EP1627029A1

EP1627029A1 - Fuel compositions containing terpolymers with improved cold flow properties

Info

Publication number: EP1627029A1
Application number: EP04732965A
Authority: EP
Inventors: Wolfgang Ahlers; Ansgar Eisenbeis; Andreas FECHTENKÖTTER; Wolfgang Kasel; Andreas Deckers
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2003-05-16
Filing date: 2004-05-14
Publication date: 2006-02-22
Also published as: WO2004101716A1; DE10322163A1

Abstract

The invention relates to the use of terpolymers comprising the following as monomer constituents: a) at least one low alkene, b) at least one long-chain alpha olefin, and c) at least one polar polymerisable monomer, as additives for fuel oils and lubricants, and especially as cold flow improvers in fuel oils. The invention also relates to the fuel oils and lubricants to which said terpolymers are added, and to additive packets containing said terpolymers.

Description

Fuel compositions containing terpolymers with improved cold flow properties

description

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.

State of the art:

Mineral oils containing paraffinic waxes, such as middle distillates, diesel and heating oils, show a marked deterioration in the flow properties when the temperature is lowered. The reason for this is the crystallization of longer-chain paraffins, which form large, platelet-shaped wax crystals, starting from the temperature of the cloud point. These wax crystals have a sponge-like structure and lead to the inclusion of other fuel components in the crystal composite. The appearance of these crystals quickly leads to the sticking of fuel filters both in tanks and in motor vehicles. Finally, at temperatures below the Pöür Point (PP), the fuel no longer flows.

To solve these problems, fuel additives have been added for a long time in small concentrations, which often consist of combinations of nucleators for the early formation of small crystallites of the paraffins with the actual cold flow improvers (also referred to as CFI or MDFI). These in turn show similar crystallization properties as the paraffins of the fuel, but prevent their growth, so that the filter can be passed at significantly lower temperatures than the unadditized fuel. The so-called Cold Filter Plugging Point (CFPP) is determined as a measure of this. So-called wax anti-settling additives (WASA) can be used as a further additive to prevent the smallest crystallites in the fuel from sinking.

Due to the refinery, the composition of a fuel is usually not constant, but varies more or less, so that the ideal fuel combination has to be readjusted for each fuel. There is a high level of economic interest in new flow improvers, which lead to good cold flow properties with low dosage of the Middle Distillate Flow Improver (MDFI). Due to the chemical structure of the MDFI, these often have to be added to the refinery streams at elevated temperatures in order to allow the MDFI to be pumped in and completely dissolved in the fuel. This - also known as the lower mixing temperature - size (see "Review of 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 by one prevent costly heating of the MDFI tank in the refineries. Another requirement is the lowest possible viscosity of the MDFI. An MDFI with a high viscosity either requires a heated and therefore expensive transport, or the contents of the container are melted at the destination to enable pumping. This variant is also cost-intensive and also carries the risk that local overheating adversely affects the product properties. An MDFI with a low viscosity must be transported at a significantly lower temperature or maintains a viscosity that is sufficient for pumping, even at lower temperatures.

Cold flow improvers are added in amounts of approximately 50 to 500 ppm, depending on the nature of the base fuel and the additive. There are ^'äüs the prior art, various CFI products known (see. Eg 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, in particular ethylene-vinyl acetate (EVA) copolymers, such as, for example, some of the products sold by BASF AG under the trade name Keroflux.

WO-A-00/69998 describes EVA / isobutene / Teφolymers in combination with copolymers consisting of α-olefins and MSA as cold flow improvers for distillate fuels.

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

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.

DE-A-19620119 describes te polymers consisting of ethylene, vinyl acetate and norbornene as CFI. WO-A-91/15562 describes terpolymers of ethylene, alpha-olefin and a different olefin or diene, which in combination with ethylene / unsaturated ester copolymers and comb polymers are intended to influence the low-temperature properties of fuel oils.

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

10 EP-A-0203554 describes ethylene / vinyl acetate / diisobutene terpolymers as mineral oil additives for improving the low-temperature behavior of the 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 a

15 unsaturated mono- or diesters. This can also be a mixture of 30 to 99 mol% ester and 70 to 1 mol% C ₃ -C ₁₆ alpha monoolefin. Propylene, n-octene-1 and n-decene-1 are mentioned as examples of such olefins. There are no manufacturing examples or test results for terpolymers, especially those with a longer carbon chain. In addition, the specialist does not find any indication of the possibility of targeted improvement.

20 lowering the lower mixing temperature of cold flow improvers. This publication

- - rather summed up with an improvement that. Production of the above copolymers by, appropiate _^ . Choice of the polymerization initiator. The process described therein is radical polymerization in solution (e.g. cyclohexane).

25 There is therefore still a need for additional additives with CFI properties, in particular those which have improved performance and simplified handling.

Brief description of the invention:

30

It is therefore an object of the present invention to provide improved additives. In particular, additives should be provided which, in terms of viscosity and / or lower mixing temperature in the fuel oil composition, with the same amount of additive, have better performance than conventional additives and at the same time produce at least 35 essentially comparable CFPP and / or CP values as conventional flow improvers , Surprisingly, this problem was solved by the unexpected observation that terpolymers of the type mentioned at the outset can be used as CFI additives and moreover have better performance than conventional EVA-CFIs.

A first object of the invention relates to the use of an oil-soluble 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, the monomer components preferably being statistical are polymerized distributed.

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

R1

M1: \ _

R ⁶

M2: \:

wherein

R is H or CrC ₅ hydrocarbyl, preferably H;

R ² , R ³ , R ⁴ and R ^{5 are the} same or different and for H, dC ^ hydrocarbyl, such as Cr

C- ₂ 0, in particular CrC-io-, preferably C _T C ^ hydrocarbyl, -COOR ⁷ or -OCOR ⁷ , where R ^{7 is} CrC o-hydrocarbyl, such as CC ₂₀ -, in particular CrC ₁₀ -, preferably CC ₄ - hydrocarbyl, and wherein 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 ₀ - or Cι ₀ -C ₃₀ -, C ₁₂ -C ₀ -, 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 CrC- ₄ alkyl, hydroxy, CC ₄ alkoxy, amino, mono- or di- CτC ₄ alkylamino, carboxy, (CO) R ¹ or one or more heteroatoms, selected from N, O and S in the coal can contain fabric 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, especially 0.05 to 0.15

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 is in the range of 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 in accordance with DIN 51562 is 120 ° C. in the range from 2 to about 1Ö0ÖÖ, preferably 10 to 5000, in particular 20 to 1000 or 10 to 200 or 20 to 100; 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, especially 15 to 20 ° C;

The terpolymers according to the invention are preferably obtainable by, preferably free-radical, polymerization, in particular high-pressure polymerization, of the monomers M1, M2 and M3. The polymerization is preferably carried out without a solvent.

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

Preferred monomers M1 are selected from 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 C atoms, oligomers with a number of 8 to 40 C atoms and terminal double bond, derived from C ₂ -C ₆ - Olefinen- Monomers, and mixtures thereof.

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

Terpolymers used with preference are selected from ethylene / vinyl acetate / 1-acosene, ethylene / vinyl acetate / pentaisobutene, ethylene / vinyl acetate / C ₂ oC ₂₄ -alpha-olefin and ethylene / vinyl acetate / 1-octene terpolymers

The terpolymers described above are used alone or in combination with other polymers, preferably alone in amounts, in order to show an effect as a cold flow improver in the additive fuel or lubricant. In particular, the additives according to the invention should be used in amounts which significantly reduce 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 can be lowered in an advantageous manner.

A ^"Another object of the invention relates to fuel oil compositions comprising a major proportion by weight of a boiling range from about 120-500 ° C Mitteldestil- latbrennstoffs and a minor proportion by weight of at least one cold flow improver according obigerer.Definition.

Such fuel oil compositions can also comprise, as a fuel component, biodiesel (from animal and / or vegetable production) in proportions of 0-30% by weight.

Preferred fuel oil compositions are selected from diesel fuels, kerosene and heating oil, it being possible for the diesel fuel to be obtainable by refining, coal gasification or gas liquefaction, to be a mixture of such products and, if appropriate, to be mixed with regenerative fuels. Such fuel oil compositions are preferred, the sulfur content of the mixture being at most 500 ppm.

The invention further relates to lubricant compositions containing a larger proportion by weight of a conventional lubricant and a smaller proportion by weight of at least one cold flow improver as defined above.

In the context of the present invention, the terpolymers in combination with other conventional cold flow improvers and / or other lubricants and fuel oil additives can be used.

A last subject of the invention also relates to additive packages comprising a terpolymer as defined above in combination with at least one further conventional lubricant and fuel oil additive.

Detailed description of the invention:

a) Terpolymers

The terpolymers according to the invention are essentially composed of the monomers M1, M2 and M3 defined above. Depending on the manufacturing process, small amounts of the compound used as a regulator (chain terminator) may be present.

If no other information is given, the following general definitions apply:

CC ₀ hydrocarbyl stands in particular for straight-chain or branched CrC 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, nonadeeyl, eicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, - hexacosyl, heptacosyl and octayl, squadyl, octayl, octacosyl Homologues and the corresponding positional isomers. The same applies to CC ₂ o-hydrocarbyl radicals.

CC ^ 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-heptene, 1-octene, 1-nonen and 1-decene, as well as the higher monounsaturated homologues with up to 40 C 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. Examples include, in particular, mixtures of alpha-olefins having 16 to 30, in particular 20 to 24, carbon atoms, for example from ethylene Oligomerization processes or native origin. 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-CrC 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, lignocinic acid and melissic acid; and CC ^ alkyl acrylates and CrC ₂ o-alkyl methacrylates, where CC ₂₀ alkyl is 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, no-nadecyl 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, 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%, e.g. 0.1 to 0.9 mol% or 0.1 to 0.5 mol% 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, each at a temperature of approximately 120 ° C.

b) Preparation of the terpolymers

The terpolymers according to the invention are prepared by processes known per se, preferably according to the state of the art (see, for example, 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 of unsaturated compounds. The terpolymers are preferably produced in stirred high-pressure autoclaves or in high-pressure tube reactors or combinations of the two. The ratio length / diameter predominates in the range from 5: 1 to 30: 1, preferably 10: 1 to 20: 1.

Suitable pressure conditions for the polymerization are 1000 to 3000 bar, preferably 1500 to 2000 bar. The reaction temperatures are e.g. in the range from 160 to 320 ° C, preferably in the range from 200 to 280 ° C.

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.

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

- hydrogen;

-C-C _B -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; C 1 -C ₄ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl;

- C ₃ -C ₁₂ cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cycloctyl, 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 is very particularly preferred.

Other suitable 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). Higher olefins, such as propylene, can be used as further additional regulators.

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

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

The usual radical initiators, such as organic peroxides, oxygen or azo compounds, can be used as starters for the radical polymerization. Also mix several? Radical initiators are suitable can ^"As Radikarstarter eg ^~ one or more peroxides selected from the following commercially available substances are ^used". ^".:

Didekanoyl peroxide, 2,5-dimethy.l-2,5-di (2-ethylhexanoyIperoxy) hexane, tert.-amylperoxy-2-ethylhexanoate, dibenzoyl peroxide, tert.-butylperoxy-2-ethylhexanoate, tert.butylperoxydiethylacetate, tert.butylperoxydiethylisobutyrat 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 isobutyl ketone 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-butyl peroxyisopropyl) 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, e.g. are known from EP-A-0 813 550

Di-tert-butyl peroxide, tert-butyl peroxypivalate, tert-butyl peroxyisononanoate or dibenzoyl peroxide or mixtures thereof are particularly suitable as peroxides. As an azo compound Azobisisobutyronitrile ("AIBN") mentioned as an example. The radical initiators are dosed in amounts customary for polymerizations.

In a preferred procedure, the terpolymers according to the invention are prepared by mixing the monomers M1, M2 (preferably dissolved, for example, in toluene) and M3 in the presence of the regulator at a temperature in the range from about 20 to 50 ° C. eg of 30 ° C, preferably continuously passed through a stirred autoclave, softer at a pressure in the range of about 1500 to 2000 bar, e.g. of about 1700 bar. By preferably continuously adding initiator, which is usually in a suitable solvent, such as. Isododecane, is dissolved, the temperature in the reactor at the desired reaction temperature, e.g. kept at 200 to 250 ° C. The polymer obtained after the relaxation of the reaction mixture is then isolated in a conventional manner.

Modifications of this driving style are of course possible and can be carried out by the expert without undue effort. For example, the comonomers and the regulator can be metered into the reaction mixture separately, and 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. Suitable fuels are petrol and middle distillates, such as diesel fuels, heating oil or kerosene, with diesel fuel and heating oil being particularly preferred.

The heating oils are, for example, low-sulfur or high-sulfur petroleum refinates or hard or lignite distillates, which usually have a boiling range of 150 to 400 ° C. 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 at most 0.005% by weight, and in particular of at most 0.001% by weight. Examples of heating oil include heating oil for domestic oil firing systems or heating oil EL. The quality requirements for such heating oils are specified, for example, in DIN 51-603-1 (cf. also Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, vol. A12, p. 617 ff., To which express reference is hereby made). Diesel fuels are, for example, petroleum raffinates, which usually have a boiling range of 100 to 400 ° C. These are mostly distillates with a 95% point up to 360 ° C or beyond. However, these can also be so-called “ultra low sulfur diesel” or “city diesel”, characterized by a 95% point of, for example, a maximum of 345 ° C. and a sulfur content of a maximum of 0.005% by weight or by a 95% point of, for example, 285 ° C. and a maximum sulfur content of 0.001% by weight. In addition to the diesel fuels obtainable by refining, those which are obtainable by coal gasification or gas liquefaction ("gas to liquid" (GTL) fuels) are suitable. Mixtures of the aforementioned diesel fuels with regenerative fuels, such as biodiesel or bioethanol, are also suitable.

The additive according to the invention is particularly preferred for the additization of diesel fuels with a low sulfur content, that is to say with a sulfur content of less than 0.05% by weight, preferably 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 the additive 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 at most 0.005 % By weight, and in particular of at most 0.001% by weight, is used.

The additive according to the invention is preferably used in a proportion, based on the total amount of the fuel oil composition, which in itself has an essentially sufficient influence on the cold flow properties of the fuel oil compositions. The additive is particularly preferably used in an amount of 0.001 to 1% by weight, in particular 0.01 to 0.1% by weight, based on the total amount of the fuel oil composition.

d) Co-additives

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

Suitable additives which may be present in the fuel oils according to the invention in addition to the terpolymers according to the invention, in particular for diesel fuels and heating oils, include detergents, corrosion inhibitors, dehazers, demulsifiers, antifoam ("antifoam"), antioxidants, metal deactivators, multifunctional stabilizers, cetane number improvers, Combustion improvers, dyes, markers, solubilizers, additive Statistics, lubricity improvers, and other additives that improve the cold properties of the fuel, such as nucleators, other conventional flow improvers ("MDFI"), paraffin dispersants ("WASA") and the combination of the last two additives mentioned ("WAFI") (see also Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, Vol.A16, p.719 ff; or the patents cited at the beginning for flow improvers).

Other conventional cold flow improvers to be mentioned are in particular: 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 esters.

In the copolymers of ethylene with at least one further 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 can be arranged both terminally (-olefins) and internally. However, preferred are α-olefins, particularly preferably α-olefins having 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 ^ do alkanols, in particular with methanol, ethanol, propanol, isopropanol, n-butanol, sec-butanol, isobutanol, tert-butanol, pentanol, hexanol, heptanol, Octanol, 2-ethylhexanol, nanol and decanol.

Suitable alkenyl carboxylic acid esters are, for example, the vinyl and propenyl esters of carboxylic acids having 2 to 20 carbon atoms, the hydrocarbon radical of which can be linear or branched. Among these, the vinyl esters are preferred. Preferred among the carboxylic acids with branched hydrocarbon radical are those whose branch is in the a position to the carboxyl group, the σ carbon atom being particularly preferably tertiary, ie the carboxylic acid is a so-called neocarboxylic acid. Preferably, the Hydrocarbon residue of the carboxylic acid, however, linear.

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

The ethylenically unsaturated monomer is particularly preferably selected from alkenyl carboxylic acid esters.

Copolymers which contain two or more different alkenyl carboxylic acid esters in copolymerized form are also suitable, these differing in the alkenyl function and / or in the carboxylic acid group. Also suitable are copolymers which, in addition to the alkenyl carboxylic acid ester (s), contain at least one olefin and / or at least one (meth) acrylic acid ester in copolymerized form.

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

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.

Comb polymers b) are, for example, those described in "Comb-Like Polymers. Structure and Properties", N.A. Plate and V.P. Shibaev, J. Poly. Be. 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 stands for R ¹⁷ , COOR ¹⁷ , OCOR ¹⁷ , R ¹⁸ , OCOR ¹⁷ or OR ¹⁷ , E stands for H, CH ₃ , D or R ¹⁸ , G stands for H or D, J stands for H, R ¹⁸ , R ¹⁸ COOR ^17, aryl or heterocyclyl, K stands for H, COOR ¹⁸ , OCOR ¹⁸ , OR ¹⁸ or COOH, L stands for H, R ¹⁸ COOR ¹⁸ , OCOR ¹⁸ , COOH or aryl, where

R ^{17 represents} a hydrocarbon radical with at least 10 carbon atoms, preferably with 10 to 30 carbon atoms,

R ^{18 stands} for 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 can be obtained, for example, by copolymerizing maleic anhydride or fumaric acid with another ethylenically unsaturated monomer, for example with a σ-olefin or an unsaturated ester such as vinyl acetate, and then esterifying the anhydride or acid function with an alcohol having at least 10 carbon atoms. Further preferred comb polymers are copolymers of σ-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 also suitable. Comb polymers can also be polyfumarates or polymaleates. Homopolymers and copolymers of vinyl ethers are also suitable comb polymers.

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 4,491,455, to which reference is hereby made in full. Preferred polyoxyalkylene esters, ethers and esters / ethers have the general formula III

R ¹⁹ {0- (CH _{2 x} OR ₂ o (III) wherein

R ¹⁹ and R ²⁰ each independently represent R ²¹ , R ^{21 "} CO-, R ²¹ -0-CO (CH ₂ ) ₂ - or R ²¹ -0- CO (CH ₂ ) _z -CO-, where R ²¹ stands for linear CC ₃ o-alkyl, y stands for a number from 1 to 4, x stands for a number from 2 to 200, and z stands for 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. 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, diocadecylamine and methylbehenylamine. Amine mixtures, in particular amine mixtures which are commercially available, such as fatty amines or hydrogenated tallamines, as described, for example, in Ulimann'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 is optionally interrupted and / or by one or more groups which are selected from O, S, NR ³⁵ and CO is substituted by one or more substituents which are selected from OH, SH and NR ³⁵ R ³⁶ , where R ^{35 is} CC ₄₀ -alkyl, which is optionally by one or more groupings which are selected from CO, NR ³⁵ , O and S. , interrupted, 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 each independently ig are selected from each other from H or d 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, hydrindene 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 σ-pinene, camphene, bornylene, norbonane, norbonen, bicyclooctane and bicyclooctene.

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 described in WO 00/44857 and in the references cited therein, to which reference is hereby made in full.

Suitable polar nitrogen compounds are also described, for example, in DE-A-198 48 621, DE-A-196 22 052 or EP-B-398 101, to which reference is hereby made. Suitable sulfocarboxylic acids / sulfonic acids or their derivatives e) are, for example, those of the general formula IV

wherein Y for S0 ₃ - (NR ²⁵ ₃ R ²⁶ ) ⁺ , S0 ₃ - (NHR ²⁵ ₂ R ²⁶ ) ⁺ , S0 ₃ - (NH ₂ R ²⁵ R ²⁶ ), S0 ₃ ^' (NH ₃ R ²⁶ ) or S0 ₂ NR ²⁵ R ²⁶ stands,

X for Y, CONR ²⁵ R ²⁷ , C0 ₂ - (NR ⁵ ₃ R ²⁷ ) ⁺ , C0 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 ) ⁺ , where R ^{25 stands} for a hydrocarbon radical,

R ²⁶ and R ^{27 are} alkyl, alkoxyalkyl or polyalkoxyalkyl with at least 10 carbon atoms in the main chain, R ^{28 is} C ₂ -C ₅ alkylene, Z ^"is an anion equivalent and A and B are alkyl, alkenyl or two substituted hydrocarbon radicals are bought or - jointly form loaliphatisches with the carbon atoms to which they are attached, an aromatic or Cyc-- ^~ ring system.

Such sulfocarboxylic acids or sulfonic acids and their derivatives are described in EP-A-0 261 957, to which 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 and cis 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, the subject of the present application is an additive concentrate containing a terpolymer as defined above and at least one diluent and, if appropriate, at least one further additive, in particular selected from 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 present in the concentrates in an amount of 0.1 to 80% by weight, particularly preferably 1 to 70% by weight and in particular 20 to 60% by weight, based on the total weight of the concentrate, in front.

The invention will now be explained in more detail with reference to the following non-limiting examples.

Experimental part: -

a) Production examples 1 to 15

A total of fifteen different polymers were produced by high pressure polymerization of ethylene, vinyl acetate (VAC) and an alpha-olefin mixture with 20 to 24 carbon atoms.

The monomers were polymerized with the addition of propionaldehyde as a regulator in a high-pressure autoclave as described in the literature (Buback, M. et al., Chem. Ing. Tech. 1994, 66, 510).

A mixture of 12 kg / h ethylene, 6.099 kg / h vinyl acetate, 0.2 kg / h C ₂₀ -C ₂₄ olefin (dissolved in toluene) and 1, 183 kg / h propionaldehyde is continuous at a temperature of 30 ° C. passed through a 1I stirred autoclave kept at a pressure of 1700 bar. 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). That after the relaxation of the reaction mixture in an amount of 4.2 kg / h of polymer obtained corresponds to a total conversion of all starting materials of approx. 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.

The polymerization conditions are listed in Table 1 and the analytical data of the polymers obtained are shown in Table 2.

The monomer content was determined by NMR spectroscopy. The viscosities were determined in accordance with Ubbelohde DIN 51562.

CM

ω n cα Table 2

Viscosity determined according to Ubbelohde DIN 51562

bL test examples 1 to 3

In the tests, the cloud point (CP) was determined in accordance with ASTM D 2500 and the cold filter plugging point (CFPP) in accordance with DIN EN 116.

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

Polymer solution: 50% solution of the polymer in solvent naphtha α-olefin: C ₂₀ -C ₂₄ -α-olefin oligo-IB: isobutylene-dimer to isobutylene-pentamer mixture 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 provide comparable CFPP results to commercially available MDFI. Test example 2: Lower mixing temperature

The procedure is analogous to QSAA FKL 103, Section 5.4.2 (Aral research): "In the fuel cooled to 10 ° C ± 2 ° C, the additive heated to 40 ° C ± 2 ° C is shaken gently (no mechanical Stir) mixed in. 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 above-mentioned 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 önmiscn 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 significantly lower lower mixing temperatures can be achieved with the polymers according to the invention than with commercially available MDFI.

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 mm ² / s.

Polymer solution: 50% solution of the polymer in solvent naphtha

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

With the polymers according to the invention it is thus possible to set the cold flow properties of the fuel to be just as good as with commercially available additives, the lower mixing temperature and the viscosity of the additive being significantly reduced at the same time and thus clear handling and thus cost advantages being made possible.

Claims

claims

1. 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.

2. Use according to claim 1, wherein the terpolymer contains the monomer components a) b) and c) copolymerized in a random distribution.

3. 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

R ¹

M1

R ⁶

M2 \ =

R ² _R 4

M3

R ³ R ⁵

wherein

R ^{1 is} H or CC ₅ hydrocarbyl; R ² , R ³ , R ⁴ and R ^{5 are the} same or different and are H, dC ₄₀ -hydrocarbyl,

-COOR ⁷ or -OCOR ⁷ , where R ^{7 is} dC ₄₀ -hydrocarbyl and at least one of the radicals R ² , R ³ , R ⁴ and R ^{5 is} -COOR ⁷ or -OCOR ⁷ ; and

R ^{6 represents} C _{> 6} hydrocarbyl; where the hydrocarbyl groups can optionally be mono- or polysubstituted by dC ₄ alkyl, hydroxy, C 1 -C ₄ alkoxy, amino, mono- or di-CC ₄ alkylamino, carboxy, (CO) R ¹ or one or several heteroatoms selected from

May contain N, O and S in the carbon chain.

, Use according to one of the preceding claims, characterized in that the terpolymer has at least one of the following properties: a) the monomers M1, M2 and M3 are present in the following molar proportions 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 is in the range from about 500 to about 10,000; c) the weight average molecular weight Mw is in the range from about 1500 to about 20,000; d) the Mw / Mn ratio is in the range of about 1.5 to about 6.0; e) the viscosity determined according to DIN 51562 is at 120 ° C in the range of about 2 to about 10000 mm ² / s; and f) the lower mixing temperature in diesel fuel, determined according to QSAA FKL

103 (Aral Research), is around 10 - 30 ° C.

5. Use according to claim 3 or 4, wherein monomer M1 is selected from ethylene, propylene and 1-butene.

6. Use according to one of the preceding claims, wherein M2 is selected. under 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.

7. Use according to any one of claims 3 to 6, wherein M3 is selected from vinyl CC ₂₀ carboxylic acids or dC ₂ o-hydrocarbyl (meth) acrylates.

8. Use according to one of the preceding claims, wherein the terpolymer is selected from ethylene-ethyl acetate-1-icosen-,

Ethylene in ethyl acetate / pentaisobutene, ethylene / vinyl acetate / C ₂₀ -C ₂ -alpha-olefin and ethylene / vinyl acetate / 1-octene terpolymers

9. Use according to one of the preceding claims, wherein the terpolymer is used as a cold flow improver.

10. Fuel oil composition containing a larger proportion by weight of an im Range of 120-500 ° C boiling middle distillate fuel and a smaller proportion by weight of at least one terpolymer cold flow improver as defined in any one of the preceding claims.

11. The fuel oil composition according to claim 10, wherein the fuel component comprises biodiesel (from animal or vegetable production) in proportions of 0-30% by weight.

12. Fuel oil composition according to claim 10, selected from diesel fuels, kerosene and heating oil.

13. The fuel oil composition according to claim 12, wherein the diesel fuel is obtainable by refining, coal gasification or gas liquefaction, is a mixture of such products and is optionally mixed with regenerative fuel.

14. A fuel oil composition according to any one of claims 10 to 13, wherein the sulfur content of the mixture is at most 500 ppm.

15. Lubricant composition containing a larger proportion by weight of a conventional lubricant and. a smaller one. GewLchtsanteil. at least one. Terpolymer cold flow improver as defined in any one of claims 1 to 9.

16. Use or composition according to one of the preceding claims, wherein the terpolymer is used in combination with other conventional cold flow improvers and / or other lubricating or fuel oil additives.

17. Additive package comprising a terpolymer as defined in any one of claims 1 to 9 in combination with at least one other conventional

Lubricant or fuel oil additive.