling point 193 ° C 181 ° C 200 ° C 20% distillation 230 ° C 235 ° C 247 ° C 90% distillation 332 ° C 344 ° C 339 ° C 95% distillation 348 ° C 361 ° C 358 ° C (90-20)% distillation 102 ° C 109 ° C 92 ° C Cloud point -6.0 ° C -8.2 ° C -4.7 ° C CFPP -8 ° C -12 ° C -9 ° C S content 20 ppm 32 ppm 9 ppm

The following Additives were used:

Ethylene copolymers A

The ethylene copolymers used are commercial products having the characteristics given in Table 4. The products were used as 65% settings in kerosene. Table 4: Characterization of the ethylene copolymers (A) used example Comonomer (s) V140 CH _3/100 CH 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 i) 14.0 mol% vinyl acetate and 1.6 mol% vinyl neodecanoate and 97 mPas 4.7 ii) 12.9 mol% of vinyl acetate in the ratio i): ii) of 6: 1 145 mPas 5.4

Comb polymers B

The Polymerization of maleic anhydride (MSA) with α-olefins takes place in a higher boiling aromatic Hydrocarbon mixture at 160 ° C in the presence of a mixture of equal parts tert-butyl peroxybenzoate and tert-butyl peroxy-2-ethylhexanoate as a radical chain starter. Table 5 shows various examples Copolymers and the molar fractions used for their preparation the monomers as well as the chain length and molar amount (based on MSA) of the used for derivatization Alcohol and the calculated factor Q listed.

• n.a. = nicht anwendbar (V) = Vergleichsbeispiel

The esterifications are carried out in the presence of solvent naphtha (40 to 50 wt .-%) at 90 to 100 ° C for half ester and at 160 to 180 ° C with azeotropic culling of water of reaction to the diester. The degree of esterification is inversely proportional to the acid number. Table 5: Characterization of the comb polymers used (B) example comonomers alcohol Q Acid number [mg KOH / g] B1 MSA-co-C12 / 14 α-olefin (1: 0.5: 0.5) C10 21.0 14.0 B2 MSA-co-C12 / 14 α-olefin (1: 0.5: 0.5) C12 23.0 51.1 B3 MSA-co-C14 / 16 α-olefin (1: 0.5: 0.5) C10 23.0 8.5 B4 MSA-co-C14 / 16 α-olefin (1: 0.5: 0.5) C12 25.0 48.2 B5 MSA-co-C14 / 16 α-olefin (1: 0.5: 0.5) C14 27.0 51.0 B6 MSA-co-C14 / 16 α-olefin (1: 0.5: 0.5) 85% C12 15% C16 25.6 49.9 B7 MSA-co-C16 α-olefin (1: 1) C12 26.0 12.3 B8 MSA-co-C16 α-olefin (1: 1) C10 24.0 47.9 B9 MSA-co-C14 / 16-α-olefin-co-allyl-methylpolyglycol (1: 0.45: 0.45: 0.1) C12 25.0 45.8 B10 (V) MSA-co-C10 α-olefin (1: 1) C12 20.0 48.8 example comonomers alcohol Q Acid number [mg KOH / g] B11 (V) MSA-co-C14 / 16 α-olefin (1: 0.5: 0.5) C16 29.0 16.5 B12 (V) Fumarate-vinyl acetate C14 n / A 0.4

• na = not applicable (V) = Comparative Example

Other flow improvers

The further flow improvers used C are commercial products with the characteristics given in Table 6. The products were used as 50% settings in solvent naphtha. Table 6: Characterization of the further flow improvers used C3 Reaction product of a copolymer of C ₁₄ / C ₁₆ olefin and maleic anhydride with 2 equivalents of secondary tallow fatty amine per maleic anhydride unit C4 Reaction product of phthalic anhydride with 2 equivalents of di (hydrogenated tallow fatty amine) to the amide ammonium salt C5 Nonylphenol resin prepared by condensing a mixture of dodecylphenol with formaldehyde, Mw 2000 g / mol C6 Mixture of 2 parts C3 and 1 part C5 C7 Mixture of equal parts C4 and C5

Effectiveness of the additives

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. Table 7: CFPP testing in a mixture of 75% by volume of test oil D 1 and 25% by volume of test oil E1 (CP = -5.2 ° C., CFPP = -9 ° C.) Ex. flow Comb polymer / CFPP after addition of flow improver improvers co-additive 50 ppm 100 ppm 150 ppm 200 ppm 1 A2 150 ppm B1 -15 -17 -19 -21 2 A2 150 ppm B2 -14 -18 -20 -22 3 A2 150 ppm B3 -18 -19 -19 -21 4 A2 150 ppm B4 -19 -21 -22 -23 5 A2 150 ppm B5 -20 -21 -21 -21 6 A1 150 ppm B6 -20 -20 -22 -23 7 A1 100 ppm B7 -19 -20 -20 -22 8th A1 100 ppm B8 -19 -19 -20 -21 9 A1 100 ppm B9 -21 -20 -22 -23 10 A2 75ppm B4 75ppm A4 -19 -21 -23 -26 11 (V) A2 150 ppm B10 -12 -14 -17 -19 12 (V) A2 150 ppm B11 -7 -11 -16 -18 13 (V) A2 150 ppm B12 -10 -11 -15 -20 14 (V) A2 - -11 -16 -17 -19 Table 8: CFPP testing in a mixture of 70% by volume of test oil D2 and 30% by volume of test oil E3 (CP = -5.8 ° C., CFPP = -12 ° C.) Ex. Ethylene copolymer comb polymer co-additive CFPP 100 ppm 150 ppm 200 ppm 300 ppm 15 80% A3 20% B1 150 ppm C6 -20 -20 -21 -24 16 80% A3 20% B2 150 ppm C6 -20 -22 -25 -24 17 80% A3 20% B3 150 ppm C6 -20 -20 -24 -25 18 80% A3 20% B4 150 ppm C6 -20 -21 -23 -26 19 75% A3 25% B5 150 ppm C6 -19 -20 -20 -26 20 85% A1 15% B6 150 ppm C6 -20 -22 -24 -27 Ex. Ethylene copolymer comb polymer co-additive CFPP 100 ppm 150 ppm 200 ppm 300 ppm 21 80% A1 20% B9 150 ppm C7 -20 -22 -25 -27 22 (V) 80% A3 20% B10 150 ppm C6 -19 -20 -19 -20 23 (V) 80% A3 20% B11 150 ppm C6 -9 -14 -18 -19 24 (V) 80% A1 20% B12 150 ppm C7 -15 -16 -18 -22 25 (V) 100% A1 - 150 ppm C6 -18 -19 -20 -22

In this series of measurements, a constant amount of co-additive as well as the stated amount of a mixture of ethylene copolymer and comb polymer were added to the oil. Table 9: CFPP test in a mixture of 80% by volume of test oil D3 and 20% by volume of test oil E2 (CP = -3.3 ° C., CFPP = -10 ° C.) Ex. Ethylene copolymer comb polymer CFPP 100 ppm 200 ppm 250 ppm 300 ppm 26 80% A3 20% B1 -17 -20 -25 -26 27 80% A3 20% B2 -21 -24 -23 -26 28 80% A3 20% B3 -21 -23 -25 -27 29 80% A3 20% B4 -20 -23 -26 -29 30 80% A3 20% B5 -16 -20 -26 -26 31 75% A1 25% B6 -20 -23 -26 -29 32 75% A1 25% B9 -21 -24 -25 -28 33 (V) 80% A3 20% B10 -17 -19 -22 -23 34 (V) 80% A3 20% B11 -10 -16 -17 -21 35 (V) 80% A1 20% B12 -15 -17 -19 -21 36 (V) 100% A1 - -11 -20 -22 -22

Claims (18)

Fuel oil composition F) containing F1) 89-50 vol .-% of a fuel oil of mineral origin and F2) 11-50 vol .-% of a fuel oil of vegetable and / or animal origin, and as a cold additive, the components 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 comprising structural units from B 1) at least one olefin as monomer 1 which has at least one C ₈ - at the olefinic double bond C ₁₈ alkyl carries, and B2) at least one ethylenically unsaturated dicarboxylic acid as monomer 2, which carries at least one bonded via an ester grouping C ₈ -C ₁₈ alkyl radical, wherein the sum Q

the molar average of C chain length distributions in the alkyl radicals of monomer 1 on the one hand and the alkyl radicals of the ester groups of monomer 2 on the other hand is from 21.0 to 28.0, 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 ester 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 ester groups of monomer 2, i are the run variables for the individual chain lengths in the alkyl radicals of monomer 1, and j are the run variables for the individual chain lengths in the alkyl radicals of the ester groups of monomer 2. Fuel oil composition according to claim 1, wherein Q is from 22.0 to 27.0. Fuel oil composition according to claim 1 and / or 2, wherein in ingredient A except ethylene 3.5 to 20 mol% vinyl acetate and 0.1 to 12 mol% vinyl neononanoate, neodecanoate or 2-ethylhexanoic acid vinyl ester wherein the total comonomer content is between 8 and 21 mol% lies. 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% of vinyl esters, 0.5 to 10 mol% Olefins, selected from propene, butene, isobutylene, hexene, 4-methylpentene, octene, diisobutylene or norbornene are included. Fuel oil composition according to one or more of claims 1 to 4, wherein the copolymers, Component A, melt viscosities between 20 and 10,000 mPas have. A fuel oil composition according to one or more of claims 1 to 5, wherein the copolymers comprise component A, which have degrees of branching 1-9 CH _3/100 CH ₂ groups, which do not stem from the comonomers. Fuel oil composition according to one or more of claims 1 to 6, wherein the copolymers, which make up component B, contain comonomers, which are esters and / or anhydrides of maleic acid, fumaric acid and / or itaconic acid are derived. Fuel oil composition according to one or more of claims 1 to 7, wherein the esters of component B derived from alcohols with linear alkyl radicals are. Fuel oil composition according to one or more of claims 1 to 8, wherein the mean molecular mass the copolymers of the invention B is between 1,200 and 200,000 g / mol. Fuel oil composition according to one or more of claims 1 to 9, wherein the copolymers, which make up Component B contain comonomers derived from α-olefins are derived. Fuel oil composition according to one or more of claims 1 to 10, wherein the mixing ratio A: B between 10: 1 and 1:10. Fuel oil composition according to one or more of claims 1 to 11, containing polar nitrogen-containing Paraffin. Fuel oil composition according to one or more of the claims 1 to 12, wherein 88-65 vol.% F1 and 12-35 vol.% F2 are contained. Fuel oil composition according to one or more of the claims 1 to 13, characterized in that the fuel oil animal or of vegetable origin one or more esters of monocarboxylic acid with Contains 14 to 24 carbon atoms and alcohol having 1 to 4 carbon atoms. Fuel oil composition according to claim 14, characterized in that the alcohol is methanol or ethanol. Fuel oil composition according to one or more of claims 1 to 15, characterized that the fuel oil of animal or vegetable origin more than 4% by weight of ester contains saturated fatty acids. Use of an additive as defined in one or more of claims 1 to 15 for improving the cold flow properties of mixtures of mineral fuel oils and fuel oils or of vegetable origin. Process for the preparation of fuel oil compositions F, containing fuel oils mineral (F1) and animal and / or vegetable (F2) origin, with improved cold properties, by mixing the mixture of fuel oils mineral (F1) and animal and / or vegetable (F2) origin an additive such as in one or more of the claims 1 to 15 adds, as well as use.