EP1541662A1 - Fuel oils comprising middle distillates and oils of vegetable or animal origin with improved cold properties. - Google Patents

Abstract

Fuel oil composition comprises a mineral oil, an oil of vegetable or animal origin, and a cold flow improver comprising a copolymer (I) of ethylene and an acrylic or vinyl ester and a comb polymer (II) of an olefin (IIa) with an alkyl group attached to the double bond and an ethylenically unsaturated dicarboxylic acid N-alkyl amide or imide (IIb), where the sum Q of the molar average alkyl chain lengths in (IIa) and (IIb) is 21-28. Fuel oil composition comprises a mineral oil, an oil of vegetable or animal origin, and a cold flow improver comprising a copolymer (I) of ethylene and 8-21 mole% of an acrylic or vinyl ester with a C1-C18 alkyl group and a comb polymer (II) of an olefin (IIa) with a C8-C18 alkyl group attached to the double bond and an ethylenically unsaturated dicarboxylic acid amide or imide (IIb) with a C8-C16 alkyl group attached to the amide or imide group, where the sum Q of the molar average alkyl chain lengths in (IIa) and (IIb) is 21-28.

Description

The present invention relates to mineral fuel oils containing ingredients of vegetable 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 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 may be known in the art Procedures are obtained.

Due to the partially unsatisfactory physical properties of the triglycerides The technique has begun to change the naturally occurring triglycerides in To convert fatty acid esters of lower alcohols such as methanol or ethanol.

As an obstacle in the use of fatty acid esters of lower monohydric alcohols As a diesel fuel substitute alone have their behavior towards engine parts such In particular, various sealing materials proved that again and again Failure of the fuels produced from these renewable raw materials run powered engines. To circumvent these problems is a use of this based on renewable raw materials as an admixture to conventional Middle distillates preferred.

Furthermore, when using triglycerides as well as from Fatty acid esters of lower monohydric alcohols as diesel fuel substitutes alone or in the Mixed with diesel fuel, the flow behavior at low temperatures than Obstacle proved. The reason for this is especially their content of esters saturated Fatty acids as well as the high uniformity (less than 10 major components) of 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, old fat methyl ester a CFPP of +1 ° C and animal fat one CFPP of + 9 ° C. With the additives of the prior art, it is often so far not possible, based on these esters or these containing mineral diesel one CFPP value of -20 ° C required for use as winter diesel in Central Europe as well as for special applications of -22 ° C and below. This problem is exacerbated by the use of oils containing larger amounts of Also included are readily available oils of sunflower and soy.

EP-B-0 665 873 discloses a fuel oil composition containing a biofuel, a petroleum based fuel oil 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 is connected to provide at least one linear chain of atoms that the Carbon atoms of the alkyl groups and one or more non-terminal ones Including 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 Fumaratoder 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.

EP-B-0 746 598 discloses comb polymers as a cold additive in fuel oils containing a Cloud point of at most -10 ° C.

With the known additives, it has hitherto often not been possible to reliably adjust middle distillates containing fatty acid esters to a CFPP value of -20 ° C. required for use as winter diesel in Central Europe and for special applications of -22 ° C. and below. A problem with the known additives is also a lack of sedimentation stability of the additized oils. The paraffins and fatty acid esters precipitating below the cloud point sediment under prolonged storage below the cloud point and lead to the bottom of the storage container to form a phase with poorer cold properties.
It was therefore the object to provide fuel oils with improved low-temperature properties that contain middle distillates and fatty acid esters, with their CFPP values at -20 ° C and below. Furthermore, the sedimentation of precipitated paraffins and fatty acid esters should be slowed down or prevented by prolonged storage of the fuel oil in the area of its cloud point or below.

Surprisingly, it has now been found that fuel oils from middle distillates and Oils of vegetable and / or animal origin containing an ethylene copolymer and certain additive containing comb polymers, excellent Show cold properties.

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 Amid und/oder Imidgruppen 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 Amidund/oder Imidgruppen von Monomer 2,

n₁

die einzelnen Kettenlängen in den Alkylresten von Monomer 1,

n₂

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

i

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

j

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

The invention 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 to 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 ₁₆ -alkyl radical bound via an amide and / or imide group,

where the sum Q

the molar average of the C chain length distributions in the alkyl radicals of monomer 1, on the one hand, and the alkyl radicals of the amide and / or imide groups of monomer 2, on the other hand, is from 21.0 to 28.0, in which

w ₁

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

w ₂

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

n ₁

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

n ₂

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

i

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

j

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

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

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 of the above-defined additive containing the Ingredients A) and B), added.

Preferred oils of mineral origin are middle distillates. The mixing ratio between the fuel oils of animal and / or vegetable origin (which are also referred to below as biofuel oils) and middle distillates may be between 1:99 and 99: 1. Particular preference is given to mixtures which contain from 2 to 50% by volume, in particular from 5 to 40% by volume and especially from 10 to 30% by volume, of biofuel oils. These mixtures give the additives of the invention superior cold properties.
In a preferred embodiment of the invention Q assumes values between 22.0 and 27.0, in particular 23.0 to 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 Understood alkyl radical, ie the chain length of the monomeric olefin minus the both olefinically bound C atoms. For olefins with non-terminal Double bonds, e.g. Olefins with vinylidene grouping is the corresponding Total chain length of the olefin minus the transition into the polymer backbone To consider double bond.

Suitable ethylene copolymers A) are those which contain 8 to 21 mol% of one or more Containing vinyl and / or (meth) acrylic ester and 79 to 92 wt .-% ethylene. Especially preferred are ethylene copolymers with 10 to 18 mol% and especially 12 to 16 mol% at least one vinyl ester. Suitable vinyl esters are derived from fatty acids linear or branched alkyl groups having 1 to 30 carbon atoms. As examples are called 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. As comonomers too suitable are esters of acrylic and methacrylic acid having 1 to 20 carbon atoms in the alkyl radical such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n- and isobutyl (meth) acrylate, Hexyl, octyl, 2-ethylhexyl, decyl, dodecyl, tetradecyl, Hexadecyl, octadecyl (meth) acrylate and mixtures of two, three, four or even several of these comonomers.

Particularly preferred terpolymers of 2-ethylhexanoic acid vinyl ester, vinyl neononanoate or vinyl neodecanoate contain, in addition to 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 the respective long-chain vinyl ester, wherein the total comonomer content is between 8 and 21 mol%, preferably between 12 and 18 mol%. Further preferred copolymers contain, in addition to ethylene and from 8 to 18 mol% of vinyl esters, from 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 prepared by the usual copolymerization methods such as for example suspension polymerization, solvent polymerization, Gas phase polymerization or high-pressure mass polymerization produced. Prefers For example, high pressure bulk polymerization at pressures of 50 to 400 MPa is preferred 100 to 300 MPa and temperatures of 100 to 300 ° C, preferably 150 to 220 ° C. carried out. In a particularly preferred production variant, the Polymerization in a multizone reactor, the difference in temperature between the peroxide dosages along the tubular reactor is kept as low as possible, i. <50 ° C, preferably <30 ° C, in particular <15 ° C. Preferably, the differ Temperature maxima in the individual reaction zones by less than 30 ° C, more preferably less than 20 ° C and especially 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 singly or as a mixture of two or more 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, this is essentially solvent-free operation. In a preferred embodiment of 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 propane or propene, aldehydes such as, for example, 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 moderators can do this together with ethylene as well as metered separately via side streams in the reactor. Here, the Monomer streams may be composed differently (EP-A-0 271 738 and EP-A-0 922 716).

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

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

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

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

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

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

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

die in EP-0 778 875 beschriebenen Terpolymere aus Ethylen, einem ersten Vinylester mit bis zu 4 C-Atomen und einem zweiten Vinylester, der sich von einer verzweigten Carbonsäure mit bis zu 7 C-Atomen oder einer verzweigten aber nicht tertiären Carbonsäure mit 8 bis 15 C-Atomen ableitet;

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

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

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

Suitable copolymers or terpolymers include, for example:

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

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

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

the mixture known from EP-B-0 254 284 comprising an ethylene-vinyl acetate-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;

the 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, they can contain different comonomers, different comonomer contents, Have molecular weights and / or degrees of branching. The mixing ratio the various ethylene copolymers is 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. Preference is given to maleic acid, fumaric acid, itaconic acid and esters thereof with lower ones Alcohols having 1 to 6 carbon atoms and their anhydrides such as Maleic anhydride. As comonomers are monoolefins with 10 to 20, in particular with 12 to 18 carbon atoms particularly suitable. These are preferably linear and the Double bond is preferably terminal such as in dodecene, tridecene, Tetradecene, pentadecene, hexadecene, heptadecene and octadecene. The ratio of Dicarboxylic acid or dicarboxylic acid derivative to olefin or olefins in the polymer preferably in the range 1: 1.5 to 1.5: 1, especially it is equimolar.

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

worin

R¹

Wasserstoff oder Methyl,

R²

Wasserstoff oder C₁-C₄-Alkyl,

m

eine Zahl von 1 bis 100,

R³

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

R⁴

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

Allyl polyglycol ethers correspond to the general formula

wherein

R ¹

Hydrogen or methyl,

R ²

Hydrogen or C ₁ -C ₄ -alkyl,

m

a number from 1 to 100,

R ³

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

R ⁴

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

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

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

The reaction of the monomers is by free-radical initiators (Radical chain starter) initiated. This class of substance includes e.g. Oxygen, Hydroperoxides and peroxides such as e.g. Cumene hydroperoxide, t-butyl hydroperoxide, Dilauroyl peroxide, dibenzoyl peroxide, bis (2-ethylhexyl) peroxide carbonate, t-butyl perpivalate, t-butyl permalate, t-butyl perbenzoate, dicumyl peroxide, t-butyl cumyl peroxide, di (t-butyl) peroxide, and azo compounds such as e.g. 2,2'-azobis (2-methylpropanonitrile) or 2,2'-azobis (2-methylbutyronitrile). The initiators are selected individually or as a mixture 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 B can either by reaction of maleic, fumaric and / or Itaconic acid or its derivatives with the corresponding amine and subsequent Copolymerization or by copolymerization of olefin or olefins with at least an unsaturated dicarboxylic acid or its derivative such as itacon and / or Maleic anhydride and subsequent reaction with amines become. Preferably, a copolymerization is carried out with anhydrides and the resulting copolymer after preparation into an amide and / or an imide transferred.

The reaction with amines takes place in both cases, for example by reaction with 0.8 to 2.5 moles of amine per mole of anhydride, preferably with 1.0 to 2.0 moles of amine per mole Anhydride at 50 to 300 ° C. When using about 1 mol of amine per mole of anhydride arise at reaction temperatures of about 50 to 100 ° C preferred hemi-amides, in addition carry one carboxyl group per amide group. At higher reaction temperatures of About 100 to 250 ° C are formed from primary amines with dehydration preferred Imides. When using larger amounts of amine, preferably 2 moles of amine per mole of anhydride arise at about 50 to 200 ° C amide ammonium salts and at higher temperatures for example, 100-300 ° C, preferably 120-250 ° C diamides. The Reaction water can be distilled off by means of an inert gas or in Presence of an organic solvent discharged by azeotropic distillation become. Preference is given to 20-80, especially 30-70, especially 35-55 wt .-% used at least one organic solvent. As half-amides are here (50% in solvent-adjusted) copolymers having acid numbers of 30 - 70 mg KOH / g, preferably from 40 to 60 mg KOH / g. Corresponding copolymers with Acid numbers less than 40, especially less than 30 mg KOH / g are considered diamides or Imide considered. Particularly preferred are hemiamides and imides.

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

Particularly preferred as primary amines are octylamine, 2-ethylhexylamine, decylamine, Undecylamine, dodecylamine, n-tridecylamine, iso-tridecylamine, tetradecylamine, Pentadecylamine, hexadecylamine and mixtures thereof.

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

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

In a preferred embodiment, mixtures of the invention Copolymers B are used, provided that the mean of the Q values of the Mixture components in turn values from 21.0 to 28.0, preferably values of 22.0 to 27.0 and especially values from 23.0 to 26.0.

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. 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 are used. Preferably, they are in Fuel oil of animal or vegetable origin based on fatty acid alkyl esters solved. The additives according to the invention preferably contain 1-80%, especially 10 - 70%, in particular 25 - 60% solvent.

In a preferred embodiment, the fuel oil is F2, the often referred to as "biodiesel", "biofuel" or "biofuel" to Fatty acid alkyl esters of fatty acids having 12 to 24 carbon atoms and alcohols having 1 to 4 carbon atoms. Usually a major part of the fatty acids contains one, two or three Double bonds.

Examples of oils F2 derived from animal or vegetable material, and which can be used according to the invention 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 derived from wheat, jute, Sesame, Scheabaumnuß, Arachisöl and linseed oil derive. Also called biodiesel designated fatty acid alkyl esters can from these oils according to the prior art derived from known methods. Rapeseed oil containing a mixture of glycerin is partially esterified fatty acids, is preferred because it is available in large quantities and is readily available by squeezing rapeseed. Furthermore are the also widespread oils of sunflower and soy and their Mixtures with rapeseed oil are preferred.

Particularly suitable as biofuels F2) 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, which preferably has an iodine value of 50 to 150, in particular 90 to 125 have. Mixtures with particularly advantageous properties are those which mainly, d. H. at least 50% by weight, methyl esters of fatty acids with 16 to Contain 22 carbon atoms and 1, 2 or 3 double bonds. The preferred ones lower alkyl esters of fatty acids are the methyl esters of oleic acid, linoleic acid, Linolenic acid and erucic acid.

Commercially available mixtures of the type mentioned are obtained, for example, by cleavage and esterification or by transesterification of animal and vegetable fats and Obtained oils with lower aliphatic alcohols. The same are also used Edible 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 Basis of a new type of rapeseed oil whose fatty acid component is more than 80% by weight derived from unsaturated fatty acids having 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 above Oils can be used as biofuels, vegetable oil derivatives are preferred, 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 used grease esters such as used fat methyl ester.

As mineral oil component F1 in particular middle distillates are suitable, by Crude oil distillation and boiling in the range of 120 to 450 ° C, For example, kerosene, jet fuel, diesel and heating oil. Preferably, such Middle distillates used, the 0.05 wt .-% sulfur and less, especially preferably less than 350 ppm sulfur, in particular less than 200 ppm sulfur and in special cases less than 50 ppm of sulfur, such as less than Contain 10 ppm of sulfur. These are generally such Middle distillates which have been subjected to a hydrogenating refining, and therefore contain only low levels of polyaromatic and polar compounds. Preferably, these are middle distillates, the 95% distillation points below 370 ° C, in particular 350 ° C and in special cases below 330 ° C. Also synthetic fuels, such as those according to the Fischer-Tropsch process are accessible, are suitable as middle distillates.

The additive may be added to the oil to be treated according to art known in the art Method be supplied. If more than one additive component or Coadditive component should be used, such components may be together or separately in any combination and order into the oil. The additives according to the invention allow the CFPP value of mixtures to be determined Improve biodiesel and mineral oils much more efficiently than with known additives of the prior art. The additives according to the invention are particularly advantageous in Oil mixtures whose mineral oil component F1) has a boiling width between the 20 and 90% distillation point of less than 120 ° C, especially less than 110 ° C. and especially less than 100 ° C. In addition, they are special advantageous in oil mixtures whose mineral oil component F1) has a cloud point of below -4 ° C, especially from -6 ° C to -20 ° C such as from -7 ° C to -9 ° C has, as they are used for use especially in winter. Of the same is the pour point of the mixtures according to the invention by the addition of reduced additives according to the invention. The additives of the invention are particularly advantageous in oil mixtures F containing more than 2% by volume of biofuel F 2, preferably more than 5% by volume of biofuel F 2 and especially more than 10% by volume Biofuel F2 such as 15 to 35 vol .-% biofuel F2 included. The In addition, additives according to the invention are particularly advantageous in problematic oils whose biofuel component F2 has a high content Saturated fatty acid esters of more than 4%, in particular more than 5% and specifically from 7 to 25%, such as from 8 to 20%, such as for example in oils from sunflower and soy is the case. Such biofuels have prefers a cloud point above -5 ° C and especially above -3 ° C. Oil mixtures F) in which the additives according to the invention are particularly advantageous Have cloud points above -9 ° C and especially above -6 ° C. It is thus also possible with the additives according to the invention Rapsölsäuremethylester and sunflower and / or soybean oil fatty acid methyl ester to adjust the oil mixtures to CFPP values of -22 ° C and below.

For the preparation of additive packages for special problem solutions, the additives according to the invention can also be used together with one or more oil-soluble co-additives, which in themselves improve the cold flow properties of crude oils, lubricating oils or fuel oils. Examples of such co-additives are polar compounds which differ from the polymers B according to the invention and which effect 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 fatty amines with alkyl radicals having 18 to 24 carbon atoms, in particular secondary fatty amines such as 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 (compare 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 (compare 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 according to 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 et seq described. The alkyl radicals of the o- or p-alkylphenol can be used in the case of the additives according to the invention Alkylphenol-aldehyde resins may be the same or different and have 1-50, preferably 1-20, especially 4-12 carbon atoms; it is preferable to n-, iso- and tert-butyl, n- and iso-pentyl, 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 to 4 carbon atoms. Particularly preferred aldehydes are formaldehyde, acetaldehyde and butyraldehyde, especially formaldehyde. The molecular weight of the alkylphenol-aldehyde resins is 400-10,000, preferably 400-5000 g / mol. Prerequisite here 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.

Other suitable flow improvers are polyoxyalkylene compounds such as For example, esters, ethers and ethers / esters containing at least one alkyl radical with 12 bis Wear 30 C atoms. When the alkyl groups are derived from an acid, the Remainder of 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. Also suitable are alkoxylates of polyols, such as for example, glycerol, trimethylolpropane, pentaerythritol, neopentyl glycol, as well as the oligomers obtainable therefrom by condensation with 2 to 10 Monomer units, e.g. Polyglycerol. Preferred alkoxylates are those of 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.

Suitable olefin polymers as part of the additive according to the invention may be derived directly from monoethylenically unsaturated monomers or indirectly by Hydrogenation of polymers derived from polyunsaturated monomers such as Isoprene or butadiene derived, are produced. Preferred copolymers contain in addition to ethylene structural units derived from α-olefins having 3 to 24 carbon atoms and have 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 mole% and especially between 30 and 45 mole%. These copolymers can also be minor amounts, e.g. up to 10 mol% more Comonomers such as e.g. non-terminal olefins or non-conjugated olefins contain. Preferred are ethylene-propylene copolymers. The olefin copolymers can prepared by known methods, e.g. by 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 Paraffin dispersants, comb polymers, alkylphenol condensates, Each of polyoxyalkylene derivatives and olefin copolymers is 1:10 to 20: 1, preferably 1: 1 to 10: 1, such as 1: 1 to 4: 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 according to EN 116 and the determination of the cloud point according to ISO 3015. Both properties are determined in ° C. Characterization of the biofuel oils (F2) used 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 used for the preparation of the test oils
Fatty acid methyl ester (main constituents, Fl .-% 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 Characterization of the mineral oils used (F1) D1 D2 D3 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. 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
ii) 12.9 mol% of vinyl acetate in the ratio i): ii) of 6: 1 97 mPas
145 mPas 4.7
5.4

Comb polymers B

The polymerization of maleic anhydride (MSA) with α-olefins takes place in one higher boiling aromatic hydrocarbon mixture at 160 ° C in the presence a mixture of equal parts of tert-butyl peroxybenzoate and tert-butyl peroxy-2-ethylhexanoate as a radical chain starter. Table 5 shows various examples Copolymers and the molar proportions of the monomers used for their preparation and chain length (R) and molar amount (relative to MSA) of the derivatization amine used and calculated from the factor Q listed. Both Amines used are, unless otherwise stated Monoalkylamines.

The reactions with amines are carried out in the presence of solvent naphtha (40 to 50 wt .-%) at 50 to 100 ° C to the half-amide or amide ammonium salt and at 160 to 200 ° C with azeotropic culling of water of reaction to imide or diamide , The degree of amidation is inversely proportional to the acid number. Characterization of the comb polymers used (B) example comonomers Amin Q acid number
[mg KOH / g] R mol B1 MSA-co-C _14/16 -α-olefin (1: 0.5: 0.5) C ₈ 1 21 52 B2 MSA-co-C _14/16 -α-olefin (1: 0.5: 0.5) C ₁₀ 1 23.0 60 B3 MSA-co-C _14/16 -α-olefin (1: 0.5: 0.5) C ₁₂ 1 25.0 58 B4 MSA-co-C _14/16 -α-olefin (1: 0.5: 0.5) C ₁₄ 1 27.0 56 B5 (V) MSA-co-C _14/16 -α-olefin (1: 0.5: 0.5) C ₁₆ 1 29.0 55 B6 (V) MSA-co-C ₁₀ -α-olefin (1: 1) C ₁₂ 1 20.0 57 B7 MSA-co-C ₁₆ α-olefin (1: 1) C ₁₂ 1 26.0 56 B8 MSA-co-C ₁₄ -α-olefin (1: 1) C ₁₄ 1 26.0 58 B9 MSA-co-C ₁₀ -α-olefin (1: 1) C ₁₆
C ₁₈ 0.5
0.5 25.0 59 B10 MSA-co-C _14/16 -α-olefin-co-Allylmethylpolyglykol (1: 0.45: 0.45: 0.1) C ₁₂ 1 25.0 56 B11 MSA-co-C _14/16 -α-olefin (1: 0.5: 0.5) C ₁₂ 25.0 0.32 B12 MSA-co-C _14/16 -α-olefin (1: 0.5: 0.5) C ₁₂ 1 25.0 1.5 B13 MSA-co-C _14/16 -α-olefin (1: 0.5: 0.5) di-C ₁₂ 1 25.0 50 B14 (V) Fumarate vinyl acetate (1: 1) C ₁₄ 2 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. 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. CFPP testing in a mixture of 75% by volume of test oil D1 and 25% by volume of test oil E1 (CP = -5.2 ° C, CFPP = -9 ° C) Ex. flow improvers Comb polymer / coadditive CFPP after addition of flow improver 50 ppm 100 ppm 150 ppm 200ppm 1 A2 150 ppm B1 -11 -18 -19 -22 2 A2 150 ppm B2 18 -19 -20 -21 3 A2 150 ppm B3 -21 -21 -21 -22 4 A2 150 ppm B4 -11 -15 -18 -20 5 (V) A2 150 ppm B5 -9 -9 -11 -17 6 (V) A2 150 ppm B6 -10 -13 -13 -15 7 A1 150 ppm B9 -19 -20 -22 -23 8th A1 100 ppm B10 -20 -20 -21 -23 9 A1 100 ppm B11 -19 -20 -20 -22 10 A1 100 ppm B12 -21 -22 -22 -23 11 A2 150 ppm B13 -18 -19 -19 -22 12 A2 75 ppm B3
75 ppm A4 -18 -20 -22 -25 13 (V) A2 150 ppm B14 -10 -11 -15 -20 14 (V) A2 - -11 -16 -17 -19 CFPP test 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 -18 -20 -22 -22 16 80% A3 20% B2 150 ppm C6 -20 -21 -21 -24 17 80% A3 20% B3 150 ppm C6 -20 -22 -23 -27 18 80% A3 20% B4 150 ppm C6 -20 -22 -22 -23 19 75% A1 25% B7 150 ppm C7 -19 -21 -22 -24 20 85% A1 15% B8 150 ppm C7 -19 -22 -24 -25 21 80% A1 20% B11 150 ppm C6 -20 -22 -23 -25 22 80% A1 20% B12 150 ppm C6 -20 -23 -24 -26 23 (V) 80% A3 20% B6 150 ppm C6 -18 -19 -20 -20 24 (V) 80% A3 20% B5 150 ppm C6 -10 -14 -17 -18 25 (V) 80% A1 20% B14 150 ppm C7 -15 -16 -18 -22 26 (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. CFPP testing 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 27 80% A3 20% B1 -16 -19 -24 -26 28 80% A3 20% B2 -20 -23 -25 -27 29 80% A3 20% B3 -21 -22 -24 -28 30 80% A1 20% B12 -21 -23 -25 -29 31 80% A3 20% B4 -19 -21 -23 -25 32 (V) 80% A3 20% B6 -15 -18 -22 -23 33 (V) 80% A3 20% B5 -10 -15 -17 -19 34 (V) 80% A1 20% B14 -15 -17 -19 -21 35 (V) 100% A1 - -11 -20 -22 -22

Claims (20)

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 to 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 ₁₆ -alkyl radical bound via an amide and / or imide group, where the sum Q

the molar average of the C chain length distributions in the alkyl radicals of monomer 1, on the one hand, and the alkyl radicals of the amide and / or imide groups of monomer 2, on the other hand, is from 21.0 to 28.0, in which

w ₁

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

w ₂

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

n ₁

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

n ₂

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

i

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

j

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

A fuel oil composition according to claim 1, wherein Q is from 22.0 to 27.0 is. A 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, vinyl neodecanoate or vinyl 2-ethylhexanoate are contained, 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, Octen, 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 amides and / or imides of maleic acid, fumaric acid and / or itaconic acid are derived. A fuel oil composition according to one or more of claims 1 to 7 wherein the amides and / or imides of ingredient B are derived from primary amines are. A fuel oil composition according to one or more of claims 1 to 8, wherein the amides and / or imides of the component B of amines with linear Alkyl radicals are derived. A fuel oil composition according to one or more of claims 1 to 9, wherein the amides and / or imides of component B are derived from monoamines. A fuel oil composition according to one or more of claims 1 to 10, wherein the average molecular weight of the inventive copolymers B between 1,200 and 200,000 g / mol. A fuel oil composition according to one or more of claims 1 to 11, wherein the copolymers constituting ingredient B contain comonomers, which are derived from α-olefins. A fuel oil composition according to one or more of claims 1 to 12, wherein the mixing ratio A: B is between 10: 1 and 1:10. A fuel oil composition according to one or more of claims 1 to 13, containing polar nitrogen-containing paraffin dispersants. A fuel oil composition according to one or more of claims 1 to 14, wherein the proportion of F2 is greater than 2 vol .-%. 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 one or more esters of monocarboxylic acid having 14 to 24 carbon atoms and alcohol having 1 to 4 carbon atoms. A fuel oil composition according to claim 16, characterized in that the alcohol is methanol or ethanol. A fuel oil composition according to one or more of claims 1 to 17, characterized in that the fuel oil of animal or vegetable origin contains more than 4% by weight of esters of saturated fatty acids. Use of an additive as in one or more of claims 1 to 14 defined to improve the cold flow properties of mixtures mineral fuel oils and animal or vegetable fuel oils Origin. Process for the preparation of fuel oil compositions F containing Fuel oils of 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 claims 1 to 14 added.