KR20060026411A - Fuel Compounds Showing Improved Low Temperature Flow Properties - Google Patents

Abstract

The present invention relates to the use of copolymers containing at least one acrylic acid ester in the form of polymers derived from heteroatomic functionalized alcohols as additives for fuel oils and lubricants, in particular as fuel oil improvers in low temperature fluids, fuel oils to which the copolymer has been added. And lubricants, and additive packages comprising such copolymers.

Description

FUEL COMPOUND EXHIBITING IMPROVED COLD FLOW PROPERTIES}

The present invention relates to the use of copolymers containing at least one acrylic ester in the form of copolymers derived from heteroatomic functionalized alcohols as additives for fuel oils and lubricants, in particular as cold flow improvers in fuel oils, It relates to fuel oils and lubricants to which copolymers are added, and additive packages containing such copolymers.

Upon temperature drop, mineral oils including paraffin wax, such as middle distillates, diesel and heating oils, exhibit a marked drop in flow characteristics. This is due to the crystallization that occurs due to the cloud point temperature of the relatively long-chain paraffin forming large platelet wax crystals. These wax crystals have a sponge-like structure that induces inclusion of other fuel components in the crystal structure. The occurrence of such a crystal quickly leads to clogging of the fuel filter in both the tank and the vehicle. At temperatures below the pour point (PP), the fuel eventually does not flow at all.

To solve this problem, fuel additives, which are often composed of a combination of paraffins and nucleators to quickly form very small crystals of actual low temperature fluidity enhancers (also known as CFIs or MDFIs), are already already at low concentrations. Has been added. In other words, the additives exhibit similar crystallization properties for the paraffins of the fuel, but do not interfere with their growth, so that the fuel can pass through the filter at significantly lower temperatures than the non-added fuel. The cold filter plugging point (CFPP) is determined as its measuring means. Additional additives available are wax antisettling additives (WASA), which prevent the precipitation of very small crystals in the fuel.

Depending on the composition of the base fuel and the additive, the low temperature fluidity improver is added in an amount of about 50 to 500 ppm. The prior art discloses various CFI products (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). Typical CFIs are commercially available products from BASF AG under the trade name of polymeric compounds, in particular ethylene-vinyl acetate (EVA) copolymers such as Keroflux.

Combinations of conventional CFI with lubricity enhancers (monocarboxylic or polycarboxylic acids and esters of monoalcohols or polyalcohols) are also described as improved CFI combinations (EP-A-0 721 492).

EP-A 0 997 517 describes a mixture of ethylene, additional olefinically unsaturated monomers containing hydroxyl groups, and optionally further ethylenically unsaturated monomers, and copolymers composed of polar nitrogen compounds. Such mixtures are considered suitable as lubrication enhancers.

There is a continuing need for additional additives with CFI properties, in particular additional additives that are relatively inexpensive to use, for example, because such additives may be used to lower the cold flow properties of fuels or lubricants at lower amounts than commercially available CFIs. Because it improves.

Brief Description of the Invention

It is an object of the present invention to provide such novel additives.

The inventors have surprisingly found that this object is achieved by accidental observation that copolymers containing certain heteroatomic functionalized acrylic esters in copolymerized form can be used as CFI additives and also have better performance than conventional EVA-CFI. It became.

The present invention first relates to the use of oil-soluble copolymers containing one or more acrylic esters in copolymerized form derived from heteroatomic functionalized alcohols as additives for fuel oils and lubricants. In particular, the copolymers used are those containing acrylic esters and additional monomers copolymerized with an irregular distribution.

As used herein, acrylic esters derived from heteroatomic functionalized alcohols refer to carbon-carbon single bonds to which the carboxyl group COOR is directly bonded, wherein the R radical is derived from heteroatomic functionalized alcohols. The remaining three substituents on the carbon-carbon double bond are selected from H and C ₁ -C ₄ -alkyl.

In the R radicals of these acrylic esters, at least one heteroatom is preferably bonded to a carbon atom in the α-, β-, γ- or δ-position relative to the carboxyl group of the acrylic ester. In particular, heteroatoms are bonded to the carbon atom at the β-position relative to the carboxyl group of the acrylic acid ester.

Heteroatoms may be bonded to a carbon atom containing a heteroatom by a single, double or triple bond. It is preferable to combine with a single bond.

For the purposes of the present invention, heteroatoms are all elements other than carbon and hydrogen which covalently bond with stable carbon under normal ambient conditions (room temperature, atmospheric humidity, incident light, etc.) and polymerization conditions, impairing the use of the copolymers of the present invention. Do not wear. Examples of such heteroatoms include Si, O, S, N and P.

The hetero atom is preferably oxygen.

Preferred are monomers comprising monomers M1, M2 and optionally M3, wherein M1, M2 and M3 preferably use copolymers having the formula:

Among the above formulas,

R ¹ is H or C ₁ -C ₄₀ -hydrocarbyl, such as C ₁ -C ₂₀ -hydrocarbyl, in particular C ₁ -C ₁₀ -hydrocarbyl, preferably C ₁ -C ₄ -hydrocarbyl ,

R ² , R ³ , R ⁴ and R ⁵ are the same or different and each is H, C ₁ -C ₄₀ -hydrocarbyl, such as C ₁ -C ₂₀ -hydrocarbyl, in particular C ₁ -C ₁₀ -hydro Carbyl, preferably C ₁ -C ₄ -hydrocarbyl -COOR ¹⁴ or -OCOR ¹⁴ , wherein R ¹⁴ is C ₁ -C ₄₀ -hydrocarbyl, such as C ₁ -C ₂₀ -hydrocarbyl, in particular C ₁ -C ₁₀ -hydrocarbyl, preferably C ₁ -C ₄ -hydrocarbyl, wherein at least one of the R ² , R ³ , R ⁴ and R ⁵ radicals is -COOR ¹⁴ or -OCOR ¹⁴ ,

R ⁶ , R ⁷ , R ⁸ are the same or different and each is H or C ₁ -C ₄ -alkyl,

R ⁹ is COOR ¹⁰ ,

Wherein R ¹⁰ is a group of formula:

Wherein A is C ₂ -C ₄ -alkylene,

R ¹¹ is H, C ₁ -C ₁₀ -alkyl or 3- to 16-membered carbocyclic or heterocyclic saturated, monounsaturated or polyunsaturated ring, or a corresponding fused ring system,

n is a number from 1 to 20.

R ¹ is preferably H.

R ² , R ³ , R ⁴ and R ⁵ radicals which are not COOR ¹⁴ or OCOR ¹⁴ are preferably H or methyl, in particular H.

It is preferable that R ⁶ , R ⁷ and R ⁸ are each independently H or methyl. More preferably R ⁶ and R ⁷ are H, R ⁸ is H or methyl, in particular H.

In the definition of R ¹¹ , 3- to 6-membered carbocyclic or heterocyclic saturated or monounsaturated or polyunsaturated rings, or corresponding fused ring systems are for example cyclopropyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclodecyl , Cyclopentenyl, cyclohexenyl, cyclooctenyl, cyclodecenyl, cyclopentadienyl, cyclohexadienyl, cyclooctadienyl, phenyl, cyclooctatetraenyl, oxiranyl, aziridinyl, oxolanyl , Dioxolanyl, oxoleyl, dioxolenyl, furanyl, oxazolinyl, oxathiolanyl, pyrrolidinyl, pyrrolinyl, pyrroyl, pyrazolyl, imidazolyl, oxazolyl, isoxazolyl, Thiazolyl, isothiazolyl, triazolyl, tetrazolyl, thiolanyl, dihydrothiophenyl, thiophenyl, piperidinyl, piperazinyl, morpholinyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl , Triazinyl, tetra Drupyranyl, pyranyl, thiopyranyl, thiazinyl, naphthyl, anthracenyl, phenanthrenyl, indolyl, carbazolyl, dibenzofuranyl, quinolinyl, isoquinolinyl, acridinyl, phena Genyl, phenoxazinyl and the like. The ring may be monosubstituted to polysubstituted. Suitable substituents are, for example, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -hydroxyalkyl and hydroxyl groups.

When R ¹¹ is H, R ¹ in M1 is preferably H, and / or the ratio x of M3 in the copolymer is preferably 0 <x ≦ 20 mol%.

It is preferable that R ¹¹ is not H.

In particular, R ¹¹ is C ₁ -C ₄ -alkyl or phenyl.

A is preferably ethylene.

n is preferably a number from 1 to 10, more preferably 1 to 5, in particular 1 or 2.

The copolymers used according to the invention may contain monomers M1, M2 and M3 in the following molar ratios (Mx / (M1 + M2 + M3)) in the copolymer:

M1: 0.55 to 0.999, preferably 0.6 to 0.95, in particular 0.7 to 0.95;

M2: 0.001 to 0.25, preferably 0.006 to 0.25, in particular 0.008 to 0.22;

M3: 0 to 0.2, preferably 0 to 0.15, especially 0.01 to 0.15.

The copolymers used according to the invention are preferably obtainable by free radical polymerization of monomers M1, M2 and optionally M3, in particular monomers M1, M2 and M3, in particular free radical high pressure polymerization.

Preferred monomers M1 are selected from ethylene, propylene and 1-butene.

Preferred monomers M2 are selected from monomers of the formula:

Preferred monomers M3 are selected from vinyl C ₁ -C ₂₀ -carboxylates and C ₁ -C ₂₀ -hydrocarbyl (meth) acrylates, in particular vinyl C ₁ -C ₂₀ -carboxylates. Particularly preferred monomer M3 is vinyl acetate.

When M 2 is acrylic acid esters 1 , 2 or 3 , especially 2 , M 1 is preferably ethylene and / or the proportion of x of M 3 in the copolymer is preferably 0 <x ≦ 20 mol%.

Especially preferred copolymers are selected from ethylene / 2- (2-ethoxyethoxy) -ethyl acrylate copolymers and ethylene / 2- (2-ethoxyethoxy) ethyl acrylate / vinyl acetate copolymers. .

It is preferable to use a copolymer as a low temperature fluidity improver.

The copolymer is used alone or in combination with other such copolymers in an amount sufficient to function as a low temperature fluidity improver in the fuel or lubricant to be added.

The present invention also provides a copolymer as defined above.

The present invention also provides a fuel oil composition comprising a multi-weight fraction middle fraction fuel boiling in the range of 120-500 ° C. and at least one low-temperature flow improver as defined above.

Such fuel oil compositions may also comprise, as fuel components, biodiesel (derived from animal or plant manufacture) in a proportion of 0 to 30% by weight.

Preferred fuel oil compositions are selected from diesel fuels, kerosene and heating oils, diesel fuels can be obtained by refining, coal vaporization or gas liquefaction, or can be mixtures of these products, optionally mixed with renewable fuels. Can be. Preference is given to fuel oil compositions in which the sulfur content of the mixture is 500 ppm or less.

The present invention also provides a lubricant composition comprising a conventional lubricant in a multiple weight ratio and at least one cold flow improver in a minor weight ratio as defined above.

For the purposes of the present invention, the copolymers according to the invention can be used in combination with further conventional low temperature fluidity improvers and / or additional lubricants and fuel oil additives.

The present invention also finally provides an additive package comprising a copolymer of the present invention as defined above in combination with one or more additional conventional lubricant and fuel oil additives.

Detailed description of the invention

(a) copolymer of the present invention

The copolymer of the present invention is preferably mainly composed of the monomers M1, M2 and optionally M3 as defined above. As a result of the preparation, minor proportions of the compounds used as regulators (chain terminators) may also be present in some cases.

Unless otherwise specified, the following definitions apply.

C ₁ -C ₄₀ -hydrocarbyl is in particular 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, hexyl, docosyl, trico Threads, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, squaalyl and higher analogs and also positional isomers thereof. The same applies to the C ₁ -C ₂₀ -hydrocarbyl radical. C ₁ -C ₁₀ -hydrocarbyl is in particular C ₁ -C ₁₀ -alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, Heptyl, octyl, 2-ethylhexyl, nonyl and decyl. C ₁ -C ₄ -hydrocarbyl is especially C ₁ -C ₄ -alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl.

C ₁ -C ₄ -hydroxyalkyl is C ₁ -C ₄ -alkyl substituted with one or more hydroxyl groups, such as 2-hydroxyethyl, 2- and 3-hydroxypropyl, 2-, 3- and 4- Hydroxybutyl.

C ₁ -C ₄ -alkoxy is especially methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy and tert-butoxy.

The alkylene is preferably methylene, ethylene, 1,2- or 1,3-propylene, 1,2-, 1,3-, 2,3-, 2,4-, 3,4- or 1,4- Butylene, especially ethylene.

Examples of suitable monomers M1 are monoalkenes with non-terminal double bonds or preferably terminal double bonds, in particular ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene And higher monounsaturated analogs having 1-decene and up to 40 carbon atoms.

Examples of preferred acrylic acid ester M2 are 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, 2-propoxyethyl acrylate, 2-isopropoxyethyl acrylate, 2-butoxyethyl acrylate, 2- Isobutoxyethyl acrylate, 2-tert-butoxyethyl acrylate, 3-methoxypropyl acrylate, 3-ethoxypropyl acrylate, 3-propoxypropyl acrylate, 3-isopropoxypropyl acrylate, 3 -Butoxypropyl acrylate, 3-isobutoxypropyl acrylate, 3-tert-butoxypropyl acrylate, 2-phenoxyethyl acrylate, 3-phenoxypropyl acrylate, 2-benzyloxyethyl acrylate, 3 Acrylic acid esters of benzyloxypropyl acrylate, diethylene glycol monomethyl, monoethyl and monopropyl ether, triethylene glycol monomethyl, monoethyl and monopropyl And a hotel of acrylic acid esters, tetraethylene glycol monomethyl, monoethyl and acrylic acid esters of mono-propyl ether, and pentaethylene glycol monomethyl, monoethyl and acrylic acid esters of mono-propyl ether. Particularly preferred acrylic esters are diethylene glycol monoethyl ether 2 (2- (2-ethoxyethoxy) ethyl acrylate; AEEE).

Examples of suitable monomers M3 are vinyl C ₁ -C ₂₀ -carboxylates, in particular formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, onanthic acid, caprylic acid, perargonic acid, capric acid, Vinyl esters of lauric acid, myristic acid, palmitic acid, stearic acid, arachic acid, behenic acid, lignoseric acid, seric acid and melisic acid; Further comprising C ₁ -C ₂₀ -alkyl acrylate and C ₁ -C ₂₀ -alkyl methacrylate, wherein C ₁ -C 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, octa Decyl, nonadecyl, or eicosyl.

The copolymers of the invention also have a number average molecular weight M _n in the range from about 1,000 to 20,000, more preferably from 1,000 to 10,000, in particular from 1,000 to 6,000.

The copolymers also have a weight average molecular weight M _w of 1,000 to 30,000, in particular 1,500 to 15,000, and the M _w / M _n ratio is 1.5 to 5.0, in particular 1.8 to 4.0.

Particularly preferred copolymers consist of monomer ethylene, acrylic ester 2 (2- (2-ethoxyethoxy) ethyl acrylate; AEEE) and optionally vinyl acetate (VAC). Based on the polymer, the weight ratio of monomer is

VAC: 0-72% by weight, preferably 0-35% by weight, in particular about 1-30% by weight, in particular 1-20% by weight

AEEE: 2 to 70% by weight, preferably 2.5 to 70% by weight, in particular about 3.5 to 65% by weight.

The viscosity of this copolymer (measured according to Ubbelohde DIN 51562) is about 5 to 25,000 mm ² / s, in particular about 10 to 1,000 or 20 to 800 mm ² / s, respectively, at a temperature of about 120 ° C.

(b) Preparation of Copolymer

Copolymers according to the invention are known per se, preferably in the prior art for direct free radical high pressure copolymerization of unsaturated compounds [see, eg, Ullmann's Encyclopedia of Industrial Chemistry , 5 ^th Edition, "Waxes", Vol. A 28, p. 146 ff.VCH Weinheim, Basle, Cambridge, New York, Tokyo, 1996).

The copolymer is preferably prepared in a stirred high pressure autoclave or in a high pressure tubular reactor or in a combination reactor of both. In this device, the length / diameter ratio mainly ranges from 5: 1 to 30: 1, preferably 10: 1 to 20: 1.

Suitable pressure conditions for the polymerization are 1,000 to 3,000 bar, preferably 1,500 to 2,000 bar. The reaction temperature is for example in the range from 160 to 320 ° C, preferably from 200 to 280 ° C.

Regulators used to control the molecular weight of the copolymers are, for example, aliphatic aldehydes or aliphatic ketones of the formula (I) or mixtures thereof.

Wherein the R ^a and R ^b radicals are the same or different,

- Hydrogen;

C ₁ -C ₆ -alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-hexyl, more preferably C ₁ -C ₄ -alkyl such as methyl, ethyl, n-propyl, isopropyl, 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, preferably cyclopentyl, cyclo Hexyl and cycloheptyl

Is selected from.

The R ^a and R ^b radicals may be covalently linked to form a four to thirteen membered ring. For example, R ^a and R ^b together represent an alkylene group; -(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 )-.

Very particular preference is given to using propionaldehyde or ethyl methyl ketone as modulator.

Further very suitable regulators are unbranched aliphatic hydrocarbons such as propane, or branched aliphatic hydrocarbons having tertiary hydrogen atoms such as isobutane, isopentane, isooctane or isododecane (2,2,4,6,6-penta) Methylheptane). Further regulators that can also be used are higher olefins such as propylene.

Preference is also given to mixtures of such modifiers with hydrogen or hydrogen alone.

The amount of regulator used corresponds to the amount customary for high pressure polymerization processes.

Initiators useful for free radical polymerization are conventional free radical initiators such as organic peroxides, oxygen or azo compounds. Mixtures of multiple free radical initiators are also suitable. Useful free radical initiators include one or more peroxides selected from the following commercially available materials:

Didecanoyl peroxide, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, tert-amyl peroxy-2-ethylhexanoate, dibenzoyl peroxide, tert-butyl Peroxy-2-ethylhexanoate, tert-butyl peroxydiethyl acetate, tert-butyl peroxydiethyl isobutyrate, 1,4-di (tert-butyl-peroxycarbo) cyclohexane, tert- as an isomer mixture Butyl perisononanoate, 1,1-di (tert-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-di (tert-butylperoxy) -cyclohexane, methyl isobutyl ketone perox Seeds, tert-butyl peroxyisopropyl carbonate, 2,2-di-tert-butylperoxy) butane or tert-butyl peroxyacetate;

tert-butyl peroxybenzoate, di-tert-amyl peroxide, dicumyl peroxide, isomer di (tert-butylperoxyisopropyl) benzene, 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

Dimer or trimer ketone peroxides as disclosed, for example, in EP-A-0 813 550.

Particularly suitable peroxides are di-tert-butyl peroxide, tert-butyl peroxypivalate, tert-butyl peroxyisononanoate or dibenzoyl peroxide or mixtures thereof. An example of an azo compound is azobisisobutyronitrile (AIBN). Free radical initiators are used in amounts conventional for polymerization.

In a preferred process, the copolymers according to the invention provide a mixture of monomers M1, M2 and optionally M3 in the presence of a modifier at a temperature in the range of about 20 to 50 ° C., such as 30 ° C., preferably continuously, from about 1,500 to Prepared by passing through a stirred autoclave maintained at a pressure in the range of 2,00 bar, such as about 1,700 bar. In general, it is preferred to continuously add an initiator dissolved in a suitable solvent such as isododecane to maintain the temperature in the reactor at a predetermined reaction temperature, such as 200 to 250 ° C. The reaction mixture is then depressurized and the polymer obtained is separated in a conventional manner.

Of course, variations on this method are possible, which can be carried out by those skilled in the art without excessive effort. Only a few, for example, comonomers and regulators can be metered separately into the reaction mixture, or the reaction temperature can be modified during the process.

(c) fuel composition

According to the invention, the fuel oil composition is preferably a fuel. Suitable fuels are gasoline fuels and intermediate fractions such as diesel fuels, heating oils or kerosene, with diesel fuels and heating oils being particularly preferred.

Heating oils are, for example, low or high sulfur crude oil raffinates or bituminous or lignite fractions usually having a boiling range of 150 to 400 ° C. Heating oils are preferably low sulfur heating oils, preferably those having a sulfur content of at most 0.1% by weight, preferably at most 0.05% by weight, more preferably at most 0.005% by weight, in particular at most 0.001% by weight. Examples of heating oils are, in particular, heating oils or EL heating oils for petroleum fired central heating of homes. For quality requirements for such heating oils see, for example, DIN 51-603-1 (also Ullmann's Encyclopedia of Industrial Chemistry , 5 ^th Edition, Vol. A 12, p. 617 ff.) Expressly incorporated herein by reference. ].

Diesel fuels are, for example, crude raffinates which typically have a boiling range of 100 to 400 ° C. This diesel fuel is typically an oil with 95% boiling point below 360 ° C or above. However, diesel fuels are characterized in that 95% have a boiling point of at most 345 ° C. and a sulfur content of at most 0.005% by weight, or 95% have a boiling point of 285 ° C. and a sulfur content of at most 0.001% by weight. Ultra low sulfur diesel ”or“ city diesel ”. In addition to diesel fuel obtainable by refining, those obtainable by coal vaporization or gas liquefaction (gas to liquid (GTL) fuel) are suitable. Renewable fuels such as biodiesel or bioethanol and mixtures of these diesel fuels are also suitable.

The additive according to the invention is added to a low sulfur content diesel fuel having a sulfur content, such as less than 0.05% by weight, preferably less than 0.02% by weight, in particular less than 0.005% by weight, in particular less than 0.001% by weight, or Particular preference is given to addition to heating oils having a sulfur content of low sulfur content, such as up to 0.1% by weight, preferably up to 0.05% by weight, more preferably up to 0.005% by weight, in particular up to 0.001% by weight.

It is preferred to use the additives according to the invention in proportions based on the total amount of fuel oil composition, which in itself has a substantially moderate influence on the cold flow properties of the fuel oil composition. Particular preference is given to using the additive 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.

When used as a low temperature fluidity improver, the copolymers according to the invention generally have a CFPP value (measured according to DIN EN 116) of the fuel to be added, which is at least 1 ° C, for example 1-30 ° C, 1-25 ° C, 3-15 ° C. Or in an amount effective to lower 5 to 10 ° C. Similarly measured CFPP values of the fuel oil to be added may vary within a wide range depending on the composition of the base fuel used and the type and amount of any coadditives added (e.g. conventional low temperature fluidity improvers). Such as about 0 to -35 ° C, -5 to -28 ° C, or -8 to -28 ° C.

(d) co-additives

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

In addition to the copolymers according to the invention, suitable additives which may be present in the fuel oils according to the invention, in particular diesel fuels and heating oils, are suitable detergents, corrosion inhibitors, dehazers, oil separators, defoamers, antioxidants, metal deactivators , Multifunctional stabilizers, cetane number improvers, combustion enhancers, dyes, markers, solubilizers, antistatic agents, lubricity enhancers and additional additives that improve the low temperature flow properties of fuels such as nucleating agents, additional conventional flow enhancers (MDFI), paraffin dispersant (WASA) and a combination of the last two additives (WAFI) (see also Ullmann's Encyclopedia of Industrial Chemistry , 5 ^th Edition, Vol. A 16, p. 719 ff., Or patents for low temperature fluidity improvers, cited in the background of the invention).

Further conventional low temperature fluidity improvers are particularly

(a) copolymers of ethylene and one or more additional ethylenically unsaturated monomers;

(b) comb polymers;

(c) polyoxyalkylenes;

(d) polar nitrogen compounds;

(e) sulfo carboxylic acids or sulfonic acids or derivatives thereof; And

(f) poly (meth) acrylic acid ester.

In the copolymer (a) of ethylene with at least one further ethylenically unsaturated monomer, the monomer is preferably selected from alkylenecarboxylic acid esters, (meth) acrylic acid esters and olefins.

Suitable olefins are, for example, those having from 3 to 10 carbon atoms and from 1 to 3, preferably 1 or 2, in particular 1 carbon-carbon double bond. In the latter case, the carbon-carbon double bond may be terminal (α-olefin) or present inside. However, α-olefins are preferred, and α-olefins having 3 to 6 carbon atoms such as propene, 1-butene, 1-pentene and 1-hexene are particularly preferred.

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

Suitable alkenylcarboxylic acid esters are, for example, vinyl and propenyl esters of carboxylic acids having 2 to 20 carbon atoms in which the hydrocarbon radical may be linear or branched. Among these, vinyl esters are preferred. Among the carboxylic acids having branched hydrocarbon radicals, those in which the branch is arranged at the α position with respect to the carboxyl group are preferred, and those having an α-carbon atom tertiary, such as carboxylic acid being neocarboxylic acid, are particularly preferred. However, it is preferred that the hydrocarbon radical of the carboxylic acid is linear.

Examples of suitable alkenylcarboxylic acid esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl neopentanoate, vinyl hexanoate, vinyl neononanoate, vinyl neodecano Although there are ates and the corresponding propenyl esters, vinyl esters are preferred. Particularly preferred alkenylcarboxylic acid esters are vinyl acetate.

Particular preference is given to ethylenically unsaturated monomers selected from alkenylcarboxylic acid esters.

Also suitable are copolymers containing two or more different copolymerized alkenylcarboxylic acid esters with different alkenyl functional groups and / or carboxylic acid groups. Copolymers containing at least one copolymerized olefin and / or at least one copolymerized (meth) acrylic acid ester in addition to the alkenylcarboxylic acid ester (s) are also suitable.

The ethylenically unsaturated monomers are copolymerized in the copolymer in an amount of preferably 1 to 50 mol%, more preferably 10 to 50 mol%, in particular 5 to 20 mol%, based on the total copolymer.

The copolymer (a) preferably has a number average molecular weight M _n of 1,000 to 20,000, more preferably 1,000 to 10,000, in particular 1,000 to 6,000.

Comb polymers (b) are described, for example, in " Comb-Like Polymers. Structure and Properties ", NA Plate and VP Shibaev, J. Poly. Sci. Marcromolecular Revs. 8, pages 117 to 253 (1974). Among those described in the literature, suitable comb polymers are, for example, those of the formula:

In the above formula,

D is R ¹⁷ , COOR ¹⁷ , OCOR ¹⁷ , R ¹⁸ , OCOR ¹⁷ or OR ¹⁷ ,

E is H, CH ₃ , D or R ¹⁸ ,

G is H or D,

J is H, R ¹⁸ , COOR ¹⁷ , R ¹⁸ COOR ¹⁷ , aryl or hetercyclyl,

K is H, COOR ¹⁸ , OCOR ¹⁸ , OR ¹⁸ or COOH,

L is H, R ¹⁸ COOR ¹⁸ , COOR ¹⁸ , OCOR ¹⁸ , COOH or aryl,

here

R ¹⁷ is a hydrocarbon radical having at least 10 carbon atoms, preferably 10 to 30 carbon atoms,

R ¹⁸ is a hydrocarbon radical having at least one carbon atom, preferably 1 to 30 carbon atoms,

m is a mole fraction in the range from 1.0 to 0.4,

n is the mole fraction in the range of 0 to 0.6.

Preferred comb polymers are, for example, copolymerizing maleic anhydride or fumaric acid with other ethylenically unsaturated monomers such as α-olefins or unsaturated esters such as vinyl acetate, followed by esters with alcohols having at least 10 carbon atoms with an unhydride or acid functional group. Can be obtained. Further preferred comb polymers are ester copolymers of α-olefins and esterified comonomers such as styrene and maleic anhydride or copolymers of styrene and fumaric acid. Mixtures of comb polymers are also suitable. The comb polymer may be polyfumarate or polymaleate. Homopolymers or 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 compound preferably contains linear alkyl group (s) having at least 1, more preferably at least 2, 10 to 30 carbon atoms and a polyoxyalkylene group having a molecular weight of 5,000 or less. 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 US 4,491,455, which are hereby incorporated by reference in their entirety. Preferred polyoxyalkylene esters, ethers and esters / ethers have the formula

R ¹⁹ [O- (CH ₂ ) _y ] _x OR ²⁰

In the above formula,

R ¹⁹ and R ²⁰ are each independently R ²¹ , R ²¹ -CO-, R ²¹ -O-CO (CH ₂ ) _z ^- or R ²¹ -O-CO (CH ₂ ) _z -CO-, wherein R ²¹ Is linear C ₁ -C ₃₀ -alkyl,

y is a number from 1 to 4,

x is a number from 2 to 200,

z is a number from 1 to 4.

Preferred polyoxyalkylene compounds of formula III wherein R ¹⁹ and R ²⁰ are both R ²¹ are polyethylene glycol and polypropylene glycol having a number average molecular weight of 100 to 5,000. Preferred polyoxyalkylenes of formula III wherein one of the R ¹⁹ radicals is R ²¹ and the other is R ²¹ -CO- are polyoxyalkylene esters of fatty acids having 10 to 30 carbon atoms, such as stearic acid or behenic acid. . Preferred polyoxyalkylene compounds in which R ¹⁹ and R ²⁰ are both R ²¹ -CO are diesters of fatty acids having 10 to 30 carbon atoms, preferably stearic acid or behenic acid.

Advantageously availability (oil-soluble) a polar nitrogen-containing compound (d) is ionic or or non-ionic may holy days, preferably 1 or more, more preferably 2 or more compounds of formula> NR ²² (wherein, R ²² is C ₈ -C ₄₀ -hydrocarbon radical). Nitrogen substituents may also be quaternized. That is, in cation form. Examples of such nitrogen compounds are amides obtained by reacting one or more amines substituted with ammonium salts and / or one or more hydrocarbon radicals with carboxylic acids or suitable derivatives having from one to four carboxyl groups. The amine preferably contains at least one linear C ₈ -C ₄₀ -alkyl radical. Suitable primary amines are, for example, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tetradecylamine and higher linear analogs. Suitable secondary amines are, for example, dioctadecylamine and methylbehenylamine. Amine mixtures, particularly amine mixtures obtainable on a commercial scale, such as fatty acid amines or hydrogenated deamines as described in the Ullnamn's Encyclopedian of Industrial Chemistry , 6 ^th Edition, 2000 electronic release, "Amines, aliphatic" chapter. Is also appropriate. Acids suitable for the reaction are, for example, cyclohexane-1,2-dicarboxylic acid, cyclohexene-1,2-dicarboxylic acid, cyclopentane-1,2-dicarboxylic acid, naphthalenedicar substituted with long chain hydrocarbon radicals. Acids, phthalic acid, isophthalic acid, terephthalic acid and succinic acid.

Another example of a polar nitrogen compound is a ring system containing two or more substituents of the formula -A-NR ²³ R ²⁴ , wherein A is a linear or branched aliphatic optionally interrupted by one or more groups selected from O, S, NR ³⁵ and CO A hydrocarbon group, R ²³ and R ²⁴ are each optionally interrupted by one or more groups selected from O, S, NR ³⁵ and CO, and / or OH, SH and NR ³⁵ R ³⁶ , wherein R ³⁵ is CO, NR ³⁵ , Optionally substituted by one or more moieties selected from O and S, and / or by one or more radicals selected from NR ³⁷ R ³⁸ , OR ³⁷ , SR ³⁷ , COR ³⁷ , COOR ³⁷ , CONR ³⁷ R ³⁸ , aryl or heterocyclyl Substituted C ₁ -C ₄₀ -alkyl, wherein R ³⁷ and R ³⁸ are each independently selected from H or C ₁ -to C ₄ -alkyl, R ³⁶ is H or R ³⁵ It is a C ₉ -C ₄₀ -hydrocarbon radical substituted by.

A is preferably a methylene group or a polymethylene group having 2 to 20 methylene units. Examples of suitable R ²³ and R ²⁴ radicals are 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 2-cetopropyl, ethoxyethyl and propoxypropyl. Cyclic systems are homocyclic, heterocyclic, fused polycyclic or unfused polycyclic systems. The ring system is preferably carboaromatic or heteroaromatic, in particular carboaromatic. Examples of such polycyclic ring systems include fused benzoide structures such as naphthalene, anthracene, phenanthrene and pyrene, fused bibenzoide structures such as azulene, indene, hydridene and fluorene, unfused polycycles such as diphenyl, hetero Cycles such as quinoline, indole, dihydroindole, benzofuran, coumarin, isocoumarin, benzothiophene, carbazole, diphenylene oxide and diphenylene sulfide, nonaromatic or some saturated ring systems such as decalin, And three-dimensional structures such as α-pinene, campene, bornylene, norbornane, norbornene, bicyclooctane and bicyclooctene.

Examples of suitable polar nitrogen compounds are condensates of long chain primary or secondary amines with carboxyl group-containing polymers.

The polar nitrogen compounds mentioned herein are described in WO 00/44857 and described in the references incorporated by reference in their entirety.

Suitable polar nitrogen compounds are also described, for example, in DE-A-198 48 621 and DE-A-196 22 052 or EP-B 398 101, incorporated herein by reference.

Suitable sulfo carboxylic acid / sulfonic acids or derivatives thereof (e) are, for example, those of the formula IV:

In the above formula,

Y is ^{_{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 ,

X is ^{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 ,

Where R ²⁵ is a hydrocarbon radical,

R ²⁶ and R ²⁷ are each alkyl, alkoxyalkyl or polyalkoxyalkyl having at least 10 carbon atoms in the main chain,

R ²⁸ is C ₂ -C ₅ -alkylene,

Z ^- is an anionic equivalent,

A and B are each 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 sulfo carboxylic acids and sulfonic acids and derivatives thereof are described in EP-A-0 261 957, which is incorporated herein by reference in its entirety.

Suitable poly (meth) acrylic acid esters (f) are homopolymers or copolymers of acrylic esters and methacrylic esters. Preferred are copolymers of two or more different (meth) acrylic acid esters with different esterified alcohols. Optionally, the copolymer contains other copolymerized olefinically unsaturated monomers. The weight average molecular weight of the polymer is preferably 50,000 to 500,000. Particularly preferred polymers are copolymers of methacrylic acid and methacrylic acid esters of saturated C ₁₄ -to C ₁₅ -alcohols in which the acid groups are neutralized with hydrogenated deamines. Suitable poly (meth) acrylic acid esters are described, for example, in WO 00/44857, which is incorporated herein by reference in its entirety.

Suitable low temperature fluidity improvers include, for example, alkylphenol-aldehyde resins known from EP-A-0857776, 1088045, 0311452 or WO-A-92 / 07047 and DE-A-3328739.

(e) additive package

Finally, the present application provides an additive concentrate comprising the copolymer of the present invention as described above and at least one diluent and also optionally at least one further additive, in particular at least one further additive selected from said coadditives.

Suitable diluents are, for example, fractions produced in the crude oil process, such as kerosene, naphtha or brightstock. Aromatic and cycloaliphatic hydrocarbons and alkoxy alkanols are also suitable. Diluents which are preferably used in the case of intermediate fractions, in particular in the case of diesel fuels and heating oils, are naphtha, kerosene, diesel fuel, aromatic hydrocarbons such as Solvent Naphtha Heavy, Solvesso® or Shelzol ( Shellsol® and mixtures of these solvents and diluents.

The copolymer according to the invention is preferably present in the concentrate in an amount of 0.1 to 80% by weight, more preferably 1 to 70% by weight and in particular 20 to 60% by weight, based on the total weight of the concentrate.

The present invention is illustrated by the following examples, but the present invention is not limited thereto.

Experiment part:

(a) Preparation Examples 1-16

A total of 16 different inventive copolymers were prepared by high pressure polymerization of ethylene, acrylic ester 2 (2- (2-ethoxyethoxy) ethyl acrylate; AEEE) and optionally vinyl acetate (VAC).

Ethylene, AEEE and optionally VAC were polymerized by adding propionaldehyde as a regulator in a high pressure autoclave as described in M. Buback et al., Chem Ing. Tech. 1994, 66, 510.

A mixture of 12.870 kg / h ethylene, 1.130 kg / h vinyl acetate, 4.497 kg / h acrylic acid ester 2 and 1.312 kg / h propionaldehyde was placed in a 1 l stirred autoclave maintained at a pressure of 1700 bar at a temperature of 30 ° C. Passed continuously. Vinyl acetate was metered in at a medium pressure zone of 260 bar, acrylic acid ester was metered in a high pressure zone of 1700 bar at the preheater inlet, and propionaldehyde was metered in a medium pressure zone. Initiator (tert-butyl peroxypivalate; TBPP) was continuously added 11.6 g per hour (in isododecane) at a high pressure zone of 1700 bar at the preheater inlet maintained at 220 ° C. in the autoclave. The polymer obtained in an amount of 6.5 kg / h after depressurizing the reaction mixture corresponded to 35% total conversion of all starting materials. The polymer contained 40 wt% ethylene, 3 wt% vinyl acetate and 57 wt% acrylic acid ester 2 . The viscosity is 60 mm ² / s at 120 ° C.

The polymerization conditions are described in Table 1 below, and Table 2 below describes the analytical data of the polymers obtained.

The contents of ethylene, AEEE and VAC in the obtained copolymers were measured by NMR spectroscopy. Viscosity was measured according to Uberode DIN 51562.

E: ethylene

VAC: Vinyl Acetate

AEEE: acrylic ester 2

PA: Propionaldehyde (modifier / modulator)

TBPP: tert-butyl peroxypivalate

ID: isodecan

^* : AEEE: ID = 1: 2

Viscosity measured according to Uberode DIN 51562.

(b) Test Examples 1-3

The following experiment was carried out using the copolymers 1 to 16 prepared above. For comparison purposes, the following conventional MDFIs were also tested:

MDFI A: Ethylene-vinyl acetate polymer mixture (Keroflux ES 6100, manufactured by BASF AG)

MDFI B: Ethylene-vinyl acetate polymer mixture (Keroflux ES 6103, manufactured by BASF AG)

MDFI C: Ethylene-vinyl acetate polymer mixture (Keroflux ES 6204, manufactured by BASF AG)

MDFI D: Ethylene-vinyl acetate polymer mixture (Keroflux ES 6310, manufactured by BASF AG)

MDFI E: Comparative Sample: Ethylene-Vinyl Acetate Copolymer

MDFI F: Comparative Sample: Ethylene-Vinyl Acetate Copolymer

MDFI G: Comparative Sample: Ethylene-Vinyl Acetate Copolymer

Conventional middle distillate fuels were added to the cold flow improver or conventional cold flow improver of the present invention at different doses and the CFPP values were measured according to DIN EN 116.

Test Example 1

Intermediate fractions used: German winter diesel fuel, CP = -5.9 ° C. (ASTM D2500), CFPP = -9 ° C. (DIN EN 116), d = 825 kg / m ³ , CFPP target = -22 ° C., IBP (initial boiling point) = 197 ° C., FBP (final boiling point) = 358 ° C., 90-20 (temperature difference between 90% and 20% by volume of boiling curve) = 94 ° C., 24.3% n-paraffin.

Table 3 below describes the measured CFPP values (° C.) of the middle distillate fuel added.

Test Example 2

Intermediate fractions used: Belgian ADO, CP = -17 ° C. (ASTM D2500), CFPP = -19 ° C. (DIN EN 116), d = 836 kg / m ³ , CFPP target = -21 ° C., IBP = 180 ° C., FBP = 340 ° C., 90-20 = 89 ° C., 18.7% n-paraffins.

Table 4 lists the measured CFPP values (° C.) of the middle distillate fuel added.

Test Example 3

Distillate used: Dutch diesel fuel, CP = -8.6 ° C. (ASTM D2500), CFPP = -9 ° C. (DIN EN 116), d = 838 kg / m ³ , CFPP target = -21 ° C., IBP = 157 ° C., FBP = 354 ° C., 90-20 = 101 ° C., 19.7% n-paraffins.

Table 5 lists the measured CFPP values (° C.) of the middle distillate fuel added.

The test results described in Tables 3 to 5 above demonstrate that the copolymers according to the invention show surprisingly good performance as low temperature fluidity improvers in middle oil fuel compositions. The additive according to the present invention makes it possible to achieve CFPP values comparable to conventional MDFI, even at lower doses first, but to achieve improved (higher) CFPP values at the same dose.

Claims (19)

Use of copolymers containing acrylic esters in the form of copolymers derived from heteroatomic functionalized alcohols as additives for fuel oils and lubricants. 2. Use according to claim 1, wherein the heteroatom is selected from O and N. 3. Use according to claim 1 or 2, wherein the copolymer contains acrylic esters copolymerized in an irregular distribution. 4. The use according to claim 1, wherein the copolymer consists of monomers comprising M 1, M 2 and optionally M 3, wherein M 1, M 2 and M 3 have the formula:

Among the above formulas, R ¹ is H or C ₁ -C ₄₀ -hydrocarbyl, R ² , R ³ , R ⁴ and R ⁵ are the same or different and each is H, C ₁ -C ₄₀ -hydrocarbyl, -COOR ¹⁴ or -OCOR ¹⁴ , wherein R ¹⁴ is C ₁ -C ₄₀ -hydro Carbil), wherein at least one of the R ² , R ³ , R ⁴ and R ⁵ radicals is -COOR ¹⁴ or -OCOR ¹⁴ , R ⁶ , R ⁷ , R ⁸ are the same or different and each is H or C ₁ -C ₄ -alkyl, R ⁹ is COOR ¹⁰ , wherein R ¹⁰ is a group of formula:

Wherein A is C ₂ -C ₄ -alkylene, R ¹¹ is H, C ₁ -C ₁₀ -alkyl or 3- to 16-membered carbocyclic or heterocyclic saturated, monounsaturated or polyunsaturated ring, or a corresponding fused ring system, n is a number from 1 to 20. The use according to claim 4, wherein the monomers M1, M2 and M3 are present in the copolymer at a molar ratio of 0.5 to 0.999 of M1, a molar ratio of 0.002 to 0.25 of M2 and a molar ratio of 0 to 0.2 of M3. The use according to claim 4 or 5, wherein the monomer M1 is selected from ethylene, propylene and 1-butene. Use according to any of the preceding claims, wherein M 2 is selected from the following compounds:

8. The use according to claim 4, wherein M 3 is selected from vinyl C ₁ -C ₂₀ -carboxylate and C ₁ -C ₂₀ -hydrocarbyl (meth) acrylate. The copolymer of claim 1, wherein the copolymer is ethylene / 2- (2-ethoxyethoxy) ethyl acrylate and ethylene / 2- (2-ethoxyethoxy) ethyl acrylate / vinyl Use selected from acetates. The use according to any one of claims 1 to 9, wherein the copolymer is used as a low temperature fluidity improver. The copolymer as defined in any one of claims 1 to 10. A fuel oil composition comprising a plurality of weight fractions of middle distillate fuel boiling in the range from 120 to 500 ° C. and at least one low temperature fluidity improver in a fractional weight ratio as defined in claim 1. 13. The fuel oil composition of claim 12, wherein the fuel component comprises biodiesel (derived from animal or plant manufacture) in a proportion of 0 to 30% by weight. 13. The fuel oil composition of claim 12, wherein the fuel oil composition is selected from diesel fuel, kerosene and heating oil. The fuel oil composition of claim 14, wherein the diesel fuel is obtainable by purification, coal vaporization, or gas liquefaction, or is a mixture of these products, and optionally mixed with a renewable fuel. 16. The fuel oil composition of any one of claims 12-15, wherein the sulfur content of the mixture is 500 ppm or less. A lubricant composition comprising a multiple weight ratio conventional lubricant and at least one low temperature fluidity improver in a minor weight ratio as defined in any one of claims 1-11. 18. The use or composition according to any one of claims 1 to 17, wherein the copolymer is used in combination with one or more additional cold flow improvers and / or one or more additional lubricants and fuel oil additives. An additive package comprising a copolymer as defined in any one of claims 1 to 10 in combination with one or more additional conventional lubricants and fuel oil additives.