DE10322163A1 - Fuel compositions containing terpolymers with improved cold flow properties - Google Patents

Abstract

The invention relates to the use of terpolymers comprising as monomer components a) at least one lower alkene, b) at least one long-chain alpha olefin and c) at least one polar polymerizable monomer, as an additive for fuel oils and lubricants and in particular as a cold flow improver in fuel oils; the fuel oils and lubricants added with these terpolymers; and additive packages containing such terpolymers.

Description

The Invention relates to the use of terpolymers comprising as Monomer components a) at least one lower alkene, b) at least a long-chain alpha-olefin and c) at least one polar polymerizable Monomer, as an additive for fuel oils and lubricants and in particular as cold flow improvers in fuel oils; the with these terpolymers additive fuel oils and lubricants; such as Additive packages containing such terpolymers.

State of the art:

paraffinic Mineral oils containing waxes, like middle distillates, diesel and heating oils, show when the temperature drops a significant deterioration in the flow properties. The cause therefor lies in the crystallization occurring from the temperature of the cloud point of longer Paraffins, the great, platelet-shaped wax crystals form. These wax crystals have a sponge-like structure and lead to include other fuel components in the crystal composite. The appearance of these crystals leads quickly for gluing fuel filters both in tanks and in Motor vehicles. At temperatures below the pour point (PP) finally finds no more flow of fuel instead.

to Resolving these problems has been used as a fuel additive for a long time added in small concentrations, often from combinations of Early nucleators Formation of tiny crystallites of the paraffins with the actual ones cold flow improvers (also known as CFI or MDFI). These in turn show similar ones Crystallization properties like the paraffins of the fuel, however prevent their growth, so that a passage through the filter at significantly lower compared to the unadditized fuel Temperatures possible is. As a measure of this, the so-called cold filter plugging point (CFPP). As another Can additive so-called wax anti-settling additives (WASA) are used, which prevent the smallest crystallites in the fuel from sinking.

refinery Limited However, the composition of a fuel is usually not constant, but more or less varying, so that the ideal fuel combination for every fuel has to be adjusted. There is a great economic interest in new flow improvers, with less Dosage of the Middle Distillate Flow Improver (MDFI) for good cold flow properties to lead. Due to the chemical structure of MDFI, these often have to be added increased Temperatures the refinery streams added to pump the MDFI and complete dissolution in the Allow fuel. These too known as the lower mixing-in temperature - size (see "Checking new MDFI / WASA additives for the production of diesel fuel in the exchange circuit ", ARAL research, QSAA FKL 103, 11/1998) should advantageously be as low as possible to a prevent costly heating of the MDFI tank in the refineries. Another requirement is the lowest possible viscosity of the MDFI. A high viscosity MDFI requires either one heated and therefore expensive transport, or the container capacity is melted at the destination to enable pumping. This Variant is also expensive and also hides that Risk of local overheating the product properties are negatively influenced. An MDFI with low viscosity must be transported at a significantly lower temperature or reserves sufficient viscosity for pumping even at lower temperatures.

cold flow improvers depending on the nature of the base fuel and the additive dosed in amounts of about 50 to 500 ppm. They are from a standing start various CFI products are known in the art (see, for example, US-A-3,038,479, 3,627,838 and 3,961,961, EP-A-0,261,957 or DE-A-31 41 507 and 25 15 805). Common CFIs are usually polymeric Compounds, especially ethylene-vinyl acetate (EVA) copolymers, such as e.g. some sold by BASF AG under the trade name Keroflux Products.

The WO-A-00/69998 describes EVA / isobutene / terpolymers in combination with copolymers consisting of α-olefins and MSA as potash flow improver for distillate fuels.

The US-A-5,681,359 describes copolymers consisting of ethylene, VAC and isobutene as a pour point depressant (PPD).

The US-A-5,256,166 describes PPD based on ethylene, VAC and isobutene.

EP-A-1116781 describes fuel additives for improving the cold flow and lubrication properties, based on mixtures of amphiphilic paraffin dispersants and MDFI, the MDFI being a terpolymer of ethylene, vinyl acetate and C ₅ -C ₇ olefin.

The DE-A-19620119 describes terpolymers consisting of ethylene, vinyl acetate and norbornene as CFI.

The WO-A-91/15562 describes terpolymers of ethylene, alpha-olefin and a different olefin or diene, which in combination with ethylene / unsaturated Ester copolymer and comb polymers affect the low temperature properties of fuel oils should.

The EP-A-0184083 describes special ethylene / vinyl acetate / 1-hexene terpolymers as CFI for Middle distillates.

The EP-A-0203554 describes ethylene / vinyl acetate / diisobutene terpolymers as mineral oil additives to improve the cold behavior of mineral oils.

DE-A-2515805 describes copolymers with ethylene backbone which are useful as flow improvers for distillate oils. The comonomer other than ethylene is preferably an unsaturated mono or diester. This can also be a mixture of 30 to 99 mol% ester and 70 to 1 mol% C ₃ -C ₁₆ alpha monoolefin. Examples of such olefins are propylene, n-octene-1 and n-decene-1. There are no manufacturing examples or test results for terpolymers, especially those with a longer carbon chain. In addition, the expert does not find any indication of the possibility of a targeted improvement in the lower mixing temperature of cold flow improvers. Rather, this document deals with an improvement in the production of the above copolymers by a suitable choice of the polymerization initiator. The process described therein is radical polymerization in solution (e.g. cyclohexane).

It there is therefore still a need for additional additives with CFI properties, especially those that have improved performance and a have simplified handling.

Brief description of the Invention:

It is therefore an object of the present invention improved additives provide. In particular, such additives should be provided be in relation to viscosity and / or lower mixing temperature in Fuel oil composition, with the same amount of additive, better performance than conventional additives have and at the same time at least essentially comparable CFPP and / or CP values like conventional ones flow improvers cause.

Surprisingly was able to solve this task are unexpectedly observed that terpolymers of the beginning designated type are useful as CFI additives and also a better performance than conventional ones Own EVA-CFI's.

On The first object of the invention relates to the use of a terpolymer, comprising as monomer components a) at least one lower alkene, b) at least one long chain alpha olefin and c) at least one polar polymerizable monomer, as an additive for fuel oils and lubricants, wherein the monomer components are preferably randomly polymerized are.

worin
R¹ für H oder C₁-C₅-Hydrocarbyl, vorzugsweise H, steht;
R², R³, R⁴ und R⁵ gleich oder verschieden sind und für H, C₁-C₄₀-Hydrocarbyl, wie z.B. C₁-C₂₀-, insbesondere C₁-C₁₀-, vorzugsweise C₁-C₄-Hydrocarbyl, -COOR⁷ oder -COOR⁷ stehen, wobei R¹ für C₁-C₄₀-Hydrocarbyl, wie z.B. C₁-C₂₀-, insbesondere C₁-C₁₀-, vorzugsweise C₁-C₄-Hydrocarbyl, steht und wobei wenigstens einer der Reste R², R³, R⁴ und R⁵ für -COOR⁷ oder -OCOR⁷ steht; und
R⁶ für C₆-C₄₀-Hydrocarbyl, wie z.B. C₈-C₄₀- oder C₈-C₃₀-, C₁₀-C₄₀- oder C₁₀-C₃₀-, C₁₂-C₄₀-, C₁₂-C₃₀-, oder C₁₆-C₄₀- oder C₁₆-C₃₀-, oder C₁₈-C₄₀- oder C₁₈-C₃₀-, insbesondere C₁₂-C₂₄-, vorzugsweise C₁₆-C₂₄- oder C₁₈-C₂₄-Hydrocarbyl steht;
wobei die Hydrocarbylgruppen gegebenenfalls ein- oder mehrfach substituiert sein können durch C₁-C₄-Alkyl, Hydroxy, C₁-C₄-Alkoxy, Amino, Mono- oder Di-C₁-C₄-alkylamino, Carboxy, (CO)R¹ oder ein oder mehrere Heteroatome, ausgewählt unter N, O und S in der Kohlen stoffkette enthalten können.Terpolymers which are essentially composed of monomers comprising the monomers M1, M2 and M3, M1, M2 and M3 having the following general formulas, are preferably used

wherein
R ^{1 is} H or C ₁ -C ₅ hydrocarbyl, preferably H;
R ² , R ³ , R ⁴ and R ^{5 are the} same or different and are H, C ₁ -C ₄₀ hydrocarbyl, such as C ₁ -C ₂₀ -, in particular C ₁ -C ₁₀ -, preferably C ₁ -C ₄ -Hydrocarbyl, -COOR ⁷ or -COOR ⁷ , where R ^{1 is} C ₁ -C ₄₀ -hydrocarbyl, such as C ₁ -C ₂₀ -, especially C ₁ -C ₁₀ -, preferably C ₁ -C ₄ -hydrocarbyl, and at least one of the radicals R ² , R ³ , R ⁴ and R ^{5 represents} -COOR ⁷ or -OCOR ⁷ ; and
R ⁶ for C ₆ -C ₄₀ hydrocarbyl, such as C ₈ -C ₄₀ - or C ₈ -C ₃₀ -, C ₁₀ -C ₄₀ - or C ₁₀ -C ₃₀ -, C ₁₂ -C ₄₀ -, C ₁₂ -C ₃₀ -, or C ₁₆ -C ₄₀ - or C ₁₆ -C ₃₀ -, or C ₁₈ -C ₄₀ - or C ₁₈ -C ₃₀ -, in particular C ₁₂ -C ₂₄ -, preferably C ₁₆ -C ₂₄ - or C ₁₈ -C ₂₄ hydrocarbyl;
where the hydrocarbyl groups can optionally be mono- or polysubstituted by C ₁ -C ₄ alkyl, hydroxy, C ₁ -C ₄ alkoxy, amino, mono- or di-C ₁ -C ₄ alkylamino, carboxy, (CO) R ¹ or one or more heteroatoms selected from N, O and S can be contained in the carbon chain.

The terpolymers used according to the invention may contain the monomers M1, M2 and M3 in the following molar proportions (Mx / (M1 + M2 + M3) in the terpolymer:
M1: 0.6 to 0.98, preferably 0.7 to 0.95, in particular 0.8 to 0.95;
M2: 0.0001 to 0.1, preferably 0.0005 to 0.05, in particular 0.001 to 0.01;
M3: 0.01 to 0.2, preferably 0.01 to 0.15, in particular 0.05 to 0.15

• a) das zahlenmittlere Molekulargewicht Mn liegt im Bereich von etwa 500 bis etwa 10000; vorzugsweise 500 bis 5000 , insbesondere 500 bis 3000;
• b) das gewichtsmittlere Molekulargewicht Mw liegt im Bereich von etwa 1500 bis etwa 20000; vorzugsweise 2000 bis 15000, insbesondere 2000 bis 10000;
• c) das Verhältnis Mw/Mn liegt im Bereich von etwa 1,5 bis etwa 6,0; vorzugsweise 1,8 bis 5,0, insbesondere 2,0 bis 5,0; und
• d) die (kinematische) Viskosität bestimmt nach DIN 51562 liegt bei 120 °C im Bereich von 2 bis etwa 10000, vorzugsweise 10 bis 5000, insbesondere 20 bis 1000;
• e) die untere Einmischtemperatur in Dieselkraftstoff, bestimmt nach ARAL-Forschung, QSAA FKL 103, 11/98, liegt bei etwa 10 bis 30°C, vorzugsweise bei 10 bis 20 °C, insbesondere bei 15 bis 20 °C;

The terpolymers according to the invention can preferably also have at least one of the following properties.

• a) the number average molecular weight Mn is in the range from about 500 to about 10,000; preferably 500 to 5000, in particular 500 to 3000;
• b) the weight average molecular weight Mw is in the range from about 1500 to about 20,000; preferably 2,000 to 15,000, in particular 2,000 to 10,000;
• c) the Mw / Mn ratio ranges from about 1.5 to about 6.0; preferably 1.8 to 5.0, in particular 2.0 to 5.0; and
• d) the (kinematic) viscosity determined according to DIN 51562 is at 120 ° C. in the range from 2 to about 10,000, preferably 10 to 5000, in particular 20 to 1000;
• e) the lower mixing temperature in diesel fuel, determined according to ARAL research, QSAA FKL 103, 11/98, is about 10 to 30 ° C, preferably 10 to 20 ° C, in particular 15 to 20 ° C;

Prefers are the terpolymers according to the invention available by, preferably radical, polymerization, in particular high-pressure polymerization, of the monomers M1, M2, and M3. Polymerization is preferred without solvent carried out.

The Monomers M1, M2 and M3 can in principle as a pure substance or a mixture of two or more monomers of same type can be used. The carbon numbers given above therefore understand themselves as numerical averages.

preferred Monomers M1 are selected among ethylene, propylene and 1-butene and mixtures thereof.

Preferred monomers M2 are selected from straight-chain or mono- or poly-branched alpha-olefins with a number of 8 to 40 carbon atoms, oligomers with a number of 8 to 40 carbon atoms and terminal double bond derived from C ₂ -C ₆ olefin monomers, and mixtures thereof.

Preferred monomers M3 are selected from vinyl C ₁ -C ₂₀ carboxylic acids or C ₁ -C ₂₀ hydrocarbyl (meth) acrylates and mixtures thereof.

Terpolymers used with preference are selected from ethylene / vinyl acetate / 1-icosen, ethylene / vinyl acetate / pentaisobutene, ethylene / vinyl acetate / C ₂₀ -C ₂₄ -alpha-olefin and ethylene / vinyl acetate / 1-octene terpolymers

The Terpolymers described above are used alone or in combination with other polymers, preferably used alone in amounts, an effect as a cold flow improver to show in the additive fuel or lubricant. In particular the additives according to the invention be used in amounts that the lower mixing temperature in Fuel oil compositions such as diesel fuels. In addition, the Pour Point of additive packages which contain a terpolymer according to the invention in advantageously be lowered.

On The invention further relates to fuel oil compositions, containing a larger proportion by weight one boiling in the range of about 120-500 ° C Middle distillate fuel and at least a smaller proportion by weight of a cold flow improver according to the above Definition.

such Fuel oil compositions can still as a fuel component biodiesel (from animal and / or vegetable production) in proportions of 0-30% by weight.

preferred Fuel oil compositions are selected among diesel fuels, kerosene and heating oil, the diesel fuel may be obtainable by refining, coal gasification or gas liquefaction, a mixture represent such products and if necessary with regenerative Fuels can be mixed. Such fuel oil compositions are preferred, the sulfur content of the mixture being at most Is 500 ppm.

On The invention further relates to lubricant compositions, containing a larger proportion by weight a conventional one Lubricant and a smaller proportion by weight of at least one cold flow improver according to the above Definition.

in the Within the scope of the present invention, the terpolymers can be used in combination with other conventional ones cold flow improvers and / or other lubricating and fuel oil additives can be used.

On last subject of the invention also relates to additive packages comprising a terpolymer according to the above Definition in combination with at least one other conventional Lubricant and fuel oil additive.

Detailed description the invention:

a) Terpolymers

The terpolymers according to the invention are essentially from the monomers M1, M2 and M3 built. Depending on the manufacturing process, small amounts may be required Proportion of the connection used as a controller (chain terminator) be included.

If no other information is given, the following general definitions apply:
C ₁ -C ₄₀ hydrocarbyl is in particular straight-chain or branched C ₁ -C ₄₀ alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, Heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacyl, octayl, hepta the higher homologues and the corresponding positional isomers. The same applies to C ₁ -C ₂₀ hydrocarbyl radicals.

C ₁ -C ₄ alkylene radicals are in particular methylene, ethylene, 1,2- or 1,3-propylene, 1,2-, 1,3-, 2,3-, 2,4-, 3,4- or 1 , 4-butylene.

Examples of suitable monomers M1 are: mono-alkenes with a non-terminal or preferably terminal double bond, in particular ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-hep ten, 1-octene, 1-nonen and 1-decene, as well as the higher monounsaturated homologues with up to 40 carbon atoms.

Examples of preferred alpha-olefins M2 are straight-chain or mono- or poly-branched alpha-olefins with 8 to 40 carbon atoms, oligomers with 8 to 40 carbon atoms and terminal double bond, derived from C ₂ -C ₆ -olefin Monomers or mixtures thereof. Mixtures of alpha-olefins having 16 to 30, in particular 20 to 24, carbon atoms, for example from ethylene oligomerization processes or of native origin, are to be mentioned in particular as examples. Oligomerization products of isobutene, which are mixtures of isobutene dimers, trimers, tetramers and / or pentamers, may also be mentioned. The chain length is about 8 to 20 carbon atoms.

Examples of suitable monomers M3 are:
Vinyl-C ₁ -C ₂₀ carboxylic acids, especially the vinyl esters of formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, oenanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachic acid, behenic acid, lignotinic acid melissinic; and C ₁ -C ₂₀ alkyl acrylates and C ₁ -C ₂₀ alkyl methacrylates, where C ₁ -C ₂₀ alkyl represents methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, Pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl or eicosyl.

Particularly preferred terpolymers are composed of the monomers ethylene, vinyl acetate (VAC) and C ₁₈ -C ₂₄ olefin or olefin mixture. Regarding the polymer, the weight fraction of the monomers is independent of one another:
Ethylene: 50 to 95% by weight, such as in particular 60 to 85% by weight;
VAC: 10-40% by weight, such as in particular 12-35% by weight;
alpha-olefin: 0.1 to 20% by weight, such as in particular 0.1 to 10% by weight, 0.1 to 5% by weight or 0.1 to 1% by weight. An alpha olefin content of less than 1 mole percent, such as 0.1 to 0.9 mole percent or 0.1 to 0.5 mole percent, is also preferred.

The viscosity of such copolymers (determined according to Ubbelohde DIN 51562) is approximately 2 to 10000 mm ² / s, in particular approximately 20 to 1000 mm ² / s, in each case at a temperature of approximately 120 ° C.

b) Preparation of the terpolymers

The terpolymers according to the invention are produced by methods known per se, preferably according to the state of the art (see e.g. Ullmann's Encyclopedia of Industrial Chemistry 5th edition, keyword: Waxes, Vol. A 28, p. 146 ff., VCH Weinheim, Basel, Cambridge, New York, Tokyo, 1996) known methods for direct radical high-pressure copolymerization unsaturated Links.

The The terpolymers are preferably produced in stirred high-pressure autoclaves or in high pressure tube reactors or combinations of both. at behaves to them predominantly The relationship Length / diameter in the range from 5: 1 to 30: 1, preferably 10: 1 to 20: 1.

suitable Printing conditions for the polymerization is 1000 to 3000 bar, preferably 1500 to 2000 bar. The reaction temperatures are e.g. in the range of 160 to 320 ° C, preferred in the range of 200 to 280 ° C.

oder Mischungen derselben.An aliphatic aldehyde or an aliphatic ketone of the general formula I is used, for example, as a regulator for adjusting the molecular weight of the terpolymers

or mixtures thereof.

• – Wasserstoff;
• – C₁-C₆-Alkyl, wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl; besonders bevorzugt C₁-C₄-Alkyl, wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert.-Butyl;
• – C₃-C₁₂-Cycloalkyl, wie Cyclopropyl, Cyclobutyl, Cyclopentyl, Cyclohexyl, Cycloheptyl, Cyclooctyl, Cyclononyl, Cyclodecyl, Cycloundecyl und Cyclododecyl; bevorzugt sind Cyclopentyl, Cyclohexyl und Cycloheptyl;.

The radicals R ^a and R ^{b are the} same or different and selected from

• - hydrogen;
• - C ₁ -C ₆ alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec. -Pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl; special preferably C ₁ -C ₄ alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl;
• - C ₃ -C ₁₂ cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; cyclopentyl, cyclohexyl and cycloheptyl are preferred.

The radicals R ^a and R ^b can also be covalently bonded to one another to form a 4- to 13-membered ring. For example, R ^a and R ^{b can} together form the following alkylene groups: - (CH ₂ ) ₄ -, - (CH ₂ ) ₅ -, - (CH ₂ ) ₆ , - (CH ₂ ) ₇ -, -CH (CH ₃ ) -CH ₂ -CH ₂ -CH (CH ₃ ) - or -CH (CH ₃ ) -CH ₂ -CH ₂ -CH ₂ -CH (CH ₃ ) -.

The Use of propionaldehyde or ethyl methyl ketone as a regulator very particularly preferred.

Further well-suited regulators are unbranched aliphatic hydrocarbons, such as propane or branched aliphatic hydrocarbons with tertiary H atoms, such as isobutane, isopentane, isooctane or Isododecane (2,2,4,6,6-pentamethylheptane). As another additional Regulators can higher olefins, such as propylene.

Also Mixtures of the above regulators with hydrogen or hydrogen alone are also preferred.

The The amount of regulator used corresponds to that customary for the high-pressure polymerization process Amounts.

• – Didekanoylperoxid, 2,5-Dimethyl-2,5-di(2-ethylhexanoylperoxy)hexan, tert.-Amylperoxy-2-ethylhexanoat, Dibenzoylperoxid, tert.-Butylperoxy-2-ethylhexanoat, tert.Butylperoxydiethylacetat, tert.Butylperoxydiethylisobutyrat, 1,4-Di(tert.-butylperoxycarbo)-cyclohexan als Isomerengemisch, tert.-Butylperisononanoat, 1,1-Di-(tert.-butylperoxy)-3,3,5-trimethylcyclohexan, 1,1-Di-(tert.-butylperoxy)-cyclohexan, Methyl-isobutylketonperoxid, tert.-Butylperoxyisopropylcarbonat, 2,2-Di-tert.-butylperoxy)butan oder tert.-Butylperoxacetat;
• – tert.-Butylperoxybenzoat, Di-tert.-amylperoxid, Dicumylperoxid, die isomeren Di-(tert.-butylperoxyisopropyl)benzole, 2,5-Dimethyl-2,5-di-tert.-butylperoxyhexan, tert.-Butylcumylperoxid, 2,5-Dimethyl-2,5-di(tert.-butylperoxy)-hex-3-in, Di-tert.-butylperoxid, 1,3-Diisopropylmonohydroperoxid, Cumolhydroperoxid oder tert.-Butylhydroperoxid; oder
• – dimere oder trimere Ketonperoxide, so wie sie z.B. aus der EP-A-0 813 550 bekannt sind

The usual radical initiators, such as organic peroxides, oxygen or azo compounds, can be used as starters for the radical polymerization. Mixtures of several radical initiators are also suitable. For example, one or more peroxides selected from the following commercially available substances can be used as radical initiators:

• - Didekanoyl peroxide, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, tert.-amylperoxy-2-ethylhexanoate, dibenzoyl peroxide, tert.-butylperoxy-2-ethylhexanoate, tert.butylperoxydiethylacetate, tert.butylperoxydiethylisobutyrate, , 4-Di (tert-butylperoxycarbo) cyclohexane as a mixture of isomers, tert-butyl perisononanoate, 1,1-di- (tert-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-di- (tert. -butylperoxy) -cyclohexane, methyl-isobutylketone peroxide, tert-butylperoxyisopropyl carbonate, 2,2-di-tert-butylperoxy) butane or tert-butylperoxacetate;
• Tert-butyl peroxybenzoate, di-tert-amyl peroxide, dicumyl peroxide, the isomeric di- (tert-butylperoxyisopropyl) benzenes, 2,5-dimethyl-2,5-di-tert-butyl peroxyhexane, tert-butyl cumyl peroxide, 2 , 5-dimethyl-2,5-di (tert-butylperoxy) hex-3-yne, di-tert-butyl peroxide, 1,3-diisopropyl monohydroperoxide, cumene hydroperoxide or tert-butyl hydroperoxide; or
• - Dimeric or trimeric ketone peroxides, as are known for example from EP-A-0 813 550

As Peroxides are di-tert-butyl peroxide, tert-butyl peroxypivalate, tert-butyl peroxyisononanoate or dibenzoyl peroxide or mixtures thereof are particularly suitable. Azobisisobutyronitrile ("AIBN") is an azo compound mentioned as an example. The radical initiators are used in polymerizations Amounts dosed.

In The terpolymers according to the invention are a preferred mode of operation prepared so that a mixture of the monomers M1, M2 (preferably solved z. B. in toluene) and M3 in the presence of the controller at one temperature in the range of about 20 to 50 ° C, such as. from 30 ° C, preferably continuously through a stirred autoclave, which at a pressure in the range of about 1500 to 2000 bar, e.g. of about 1700 bar. Due to the preferably continuous Addition of initiator, which is usually in a suitable solvent, such as. Isododecane, solved the temperature in the reactor is at the desired reaction temperature, such as. at 200 to 250 ° C, held. That after the relaxation of the reaction mixture Polymer is then in conventional Way isolated.

modifications this way of driving are natural possible and can be carried out by a specialist without undue effort. For example the comonomers and the regulator are metered into the reaction mixture separately the reaction temperature can be varied during the process to name just a few examples.

c) fuel compositions

According to the invention, fuel oil compositions are preferably understood to mean fuels. Ge Suitable fuels are petrol and middle distillates, such as diesel fuels, heating oil or kerosene, with diesel fuel and heating oil being particularly preferred.

at the heating oils it is, for example, low or high sulfur Oil refines or around hard coal or brown coal distillates, which usually have a boiling range from 150 to 400 ° C exhibit. The heating oils are preferably low-sulfur heating oils, for example those with a sulfur content of at most 0.01% by weight, preferably at most 0.05% by weight, particularly preferably of at most 0.005% by weight, and in particular of at most 0.001% by weight. As examples of heating oil be especially heating oil for domestic oil firing systems or heating oil Called EL. The quality requirements for such Fuel oils are specified, for example, in DIN 51-603-1 (see also Ullmann's Encyclopedia of Industrial Chemistn, 5th edition, Vol. A12, p. 617 ff., Whereupon herewith expressly Is referred to).

at diesel fuels are, for example, petroleum refined, the usual have a boiling range of 100 to 400 ° C. These are mostly distillates with a 95% point up to 360 ° C or even above out. You can but also so-called "Ultra low sulfur diesel "or" city diesel " by a 95% point of, for example, a maximum of 345 ° C and one Sulfur content of up to 0.005% by weight or through a 95% point of, for example, 285 ° C and a sulfur content of at most 0.001% by weight. In addition to through Refining available Diesel fuels are those produced by coal gasification or gas liquefaction ("gas to liquid" (GTL) fuels) available are suitable. Mixtures of the above are also suitable Diesel fuels with renewable fuels, such as biodiesel or bioethanol.

Especially the additive according to the invention is preferred for the additivation of diesel fuels with low sulfur content, this means with a sulfur content of less than 0.05 wt .-%, preferably of less than 0.02% by weight, in particular less than 0.005% by weight and especially less than 0.001% by weight sulfur or for additives of heating oil with a low sulfur content, for example with a sulfur content of at most 0.1% by weight, preferably at most 0.05% by weight, particularly preferably of at most 0.005% by weight, and in particular of at most 0.001% by weight.

The additive according to the invention is preferably in a proportion, based on the total amount the fuel oil composition, used the for seen an essentially sufficient influence on the Cold flow properties of fuel oil compositions has. The additive is particularly preferred in an amount of 0.001 to 1 wt .-%, in particular from 0.01 to 0.1 wt .-%, based on the total amount of fuel oil composition used.

d) Co-additives

The terpolymers according to the invention can individually or as a mixture of such copolymers and optionally in Combination with other additives known per se, the fuel oil compositions be added.

suitable Additives that are present in fuel oils according to the invention the terpolymers according to the invention may be included especially for Diesel fuels and heating oils, include detergents, corrosion inhibitors, dehazers, demulsifiers, Anti-foaming agents ("Antifoam"), antioxidants, Metal deactivators, multifunctional stabilizers, cetane number improvers, Combustion improvers, dyes, markers, solubilizers, antistatic agents, lubricity, as well as the cold properties fuel-improving additives, such as nucleators, and others conventional flow improvers ("MDFI"), paraffin dispersants ("WASA") and the combination of the last two additives mentioned ("WAFI") (see also Ullmann's Encyclopedia of Industrial Chemistn, 5th edition, Vol.A16, p.719 ff; or the above-mentioned patent specifications for flow improvers).

• a) Copolymere von Ethylen mit wenigstens einem weiteren ethylenisch ungesättigten Monomer;
• b) Kammpolymere;
• c) Polyoxyalkylene;
• d) polare Stickstoffverbindungen;
• e) Sulfocarbonsäuren oder Sulfonsäuren oder deren Derivate; und
• f) Poly(meth)acrylsäureester.

The following are further conventional cold flow improvers:

• a) copolymers of ethylene with at least one further ethylenically unsaturated monomer;
• b) comb polymers;
• c) polyoxyalkylenes;
• d) polar nitrogen compounds;
• e) sulfocarboxylic acids or sulfonic acids or their derivatives; and
• f) poly (meth) acrylic acid ester.

In the copolymers of ethylene with at least one other ethylenically unsaturated monomer a) the monomer is preferably selected from alkenyl carboxylic acid esters, (meth) acrylic acid esters and olefins.

suitable Olefins are, for example, those with 3 to 10 carbon atoms and with 1 to 3, preferably with 1 or 2, in particular with one, Carbon-carbon double bond. In the latter case, the carbon-carbon double bond both terminal (α-olefins) can also be arranged internally. However, α-olefins are particularly preferred preferably α-olefins with 3 to 6 carbon atoms, such as propene, 1-butene, 1-pentene and 1-hexene.

Suitable (meth) acrylic acid esters are, for example, esters of (meth) acrylic acid with C ₁ -C ₁₀ -alkanols, in particular with methanol, ethanol, propanol, isopropanol, n-butanol, sec-butanol, isobutanol, tert-butanol, pentanol, hexanol, Heptanol, octanol, 2-ethylhexanol, nonanol and decanol.

suitable alkenylcarboxylic are, for example, the vinyl and propenyl esters of carboxylic acids 2 to 20 carbon atoms, the hydrocarbon radical of which is linear or can be branched. Among these, the vinyl esters are preferred. Under the carboxylic acids with branched hydrocarbon radical are preferred those whose Branching in the α position to the carboxyl group is located, with the α-carbon atom particularly preferably tertiary is, d. H. the carboxylic acid a so-called neocarboxylic acid is. However, the hydrocarbon residue of the carboxylic acid is preferred linear.

Examples for suitable alkenylcarboxylic are vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, neopentanoate, hexanoate, neononanoate, neodecanoate and the corresponding propenyl esters, the vinyl esters being preferred are. A particularly preferred alkenyl carboxylic acid ester is vinyl acetate.

Especially the ethylenically unsaturated monomer is preferably selected from Alkenylcarboxylic esters.

Suitable are also copolymers that are two or more different from each other alkenylcarboxylic contain in copolymerized form, these being in the alkenyl function and / or differentiate in the carboxylic acid group. Also suitable are copolymers which, in addition to the alkenyl carboxylic acid ester (s) at least one olefin and / or at least one (meth) acrylic acid ester polymerized included.

The ethylenically unsaturated Monomer is in the copolymer in an amount of preferably 1 to 50 mol%, particularly preferably from 10 to 50 mol% and in particular from 5 up to 20 mol%, based on the total copolymer, copolymerized.

The copolymer a) preferably has a number average molecular weight M _n from 1000 to 20,000, particularly preferably from 1000 to 10,000 and in particular from 1000 to 6000.

worin
D für R¹⁷, COOR¹⁷, OCOR¹⁷, R¹⁸, OCOR¹⁷ oder OR¹⁷ steht,
E für H, CH₃, D oder R¹⁸ steht,
G für H oder D steht,
J für H, R¹⁸, R¹⁸COOR¹⁷, Aryl oder Heterocyclyl steht,
K für H, COOR¹⁸, OCOR¹⁸, OR¹⁸ oder COOH steht,
L für H, R¹⁸COOR¹⁸, OCOR¹⁸, COOH oder Aryl steht,
wobei
R¹⁷ für einen Kohlenwasserstoffrest mit wenigstens 10 Kohlenstoffatomen, vorzugsweise mit 10 bis 30 Kohlenstoffatomen, steht,
R¹⁸ für einen Kohlenwasserstoffrest mit wenigstens einem Kohlenstoffatom, vorzugsweise mit 1 bis 30 Kohlenstoffatomen, steht,
m für einen Molenbruch im Bereich von 1,0 bis 0,4 steht und
n für einen Molenbruch im Bereich von 0 bis 0,6 steht.Comb polymers b) are, for example, those described in "Comb-Like Polymers. Structure and Properties", NA Platé and VP Shibaev, J. Poly. Sci. Macromolecular Revs. 8, pages 117 to 253 (1974). Of the compounds described there, comb polymers of the formula II are suitable, for example

wherein
D represents R ¹⁷ , COOR ¹⁷ , OCOR ¹⁷ , R ¹⁸ , OCOR ¹⁷ or OR ¹⁷ ,
E represents H, CH ₃ , D or R ¹⁸ ,
G represents H or D,
J represents H, R ¹⁸ , R ¹⁸ COOR ¹⁷ , aryl or heterocyclyl,
K represents H, COOR ¹⁸ , OCOR ¹⁸ , OR ¹⁸ or COOH,
L represents H, R ¹⁸ COOR ¹⁸ , OCOR ¹⁸ , COOH or aryl,
in which
R ^{17 represents} a hydrocarbon radical with at least 10 carbon atoms, preferably with 10 to 30 carbon atoms,
R ^{18 represents} a hydrocarbon radical with at least one carbon atom, preferably with 1 to 30 carbon atoms,
m stands for a mole fraction in the range from 1.0 to 0.4 and
n stands for a mole fraction in the range from 0 to 0.6.

preferred Comb polymers are, for example, by the copolymerization of Maleic anhydride or fumaric acid with another ethylenically unsaturated monomer, for example with an α-olefin or an unsaturated Esters, such as vinyl acetate, and subsequent esterification of the anhydride or acid function available with an alcohol with at least 10 carbon atoms. Other preferred comb polymers are copolymers of α-olefins and esterified comonomers, for example esterified copolymers of styrene and maleic anhydride or esterified copolymers of styrene and fumaric acid. Mixtures of comb polymers are suitable. Comb polymers can also be polyfumarates or polymaleinates. They are also homo- and copolymers comb polymers suitable for vinyl ethers.

worin
R¹⁹ und R²⁰ jeweils unabhängig voneinander für R²¹, R²¹-CO-, R²¹-O-CO(CH₂)_z- oder R²¹-O-CO(CH₂)_z-CO- stehen, wobei R²¹ für lineares C₁-C₃₀-Alkyl steht,
y für eine Zahl von 1 bis 4 steht,
x für eine Zahl von 2 bis 200 steht, und
z für eine Zahl von 1 bis 4 steht.Suitable polyoxyalkylenes c) are, for example, polyoxyalkylene esters, ethers, esters / ethers and mixtures thereof. The polyoxyalkylene compounds preferably contain at least one, particularly preferably at least two linear alkyl groups with 10 to 30 carbon atoms and a polyoxyalkylene group with a molecular weight of up to 5000. The alkyl group of the polyoxyalkylene radical preferably contains 1 to 4 carbon atoms. Such polyoxyalkylene compounds are described, for example, in EP-A-0 061 895 and in US Pat US 4,491,455 described, to which reference is hereby made in full. Preferred polyoxyalkylene esters, ethers and esters / ethers have the general formula III

wherein
R ¹⁹ and R ²⁰ each independently represent R ²¹ , R ²¹ -CO-, R ²¹ -O-CO (CH ₂ ) _z - or R ²¹ -O-CO (CH ₂ ) _z -CO-, where R ²¹ represents linear C ₁ -C ₃₀ alkyl,
y represents a number from 1 to 4,
x represents a number from 2 to 200, and
z represents a number from 1 to 4.

Preferred polyoxyalkylene compounds of the formula III, in which both R ¹⁹ and R ^{20 are} R ²¹ , are polyethylene glycols and polypropylene glycols with a number average molecular weight of 100 to 5000. Preferred polyoxyalkylenes of the formula III, in which one of the radicals R ^{19 is} R ²¹ and the other stands for R ²¹ -CO-, are polyoxyalkylene esters of fatty acids with 10 to 30 carbon atoms, such as stearic acid or behenic acid. Preferred polyoxyalkylene compounds in which both R ¹⁹ and R ^{20 represent} a radical R ²¹ -CO- are diesters of fatty acids having 10 to 30 carbon atoms, preferably stearic or behenic acid.

The polar nitrogen compounds d), which are suitably oil-soluble, can be both ionic and non-ionic and preferably have at least one, particularly preferably at least 2, substituents of the formula> NR ²² , where R ^{22 is} a C ₈ -C ₄₀ -hydrocarbon radical. The nitrogen substituents can also be quaternized, that is to say in cationic form. An example of such nitrogen compounds are ammonium salts and / or amides which can be obtained by reacting at least one amine substituted with at least one hydrocarbon radical with a carboxylic acid having 1 to 4 carboxyl groups or with a suitable derivative thereof. The amines preferably contain at least one linear C ₈ -C ₄₀ alkyl radical. Suitable primary amines are, for example, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tetradecylamine and the higher linear homologues. Suitable secondary amines are, for example, dioctadecylamine and methylbehenylamine. Amine mixtures, in particular amine mixtures which are commercially available, such as fatty amines or hydrogenated tallamines, as described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 6th edition, 2000 electronic release, chapter "Amines, aliphatic", are also suitable. Acids suitable for the reaction are, for example, cyclohexane-1,2-dicarboxylic acid, cyclohexene-1,2-dicarboxylic acid, cyclopentane-1,2-dicarboxylic acid, naphthalenedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid and succinic acids substituted with long-chain hydrocarbon radicals.

Another example of polar nitrogen compounds are ring systems which carry at least two substituents of the formula -A-NR ²³ R ²⁴ , in which A stands for a linear or branched aliphatic hydrocarbon group, which may be replaced by one or more groups which are selected from O, S , NR and CO, is interrupted, and R ²³ and R ²⁴ stand for a C ₉ -C ₄₀ hydrocarbon radical which, if appropriate interrupted by one or more groups which are selected from O, S, NR ³⁵ and CO and / or by one or more substituents which are selected from OH, SH and NR ³⁵ R ³⁶ , where R ^{35 is} C ₁ -C ₄₀ alkyl which is optionally interrupted by one or more groupings which are selected from CO, NR ³⁵ , O and S, and / or by one or more radicals which are selected from NR ³⁷ R ³⁸ , OR ³⁷ , SR ³⁷ , COR ⁷ , COOR ³⁷ , CONR ³⁷ R ³⁸ , aryl or heterocyclyl, where R ³⁷ and R ^{38 are} each independently selected from H or C ₁ to C ₄ alkyl; and R ^{36 represents} H or R ³⁵ .

A is preferably a methylene or polymethylene group having 2 to 20 methylene units. Examples of suitable radicals R ²³ and R ²⁴ are 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 2-ketopropyl, ethoxyethyl and propoxypropyl. The cyclic system can be both homocyclic, heterocyclic, condensed polycyclic or uncondensed polycyclic systems. The ring system is preferably carbo- or heteroaromatic, in particular carboaromatic. Examples of such polycyclic ring systems are condensed benzoid structures, such as naphthalene, anthracene, phenanthrene and pyrene, condensed nonbenzoic structures, such as azulene, indene, hydrindens and fluorene, uncondensed polycycles, such as diphenyl, heterocycles, such as quinoline, indole, dihydroindole, benzofuran, Coumarin, isocoumarin, benzthiophene, carbazole, diphenylene oxide and diphenylene sulfide, non-aromatic or partially saturated ring systems, such as decalin, and three-dimensional structures, such as α-pinene, camphene, bornylene, norbonane, norbones, bicyclooctane and bicyclooctene.

On another example of suitable polar nitrogen compounds are condensates of long-chain primary or secondary Amines with polymers containing carboxyl groups.

The Polar nitrogen compounds mentioned here are in WO 00/44857 as well as in the literature cited therein, whereupon reference is hereby made in full.

suitable polar nitrogen compounds are e.g. also in DE-A-198 48 621 of DE-A-196 22 052 or EP-B-398 101, to which reference is hereby made becomes.

worin
Y für SO₃ ^–(NR²⁵ ₃R²⁶)⁺, SO₃ ^–(NHR²⁵ ₂R²⁶)⁺, SO₃ ^–(NH₂R²⁵R²⁶), SO₃ ^–(NH₃R²⁶) oder SO₂NR²⁵R²⁶ steht,
X für Y, CONR²⁵R²⁷, CO₂ ^–(NR²⁵ ₃R²⁷)⁺, CO₂ ^–(NHR²⁵ ₂R²⁷)⁺, R²⁸-COOR²⁷, NR²⁵COR²⁷, R²⁸OR²⁷,
R²⁸OCOR²⁷, R²⁸R²⁷, N(COR²⁵)R²⁷ oder Z^–(NR²⁵ ₃R²⁷)⁺ steht,
wobei
R²⁵ für einen Kohlenwasserstoffrest steht,
R²⁶ und R²⁷ für Alkyl, Alkoxyalkyl oder Polyalkoxyalkyl mit wenigstens 10 Kohlenstoffatomen in der Hauptkette stehen,
R²⁸ für C₂-C₅-Alkylen steht,
Z^– für ein Anionenäquivalent steht und
A und B für Alkyl, Alkenyl oder zwei substituierte Kohlenwasserstoffreste stehen oder gemeinsam mit den Kohlenstoffatomen, an die sie gebunden sind, ein aromatisches oder cycloaliphatisches Ringsystem bilden.Suitable sulfocarboxylic acids / sulfonic acids or their derivatives e) are, for example, those of the general formula IV

wherein
Y for SO ₃ ^- (NR ²⁵ ₃ R ²⁶ ) ⁺ , SO ₃ ^- (NHR ²⁵ ₂ R ²⁶ ) ⁺ , SO ₃ ^- (NH ₂ R ²⁵ R ²⁶ ), SO ₃ ^- (NH ₃ R ²⁶ ) or SO ₂ NR ²⁵ R ²⁶ stands,
X for Y, CONR ²⁵ R ²⁷ , CO ₂ ^- (NR ²⁵ ₃ R ²⁷ ) ⁺ , CO ₂ ^- (NHR ²⁵ ₂ R ²⁷ ) ⁺ , R ²⁸ -COOR ²⁷ , NR ²⁵ COR ²⁷ , R ²⁸ OR ²⁷ ,
R ²⁸ OCOR ²⁷ , R ²⁸ R ²⁷ , N (COR ²⁵ ) R ²⁷ or Z ^- (NR ²⁵ ₃ R ²⁷ ) ⁺ ,
in which
R ^{25 represents} a hydrocarbon radical,
R ²⁶ and R ^{27 represent} alkyl, alkoxyalkyl or polyalkoxyalkyl with at least 10 carbon atoms in the main chain,
R ^{28 represents} C ₂ -C ₅ alkylene,
Z ^{- stands} for an anion equivalent and
A and B represent alkyl, alkenyl or two substituted hydrocarbon radicals or together with the carbon atoms to which they are attached form an aromatic or cycloaliphatic ring system.

such sulfocarboxylic or sulfonic acids and their derivatives are described in EP-A-0 261 957, whereupon reference is hereby made in full.

Suitable poly (meth) acrylic acid esters f) are both homo- and copolymers of acrylic and methacrylic acid esters. Copolymers of at least two mutually different (meth) acrylic acid esters which differ with respect to the condensed alcohol are preferred. Optionally, the copolymer contains another, different olefinically unsaturated monomer copolymerized. The weight average molecular weight of the polymer is preferably 50,000 to 500,000. A particularly preferred polymer is a copolymer of methacrylic acid and methacrylic acid esters of saturated C _{1 4} and C ₁₅ alcohols, the acid groups being neutralized with hydrogenated tallamine. Suitable poly (meth) acrylic Acid esters are described, for example, in WO 00/44857, to which reference is hereby made in full.

e) Additive packages

Finally is The present application contains an additive concentrate a terpolymer as defined above and at least one diluent and optionally at least one further additive, in particular selected among the above co-additives.

Suitable diluents are, for example, fractions obtained in petroleum processing, such as kerosene, naphtha or brightstock. Aromatic and aliphatic hydrocarbons and alkoxyalkanols are also suitable. In the case of middle distillates, particularly preferred diluents for diesel fuels and heating oils, naphtha, kerosene, diesel fuels, aromatic hydrocarbons such as heavy solvent naphtha, Solvesso ^R or Shellsol ^R and mixtures of these solvents and diluents.

The terpolymer according to the invention is preferably in an amount of 0.1 to 80 in the concentrates % By weight, particularly preferably from 1 to 70% by weight and in particular from 20 to 60% by weight, based on the total weight of the concentrate, in front.

The Invention will now be illustrated by the following non-limiting examples explained in more detail.

Experimental part:

a) Manufacturing examples 1 to 15

It were fifteen in total various terpolymers by high pressure polymerization of ethylene, Vinyl acetate (VAC) and an alpha-olefin mixture with 20 to 24 carbon atoms manufactured.

The Monomers were added in one with the addition of propionaldehyde as a regulator High pressure autoclaves as described in the literature (M. Buback et al., Chem. Ing. Tech. 1994, 66, 510), polymerized.

A mixture of 12 kg / h of ethylene, 6.099 kg / h of vinyl acetate, 0.2 kg / h of C ₂₀ -C ₂₄ olefin (dissolved in toluene) and 1.183 kg / h of propionaldehyde is continuously passed through at a temperature of 30 ° C. passed to a pressure of 1700 bar 1l stirred autoclave. The temperature in the autoclave reactor is kept at 221 ° C. by the continuous addition of 9.06 g of tert-butyl peroxypivalate (TBPP) per hour (usually in a suitable solvent, for example isodecane). The polymer obtained after the expansion of the reaction mixture in an amount of 4.2 kg / h corresponds to a total conversion of all starting materials of approximately 23%. It contains 68% by weight of ethylene, 31% by weight of vinyl acetate and 1% by weight of C ₂₀ -C ₂₄ olefin. The viscosity is 60 mm ² / s at 120 ° C.

In Table 1 are the polymerization conditions and in the table 2 compiled the analytical data of the polymers obtained.

The The monomer content was determined by NMR spectroscopy. The viscosities were determined according to Ubbelohde DIN 51562.

Table 2

b) Test examples 1 to 3

In The tests were based on the Cloud Point (CP) according to ASTM D 2500 and the Cold Filter plugging point (CFPP) determined according to DIN EN 116.

The following polymers according to the invention were used in the test examples:

The following conventional MDFI were used for comparison purposes:
Keroflux ES 6100, Keroflux ES 6103, Keroflux ES 6202, commercial ethylene-vinyl acetate copolymer (EVC) and ethylene-vinyl acetate copolymer mixture (EVCM);
The following test oils were used:
Test oil 1: sulfur-free diesel fuel, CP = –10 ° C, CFPP = –12 ° C, d = 830.6 kg / m ³
Test oil 2: Light Heating Oil, CP = 0.5 ° C, CFPP = 0 ° C, d = 861.1 kg / m ³
Test oil 3: Diesel fuel, CP = -3.8 ° C, CFPP = -7 ° C, d = 834 kg / m ³
Test oil 4: diesel fuel, CP = –8.6 ° C, CFPP = –9 ° C, d = 838 kg / m ³

Test example 1: CFPP comparison

The Experiments show that the polymers according to the invention are comparable CFPP results like commercial ones MDFI delivered.

Test Example 2: Lower Einmisch temperature

The procedure is analogous to QSAA FKL 103, Section 5.4.2 (Aral research):
"The additive heated to 40 ° C ± 2 ° C is mixed into the fuel, which has cooled to 10 ° C ± 2 ° C, by shaking it gently (no mechanical stirring). The filtration is then carried out immediately in the SEDAB test apparatus (see QSAA FKL 005). The test is passed if at this temperature (10 ° C) 500 ml of the additive fuel passes the filter within 2 minutes under the specified conditions. The lowest admissible mixing temperature for the checked additive is then 10 ° C. This temperature must be noted accordingly on the approval list. If the mixture cannot be filtered at 10 ° C within 2 minutes, a new mixing / test must be carried out in 5 ° C steps above 10 ° C. The temperature at which the mixture can be filtered must be defined as the lowest admissible mixing temperature for the checked additive and specified in the approval list. Lower mixing temperatures can be achieved by premixing the additive to be tested with the diesel fuel. The type of predilution must be adapted to the particular conditions of the refinery in which the additive is to be used ".

The lower mixing-in temperature is the temperature at which 500 ml of additive diesel fuel can just pass through the filter within a maximum of two minutes. The temperature is given in ° C.

The Dosage is 500 ppm.

The Results show that the polymers according to the invention are significantly lower lower mixing temperatures can be achieved than with commercially available MDFIs.

Test Example 3: Viscosities

The Ubbelohde viscosities (DIN 51562; kinematic viscosities) of the polymers according to the invention were measured in comparison to commercially available MDFI. The values are given in mm2 / s.

The results show that with the polymers according to the invention surprisingly lower viscosity than can be achieved with commercially available MDFI.

With the polymers of the invention So it succeeds in an equally good cold flow property of the fuel like with commercial ones Adjust additives, while the lower mixing temperature and the viscosity of the additive significantly reduced and thus significant handling and thus enables cost advantages become.

Claims (17)

Use of a terpolymer comprising as monomer components a) at least one lower alkene, b) at least one long-chain alpha-olefin and c) at least one polar polymerizable monomer, as an additive for fuel oils and lubricants. Use according to claim 1 wherein the terpolymer is Contains copolymerized monomers in a random distribution. Use according to one of the preceding claims, characterized in that the terpolymer is composed of the monomers comprising M1, M2 and M3, where M1, M2 and M3 have the following general formulas

wherein R ^{1 is} H or C ₁ -C ₅ hydrocarbyl; R ² , R ³ , R ⁴ and R ^{5 are the} same or different and stand for H, C ₁ -C ₄₀ hydrocarbyl, -COOR ⁷ or -OCOR ⁷ , where R ^{7 stands} for C ₁ -C ₄₀ hydrocarbyl and wherein at least one of the radicals R ² , R ³ , R ⁴ and R ^{5 represents} -COOR ⁷ or -COOR ⁷ ; and R ^{6 is} C _{> 6} hydrocarbyl; where the hydrocarbyl groups can optionally be mono- or polysubstituted by C ₁ -C ₄ alkyl, hydroxy, C ₁ -C ₄ alkoxy, amino, mono- or di- C ₁ -C ₄ alkylamino, carboxy, (CO) R ¹ or one or more heteroatoms selected from N, O and S can be contained in the carbon chain. Use according to claim 3, characterized in that that the terpolymer has at least one of the following properties having: a) Monomers M1, M2 and M3 are in the following molar proportions are contained in the terpolymer M1: 0.6 to 0.98 M2: 0.0001 to 0.1 M3: 0.01 to 0.2; b) the number average Molecular weight Mn ranges from about 500 to about 10,000; c) the weight average molecular weight Mw is in the range of about 1500 to about 20,000; d) the ratio Mw / Mn is in the range from about 1.5 to about 6.0; e) the viscosity is determined according to DIN 51562 at 120 ° C in the range of about 2 to about 10,000; and f) the lower mixing temperature in diesel fuel, determined according to QSAA FKL 103 (Aral Research), is around 10–30 ° C. Use according to claim 3 or 4, wherein monomer M1 selected is among ethylene, propylene and 1-butene. Use according to one of the preceding claims, wherein M2 is selected from straight-chain or mono- or poly-branched alpha-olefins with 8 to 40 C atoms, oligomers with 8 to 40 C atoms and terminal double bond, derived from C ₂ -C ₆ - olefin monomers. Use according to one of claims 3 to 6, wherein M3 is selected from vinyl C ₁ -C ₂₀ carboxylic acids or C ₁ -C ₂₀ hydrocarbyl (meth) acrylates. Use according to one of the preceding claims, wherein the terpolymer is selected from ethylene / vinyl acetate / 1-icosene, ethylene / vinyl acetate / pentaisobutene, ethylene / vinyl acetate / C ₂₀ -C ₂₄ alpha-olefin and ethylene / vinyl acetate / 1- octene terpolymers Use according to one of the preceding claims, wherein the terpolymer as a cold flow improver is used. Fuel oil composition, containing a larger proportion by weight one boiling in the range of 120-500 ° C Middle distillate fuel and at least a smaller proportion by weight of a terpolymer cold flow improver as defined in one of the preceding claims. Fuel oil composition The claim 10, wherein the fuel component is biodiesel (from animal or vegetable production) in proportions of 0-30% by weight includes. Fuel oil composition according to claim 10, selected among diesel fuels, kerosene and heating oil. Fuel oil composition according to claim 12, wherein the diesel fuel by refining, Coal gasification or gas liquefaction available is a mixture of such products and optionally with regenerative Fuel is mixed. Fuel oil composition according to one of the claims 10 to 13, the maximum sulfur content of the mixture Is 500 ppm. Lubricant composition containing a larger proportion by weight a conventional lubricant and a minor proportion by weight of at least one terpolymer cold flow improver as defined in one of the claims 1 to 9. Use or composition according to any of the previous Expectations, the terpolymer in combination with other conventional Kalffließverbesserern and / or other lubricating and fuel oil additives is used. Additive package comprising a terpolymer as defined in one of the claims 1 to 9 in combination with at least one other conventional Lubricant and fuel oil additive.