EP1881053A2 - Additives for improving the cold properties of fuel oils - Google Patents

Abstract

Additive mixture (I) comprises at least a terpolymer (a) of ethylene, propene and at least an ethylenically unsaturated ester, containing 6-12 mol.% of at least an ethylenically unsaturated ester with 1-3C-alkyl residue derived structural units, 0.5-4 of propene derived methyl group/100-aliphatic carbon-atoms and less than 8 carbon atoms based on methyl group/100-methyl group; and 0.5-20 parts by weight of at least further cold additives (b) for mineral oil such as copolymer of ethylene and ethylenically unsaturated compound, and/or comb polymer. Additive mixture (I) comprises at least a terpolymer (a) of ethylene, propene and at least an ethylenically unsaturated ester, containing 6-12 mol.% of at least an ethylenically unsaturated ester with 1-3C-alkyl residue derived structural units, 0.5-4 of propene derived methyl group/100-aliphatic carbon-atoms and less than 8 carbon atoms based on methyl group/100-methyl group; and 0.5-20 parts by weight of at least further cold additives (b) such as copolymer of ethylene and ethylenically unsaturated compound, whose content is at least 2 mol.% greater than the content of ethylenically unsaturated ester of (a), and/or comb polymer. Independent claims are included for: (1) a preparation of (a) comprising adding a mixture of ethylene, propene and at least a vinyl ester under increased pressure and temperature in the presence of a radical forming initiator, and where the molecular weight of (a) is adjusted by a moderator; (2) a method of improving the fluidity of fuel oil comprising adding (I) to the fuel oil; (3) a composition comprising at least (I) and at least an oil soluble polar nitrogen compound, at least an alkyl phenol-aldehyde resin, olefin polymer or at least a polyoxyalkylene compound; and (4) a fuel oil composition comprising a distillate means and at least (I).

Description

The present invention relates to additive mixtures comprising ethylene-propene-vinyl ester terpolymers, in addition to a further cold additive, which have improved handling properties and improved performance properties as cold additives for fuel oils.

Depending on the origin of the crude oils, crude oils and middle distillates obtained by distillation of crude oils, such as gas oil, diesel oil or fuel oil, contain different amounts of n-paraffins, which crystallize out as platelet-shaped crystals when the temperature is lowered and partly agglomerate with the inclusion of oil. As a result of this crystallization and agglomeration, the flow properties of the oils or distillates deteriorate, which can lead to disruptions in the extraction, transport, storage and / or use of the mineral oils and mineral oil distillates. When transporting mineral oils through pipelines, the phenomenon of crystallization, especially in winter, can lead to deposits on the pipe walls and in individual cases, e.g. at standstill of a pipeline, even lead to their complete blockage. During storage and further processing of the mineral oils, it may also be necessary in winter to store the mineral oils in heated tanks to ensure their flowability. In the case of mineral oil distillates, as a result of the crystallization, blockages of the filters in diesel engines and firing systems may occur, as a result of which reliable metering of the fuels is prevented and, under certain circumstances, a complete interruption of the fuel or heating agent supply occurs.

In addition to the classical methods for removing the crystallized paraffins (thermal, mechanical or with solvents), which relate only to the removal of already formed precipitates, increasingly chemical additives, so-called flow improvers are used. These additives often contain two components: on the one hand as additional crystal nuclei acting and with the paraffins crystallizing ingredients that cause a larger number of smaller paraffin crystals with altered crystal form (nucleators) and on the other hand, the growth of crystals once formed limiting components (arrestors). The modified paraffin crystals are less prone to agglomeration, so that the oils added with these additives can still be pumped or processed at temperatures which are often more than 20 ° C. lower than for non-additized oils.

In the course of decreasing world oil reserves, increasingly heavier and thus paraffin-rich crude oils are extracted and processed, which consequently also lead to paraffin-rich fuel oils. In addition, due to environmental reasons, increasing hydrodesulfurization of fuel oils causes a change in the processing of crude oils, which in part leads to an increased proportion of cold-critical paraffins in the fuel oil. In such oils, the solubility and effectiveness of the known additives of the prior art are often unsatisfactory. Furthermore, the low tolerances of modern engine technology required for compliance with emission levels require very pure fuel oils. The known additives of the prior art, in particular the additive components used as nucleating agents, however, often contain small amounts of sparingly soluble and partially recrystallizing constituents, which can lead to problems in the injection systems or to allocations in the upstream fuel filters.

A known and widely used for the improvement of the cold properties of mineral oils and middle distillates produced therefrom additive class are copolymers of ethylene and vinyl esters, especially ethylene and vinyl acetate. These are partially crystalline polymers, the mode of action of which is explained by co-crystallization of their poly (ethylene) sequences with the n-paraffins precipitated on cooling from the middle distillates. Through this physical interaction, the shape, size and adhesion properties of the precipitated wax crystals are modified to produce many small crystals that pass through the fuel filter and can be supplied to the combustion chamber.

In particular, the ethylene copolymers used as nucleating agents or nucleating agents must have a low solubility in the oil in order to fulfill their function in order to crystallize out on cooling of the oil with or shortly before the paraffins. Ethylene copolymers having a low comonomer content and thus long free poly (ethylene) sequences which are particularly well suited for co-crystallization with the long-chain paraffins which precipitate out of the oil are preferably used as nucleators. However, in order to be completely dissolved above the cloud point of the oil and not itself a cause for filter blockages, these ethylene-vinyl ester copolymers require due to their increased intrinsic crystallinity, handled at elevated temperature and dosed or alternatively transported and processed in high dilution with solvents to become. Otherwise, there is a risk that the additives remain undissolved, whereby they can not develop their full effectiveness and can also give rise to filter occupancy and filter blockages.

Furthermore, in particular, the injection units and pumps require current engine concepts very clean fuels. Even small amounts of undissolved additive components are highly undesirable in this context. Removal of such minor constituents of polymers by filtration is very expensive, if at all possible.

It is also known to improve the self-flowability of ethylene-vinyl ester copolymers and their dispersions by a high proportion of so-called short-chain branches, as can be adjusted for example by polymerization at high temperatures and / or low pressures. These short-chain branches are formed by intramolecular chain transfer reactions ("back-biting mechanism") during radical polymerization and consist essentially of butyl and ethyl radicals (see, for example, US Pat Macromolecules 1997, 30, 246-256 ). However, these short chain branches significantly reduce the effectiveness of these polymers as cold additives.

Similar structures and related effects to short chain branches are obtained by the incorporation of branched comonomers such as isobutylene ( EP-A-0 099 646 ), 4-methylpentene ( EP-A-0 807 642 ) or diisobutylene ( EP-A-0 203 554 Obtained in EVA copolymers: As the incorporation of these monomers, although an improvement in the flowability and the solubility of the polymers is observed, but also decreases their effectiveness as a cold additive.

U.S. 3,961,916 discloses fuel oils containing two copolymers of ethylene and unsaturated esters which act as nucleators for paraffin crystallization to improve cold flow properties.

EP-A-0 190 553 discloses terpolymers of ethylene, 20-40 wt .-% of vinyl acetate and propene having a degree of branching 8-25 CH _3/100 CH ₂ groups. These polymers, which are to be regarded as growth inhibitors, show hardly any activity as cold flow improvers alone and are used to improve the solubility of conventional EVA copolymers with a comparable vinyl acetate content.

U.S. 4,178,950 discloses terpolymers of ethylene, 10 to 45% by weight of vinyl acetate, 0.01 to 5.0% by weight of propene or butene and their use as a pour point depressant for residual oils. Polymer blends are not disclosed.

DE-A-2 037 673 discloses polymer blends of ethylene-vinyl acetate copolymers of different molecular weight as cold flow improvers, which may also contain propene in addition to ethylene as the olefin.

EP-A-0 406 684 discloses polymer blends comprising A) copolymers of ethylene, 25-35% by weight of vinyl acetate, optionally 5 to 15% by weight of an olefin and a degree of branching of 3 to 15 CH ₃ groups, and B) another ethylene-vinyl acetate Copolymer and optionally C) contain a polyalkyl (meth) acrylate. The terpolymer of ethylene, vinyl acetate and diisobutylene used in the example is used as a cold flow improver together with a low comonomer content EVA copolymer to be considered as a nucleating agent. The use of propene as a comonomer for nucleators is shown neither in combination with arrestors nor in combination with comb polymers.

Although short chain branching as well as longer chain and especially branched olefinic comonomers improve the inherent flowability of polymers of ethylene and unsaturated esters, this is often accompanied by a loss of efficacy as cold flow improver since the range of polyethylene sequence lengths optimum for co-crystallization with paraffins is exited or even already smaller amounts of the comonomers cause such a strong disruption of the polyethylene sequences that an effective cocrystallization with the paraffins of the oil and in particular a stimulation of the paraffin crystallization (nucleation) is no longer possible. In addition, these nucleators often contain very poorly soluble and recrystallizing from the oil fractions, which can lead to blockages of filters and injection systems.

The incorporation of larger amounts of the known branched olefins such as isobutylene, 4-methylpentene or diisobutylene in polymers of ethylene and unsaturated esters is also limited by the fact that these olefins have such a strong moderating effect on the polymerization, so that the need for initiators for commercial Applications prohibitive level reached, not sufficiently high molecular weight is achieved and / or that no commercially interesting turnover in the polymerization can be achieved. In addition, the resulting strongly short-chain branched products do not show sufficient activity as nucleating agents for paraffin crystallization.

It was therefore an object of the present invention to provide additives for improving the cold flowability of fuel oils which are flowable and easily pumpable at the lowest possible temperatures in the most concentrated form possible, compared to the additives of the prior art improved effectiveness as a cold flow improver and no insoluble, too Valve and / or filter blockages contain leading portions.

It has now been found that additive concentrates which contain, as nucleating agents for paraffins, terpolymers of ethylene, propene and unsaturated esters with few short-chain branching properties are very easy to handle and mix at low temperatures, and at the same time a superior one Show effectiveness as a cold additive. In addition, these additives contain less difficultly soluble portions of the known ethylene copolymers of the prior art.

1. A) mindestens ein Terpolymer aus Ethylen, Propen und mindestens einem ethylenisch ungesättigten Ester, welches
   1. i) 6,0 bis 12,0 mol-% von mindestens einem ethylenisch ungesättigten Ester mit einem C₁- bis C₃-Alkylrest abgeleitete Struktureinheiten enthält,
   2. ii) 0,5 bis 4,0 vom Propen abgeleitete Methylgruppen pro 100 aliphatische C-Atome enthält,
   3. iii) weniger als 8,0 von Kettenenden stammende Methylgruppen pro 100 CH₂-Gruppen aufweist und
2. B) 0,5 bis 20 Gewichtsteile bezogen auf A) mindestens einer weiteren, als Kälteadditiv für Mineralöle wirksamen, Komponente ausgewählt aus
   • B1) Copolymeren aus Ethylen und ethylenisch ungesättigten Verbindungen, deren Gehalt an ethylenisch ungesättigten Verbindungen mindestens 2 mol-% höher ist als der Gehalt des unter A) definierten Terpolymers an ethylenisch ungesättigten Estern,
   • B2) Kammpolymeren, und
   • B3) Mischungen aus B1) und B2).

The invention thus relates to additive mixtures containing

1. A) at least one terpolymer of ethylene, propene and at least one ethylenically unsaturated ester which
   1. i) contains from 6.0 to 12.0 mol% of structural units derived from at least one ethylenically unsaturated ester with a C ₁ to C ₃ alkyl radical,
   2. ii) contains 0.5 to 4.0 propene-derived methyl groups per 100 aliphatic C atoms,
   3. iii) has less than 8.0 chain end methyl groups per 100 CH ₂ groups, and
2. B) 0.5 to 20 parts by weight based on A) of at least one further, as a cold additive for mineral oils effective, component selected from
   • B1) copolymers of ethylene and ethylenically unsaturated compounds whose content of ethylenically unsaturated compounds is at least 2 mol% higher than the content of the terpolymer defined in A) of ethylenically unsaturated esters,
   • B2) comb polymers, and
   • B3) mixtures of B1) and B2).

Another object of the invention is the use of additive mixtures of A) and B) to improve the low-flowability of fuel oils.

Another object of the invention is a method for improving the low-temperature flowability of fuel oils by adding an additive mixture of A) and B) to the fuel oil.

Another object of the invention are fuel oils with improved cold flowability, containing an additive mixture of A) and B).

Unsaturated esters suitable for component A) according to the invention are in particular vinyl esters of carboxylic acids having 1 to 4 carbon atoms and also esters of acrylic and methacrylic acid with fatty alcohols having 1 to 3 carbon atoms.

Particularly preferred ethylenically unsaturated esters are vinyl esters of carboxylic acids having 2 to 12 carbon atoms. These are preferably those of the formula 1

CH ₂ = CH-OCOR ¹ (1)

wherein R ^{1 is} C ₁ - to C ₃ -alkyl and preferably C ₂ - to C ₃ -alkyl. Examples of suitable vinyl esters are vinyl acetate, vinyl propionate, vinyl butyrate and vinyl isobutyrate. Especially preferred is vinyl acetate.

Also preferred as ethylenically unsaturated esters are esters of acrylic and methacrylic acid with fatty alcohols having 1 to 12 carbon atoms. These are preferably those of the formula 2

CH ₂ = CR ² -COOR ³ (2)

wherein R ^{2 is} hydrogen or methyl and R ^{3 is} C ₁ - to C ₃ -alkyl and preferably C ₁ - or C ₂ -alkyl. Suitable esters of acrylic and methacrylic acid include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n- and iso-propyl (meth) acrylate and mixtures of these comonomers. Methyl acrylate and ethyl acrylate are particularly preferred.

The content of the terpolymer A) of unsaturated ester is preferably between 7.0 and 11.5 mol% and in particular between 8.0 and 11.0 mol%, for example between 8.5 and 10.5 mol%. In the case of the vinyl acetate which is particularly preferred as the ethylenically unsaturated ester, the content is preferably between 12.0 and 29.0% by weight and in particular between 18 and 28% by weight, for example between 20.0 and 27.0% by weight. , The comonomer content is determined by pyrolysis of the polymer and subsequent titration of the eliminated carboxylic acid.

The terpolymers A may additionally contain minor amounts of, for example, up to 4 mol%, preferably up to 2.5 mol%, such as 0.1 to 2.0 mol%, of structural units derived from unsaturated esters with longer alkyl chains , Suitable unsaturated esters for this purpose are vinyl esters of the formula (1) and / or (meth) acrylic acid esters of the formula (2) in which R ² and R ³ independently of one another are an alkyl radical having 4 to 20 C atoms. These alkyl radicals can be linear or branched. Preferably, they are branched.

The content of the terpolymer A) of methyl groups derived from the propene is preferably between 0.7 and 3.5 and in particular between 1.0 and 3.0, for example between 1.1 and 2.5 methyl groups per 100 aliphatic carbon atoms. atoms.

The number of propene-derived methyl groups per 100 aliphatic carbon atoms in terpolymer A) (propene-CH ₃ ) is determined by ¹³ C NMR spectroscopy. Thus, terpolymers of ethylene, vinyl ester and propene show characteristic signals of methyl groups attached to the polymer backbone of between about 19.3 and 20.2 ppm, which have a positive sign in the DEPT experiment. The integral of this signal of the propene-derived methyl side groups of the polymer backbone is related to that of all aliphatic carbon atoms of the polymer backbone between about 22 and 44 ppm. Optionally derived from the alkyl radicals of the unsaturated ester and superimposed with the signals of the polymer backbone signals are subtracted based on the signal of the carbonyl group of the unsaturated ester adjacent methine group of the total integral of the aliphatic C-atoms. Leave such measurements For example, with NMR spectrometers at a measurement frequency of 125 MHz at 30 ° C in solvents such as CDCl ₃ or C ₂ D ₂ Cl ₄ perform.

The number of chain ends originating from the methyl groups in the terpolymers A) is preferably from 2.0 to 7.0 CH _3/100 CH ₂ groups and in particular from 2.5 to 6.5 CH _3/100 CH ₂ groups such as 3.0 to 6.0 CH _3/100 CH ₂ groups.

The number of methyl groups derived from chain ends is understood to mean all those methyl groups of the terpolymer A) which do not originate from the unsaturated esters used as comonomers. Consequently, this includes both the methyl groups located at the main chain ends, including the methyl groups derived from structural units of the moderator, and the methyl groups derived from short chain branches.

The number of methyl groups derived from chain ends is determined by ¹ H-NMR spectroscopy, in which the integral of the signals usually appearing in the ¹ H-NMR spectrum with a chemical shift of between about 0.7 and 0.9 ppm (versus TMS) Methyl protons is compared with the integral of appearing at 0.9 to 1.9 ppm signals of the methylene protons. The methyl and methylene groups derived from alkyl radicals of the comonomers, for example the acetyl group of the vinyl acetate, are not included or excluded. The signals generated by the structural units of the moderator are assigned according to the methyl or methylene protons. From the resulting value, the number of propene-derived methyl groups, as determined by ¹³ C-NMR spectroscopy, is subtracted to obtain the number of methyl groups derived from chain ends. Suitable ¹ H NMR spectra, for example, at a measurement frequency of 500 MHz at 30 ° C in solvents such as CDCl ₃ or C ₂ D ₂ Cl _{4 are} recorded.

zwischen 8,0 und 14,0 und speziell zwischen 9,5 und 13,0 wie beispielsweise zwischen 10,0 und 12,5. Die beiden Summanden sind als dimensionslose Zahlen zu addieren.Preferably, the sum G of molar content of unsaturated ester i) and the number of propene-derived methyl groups per 100 aliphatic carbon atoms of the polymer ii) $$\mathrm{G}=\left[\mathrm{mol}-\%\mathrm{unsaturated\; ester}\right]+\left[\mathrm{propene}-{\mathrm{CH}}_3\right]$$

between 8.0 and 14.0 and especially between 9.5 and 13.0 such as between 10.0 and 12.5. The two summands are to be added as dimensionless numbers.

The weight-average molecular weight M w of the terpolymers A) determined by means of gel permeation chromatography against poly (styrene) standards is preferably between 2,500 and 50,000 g / mol, preferably between 4,000 and 30,000 g / mol, for example between 5,000 and 25,000 g / mol. The melt viscosity of the terpolymers A) determined at 140 ° C. is between 100 and 5,000 mPas, preferably between 150 and 2,500 mPas and in particular between 200 and 2,000 mPas.

For all analyzes, the polymer is previously freed for two hours at 140 ° C in vacuo (100 mbar) of residual monomers and any solvent components.

The ethylene polymers A) and also B1) can be prepared independently of one another by customary copolymerization processes, for example suspension polymerization, solvent polymerization, gas-phase polymerization or high-pressure bulk polymerization. The high-pressure mass polymerization is preferably carried out at pressures above 100 MPa, preferably between 100 and 300 MPa, for example between 150 to 275 MPa and temperatures of 100 to 340 ° C., preferably 150 to 310 ° C., for example between 200 and 280 ° C. By suitable choice of the reaction conditions and the amounts of monomers used, the propene content as well as the extent of short chain branches / chain ends can be adjusted. In particular, low reaction temperatures and / or high pressures lead to low fractions of short chain branches and thus to a low number of chain ends.

The reaction of the monomers is initiated by free radical initiators (free radical initiators). This class of substances includes, for example, 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 permaleinate, t-butyl perbenzoate, dicumyl peroxide, t-butyl cumyl peroxide, di (t-butyl) peroxide, 2,2'-azobis (2-methylpropanonitrile), 2,2'-azobis ( 2-methylbutyronitrile). The initiators are used individually or as a mixture of two or more substances in amounts of 0.01 to 10 wt .-%, preferably 0.05 to 5 wt .-%, based on the monomer mixture.

The high-pressure mass polymerization is carried out batchwise or continuously in known high-pressure reactors, for example autoclaves or tubular reactors, and continuously operated tubular reactors have proven particularly suitable. 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. 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 ).

It has proved to be advantageous to set the molecular weight of the polymers not only on the moderating effect of propene but also to use such moderators, which effect essentially only a chain transfer and are not incorporated in the form of comonomers in the polymer chain. Thus, methyl groups can be selectively incorporated into the polymer backbone as impurities, and polymers with improved effectiveness as cold flow improvers are obtained. Preferred moderators are, for example, saturated and unsaturated hydrocarbons such as propane, hexane, heptane and cyclohexane and alcohols such as butanol and in particular aldehydes such as acetaldehyde, propionaldehyde, n-butyraldehyde and isobutyraldehyde and ketones such as acetone, methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketone, Methyl butyl ketone, methyl isobutyl ketone and cyclohexanone. Hydrogen is also suitable as a moderator.

In a particularly preferred embodiment, the polymers according to the invention contain, in addition to vinyl esters and propene, 0.3 to 5.0% by weight, preferably 0.5 to 3.5% by weight, of structural units derived from at least one carbonyl-containing moderator , The concentration of these structural elements derived from the moderator in the polymer can also be determined by means of ¹ H NMR spectroscopy. This can be done, for example, by correlating the intensity of the vinyl ester-derived signals, the proportion of which in the polymer is known, with the signals appearing at about 2.4 to 2.5 ppm of the methylene or methine group adjacent to the carbonyl group of the moderators.

Suitable as component B1) are one or more copolymers of ethylene and olefinically unsaturated compounds whose total comonomer content is at least 2, preferably 3 mol% higher than that of component A. Suitable ethylene copolymers are, in particular, those which have ethylene 9 to 21 mol%, in particular 10 to 18 mol% comonomers. Comonomers may be other olefinically unsaturated compounds in addition to olefinically unsaturated esters. By total comonomer content is meant the content of monomers other than ethylene.

The olefinically unsaturated compounds are preferably vinyl esters, acrylic esters, methacrylic esters, alkyl vinyl ethers and / or alkenes, it being possible for the abovementioned compounds to be substituted by hydroxyl groups. One or more comonomers may be included in the polymer.

The vinyl esters are preferably those of the formula 3

CH ₂ = CH-OCOR ⁴ (3)

wherein R ^{4 is} C ₁ to C ₃₀ alkyl, preferably C ₄ to C ₁₆ alkyl, especially C ₆ to C ₁₂ alkyl. In a further embodiment, said alkyl groups may be substituted with one or more hydroxyl groups.

In a further preferred embodiment, these ethylene copolymers contain vinyl acetate and at least one further vinyl ester of the formula 1 in which R ^{4 is} C ₄ to C ₃₀ -alkyl, preferably C ₄ to C ₁₆ -alkyl, especially C ₆ - to C ₁₂ -alkyl ,

In a further preferred embodiment, R ^{4 is} a branched alkyl radical or a neoalkyl radical having 7 to 11 carbon atoms, in particular having 8, 9 or 10 carbon atoms. Particularly preferred vinyl esters are derived from secondary and especially tertiary carboxylic acids whose branching is in the alpha position to the carbonyl group. Suitable vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl hexanoate, vinyl heptanoate, vinyl octanoate, vinyl pivalate, vinyl 2-ethylhexanoate, vinyl laurate, vinyl stearate and versatic acid esters such as vinyl neononanoate, vinyl neodecanoate, vinyl neoundecanoate.

The acrylic esters are preferably those of the formula 4

CH ₂ = CR ² -COOR ⁵ (4)

wherein R ^{2 is} hydrogen or methyl and R ^{5 is} C ₁ - to C ₃₀ -alkyl, preferably C ₄ - to C ₁₆ -alkyl, especially C ₆ - to C ₁₂ -alkyl. Suitable acrylic esters include, for example, 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 these comonomers. In a further embodiment, said alkyl groups may be substituted with one or more hydroxyl groups. An example of such an acrylic ester is hydroxyethyl methacrylate.

The alkyl vinyl ethers are preferably compounds of the formula 5

CH ₂ = CH-OR ⁶ (5)

wherein R ^{6 is} C ₁ - to C ₃₀ -alkyl, preferably C ₄ - to C ₁₆ -alkyl, especially C ₆ - to C ₁₂ -alkyl. Examples which may be mentioned are methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether. In a further embodiment, said alkyl groups may be substituted with one or more hydroxyl groups.

The alkenes are preferably simple unsaturated hydrocarbons having 3 to 30 carbon atoms, especially 4 to 16 carbon atoms and especially 5 to 12 carbon atoms. Suitable alkenes include propene, butene, isobutylene, pentene, hexene, 4-methylpentene, octene, diisobutylene and norbornene and its derivatives such as methylnorbornene and vinylnorbornene. In a further embodiment, said alkyl groups may be substituted with one or more hydroxyl groups.

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 9 and 21 mol%, preferably between 12 and 18 mol%. Further particularly preferred copolymers contain, in addition to ethylene and 8 to 18 mol% of vinyl esters, 0.5 to 10 mol% of olefins such as propene, butene, isobutylene, hexene, 4-methylpentene, octene, diisobutylene and / or norbornene.
These ethylene copolymers and terpolymers preferably have melt viscosities at 140 ° C. of from 20 to 10,000 mPas, in particular from 30 to 5,000 mPas, especially from 50 to 2,000 mPas. The means of ¹ H-NMR spectroscopy, certain 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, which do not stem from the comonomers.

Depending on the application, the mixing ratio between the terpolymers A) and ethylene copolymers B1) can vary within wide limits, the terpolymers A) often being the smaller fraction as crystal nucleating agents. Preferably, such additive mixtures contain 2 to 70 wt .-%, preferably 3 to 50 wt .-% and especially 5 to 20 wt .-% of component A and 30 to 98 wt .-%, preferably 50 to 97 wt .-% and especially 70 to 95 wt .-% of component B1.

Comb polymers as component B2) are generally characterized as containing a polymer backbone to which are attached at regular intervals long chain branches, such as hydrocarbon chains of about 8 to 50 carbon atoms. These side chains can be bonded directly to the polymer backbone via a C-C bond or via an ether, ester, amide or imide bond.

beschrieben werden. Darin bedeuten

A

R', COOR', OCOR', R"-COOR', OR';

D

H, CH₃, A oder R";

E

H, A;

G

H, R", R"-COOR', einen Arylrest oder einen heterocyclischen Rest;

M

H, COOR", OCOR", OR", COOH;

N

H, R", COOR", OCOR", einen Arylrest;

R'

eine Kohlenwasserstoffkette mit 8 bis 50 Kohlenstoffatomen;

R"

eine Kohlenwasserstoffkette mit 1 bis 10 Kohlenstoffatomen;

m

eine Zahl zwischen 0,4 und 1,0; und

n

eine Zahl zwischen 0 und 0,6.

Suitable comb polymers as component B2) can, for example, be represented by the formula

to be discribed. Mean in it

A

R ', COOR', OCOR ', R "-COOR', OR ';

D

H, CH _3, A or R ";

e

H, A;

G

H, R ", R" -COOR ', an aryl radical or a heterocyclic radical;

M

H, COOR ", OCOR", OR ", COOH;

N

H, R ", COOR", OCOR ", an aryl radical;

R '

a hydrocarbon chain of 8 to 50 carbon atoms;

R "

a hydrocarbon chain of 1 to 10 carbon atoms;

m

a number between 0.4 and 1.0; and

n

a number between 0 and 0.6.

R 'preferably represents a hydrocarbon radical having 10 to 24 C atoms and in particular a hydrocarbon radical having 12 to 18 C atoms. Preferably, R 'is linear or predominantly linear, that is, R' contains at most one methyl or ethyl branch.

Suitable comb polymers are, for example, esterified copolymers of ethylenically unsaturated dicarboxylic acids such as maleic or fumaric acid or their reactive Derivatives with other ethylenically unsaturated monomers such as olefins or vinyl esters. Particularly suitable olefins are α-olefins having 10 to 24 carbon atoms such as 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and mixtures thereof. Even longer-chain olefins based on oligomerized C ₂ -C ₆ -olefins such as poly (isobutylene) with a high proportion of terminal double bonds are suitable as comonomers. Copolymers of maleic acid or maleic anhydride and / or fumaric acid with hexadecene, octadecene and mixtures of these olefins are particularly preferred. In a further preferred embodiment, the copolymers contain up to 15 mol%, such as, for example, 1 to 10 mol% of poly (isobutylene) having a molecular weight Mw between 300 and 5,000 g / mol. Vinyl esters which are particularly suitable as comonomers are derived from fatty acids having 1 to 12 C atoms and in particular 2 to 8 C atoms such as vinyl acetate, vinyl propionate, vinyl butyrate, 2-ethylhexanoic acid vinyl, neononanoic vinyl ester, vinyl neodecanoate and vinyl neoundecanoate. Also mixtures of different vinyl esters are suitable. Particularly preferred are copolymers of fumaric acid with vinyl acetate.

Usually, these copolymers are at least 50% esterified with alcohols having 10 to 24 carbon atoms such as with 12 to 18 carbon atoms. Suitable alcohols include n-decan-1-ol, n-dodecan-1-ol, n-tetradecan-1-ol, n-hexadecan-1-ol, n-octadecan-1-ol, n-eicosan-1-ol and their mixtures. Particular preference is given to n-tetradecan-1-ol, n-hexadecan-1-ol and mixtures thereof.

Also suitable as comb polymers B2) are polymers and copolymers of α-olefins, and also esterified copolymers of styrene and maleic anhydride, and esterified copolymers of stryol and fumaric acid. Again, the above-mentioned alcohols having 10 to 24 carbon atoms are preferred for esterification. Further, poly (alkyl acrylates), poly (alkyl methacrylates) and poly (alkyl vinyl ethers) derived from alcohols having 12 to 20 carbon atoms and poly (vinyl esters) derived from fatty acids having 12 to 20 carbon atoms, as Comb polymers suitable. Also suitable are copolymers based on the abovementioned alkyl acrylates, methacrylates, alkyl vinyl ethers and / or vinyl esters, for example copolymers of alkyl acrylates and vinyl esters. Also mixtures of two or more comb polymers are suitable according to the invention.

The comb polymers of components B2) preferably have molecular weights Mw between about 2,000 and about 50,000 g / mol, preferably between 3,000 and 20,000 g / mol.

The mixing ratio between component A) and comb polymer B2) is usually in the range from 10: 1 to 1: 3, preferably between 6: 1 and 1: 2, for example between 5: 1 and 1: 1. The mixing ratio between component B1) and comb polymer B2) is usually between 10: 1 to 1: 3, preferably between 6: 1 and 1: 2, for example between 5: 1 and 1: 1

The additive mixtures according to the invention are usually used for the purpose of better handling as concentrates in organic solvents. Suitable solvents or dispersants are, for example, higher-boiling aliphatic hydrocarbons, aromatic hydrocarbons, alcohols, esters, ethers and mixtures thereof. Preferably, solutions or dispersions of the additive mixtures according to the invention contain from 10 to 90% by weight, in particular from 20 to 80% by weight and especially from 40 to 75% by weight, of solvent.

Surprisingly, it has been found that the solutions of the additive mixtures according to the invention have a lower ownstock point than corresponding mixtures based on terpolymers of ethylene, unsaturated esters and higher olefins according to the prior art. In addition, they show improved efficacy in terms of the cold flow improvement of fuel oils, and in particular, improved solubility in fuel oils even at low temperatures. Thus, these additives can also be used at low temperatures without prior heating of oil and / or additive, without filtration problems in the additized oil resulting from undissolved or recrystallized portions of the polymer A). On the other hand, the additives according to the invention can be transported at the same temperature with a lower solvent content and processed as corresponding additives of the prior art, whereby transport and storage costs are reduced.

The additive mixtures according to the invention can also be added to middle distillates for improving the cold flowability in combination with other additives such as, for example, oil-soluble polar nitrogen compounds, alkylphenol resins, polyoxyalkylene compounds and / or olefin copolymers.

Suitable oil-soluble polar nitrogen compounds are preferably reaction products of fatty amines with compounds containing an acyl group. The preferred amines are compounds of the formula NR ⁷ R ⁸ R ⁹ , in which R ⁷ , R ⁸ and R ^{9 may be} identical or different, and at least one of these groups is C ₈ -C ₃₆ -alkyl, C ₆ - C ₃₆ -cycloalkyl, C ₈ -C ₃₆ -alkenyl, in particular C ₁₂ -C ₂₄ -alkyl, C ₁₂ -C ₂₄ -alkenyl or cyclohexyl, and the other groups are either hydrogen, C ₁ -C ₃₆ -alkyl, C ₂ -C ₃₆ alkenyl, cyclohexyl, or a group of the formulas - (AO) _x -E or - (CH ₂ ) _n -NYZ, where A is an ethyl or propyl group, x is a number from 1 to 50, E = H, C ₁ -C ₃₀ -alkyl, C ₅ -C ₁₂ -cycloalkyl or C ₆ -C ₃₀ -aryl, and n = 2, 3 or 4, and Y and Z independently of one another are H, C ₁ -C ₃₀ Alkyl or - (AO) _x . The alkyl and alkenyl radicals can be linear or branched and contain up to two double bonds. They are preferably linear and substantially saturated, ie they have iodine numbers of less than 75 gl ₂ / g, preferably less than 60 gl ₂ / g and in particular between 1 and 10 gl ₂ / g. Particular preference is given to secondary fatty amines in which two of the groups R ⁷ , R ⁸ and R ^{9 are} C ₈ -C ₃₆ -alkyl, C ₆ -C ₃₆ -cycloalkyl, C ₈ -C ₃₆ -alkenyl, in particular C ₁₂ -C ₂₄ alkyl, C ₁₂ -C ₂₄ alkenyl or cyclohexyl. Suitable fatty amines are, for example, octylamine, decylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, eicosylamine, behenylamine, didecylamine, didodecylamine, ditetradecylamine, dihexadecylamine, dioctadecylamine, dieicosylamine, dibehenylamine and mixtures thereof. Specifically, the amines contain chain cuts based on natural raw materials such as coco fatty amine, tallow fatty amine, hydrogenated tallow fatty amine, dicocosfettamine, ditallow fatty amine and di (hydrogenated tallow fatty amine). Particularly preferred amine derivatives are amine salts, imides and / or amides such as, for example, amide ammonium salts of secondary fatty amines, in particular dicocosfettamine, ditallow fatty amine and distearylamine.

By acyl group is meant here a functional group of the following formula:

> C = O

Suitable carbonyl compounds for the reaction with amines are both monomeric and polymeric compounds having one or more carboxyl groups. In the case of the monomeric carbonyl compounds, preference is given to those having 2, 3 or 4 carbonyl groups. They can also contain heteroatoms such as oxygen, sulfur and nitrogen. Examples of suitable carboxylic acids are maleic, fumaric, crotonic, itaconic, succinic, C ₁ -C ₄₀ -alkenylsuccinic, adipic, glutaric, sebacic, and malonic acids and benzoic, phthalic, trimellitic and pyromellitic acid, nitrilotriacetic acid , Ethylenediaminetetraacetic acid and their reactive derivatives such as esters, anhydrides and acid halides. Copolymers of ethylenically unsaturated acids, such as, for example, acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid, have proven particularly suitable as polymeric carbonyl compounds, particular preference is given to copolymers of maleic anhydride. Suitable comonomers are those which impart oil solubility to the copolymer. Oil-soluble means here that the copolymer dissolves without residue in the middle distillate to be additive after reaction with the fatty amine in practice-relevant metering rates. Suitable comonomers are, for example, olefins, alkyl esters of acrylic acid and methacrylic acid, alkyl vinyl esters and alkyl vinyl ethers having 2 to 75, preferably 4 to 40 and in particular 8 to 20 carbon atoms in the alkyl radical. In the case of olefins, the carbon number refers to the alkyl radical attached to the double bond. The molecular weights of the polymeric carbonyl compounds are preferably between 400 and 20,000, particularly preferably between 500 and 10,000, for example between 1,000 and 5,000 g / mol.

Oil-soluble polar nitrogen compounds 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 proved particularly suitable (cf. US 4 211 534 ). Similarly, amides and ammonium salts of aminoalkylene polycarboxylic acids such as nitrilotriacetic acid or ethylenediaminetetraacetic acid with secondary amines are suitable as oil-soluble polar nitrogen compounds (cf. EP 0 398 101 ). Other oil-soluble polar nitrogen compounds are copolymers of maleic anhydride with α, β-unsaturated compounds which can be reacted, if appropriate, with primary monoalkylamines and / or aliphatic alcohols (cf. EP-A-0 154 177 . EP 0 777 712 ), the reaction products of Alkenylspirobislactonen with amines (see. EP-A-0 413 279 B1) and after EP-A-0 606 055 A2 reaction products of terpolymers based on α, β-unsaturated dicarboxylic acid anhydrides, α, β-unsaturated compounds and polyoxyalkylene ethers of lower unsaturated alcohols.

The mixing ratio between the additive mixtures according to the invention and oil-soluble polar nitrogen compounds may vary depending on the application. Such mixtures preferably contain 0.1 to 10 parts by weight, preferably 0.2 to 5 parts by weight, based on the active ingredients, of at least one oil-soluble polar nitrogen compound per part by weight of the additive mixture according to the invention.

Suitable alkylphenol-aldehyde resins are in particular those alkylphenol-aldehyde resins which are derived from alkylphenols having one or two alkyl radicals in ortho and / or para position to the OH group. Particularly preferred as starting materials are alkylphenols which carry at least two hydrogen atoms capable of condensation with aldehydes on the aromatic and in particular monoalkylated phenols. Particularly preferably, the alkyl radical is in the para position to the phenolic OH group. The alkyl radicals (which are generally understood as hydrocarbon radicals as defined below for the alkylphenol resins) may be identical or different in the alkylphenol-aldehyde resins which can be used with the additive mixtures according to the invention. The alkyl radicals can be saturated or unsaturated. They can be linear or branched, preferably they are linear. They have 1 to 200, preferably 1 to 24, especially 4 to 16 such as 6 to 12 carbon atoms. It is preferably 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, tetradecyl, hexadecyl, octadecyl, eicosyl, tripropenyl, tetrapropenyl, poly (propenyl) - and poly (isobutenyl) radicals. In a preferred embodiment, mixtures of alkylphenols having different alkyl radicals are used for the preparation of the alkylphenol resins. For example, resins based on Butylphenol on the one hand and octyl, nonyl and / or dodecylphenol in a molar ratio of 1:10 to 10: 1 on the other hand particularly proven.

Suitable alkylphenol resins may also contain or consist of structural units of other phenol analogs such as salicylic acid, hydroxybenzoic acid and derivatives thereof such as esters, amides and salts.

Suitable aldehydes for the alkylphenol-aldehyde resins are those having 1 to 12 carbon atoms and preferably those having 1 to 4 carbon atoms such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, 2-ethylhexanal, benzaldehyde, glyoxalic acid and their reactive equivalents such as paraformaldehyde and trioxane. Particularly preferred is formaldehyde in the form of paraformaldehyde, and especially formalin.

The molecular weight of the alkylphenol-aldehyde resins measured by gel permeation chromatography against poly (styrene) standards in THF is preferably 500-25,000 g / mol, more preferably 800-10,000 g / mol, and especially 1,000-5,000 g / mol such as 1,500-3,000 g / mol. The prerequisite here is that the alkylphenol-aldehyde resins, at least in application-relevant concentrations of 0.001 to 1 wt .-% are oil-soluble.

sind, worin R¹⁰ für C₁-C₂₀₀-Alkyl oder -Alkenyl, O-R¹¹ oder O-C(O)-R¹¹, R¹¹ für C₁-C₂₀₀-Alkyl oder -Alkenyl und n für eine Zahl von 2 bis 100 stehen. R¹¹ steht bevorzugt für C₁-C₂₀-Alkyl oder -Alkenyl und insbesondere für C₄-C₁₆-Alkyl oder -Alkenyl wie beispielsweise für C₆-C₁₂-Alkyl oder -Alkenyl. Besonders bevorzugt steht R¹⁰ für C₁-C₂₀-Alkyl oder -Alkenyl und insbesondere für C₄-C₁₆-Alkyl oder -Alkenyl wie beispielsweise für C₆-C₁₂-Alkyl oder -Alkenyl. Bevorzugt steht n für eine Zahl von 2 bis 50 und speziell für eine Zahl von 3 bis 25 wie beispielsweise eine Zahl von 5 bis 15.In a preferred embodiment of the invention, these are alkylphenol-formaldehyde resins, the oligo- or polymers having a repetitive structural unit of the formula

wherein R ^{10 is} C ₁ -C ₂₀₀ alkyl or alkenyl, OR ¹¹ or OC (O) -R ¹¹ , R ^{11 is} C ₁ -C ₂₀₀ alkyl or alkenyl and n is a number from 2 to 100 stand. R ¹¹ stands preferably C ₁ -C ₂₀ -alkyl or -alkenyl and in particular C ₄ -C ₁₆ -alkyl or -alkenyl, for example C ₆ -C ₁₂ -alkyl or -alkenyl. R ¹⁰ particularly preferably represents C ₁ -C ₂₀ -alkyl or -alkenyl and in particular C ₄ -C ₁₆ -alkyl or -alkenyl, for example C ₆ -C ₁₂ -alkyl or -alkenyl. Preferably, n is a number from 2 to 50 and especially a number from 3 to 25, such as a number from 5 to 15.

Particularly preferred for use in middle distillates such as diesel and heating oil are alkylphenol-aldehyde resins having C ₂ -C ₄₀ -alkyl radicals of the alkylphenol, preferably having C ₄ -C ₂₀ -alkyl radicals such as C ₆ -C ₁₂ -alkyl radicals. The alkyl radicals can be linear or branched, preferably they are linear. Particularly suitable alkylphenol-aldehyde resins are derived from linear alkyl radicals having 8 and 9 C atoms.

Particularly preferred for use in heavy fuel oils and in particular in distillation residues containing fuel oils are alkylphenol-aldehyde resins whose alkyl radicals carry 4 to 50 carbon atoms, preferably 10 to 30 carbon atoms. The degree of polymerization (n) here is preferably between 2 and 20, preferably between 3 and 10 alkylphenol units.

These alkylphenol-aldehyde resins are, for example, by condensation of the corresponding alkylphenols with formaldehyde, ie with 0.5 to 1.5 moles, preferably 0.8 to 1.2 moles of formaldehyde per mole of alkylphenol. The condensation can be carried out solvent-free, but preferably it is carried out in the presence of a non or only partially water-miscible inert organic solvent such as mineral oils, alcohols, ethers, and the like. Particularly preferred are solvents which can form azeotropes with water. As such solvents in particular aromatics such as toluene, xylene diethylbenzene and higher-boiling commercial solvent mixtures such as ^® Shellsol AB, and solvent naphtha are used. Also, fatty acids and their derivatives such as esters with lower alcohols having 1 to 5 carbon atoms such as ethanol and especially methanol are suitable as solvents. The condensation is preferably carried out between 70 and 200 ° C such as between 90 and 160 ° C. It is usually catalysed by 0.05 to 5 wt .-% bases or preferably by 0.05 to 5 wt .-% acids. As sour Catalysts are in addition to carboxylic acids such as acetic acid and oxalic acid in particular strong mineral acids such as hydrochloric acid, phosphoric acid and sulfuric acid and sulfonic acids common catalysts. Particularly suitable catalysts are sulfonic acids which contain at least one sulfonic acid group and at least one saturated or unsaturated, linear, branched and / or cyclic hydrocarbon radical having 1 to 40 C atoms and preferably having 3 to 24 C atoms. Particular preference is given to aromatic sulfonic acids, especially alkylaromatic monosulfonic acids having one or more C ₁ -C ₂₅ -alkyl radicals and, in particular, those having C ₃ -C ₂₂ -alkyl radicals. Suitable examples are methanesulfonic acid, butanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, xylenesulfonic acid, 2-mesitylenesulfonic acid, 4-ethylbenzenesulfonic acid, isopropylbenzenesulfonic acid, 4-butylbenzenesulfonic acid, 4-octylbenzenesulfonic acid; Dodecylbenzenesulfonic acid, didodecylbenzenesulfonic acid, naphthalenesulfonic acid. Mixtures of these sulfonic acids are suitable. Usually, these remain after completion of the reaction as such or in neutralized form in the product. For neutralization, amines and / or aromatic bases are preferably used, since they can remain in the product; Metal ions containing and thus ash-forming salts are usually separated.

Further suitable polyoxyalkylene compounds are, for example, esters, ethers and ethers / esters of polyols which carry at least one alkyl radical having 12 to 30 carbon atoms. When the alkyl groups are derived from an acid, the remainder is derived from a polyhydric alcohol; If the alkyl radicals come from a fatty alcohol, the remainder of the compound derives 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 g / mol. Also suitable are alkoxylates of polyols, for example of glycerol, trimethylolpropane, pentaerythritol, neopentyl glycol, and the oligomers having from 2 to 10 monomer units obtainable therefrom by condensation, such as, for example, polyglycerol. Preferred alkoxylates are those having from 1 to 100, in particular from 5 to 50, mol of ethylene oxide, propylene oxide and / or butylene oxide per mole of 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, more preferably 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 from 150 to 2,000, preferably from 200 to 600. Particularly suitable are PEG-600 dibehenate and glycerol-ethylene glycol tribehenate.

Olefincopolymers which are suitable as further constituent of the additive according to the invention can be derived directly from monoethylenically unsaturated monomers or can be prepared indirectly by hydrogenation of polymers derived from polyunsaturated monomers such as isoprene or butadiene. In addition to ethylene, preferred copolymers contain structural units which are derived from α-olefins having 3 to 24 carbon atoms and have molecular weights of up to 120,000 g / mol.
Preferred α-olefins are propene, butene, isobutene, n-hexene, isohexene, n-octene, isooctene, n-decene, isodecene. The comonomer content of α-olefins having 3 to 24 C atoms is preferably between 15 and 50 mol%, more preferably between 20 and 35 mol% and especially between 30 and 45 mol%. These copolymers may also contain minor amounts, eg up to 10 mol% of other comonomers, such as non-terminal olefins or non-conjugated olefins. Preferred are ethylene-propene copolymers. The olefin copolymers can be prepared by known methods, for example 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 between the additive mixtures according to the invention and alkylphenol resins, polyoxyalkylene compounds or olefin copolymers can vary depending on the application. Such mixtures preferably contain 0.1 to 10 parts by weight, preferably 0.2 to 5 parts by weight, based on the active compounds at least one alkylphenol resin, a polyoxyalkylene compound and / or an olefin copolymer per part by weight of the additive mixture according to the invention.

The additive mixtures according to the invention can be used alone or together with other additives, e.g. with other pour point depressants or dewaxing aids, with antioxidants, cetane number improvers, dehazers, demulsifiers, detergents, dispersants, defoamers, dyes, corrosion inhibitors, lubricity additives, sludge inhibitors, odorants and / or cloud point depressants.

The additive mixtures according to the invention are suitable for improving the cold flow properties of animal, vegetable mineral and / or synthetic fuel oils. At the same time, these additive blends and their concentrated formulations in mineral oil based solvents have low levels of inherent stickiness. This allows a problem-free use of these additive mixtures at lower temperatures or in higher concentrations than is possible with additives of the prior art. Also, the additive mixtures can be dosed due to their good solubility in cold oils, without causing filter blockages by undissolved or recrystallized portions of the additive mixtures.

They are particularly suitable for improving the properties of mineral oils and mineral oil distillates in the middle distillate range, such as, for example, jet fuel, kerosene, diesel and heating oil. Additive mixtures containing components A and B1 are particularly suitable for middle distillates with cloud points below + 5 ° C such as between -15 ° C and + 3 ° C. They are particularly suitable for those oils which have a high content of particularly cold-critical paraffins with a carbon chain length of 20 or more carbon atoms of more than 3.0 area% and in particular more than 4.0 area%. Additive mixtures containing components A and B2 are particularly suitable for middle distillates with cloud points above -4 ° C such as above -2 ° C. They are particularly suitable for those oils which have a high content of particularly cold-critical paraffins with a carbon chain length of 20 or more carbon atoms of more than 3.5 area% and in particular more than 4.5 area%. The paraffin content is determined by gas chromatographic separation of the oil under detection by a FID detector and calculation of the integral of n-paraffins with a chain length of at least 20 C atoms in relation to the total integral of the oil. In order to lower the sulfur content, they have often been subjected to hydrogenation refining and preferably contain less than 350 ppm sulfur, and more preferably less than 100 ppm sulfur, such as less than 50 ppm or 10 ppm sulfur.

The fuel oils according to the invention preferably contain 5 to 5,000 ppm, particularly preferably 10 to 2,000 ppm and especially 50 to 1,000 ppm of the additive mixtures according to the invention.

The middle distillate is in particular those mineral oils which are obtained by distillation of crude oil and boil in the range of 120 to 450 ° C, for example kerosene, jet fuel, diesel and fuel oil. The additive mixtures according to the invention are particularly advantageous in those middle distillates which have 90% distillation points according to ASTM D86 above 340 ° C., in particular above 360 ° C. and in special cases above 370 ° C. Middle distillates also include synthetic fuel oils boiling in the temperature range of about 120 to 450 ° C and mixtures of these synthetic and mineral middle distillates. Examples of synthetic middle distillates are, in particular, fuels produced from coal, natural gas or even biomass by the Fischer-Tropsch process. Synthesis gas is first produced and this is converted into normal paraffins via the Fischer-Tropsch process. The normal paraffins thus prepared can then be modified, for example, by catalytic cracking, isomerization, hydrocracking or hydrosiomerization.

The additive mixtures according to the invention are also particularly effective in middle distillates which contain minor amounts, for example up to 30% by volume, of oils of animal and / or vegetable origin. Examples of suitable oils of animal and / or plant origin are both triglycerides and esters derived therefrom with lower alcohols having 1 to 5 carbon atoms such as ethyl and in particular methyl esters, for example, from cotton, palm kernels, rapeseed, soy, sunflower, tallow and the like are accessible.

Examples The following additives were used: Preparation of ethylene copolymers A

• Process A): In a continuously operated tubular reactor, ethylene, propene and vinyl acetate were copolymerized at 200 MPa and a peak temperature of 250 ° C with the addition of a mixture of various free-radical initiators and the molecular weight regulator indicated in Table 1. The resulting polymer was separated from the reaction mixture and then freed of residual monomers.
• Method B): In a continuously operated high-pressure autoclave, ethylene, vinyl acetate and propene were copolymerized with addition of a 10% strength by weight solution of bis (2-ethylhexyl) peroxydicarbonate as initiator and the molecular weight regulator indicated in Table 1. The resulting polymer was separated from the reaction mixture and then freed of residual monomers.

For comparison, a terpolymer of ethylene, vinyl acetate and propene according to EP 0 190 553 , a terpolymer of ethylene, vinyl acetate and 4-methylpentene-1 according to EP 0 807 642 and a terpolymer of ethylene, vinyl acetate and isobutylene.

The vinyl acetate content is determined by means of pyrolysis of the polymer freed from residual monomers at 150 ° C./100 mbar. For this purpose, 100 mg of the polymer are thermally split with 200 mg of pure polyethylene in a pyrolysis flask for 5 minutes at 450 ° C in a closed system under vacuum and collected the fission gases in a 250 ml round bottom flask. The cleavage product acetic acid is reacted with a NaJ / KJO ₃ solution and titrated with Na ₂ S ₂ O ₃ solution, the liberated iodine.

The determination of the total number of non-vinyl ester methyl groups of the polymer by means of ¹ H-NMR spectroscopy at a Measuring frequency of 500 MHz at 10 to 15% strength solutions in C ₂ D ₂ Cl ₄ at 300 K. The integral of the methyl protons between 0.7 to 0.9 ppm becomes that of the methylene and methine protons between 0.9 and 1, 9ppm. A correction of the number of methyl groups around the structural units derived from the moderator used and superposed with the signals of the main chain is based on the separately appearing methine proton of the moderator (for example, methyl ethyl ketone multiples at 2.4 and 2.5 ppm).

The determination of the content of methyl groups derived from propene is carried out by means of ¹³ C-NMR spectroscopy at a measurement frequency of 125 MHz at also 10 to 15% solutions in C ₂ D ₂ Cl ₄ at 300 K. The integral of the Propene-derived methyl groups between 19.3 and 20.2 ppm are proportioned to that of the aliphatic carbon atoms of the polymer backbone between 22 and 44 ppm. Advantageously, ¹ H and ¹³ C NMR measurements are carried out on the same sample.

The number of chain ends is determined by subtracting the number of methyl groups derived from propene by ¹³ C-NMR from the total number of methyl groups determined by ¹ H-NMR. Both values are to be treated as dimensionless numbers. Table 1: Characterization of the ethylene copolymers A used polymer Polymerization process / moderator Vinyl acetate in the polymer [mol%] Propene-CH ₃ per 100 aliph. CH ₂ Number of chain ends [CH _3/100 CH _2] Total G V ₁₄₀ [mPas] P1 A / PA 8.9 2.1 4.3 10.3 314 P2 A / PA 9.3 1.5 4.7 10.8 357 P3 B / MEK 9.7 1.4 3.2 11.1 346 P4 B / MEK 10.1 1.8 3.4 11.9 316 P5 A / PA 9.6 1.3 4.0 10.9 286 P6 A / MEK 9.8 1.2 3.9 11.0 288 P7 A / PA 11.4 0.8 4.9 12.2 371 P8 A / PA 7.8 2.7 5.1 10.5 302 P9 (Cf.) B / Propene 9.4 6.4 6.2 15.8 347 P10 (Cf.) B / PA 9.7 2.1 mol% 4-MP-1 n / A n / A 325 P11 (Cf.) B / PA 9.5 2.5 mol% DIB n / A n / A 297 PA = propionaldehyde; MEK = methyl ethyl ketone; 4-MP-1 = 4-methylpentene-1; DIB = diisobutylene; na = not applicable

• B1-I) Terpolymer aus Ethylen, 14 mol-% Vinylacetat und 2 mol-% Neodecansäurevinylester mit einer bei 140 °C gemessenen Schmelzviskosität von 95 mPas
• B1-II) Copolymer aus Ethylen und 13,5 mol-% Vinylacetat mit einer bei 140°C gemessenen Schmelzviskosität von 150 mPas.
• B2-I) Alternierendes Copolymer aus Maleinsäureanhydrid und Octadecen, vollständig verestert mit einer Mischung gleicher Teile Tetradecanol und Hexadecanol.
• C-I) Mischung aus einem Umsetzungsprodukt eines Copolymers aus C₁₆-α-Olefin und Maleinsäureanhydrid mit 2 Equivalenten Di(hydriertem Talgfett)amin und einem Nonylphenol-Formaldehydharz im Gewichtsverhältnis von 2:1.

Characterization of flow improver components (B) and further flow improver components (C):

• B1-I) Terpolymer of ethylene, 14 mol% of vinyl acetate and 2 mol% of vinyl neodecanoate with a melt viscosity of 95 mPas measured at 140 ° C.
• B1-II) copolymer of ethylene and 13.5 mol% of vinyl acetate with a measured at 140 ° C melt viscosity of 150 mPas.
• B2-I) Alternating copolymer of maleic anhydride and octadecene completely esterified with a mixture of equal parts of tetradecanol and hexadecanol.
• CI) Mixture of a reaction product of a copolymer of C ₁₆ -α-olefin and maleic anhydride with 2 equivalents of di (hydrogenated tallow fat) amine and a nonylphenol-formaldehyde resin in a weight ratio of 2: 1.

All additives A, B and C used were, unless stated otherwise, used as 50 wt .-% settings in higher-boiling, mainly aliphatic solvent. Table 2: Characterization of the used test oils The test oils used were current oils from European refineries. The CFPP value was determined according to EN 116 and the determination of the cloud point according to ISO 3015. The paraffin content was determined by gas chromatographic separation of the oil under detection by an FID detector and calculation of the integral of the n-paraffins with a chain length of at least 20 C atoms in relation to the total integral. Test oil 1 Test oil 2 Test oil 3 Test oil 4 Test oil 5 Test oil 6 distillation IBP [° C] 163 160 174 167 153 187 20% [° C] 222 206 222 238 195 223 90% [° C] 343 339 354 341 354 337 FBP [° C] 366 363 371 359 375 360 Cloud Point [° C] -3.9 -2.5 0.0 -3.9 +0.7 -5.1 CFPP [° C] -6 -4 -3 -7 -3 -9 Sulfur [ppm] 19 25 8th 5 66 8th Density @ 15 ° C [g / cm ³ ] 0.835 0.829 0.858 0.845 0.858 0.834 Paraffin content ≥C ₂₀ [Fl .-%] 5.7 5.9 7.6 5.2 7.0 7.9

Effectiveness of the additives as cold flow improvers

The superior efficacy of the inventive additives for mineral oils and mineral oil distillates is described by means of the CFPP test (Cold Filter Plugging Test according to EN 116). Table 3: Test as cold flow improver in test oil 1 additive CFPP [° C] example A B C 200 ppm 400 ppm 600ppm 1 20% P1 55% B1-I 25% CI -19 -22 -25 2 20% P2 55% B1-I 25% CI -23 -28 -27 3 20% P3 55% B1-I 25% CI -24 -22 -26 4 20% P4 55% B1-I 25% CI -18 -22 -26 5 20% P5 55% B1-I 25% CI -23 -26 -27 6 20% P6 55% B1-I 25% CI -23 -29 -28 7 20% P7 55% B1-I 25% CI -18 -21 -24 8th 20% P8 55% B1-I 25% CI -19 -22 -24 9 (Cf.) 20% P9 55% B1-I 25% CI -14 -16 -18 10 (Cf.) 20% P10 55% B1-I 25% CI -17 -20 -23 11 (Cf.) - 69% B1-I 31% CI -10 -12 -17 additive CFPP [° C] example A B C 200 ppm 400 ppm 600 ppm 12 20% P1 55% B1-I 25% CI -15 -20 -20 13 20% P2 55% B1-I 25% CI -17 -23 -23 14 20% P3 55% B1-I 25% CI -18 -21 -22 15 20% P4 55% B1-I 25% CI -16 -20 -22 16 20% P5 55% B1-I 25% CI -16 -22 -25 17 20% P6 55% B1-I 25% CI -18 -19 -22 18 20% P7 55% B1-I 25% CI -14 -18 -19 19 20% P8 55% B1-I 25% CI -15 -19 -20 20 (Cf.) 20% P9 55% B1-I 25% CI -9 -13 -14 21 (Cf.) 20% P11 55% B1-I 25% CI -14 -17 -18 22 (See) - 69% B1-I 31% CI -8th -12 -16 additive CFPP [° C] example A B 50 ppm 100 ppm 150 ppm 23 85% P1 15% B1-II -5 -10 -12 24 85% P2 15% B1-II -4 -8th -13 25 85% P3 15% B1-II -4 -7 -14 26 85% P4 15% B1-II -4 -9 -11 27 85% P5 15% B1-II -5 -12 -15 28 85% P6 15% B1-II -4 -8th -14 29 (Cf.) 85% P9 15% B1-II -3 -5 -7 30 (Cf.) 85% P10 15% B1-II -4 -6 -11 31 (Cf.) - 100% B1-II -4 -4 -5 32 (Cf.) 100% P1 - 0 -2 -4 additive CFPP [° C] example A B 50 ppm 100 ppm 200 ppm 33 35% P1 65% B1-I -10 -16 -20 34 35% P2 65% B1-I -10 -17 -20 35 35% P3 65% B1-I -11 -17 -20 36 35% P5 65% B1-I -11 -17 -19 37 35% P6 65% B1-I -10 -16 -18 38 (Cf.) 35% P9 65% B1-I -10 -13 -15 39 (Cf.) 35% P10 65% B1-I -11 -15 -18 40 (Cf.) - 100% Bl-I -10 -9 -14 41 (Cf.) 100% P1 - -8th -13 -16 additive CFPP [° C] example A B 300 ppm 400 ppm 42 65% P1 35% B2-I -7 -11 43 65% P2 35% B2-I -7 -12 44 65% P4 35% B2-I -6 -11 45 65% P6 35% B2-I -6 -10 46 (See) 65% P9 35% B2-I -4 -8th 47 (Cf.) 65% P11 35% B2-I -4 -9

Handleability and filter clogging tendency of the polymers

To assess the cold flowability of concentrates of the polymers according to the invention, the polymers described in Table 1 were dissolved in a predominantly aliphatic solvent mixture having a boiling range of 175-260 ° C. and a flash point of 66 ° C., 35% strength by weight. For this purpose, the polymer and solvent were heated with stirring to 80 ° C and cooled after homogenization to room temperature.

Subsequently, the pour point of the concentrate was determined in accordance with DIN ISO 3016. Table 8: Eigenstock point of the polymer concentrates example template Pour point 48 P1 + 6 ° C 49 P2 + 6 ° C 50 P3 0 ° C 51 P4 - 6 ° C 52 P5 + 3 ° C 53 P6 0 ° C 54 (Cf.) P9 - 3 ° C 55 (Cf.) P10 (Cf.) + 9 ° C 56 (Cf.) P11 (Cf.) + 9 ° C

Furthermore, the Filterverstopfungstendenz a treated with additives of the invention test oil was determined according to IP 387/97. In this test, 300 ml of an additive diesel fuel at a defined temperature and a pump capacity of 20 ml / min are filtered through a 1.6 micron glass fiber filter. The test is passed when a volume of 300 ml has passed through the filter without the pressure (P) reaching or exceeding 105 kPa (filter clogging tendency FBT = (1+ (P / 105) ² ) ^0.5 ≤ 1, 41). It is considered to fail when the pressure reaches 105 kPa before the total volume (V) of 300 ml has passed the filter (Filter clogging tendency FBT = (1+ (300 / V) ² ) ^0.5 > 1.41). It is also important for the assessment of the additives that the filter clogging tendency of the unadditized fuel is increased as little as possible by adding the additive.

To carry out the test, 350 ml of the tempered to 20-22 ° C test oil 6 with 500 ppm of tempered to 60 ° C additive (50% solution) were added. After manual shaking and storage at 60 ° C for 30 minutes, the additized oil was stored at 20 ° C for 16 hours. Subsequently, the additized oil was used without further shaking for filtration. Table 9: Filter clogging tendency of the additized test oil 6 according to IP 387/97 example template Filter clogging tendency 57 without 1.01 58 P1 1.02 59 P2 1.02 60 P3 1.11 61 P4 1.02 62 P5 1.03 63 P6 1.09 64 P7 1.25 65 P8 1.27 66 (Cf.) P9 1.05 67 (Cf.) P10 1.57 68 (See) P11 1.76

The experiments show that the additives according to the invention are superior to the additives of the prior art in terms of improving the cold flowability and in particular the CFPP reduction of middle distillates. At the same time, they can be used at lower temperatures. They are particularly useful in applications where particularly clean fuels with very low tendency to filter clogging are required.

Claims (14)

Additive mixtures containing A) at least one terpolymer of ethylene, propene and at least one ethylenically unsaturated ester which i) contains from 6.0 to 12.0 mol% of structural units derived from at least one ethylenically unsaturated ester with a C ₁ to C ₃ alkyl radical, ii) contains 0.5 to 4.0 propene-derived methyl groups per 100 aliphatic C atoms, iii) has less than 8.0 chain end methyl groups per 100 CH ₂ groups, and B) 0.5 to 20 parts by weight based on A) of at least one further, as a cold additive for mineral oils effective, component selected from B1) copolymers of ethylene and ethylenically unsaturated compounds whose content of ethylenically unsaturated compounds is at least 2 mol% higher than the content of the terpolymer defined in A) of ethylenically unsaturated esters, B2) comb polymers, and B3) mixtures of B1) and B2). An additive mixture according to claim 1, wherein the ethylenically unsaturated ester of component A) is the vinyl ester of a carboxylic acid having 1 to 4 carbon atoms. An additive mixture according to claim 2, wherein the unsaturated ester is vinyl acetate. An additive mixture as claimed in one or more of claims 1 to 3, in which the sum G of molar content of unsaturated ester i) and the number of propene-derived methyl groups per 100 aliphatic C atoms of the polymer ii) $$\mathrm{G}=\left[\mathrm{mol}-\%\mathrm{unsaturated\; ester}\right]+\left[\mathrm{propene}-{\mathrm{CH}}_3\right]$$

between 8.0 and 14.0. An additive mixture according to one or more of claims 1 to 4, wherein component A) additionally contains 0.3 to 5.0% by weight of at least one structural unit derived from a carbonyl group-containing moderator. An additive mixture according to one or more of claims 1 to 5, wherein the content of the copolymer B1) of ethylenically unsaturated compounds is at least three mol% higher than that of the terpolymer A) of ethylenically unsaturated esters. A process for preparing the terpolymer A) by reacting a mixture of ethylene, propene and at least one vinyl ester under elevated pressure and temperature in the presence of a free radical initiator, and wherein the molecular weight of the terpolymer A) is adjusted by a carbonyl group-containing moderator becomes. Use of an additive mixture according to one or more of claims 1 to 6 for improving the cold flowability of fuel oils. A method for improving the flowability of fuel oils by adding to the fuel oil an additive mixture according to one or more of claims 1 to 6. Composition comprising at least one additive mixture according to one or more of claims 1 to 6 and at least one oil-soluble polar nitrogen compound. Composition comprising at least one additive mixture according to one or more of claims 1 to 6 and at least one alkylphenol-aldehyde resin. Composition comprising at least one additive mixture according to one or more of claims 1 to 6 and at least one olefin polymer. Composition according to one or more of the preceding claims comprising at least one additive mixture according to one or more of claims 1 to 6 and at least one polyoxyalkylene compound. A fuel oil composition comprising a middle distillate and at least one additive mixture according to one or more of claims 1 to 6.