EP1705196A1 - Olefins, unsaturated carboxylic esters and vinyl aromatics based terpolymers as additives for fuel oils and lubricants. - Google Patents

Abstract

Copolymer (A) obtained by polymerizing olefin monomers (M), is new. Copolymer (A) obtained by polymerizing olefin monomers (M) of formulae R1>-CH=CH2 (M1); (R2>)(R3>)C=C(R4>)(R5>) (M2); and (R7>)(R6>)C=C(R8>)(R9>) (M3), is new. R1>H or 1-40C hydrocarbyl; R2>-R5>H, 1-40C-hydrocarbyl, -COOR10> or-OCOR10> (where at least one of R2>-R5 is COOR10> or OCOR10>); R6>-R8>H or 1-4C-alkyl; R9>aryl; and R10>1-40C hydrocarbyl. Independent claims are included for: (1) a fuel oil composition comprising a larger amount of a distillate fuel with a boiling point of 120-500[deg]C and smaller amount of at least a copolymer; (2) a lubricant composition comprising a larger amount of a conventional lubricant and smaller amount of at least a copolymer; and (3) an additive package comprising at least a copolymer in combination with at least a conventional grease additive or a fuel oil additive.

Description

The invention relates to copolymers which comprise, in addition to an α-olefin and an alkenyl ester of an aliphatic carboxylic acid or an ester of an α, β-unsaturated aliphatic carboxylic acid in copolymerized form a vinylaromatic. Moreover, the invention relates to the use of these copolymers as an additive for fuel oils and lubricants, and in particular as cold flow improvers in fuel oils; the fuel oils and lubricants additized with these copolymers; and additive packages containing such copolymers.

State of the art

Paraffinic wax-containing mineral oils, such as middle distillates, e.g. Diesel and fuel oils show a significant deterioration of the flow properties when the temperature is lowered. The reason for this lies in the crystallization of longer-chain paraffins occurring from the temperature of the cloud point, which form large, platelet-shaped wax crystals. These wax crystals have a sponge-like structure and lead to the inclusion of other fuel constituents in the crystal composite. The appearance of these crystals quickly leads to the bonding of fuel filters both in tanks and in motor vehicles. At temperatures below the pour point (PP), finally, no more flow of fuel takes place.

To overcome these problems, fuel additives in small concentrations have been added for quite some time, often from combinations of nucleators for the early formation of microcrystalline paraffins with the actual cold flow improvers (also referred to as CFI (cold flow improver) or MDFI (middle distillate flow improver) ) consist. These in turn show similar crystallization properties as the paraffins of the fuel, but prevent their growth, so that a passage of the filter is possible at significantly lower temperatures compared to the unadditivated fuel. As a measure for the so-called Cold Filter Plugging Point (CFPP) is determined. As a further additive so-called wax anti-settling additives (WASA) can be used, which prevent the decrease of the microcrystallites in the fuel.

Cold flow improvers are added in amounts of about 50 to 500 ppm, depending on the nature of the base fuel and the additive. Various CFI products are known from the prior art (cf., for example, US Pat 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 CFI's are usually polymeric compounds, especially ethylene-vinyl acetate (EVA) copolymers, such as those disclosed in U.S. Pat. Trade name Keroflux products sold by BASF AG.

The WO 2004/106471 describes the use of terpolymers containing in copolymerized form ethylene, vinyl acetate and special acrylates as additives for fuel oils and lubricants, in particular as cold flow improvers for fuel oils.

The WO 2004/106470 describes the use of terpolymers containing polymerized ethylene, vinyl acetate and heteroatom-functionalized vinyl compounds as additives for fuel oils and lubricants, especially as a cold flow improver for fuel oils.

There is a continuing need for further additives with CFI properties, in particular those which are cheaper to use, for example because they improve the cold flow properties of fuels or lubricants at a lower dosage than commercial CFIs. In addition, there is a need for additives having improved formulability, for example, improved solubility in the fuels and lubricants or in the additive packages, or improved handleability, e.g. due to a lower viscosity.

Brief description of the invention

It is accordingly an object of the present invention to provide additives which satisfy the above requirements.

Surprisingly, this problem could be solved by the unexpected observation that copolymers containing polymerized in addition to α-olefins and unsaturated carboxylic acid esters vinyl aromatics are useful as CFI additives and also have a better performance than conventional EVA CFI's.

worin

R¹

für H oder C₁-C₄₀-Hydrocarby) steht;

R², R³, R⁴ und R⁵

gleich oder verschieden sind und für H, C₁-C₄₀-Hydrocarbyl, -COOR¹⁰ oder -OCOR¹⁰ stehen, wobei wenigstens einer der Reste R², R³, R⁴ und R⁵ für -COOR¹⁰ oder -OCOR¹⁰ steht;

R⁶, R⁷ und R⁸

gleich oder verschieden sind und für H oder C₁-C₄-Alkyl stehen;

R⁹

für Aryl steht; und

R¹⁰

für C₁-C₄₀-Hydrocarbyl steht;

wobei das Copolymer die Monomeren M1, M2 und M3 statistisch einpolymersiert enthält.A first aspect of the invention accordingly relates to a copolymer which is made up of monomers comprising M1, M2 and M3, where M1, M2 and M3 have the following general formulas:

wherein

R ¹

is H or C ₁ -C ₄₀ hydrocarbyl);

R ² , R ³ , R ⁴ and R ⁵

are the same or different and are H, C ₁ -C ₄₀ -hydrocarbyl, -COOR ¹⁰ or -OCOR ¹⁰ , wherein at least one of R ² , R ³ , R ⁴ and R ^{5 is} -COOR ¹⁰ or -OCOR ¹⁰ ;

R ⁶ , R ⁷ and R ⁸

are the same or different and are H or C ₁ -C ₄ alkyl;

R ⁹

is aryl; and

R ¹⁰

is C ₁ -C ₄₀ hydrocarbyl;

wherein the copolymer contains monomers M1, M2 and M3 randomly polymerized.

Another object of the invention is the use of these copolymers as an additive for fuel oils and lubricants and especially as a cold flow improver in fuel oils. Furthermore, the subject matter of the invention is the fuel oils and lubricants additized with these copolymers. Finally, the invention relates to additive packages containing such copolymers.

Detailed description of the invention

Unless otherwise stated, the following general definitions apply in the context of the present invention:

C ₁ -C ₄₀ -hydrocarbyl is a hydrocarbon radical having 1 to 40 carbon atoms. It is preferably an aliphatic hydrocarbon radical, such as alkyl, alkenyl, alkadienyl or alkynyl. In particular, C ₁ -C ₄₀ -hydrocarbyl is C ₁ -C ₄₀ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl , Octyl, 2-ethylhexyl, neooctyl, nonyl, neononyl, decyl, neodecyl, undecyl, neoundecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, hencosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl , Heptacosyl, octacosyl, nonacosyl, squalyl, their constitutional isomers, higher homologues and the corresponding constitutional isomers.

The same applies to C ₁ -C ₂₀ -hydrocarbyl radicals, ie it is a hydrocarbon radical having 1 to 20 carbon atoms. It is preferably an aliphatic hydrocarbon radical, such as alkyl, alkenyl, alkadienyl or alkynyl. In particular, C ₁ -C ₂₀ hydrocarbyl is C ₁ -C ₂₀ alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, lsöbutyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl , Octyl, 2-ethylhexyl, neo-octyl, nonyl, neononyl, Decyl, neodecyl, undecyl, neoundecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl and their constitutional isomers.

C ₁ -C ₁₀ -hydrocarbyl is a hydrocarbon radical having 1 to 10 carbon atoms. It is preferably an aliphatic hydrocarbon radical, such as alkyl, alkenyl, alkadienyl or alkynyl. In particular, C ₁ -C ₁₀ -hydrocarbyl is C ₁ -C ₁₀ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl , Octyl, 2-ethylhexyl, neooctyl, nonyl, neononyl, decyl, neodecyl and their constitutional isomers.

C ₁ -C ₄ -hydrocarbyl is a hydrocarbon radical having 1 to 4 carbon atoms. It is preferably an aliphatic hydrocarbon radical, such as alkyl, alkenyl, alkadienyl or alkynyl. In particular, C ₁ -C ₄ -hydrocarbyl is C ₁ -C ₄ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl.

C ₁ -C ₉ -alkyl represents a linear or branched alkyl radical having 1 to 9 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl , Heptyl, octyl, 2-ethylhexyl, neo-octyl, nonyl and neononyl and their constitutional isomers.

In addition, C ₁ -C ₁₉ -alkyl is, for example, decyl, neodecyl, undecyl, neoundecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and their constitutional isomers.

The hydrocarbyl radicals, for example the alkyl radicals, may be unsubstituted or monosubstituted or polysubstituted. Suitable substituents are, for example, OH, C ₁ -C ₄ -alkoxy, NR ¹¹ R ¹² (R ¹¹ and R ¹² are each independently H or C ₁ -C ₄ -alkyl) or carbonyl (COR ¹¹ ). Preferably, however, they are unsubstituted.

Aryl represents an aromatic hydrocarbon radical having 6 to 14 carbon atoms, such as phenyl, naphthyl, anthracenyl or phenanthrenyl. The aryl radical can be unsubstituted or monosubstituted or polysubstituted. Suitable substituents are C ₁ -C ₁₀ alkyl, OH, C ₁ -C ₄ alkoxy and NO ₂ . Preferred substituents are C ₁ -C ₁₀ -alkyl radicals, C ₁ -C ₄ -alkyl being particularly preferred. In particular, the substituents are ethyl or methyl and especially methyl.

C ₁ -C ₄ alkoxy is a bonded via an oxygen atom C ₁ -C ₄ alkyl radical. Examples of these are methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, 2-butoxy, isobutoxy and tert-butoxy.

C ₁ -C ₄ -alkanol represents a C ₁ -C ₄ -alkyl radical which is substituted by 1 to 3 hydroxyl groups on different carbon atoms. C ₁ -C ₁₀ -alkanol represents a C ₁ -C ₁₀ -alkyl radical which is substituted by 1 to 6 hydroxyl groups on different carbon atoms. C ₁ -C ₂₀ -alkanol is a C ₁ -C ₂₀ -alkyl radical which is replaced by 1 to 6 hydroxyl groups at different Carbon atoms is substituted. C ₁ -C ₄₀ -alkanol is a C ₁ -C ₄₀ -alkyl radical which is substituted by 1 to 6 hydroxyl groups on different carbon atoms. Examples of C ₁ -C ₄ -alkanols are methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, isobutanol, tert-butanol, ethylene glycol, propylene glycol and glycerol. In addition, C ₁ -C ₁₀ -alkanol is, for example, pentanol, hexanol, heptanol, octanol, 2-ethylhexanol, nonanol, decanol, their constitutional isomers, as well as erythritol, pentaerythritol and sorbitol. In addition, C ₁ -C ₂₀ -alkanol is, for example, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol and eicosanol and also their constitutional isomers. In addition, C ₁ -C ₄₀ -alkanol is, for example, hencosanol, docosanol, tricosanol, tetracosanol, pentacosanol, hexacosanol, heptacosanol, octacosanol, nonacosanol, squalanol, the higher homologues and constitutional isomers thereof.

• M1: 0,70 bis 0,98, vorzugsweise 0,75 bis 0,96, insbesondere 0,8 bis 0,95;
• M2: 0,01 bis 0,299, vorzugsweise 0,02 bis 0,20, insbesondere 0,03 bis 0,15;
• M3: 0,001 bis 0,10, vorzugsweise 0,003 bis 0,08 insbesondere 0,005 bis 0,06.

In the copolymers used according to the invention, the monomers M1, M2 and M3 may be present in the copolymer in the following molar proportions (Mx / (M1 + M2 + M3):

• M1: 0.70 to 0.98, preferably 0.75 to 0.96, especially 0.8 to 0.95;
• M2: 0.01 to 0.299, preferably 0.02 to 0.20, especially 0.03 to 0.15;
• M3: 0.001 to 0.10, preferably 0.003 to 0.08, especially 0.005 to 0.06.

The monomers M1 are preferably monoalkenes having a terminal double bond, such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, their constitution isomers and the higher monounsaturated homologs with up to 40 carbon atoms.

In the monomers M1, R ^{1 is} preferably H or C ₁ -C ₁₀ -alkyl, particularly preferably H or C ₁ -C ₄ -alkyl and in particular H, methyl or ethyl. Accordingly, monomer M1 is in particular ethylene, propylene or 1-butene. Specifically, M1 is ethylene.

If one of the radicals R ² , R ³ , R ⁴ or R ⁵ in the comonomer M2 is -COOR ¹⁰ , this is, for example, an ester of an α, β-ethylenically unsaturated carboxylic acid. If one of the radicals R ² , R ³ , R ⁴ or R ⁵ in M2 is -OCOR ¹⁰ , this is, for example, the alkenyl ester, for example the vinyl or propenyl ester of an aliphatic carboxylic acid, which may be unsaturated or preferably saturated. If two radicals R ² , R ³ , R ⁴ or R ⁵ stand for -COOR ¹⁰ , then M2 is the diester of an ethylenically unsaturated dicarboxylic acid.

Examples of α, β-unsaturated carboxylic acids are acrylic acid, methacrylic acid and crotonic acid.

Examples of suitable esters of α, β-unsaturated carboxylic acids are the esters with C ₁ -C ₄₀ -alkanols, preferably with C ₁ -C ₂₀ -alkanols, in particular with C ₁ -C ₁₀ -alkanols. Examples these are the methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl -, nonyl or decyl esters of acrylic acid, methacrylic acid or crotonic acid. Preference is given to the esters of acrylic or methacrylic acid with the abovementioned C ₁ -C ₁₀ -alkanols.

Examples of the alkenyl esters, in particular for the vinyl or propenyl esters of an aliphatic carboxylic acid, which may be unsaturated or preferably saturated, are the vinyl or propenyl esters of aliphatic C ₂ -C ₃₀ carboxylic acids, such as acetic acid, propionic acid, butyric acid, valeric acid, neo-pentanoic acid , caproic acid, enanthic acid, caprylic acid, pelargonic acid, 2-ethylhexanoic acid, Versatinsäuren (Versatic ^™ acid), in particular neononanoic acid and neodecanoic acid (for example, VeoVa ^™ = Vinylester of Versatic acid), capric acid, Neoundecansäure, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, Lignoceric, cerotic and melissic acids. The vinyl esters of the stated carboxylic acids are preferred.

Examples of diesters of unsaturated dicarboxylic acids are the diesters with C ₁ -C ₄₀ -alkanols, preferably with C ₁ -C ₂₀ -alkanols, in particular with C ₁ -C ₁₀ -alkanols. Unsaturated dicarboxylic acids are, for example, maleic acid, fumaric acid and citraconic acid. Examples of such esters are the methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl or decyl esters of maleic acid, fumaric acid or citraconic acid, it being possible for the carboxyl groups of the dicarboxylic acids to be esterified with identical or different alkanols.

In the monomers M2, preferably only one of the radicals R ² , R ³ , R ⁴ or R ^{5 is} -COOR ¹⁰ or -OCOR ¹⁰ and particularly preferably -OCOR ¹⁰ . The other three radicals are preferably H or C ₁ -C ₁₀ -alkyl, more preferably H or C ₁ -C ₄ -alkyl. Two of the radicals are preferably H and the third radical is H or C ₁ -C ₄ -alkyl. In particular, all three remaining radicals are H or methyl, it being preferred that two of the radicals is H and the third is H or methyl. Specifically, all three remaining radicals are H.

In the radicals -COOR ¹⁰ R ¹⁰ is C ₁ -C ₂₀ alkyl, preferably C, more preferably C _1- C ₁₀ alkyl.

In the radicals -OCOR ¹⁰ R ¹⁰ is C ₁ -C ₁₉ alkyl, preferably C, particularly preferably C ₁ -C ₉ alkyl, in particular methyl or ethyl and especially methyl.

Preferably, the monomer M2 is the vinyl ester of an aliphatic saturated C ₁ -C ₂₀ carboxylic acid. Examples are the Vinylester of acetic acid, propionic acid, butyric acid, valeric acid, neopentanoic acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, 2-ethylhexanoic acid, Versatinsäuren (Versatic ^™ acid), in particular neononanoic acid and neodecanoic acid (for example, VeoVa ^™ = Vinylester of Versatic acid), capric acid , Neoundecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid and arachic acid. More preferably, the monomer M2 is the vinyl ester of an aliphatic saturated C ₁ -C ₁₀ carboxylic acid. Examples of these are the vinyl esters of acetic acid, propionic acid, butyric acid, valeric acid, neononanoic acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, 2-ethylhexanoic acid, versatic acids (Versatic ^™ acid), in particular neononanoic acid and neodecanoic acid (eg VeoVa ^™ = vinyl ester of versatic acid) and capric acid , In particular, the monomer M2 is vinyl acetate or vinyl propionate. Specifically, the monomer M2 is vinyl acetate.

In monomer M3, R ⁶ , R ⁷ and R ⁸ independently of one another are H or C ₁ -C ₄ -alkyl. Preferably, they stand for H or methyl. More preferably, at most one of these radicals is methyl and the other two are H. Specifically, all three radicals R ⁶ , R ⁷ and R ^{8 are} H.

R ⁹ is preferably optionally substituted phenyl. Preferred substituents are OH and C ₁ -C ₄ -alkyl, with methyl and ethyl and especially methyl being particularly preferred. R ⁹ particularly preferably represents phenyl, methylphenyl, such as 2-, 3- or 4-methylphenyl, or dimethylphenyl, such as 2,3-, 2,4-, 2,5- or 2,6-dimethylphenyl. Specifically, R ^{9 is} unsubstituted phenyl.

Specifically, the monomer M3 is styrene (vinylbenzene).

The copolymers according to the invention have a number-average molecular weight M _n in the range from preferably 1000 to 20 000, more preferably from 1000 to 10000 and in particular from 1500 to 7000.

The copolymers may also have a weight-average molecular weight M _{w of} from 1000 to 30 000, in particular 1500 to 20 000 and / or an M _w / M _n ratio of 1.5 to 5.0, in particular 1.8 to 3.0.

The copolymer according to the invention is particularly preferably an ethylene / vinyl acetate / styrene terpolymer.

• VAC: vorzugsweise 5 bis 40 Gew.-%, besonders bevorzugt 10 bis 35 Gew.-%, insbesondere 12 bis 30 Gew.-%,
• Styrol: vorzugsweise 1 bis 25 Gew.-%, besonders bevorzugt 1,5 bis 20 Gew.-%, insbesondere 2 bis 15 Gew.-%.

Die Differenz zu 100 Gew.-% entspricht dem Anteil an Ethylen.Based on the polymer, the proportion by weight of the copolymerized monomers in this particularly preferred terpolymer

• VAC: preferably 5 to 40% by weight, particularly preferably 10 to 35% by weight, in particular 12 to 30% by weight,
• Styrene: preferably 1 to 25 wt .-%, particularly preferably 1.5 to 20 wt .-%, in particular 2 to 15 wt .-%.

The difference to 100 wt .-% corresponds to the proportion of ethylene.

The viscosity of such copolymers (determined according to Ubbelohde DIN 51562) is about 5 - 25000 mm ² / s, in particular about 10 to 2000 mm ² / s, each at a temperature of about 120 ° C.

The copolymers used according to the invention are preferably obtainable by, preferably free-radical, polymerization, in particular high-pressure polymerization, of the monomers M1, M2 and M3. Suitable polymerization processes are well known. Thus, processes for the direct radical high-pressure copolymerization of unsaturated compounds, for example in Ullmann's Encyclopedia of Industrial Chemistry 5th edition, keyword: Waxes, Vol. A 28, p. 146 ff., VCH Weinheim, Basel, Cambridge, New York, Tokyo, 1996 to which reference is hereby incorporated by reference. In addition, suitable methods are for example in DE-A-2515805 . DE-A-3141507 . EP-A-0007590 and US 3,627,838 which is also incorporated herein by reference in its entirety.

The copolymers of the invention obtainable by the polymerization process are preferably composed essentially of the above-defined monomers M1, M2 and M3. Depending on the manufacturing process, small amounts of a compound used as regulator (chain terminator) may possibly be present.

The copolymers according to the invention are preferably prepared in stirred high-pressure autoclaves or in high-pressure tubular reactors or combinations of the two. For them, the ratio of length / diameter in the range from 5: 1 to 30: 1, preferably 10: 1 to 20: 1, predominantly.

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 of 160 to 320 ° C, preferably in the range of 200 to 280 ° C.

oder Mischungen derselben.As a regulator for adjusting the molecular weight of the copolymers used, for example, an aliphatic aldehyde or an aliphatic ketone of the general formula I.

or mixtures thereof.

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

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

• Hydrogen;
• C ₁ -C ₆ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1,2 Dimethyl propyl, isoamyl, n-hexyl, isohexyl, sec-hexyl; particularly preferably 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, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; preferred are cyclopentyl, cyclohexyl and cycloheptyl;

The radicals R ^a and R ^b may also be covalently linked together to form a 4- to 13-membered ring. For example, R ^a and R ^b may 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 most preferred.

Further suitable regulators are unbranched aliphatic hydrocarbons, for example propane or branched aliphatic hydrocarbons having tertiary H atoms, for example isobutane, isopentane, isooctane or isododecane (2,2,4,6,6-pentamethylheptane). As further additional regulator higher olefins, such as propylene, can be used.

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.

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

As starters for the radical polymerization, the usual radical initiators, such as organic peroxides, oxygen or azo compounds, can be used. Also mixtures of several radical starters are suitable. As free-radical initiators, it is possible, for example, to use one or more peroxides selected from the following commercially available substances:

• Didecanoyl peroxide, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, tert-amylperoxy-2-ethylhexanoate, dibenzoyl peroxide, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxydiethylacetate, tert-butyl peroxydiethyl isobutyrate, 1,4- Di (tert-butylperoxycarbo) -cyclohexane as 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-butyl peroxy isopropyl carbonate, 2,2-di-tert-butylperoxy) butane or tert-butyl peroxyacetate;
• tert-butyl peroxybenzoate, di-tert-amyl peroxide, dicumyl peroxide, the isomeric di- (tert-butylperoxyisopropyl) benzenes, 2,5-dimethyl-2,5-di-tert-butylperoxyhexane, tert-butylcumyl 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, such as those from the EP-A-0 813 550 are known

As peroxides, di-tert-butyl peroxide, tert-butyl peroxypivalate, tert-butyl peroxyisononanoate, tert-amyl peroxypivalate or dibenzoyl peroxide or mixtures thereof are particularly suitable. As the azo compound, azobisisobutyronitrile ("AIBN") is exemplified. The free-radical initiators are metered in amounts customary for polymerizations.

In a preferred procedure, the copolymers of the present invention are prepared by reacting a mixture of monomers M1, M2 and M3 in the presence of the regulator at a temperature in the range of about 20 to 50 ° C, e.g. of 30 ° C, preferably continuously passed through a stirred autoclave, which at a pressure in the range of about 1500 to 2000 bar, such. of about 1700 bar, is maintained. By the preferably continuous addition of initiator, usually in a suitable solvent, e.g. Isododecane is dissolved, the temperature in the reactor at the desired reaction temperature, such as. at 200 to 250 ° C, held. The resulting after the relaxation of the reaction mixture polymer is then isolated in a conventional manner.

Modifications of this procedure are of course possible and can be made by the skilled person without undue burden. Thus, for example, the comonomers and the regulator can be added separately to the reaction mixture, the reaction temperature can be varied during the process, to name just a few examples.

Use of the copolymers of the invention

Another object of the present invention is the use of the copolymers of the invention as an additive for fuel oils and lubricants.

Preferably, the copolymers are used as cold flow improvers, preferably for fuel oils.

The copolymers of the invention are used alone or in combination with other co-additives in amounts to show an effect as a cold flow improver in the additized fuel oil or lubricant.

Fuel oil and lubricant compositions

Another object of the invention relates to fuel oil compositions containing a greater weight fraction of a boiling in the range of about 120-500 ° C middle distillate fuel and a smaller proportion by weight of at least one copolymer of the invention.

Another object of the invention relates to lubricant compositions containing a greater proportion by weight of a conventional lubricant and a smaller proportion by weight of at least one cold flow improver as defined above.

By fuel oil compositions is meant according to the invention preferably fuels. Suitable fuels are gasolines and middle distillates, with middle distillates being preferred. Suitable middle distillates are, for example, diesel fuels, heating oil or kerosene; wherein diesel fuel and heating oil are particularly preferred.

The fuel oils are, for example, low-sulfur or high-sulfur petroleum refines or stone or lignite distillates, which usually have a boiling range of 150 to 400 ° C. The fuel oils may be standard fuel oil according to DIN 51603-1, which has a sulfur content of 0.005 to 0.2 wt .-%, or it is low sulfur fuel oils having a sulfur content of 0 to 0.005 wt. As examples for heating oil is in particular heating oil for domestic oil firing systems or heating oil called EL. The quality requirements for such heating oils are specified, for example, in DIN 51603-1 (cf. Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, Vol. A12, p. 617 ff ., which is hereby incorporated by reference).

The 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 even beyond. However, these may 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 maximum sulfur content of 0.005 wt .-% or by a 95% point of, for example 285 ° C and a maximum sulfur content of 0.001 wt .-%. In addition to refining diesel fuels, those available from coal gasification or gas liquefaction (GTL) or biomass to liquid (BTL) fuels are also suitable. Also suitable are mixtures of the abovementioned diesel fuels with regenerative fuels, such as biodiesel or bioethanol.

The additive according to the invention is particularly preferred for the addition of low-sulfur diesel fuels, that is to say having 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 of sulfur or for the addition of heating oil with a low sulfur content, for example with a sulfur content of at most 0.2% by weight, preferably of at most 0.05% by weight, more preferably of at most 0.005 Gew., Used.

Such fuel oil compositions may further comprise as 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 fuel oil, wherein the diesel fuel may be obtainable by refining, coal gasification, gas liquefaction or biomass liquefaction, may be a mixture of such products and optionally mixed with regenerative fuels. Such fuel oil compositions are preferred in which the sulfur content of the mixture is at most 500 ppm.

The additive of the present invention is preferably used in a proportion based on the total amount of the fuel oil composition, which in itself has a substantially sufficient influence on the cold flow properties of the fuel oil compositions. Particularly preferably, the additive is used in an amount of 0.001 to 1 wt .-%, in particular from 0.01 to 0.1 wt .-%, based on the total amount of the fuel oil composition.

In the context of the present invention, the copolymers according to the invention can be used in combination with other conventional cold flow improvers and / or further lubricating and fuel oil additives.

Co-additives

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

Suitable additives which may be included in the fuel oils of this invention besides the copolymer of the present invention, especially for diesel fuels and heating oils, include detergents, corrosion inhibitors, dehazers, demulsifiers, antifoams, antioxidants, metal deactivators, multifunctional stabilizers, cetane improvers, combustion improvers, dyes, Markers, solubilizers, antistatic agents, lubricity improvers, and other additives which 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 ("WAFI") (cf. . also Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Vol. A16, p. 719 ff ; or the patents cited at the outset for flow improvers).

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

Other conventional cold flow improvers which may be mentioned in particular are:

• a) copolymers of ethylene with at least one other ethylenically unsaturated monomer, which are different from the copolymers of the invention;
• b) comb polymers;
• c) polyoxyalkylenes;
• d) polar nitrogen compounds;
• e) sulfocarboxylic acids or sulfonic acids or their derivatives; and
• f) poly (meth) acrylic esters.

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

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

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

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

Examples of suitable alkenylcarboxylic 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 vinyl esters being preferred. A particularly preferred alkenyl carboxylic acid ester is vinyl acetate.

Particularly preferably, the ethylenically unsaturated monomer is selected from alkenylcarboxylic esters.

Also suitable are copolymers which contain two or more mutually different alkenylcarboxylic acid esters in copolymerized form, these differing in the alkenyl function and / or in the carboxylic acid group. Also suitable are copolymers which, in addition to the alkenylcarboxylic 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 from 1 to 50 mol%, particularly preferably from 10 to 50 mol% and in particular from 5 to 20 mol%, based on the total copolymer.

The copolymer a) preferably has a number-average molecular weight M _{n of} from 1,000 to 20,000, more preferably from 1,000 to 10,000 and in particular from 1,000 to 6,000.

worin

• D für R¹⁷, COOR¹⁷, OCOR¹⁷, R¹⁸, OCOR¹⁷ oder OR¹⁷ steht,
• E für H, CH₃, D oder R¹⁸ steht,
• G für H oder D steht,
• J für H, R¹⁸, R¹⁸COOR¹⁷. Aryl oder Heterocyclyl steht,
• K für H, COOR¹⁸, OCOR¹⁸, OR¹⁸ oder COOH steht,
• L für H, R¹⁸ COOR¹⁸, OCOR¹⁸, COOH oder Aryl steht,
  wobei
  • R¹⁷ für einen Kohlenwasserstoffrest mit wenigstens 10 Kohlenstoffatomen, vorzugsweise mit 10 bis 30 Kohlenstoffatomen, steht,
  • R¹⁸ für einen Kohlenwasserstoffrest mit wenigstens einem Kohlenstoffatom, vorzugsweise mit 1 bis 30 Kohlenstoffatomen, steht,
• m für einen Molenbruch im Bereich von 1,0 bis 0,4 steht und
• n für einen Molenbruch im Bereich von 0 bis 0,6 steht.

Comb polymers b) are for example those described in " Comb-like polymers. Structure and Properties ", NA Platé and VP Shibaev, J. Poly. Sci. Macromolecular Revs., 8, pp. 117-253 (1974) are described. Of the described there, for example, comb polymers of the formula II are suitable

wherein

• 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 for H, R ¹⁸ , R ¹⁸ COOR ¹⁷ . Aryl or heterocyclyl,
• K is H, COOR ¹⁸ , OCOR ¹⁸ , OR ¹⁸ or COOH,
• L is H, R ¹⁸ COOR ¹⁸ , OCOR ¹⁸ , COOH or aryl,
  in which
  • R ^{17 is} a hydrocarbon radical having at least 10 carbon atoms, preferably having 10 to 30 carbon atoms,
  • R ^{18 is} a hydrocarbon radical having at least one carbon atom, preferably having 1 to 30 carbon atoms,
• m for a mole fraction in the range of 1.0 to 0.4 and
• n represents a mole fraction in the range of 0 to 0.6.

Preferred comb polymers are obtainable, for example, by the copolymerization of maleic anhydride or fumaric acid with another ethylenically unsaturated monomer, for example with an α-olefin or an unsaturated ester, such as vinyl acetate, followed by esterification of the anhydride or acid function with an alcohol having at least 10 carbon atoms. Other preferred comb polymers are copolymers of α-olefins and esterified comonomers, for example, esterified copolymers of styrene and maleic anhydride or esterified copolymers of styrene and fumaric acid. Also mixtures of comb polymers are suitable. Comb polymers may also be polyfumarates or polymaleinates. In addition, homopolymers and copolymers of vinyl ethers are suitable comb polymers.

• R¹⁹ und R²⁰ jeweils unabhängig voneinander für R²¹, R²¹CO-, R²¹-O-CO(CH₂)_z- oder R²¹-O-CO(CH₂)_z-CO- stehen, wobei R²¹ für lineares C₁-C₃₀-Alkyl steht,
• y für eine Zahl von 1 bis 4 steht,
• x für eine Zahl von 2 bis 200 steht, und
• z für eine Zahl von 1 bis 4 steht.

Suitable polyoxyalkylenes c) are, for example, polyoxyalkylene esters, ethers, esters / ethers and mixtures thereof. Preferably, the polyoxyalkylene compounds contain at least one, more preferably at least two linear alkyl groups having from 10 to 30 carbon atoms and a polyoxyalkylene group having a molecular weight of up to 5,000. The alkyl group of the polyoxyalkylene radical preferably contains 1 to 4 carbon atoms. Such polyoxyalkylene compounds are for example in the EP-A-0 061 895 as well as in the US 4,491,455 which is incorporated herein by reference in its entirety. Preferred polyoxyalkylene esters, ethers and esters / ethers have the general formula III

R ¹⁹ [O- (CH ₂ ) _y ] _x OR ²⁰ (III)

wherein

• R ¹⁹ and R ^{20 are} each independently R ²¹ , R ^{21 is} CO-, R ^{21 is} -O-CO (CH ₂ ) _z - or R ^{21 is} -O-CO (CH ₂ ) _z -CO-, wherein R ^{21 is} is linear C ₁ -C ₃₀ -alkyl,
• y is a number from 1 to 4,
• x is a number from 2 to 200, and
• z is 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 having 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 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 both R ¹⁹ and R ^{20 are} R ²¹ -CO- are diesters of fatty acids having 10 to 30 carbon atoms, preferably stearic or behenic acid.

The polar nitrogen compounds d), suitably oil-soluble, may be both ionic and nonionic, and preferably have at least one, more preferably at least 2, substituents of the formula> NR ²² wherein R ^{22 is} a C ₈ -C ₄₀ hydrocarbon radical. The nitrogen substituents may also be quaternized, that is in cationic form. An example of such nitrogen compounds are ammonium salts and / or amides obtainable by reacting at least one amine substituted with at least one hydrocarbyl 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. Examples of suitable primary amines are octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tetradecylamine and the higher linear homologs. Suitable secondary amines are, for example, dioctadecylamine and methylbehenylamine. Also suitable are amine mixtures, in particular industrially available amine mixtures, such as fatty amines or hydrogenated tallamines, as used, for example, in US Pat Ullmann's Encyclopedia of Industrial Chemistry, 6th edition, 2000 electronic release, chapter "Amines, aliphatic". Suitable acids 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 by long-chain hydrocarbon radicals.

Another example of polar nitrogen compounds are ring systems bearing at least two substituents of the formula -A-NR ²³ R ²⁴ wherein A is a linear or branched aliphatic hydrocarbon group optionally substituted by one or more groups selected from O, S , NR ³⁵ and CO, and R ²³ and R ^{24 are} a C ₉ -C ₄₀ hydrocarbon radical optionally interrupted by one or more groups selected from O, S, NR ³⁵ and CO, and / or or substituted by one or more substituents selected from OH, SH and NR ³⁵ R ³⁶ , wherein R ^{35 is} C ₁ -C ₄₀ alkyl optionally substituted by one or more moieties selected from CO, NR ³⁵ , O and S, interrupted, and / or substituted 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, wherein R ³⁷ and R ³⁸ each una depending on one another, are selected from H or C ₁ -C ₄ -alkyl; and R ^{36 is} H or R ³⁵ .

Preferably, A is 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 either homocyclic, heterocyclic, condensed polycyclic or non-condensed polycyclic systems. Preferably, the ring system is carbo- or heteroaromatic, in particular carboaromatic. Examples of such polycyclic ring systems are condensed benzoic structures, such as naphthalene, anthracene, phenanthrene and pyrene, condensed non-benzoidic 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 α-pinene, camphene, bornylene, norborane, norbornene, bicyclooctane and bicyclooctene.

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

The polar nitrogen compounds mentioned here are in the WO 00/44857 and in the references cited therein, which is hereby incorporated by reference in its entirety.

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

worin

• Y für SO₃ ^-(NR²⁵ ₃R²⁶)⁺, SO₃ ^-(NHR²⁵ ₂R²⁶)⁺, SO₃ ^-(NH₂R²⁵R²⁶), SO₃(NH₃R²⁶) oder SO₂NR²⁵R²⁶ steht,
• X für Y, CONR²⁵R²⁷, CO₂ ^-(NR²⁵ ₃R²⁷)⁺, CO₂-(NHR²⁵ ₂R²⁷)⁺, R²⁸-COOR²⁷, NR²⁵COR²⁷, R²⁸OR²⁷, R²⁸OCOR²⁷, R²⁸R²⁷, N(COR²⁵)R²⁷ oder Z-(NR²⁵ ₃R²⁷)⁺ steht,
  wobei
  • R²⁵ für einen Kohlenwasserstoffrest steht,
  • R²⁶ und R²⁷ für Alkyl, Alkoxyalkyl oder Polyalkoxyalkyl mit wenigstens 10 Kohlenstoffatomen in der Hauptkette stehen,
  • R²⁸ für C₂-C₅-Alkylen steht,
• Z^- für ein Anionenäquivalent steht und
• A und B für Alkyl, Alkenyl oder zwei substituierte Kohlenwasserstoffreste stehen oder gemeinsam mit den Kohlenstoffatomen, an die sie gebunden sind, ein aromatisches oder cycloaliphatisches Ringsystem bilden.

Suitable sulfocarboxylic acids / sulfonic acids or their derivatives e) are, for example, those of the general formula IV

wherein

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

Such sulfocarboxylic acids or sulfonic acids and their derivatives are in the EP-A-0 261 957 which is incorporated herein by reference in its entirety.

Suitable poly (meth) acrylic esters f) are both homo- and copolymers of acrylic and methacrylic acid esters. Preferred are copolymers of at least two mutually different (meth) acrylic acid esters, which differ with respect to the fused alcohol. Optionally, the copolymer contains a further, different of which olefinically unsaturated monomer copolymerized. The weight average molecular weight of the polymer is preferably from 50000 to 500000. A particularly preferred polymer is a copolymer of methacrylic acid and methacrylic esters of saturated C ₁₄ - ₁₅ alcohols and C, wherein the acid groups are neutralized with hydrogenated tallow amine. Suitable poly (meth) acrylic esters are, for example, in WO 00/44857 which is incorporated herein by reference in its entirety.

Another object of the invention is the use of the copolymers according to the invention for improving the action of cold flow improvers of the prior art. In this case, the copolymers of the invention are used in such an amount that they alone have no significant effect on the cold flow properties of the fuel oil thus additized. Thus, the copolymers according to the invention and the conventional cold flow improvers are employed in a weight ratio of from 1: 5 to 1:50, more preferably from 1: 7 to 1:20, in particular from 1: 8 to 1:15, especially about 1: 9. The conventional cold flow improvers are preferably those the group a) of the co-additives, among which ethylene (meth) acrylic acid ester copolymers and in particular ethylene-vinyl ester copolymers, for example ethylene-vinyl acetate copolymers, are particularly preferred. The conventional cold flow improvers are used in conventional amounts, for example in an amount of 0.001 to 1 wt .-%, preferably 0.01 to 0.1 wt .-%, based on the total weight of the fuel oil composition.

additive packages

Finally, the subject of the present application is an additive concentrate containing at least one copolymer of the invention and at least one diluent and optionally 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 bright stock. Also suitable are aromatic and aliphatic hydrocarbons and alkoxyalkanols. Dilutants preferred for middle distillates, especially for diesel fuels and fuel oils, are naphtha, kerosene, diesel fuels, aromatic hydrocarbons, such as Solvent Naphtha heavy, Solvesso® or Shellsol®, and mixtures of these solvents and diluents.

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

Another object of the invention is an additive composition comprising a copolymer of the invention and a conventional cold flow improver. Suitable cold flow improvers are the aforementioned. Preferably, cold flow improvers from group (a), in particular ethylene / vinyl ester copolymers, e.g. to EVA copolymers. In the composition, the copolymers according to the invention and the conventional cold flow improvers are present in a weight ratio of preferably from 1: 5 to 1:50, more preferably from 1: 7 to 1:20, in particular from 1: 8 to 1:15 and especially from about 1: 9 before. The composition may also contain other conventional cold flow improvers and other coadditives as well as diluents. With regard to suitable co-additives and diluents, reference is made to the above statements.

The copolymers of the invention show improved performance compared to conventional fuel additives. In particular, they improve the cold flow properties of additive fuel oils more effectively than comparable additives of the prior art. In addition, they are capable of significantly increasing the effect of conventional cold flow improvers when used in combination with them. In particular, they increase the effect of conventional cold flow improvers in fuel oils. It is sufficient if they are used in amounts that have no effect on the cold flow properties have additive-fuel oils. Furthermore, they are characterized by a good formability. So they have an improved solubility in fuels and lubricants and in the diluents of additive packages and can be handled well (eg metering) due to their relatively low viscosity.

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

1. Production examples

A total of seven different copolymers of the invention were prepared by high pressure polymerization of ethylene, styrene and vinyl acetate.

Ethylene, styrene and vinyl acetate were added with the addition of propionaldehyde as a regulator in a high-pressure autoclave, as described in the literature ( M. Buback et al., Chem. Lng. Tech. 1994, 66, 510 ), continuously polymerized. By way of illustration, the preparation of polymers 4 and 7 is described:

1.1 Preparation of Polymer 4

• Ethylen: 84,2 Mol-% (62,0 Gew.-%); Vinylacetat 11 ,5 Mol-% (26,0 Gew.-%); Styrol 4,3 Mol-% (11,9 Gew.-%). Weitere Polymereigenschaften sind aus der nachstehenden Tabelle ersichtlich.

12 kg / h of ethylene, 7.55 l / h of vinyl acetate and 0.91 l / h of styrene were continuously fed into a high-pressure autoclave at a reaction pressure of 1700 bar. For this purpose, the comonomers were first compressed to an intermediate pressure of about 260 bar and then with a compressor to the final pressure of 1700 bar. At the same time, to adjust the melt viscosity, 2.0 l / h of propionaldehyde as regulator were compressed to 1700 bar and fed into the high pressure autoclave. Separately, 1.81 l / h of an initiator solution of tert-butyl peroxypivalate in isododecane (2,2,4,6,6-pentamethylheptane) (peroxide concentration 0.4 mol / l) were fed into the high-pressure autoclave at a reaction pressure of 1700 bar. The reaction temperature was about 220 ° C. The waxy polymer obtained in an amount of 4.7 kg / h corresponds to a total conversion of all starting materials of about 24%. The viscosity of the product (dynamic melt viscosity, measured at 120 ° C. according to DIN 51562) was 60 mm ² / s. The content of the individual comonomers was determined by means of ¹ H-NMR spectroscopy:

• Ethylene: 84.2 mol% (62.0 wt%); Vinyl acetate 11, 5 mol% (26.0 wt%); Styrene 4.3 mol% (11.9 wt%). Other polymer properties are shown in the table below.

1.2 Preparation of Polymer 7

• Ethylen: 93,6 Mol-% (82,1 Gew.-%); Vinylacetat 5,2 Mol-% (13,9 Gew.-%); Styrol 1,1 1 Mol-% (3,6 Gew.-%). Weitere Polymereigenschaften sind aus der nachstehenden Tabelle ersichtlich.

The procedure was analogous to Preparation 1.1. 12 kg / h of ethylene, 2.48 l / h of vinyl acetate, 1.03 l / h of a solution of styrene in isododecane (ratio 1: 3), 0.55 l / h of a solution of propionaldehyde in isododecane (ratio 1 : 1) and 1.65 l / h of tert-amyl peroxypivalate in isododecane (peroxide concentration 0.06 mol / l). The resulting in an amount of 3.1 kg / h waxy polymer corresponds to a total sales of all Feedstocks of approx. 21%. The viscosity of the product (dynamic melt viscosity, measured at 120 ° C. according to DIN 51562) was 1560 mm ² / s. The content of the individual comonomers was determined by means of ¹ H-NMR spectroscopy:

• Ethylene: 93.6 mole percent (82.1 weight percent); Vinyl acetate 5.2 mol% (13.9 wt%); Styrene 1.1 1 mol% (3.6 wt%). Other polymer properties are shown in the table below.

The content of ethylene, VAC and styrene in the other copolymers was determined by NMR spectroscopy as in Examples 1.1 and 1.2. The viscosities were determined according to Ubbelohde DIN 51562. Table 1: Analytical data of the polymers obtained Polymer Ex. No. Ethylene [mol%] Vinyl acetate [mol%] Styrene [mol%] Viscosity mm ² / s] M _n M _w PDI = M _n / M _w 1 85.2 11.9 2.9 65 1754 3488 1.99 2 84.2 12.9 2.9 150 2480 5338 2.15 3 84.8 12.8 2.4 585 4115 10364 2.52 4 84.2 11.5 4.3 60 1629 3199 1.96 5 83.2 11.8 4.9 575 3568 9576 2.68 6 93.6 5.6 0.7 1480 6300 15624 2.48 7 93.6 5.2 1.1 1560 6368 16620 2.61

2. Application examples

With the above-prepared copolymers 1 to 7, the following experiments were carried out. For this purpose, 50% polymer solutions were prepared in solvent naphtha (which is referred to as "polymer solution x" hereinafter, corresponds to 50 wt .-% polymer x + 50 wt .-% solvent naphtha).

• MDFI A: Ethylen-Vinylacetat-basierte Polymermischung, 60 % Polymergehalt (Keroflux 6100, BASF AG)
• MDFI B: Ethylen-Vinylacetat-basierte Polymermischung, 50 % Polymergehalt (Keroflux 6103, BASF AG)
• MDFI C: Ethylen-Vinylacetat-Vinylester-Terpolymer-basierte Polymermischung, 75 % Polymergehalt
• MDFI D: Ethylen-Vinylacetat-basierte Polymermischung, 60 % Polymergehalt

For comparison purposes, the following conventional MDFI (cold flow improvers) were tested:

• MDFI A: ethylene-vinyl acetate-based polymer blend, 60% polymer content (Keroflux 6100, BASF AG)
• MDFI B: ethylene-vinyl acetate-based polymer blend, 50% polymer content (Keroflux 6103, BASF AG)
• MDFI C: ethylene vinyl acetate-vinyl ester terpolymer based polymer blend, 75% polymer content
• MDFI D: ethylene-vinyl acetate-based polymer blend, 60% polymer content

Conventional middle distillate fuels with the above inventive or conventional Kaltfließverbesserern were added in different dosing rates and the CFPP value was determined.

The Cloud Point (CP) was determined according to ASTM D 2500, the Cold Filter Plugging Point (CFPP) to DIN EN 116 and the Pour Point (PP) to ASTM D 97.

2.1 Test Example 1

Used middle distillate: diesel fuel, Netherlands, CP = -8.6 ° C, CFPP = -9 ° C, CFPP target = -21 ° C, 90-20 (temperature difference of 90 vol.% And 20 vol. -% - boiling curve value) = 101 ° C, 19.8% n-paraffins

The determined CFPP values (in ° C) of the additized middle distillate fuels are summarized in Table 2. Table 2 MDFI (200 ppm) CFPP [° C] Polymer solution 1 -23 Polymer solution 2 -22 Polymer solution 3 -21 MDFI A -20 MDFI B -19 MDFI C -20 MDFI D -18

2.2 Test Example 2

Middle distillate used: diesel fuel, Netherlands, CP = -3.7 ° C, CFPP = -6 ° C, CFPP target = -21 ° C

The determined CFPP values (in ° C) of the additized middle distillate fuels are summarized in Table 3. Table 3 MDFI (400 ppm) CFPP [° C] Polymer solution 2 -22 Polymer solution 3 -22 MDFI A -20 MDFI B -19 MDFI C -19 MDFI D -19

2.3 Test Example 3

Middle distillate used: diesel fuel, Belgium, CP = -17 ° C, CFPP = -19 ° C, CFPP target = -21 ° C, 90-20 = 89 ° C, 18.8% n-paraffins

The determined CFPP values (in ° C) of the additized middle distillate fuels are summarized in Table 4. Table 4 MDFI (300 ppm) CFPP [° C] Polymer solution 1 -23 Polymer solution 2 -23 Polymer solution 3 -23 Polymer solution 4 -23 Polymer solution 5 -23 MDFI A -20 MDFI B -21 MDFI C -19 MDFI D -20

2.4 Test Example 4

Middle distillate used: diesel fuel, Germany, CP = -5.9 ° C, CFPP = -9 ° C, CFPP target = -20 ° C, 90-20 = 94 ° C, 24.3% n-paraffins

The determined CFPP values (in ° C) of the additized middle distillate fuels are summarized in Table 5. Table 5 MDFI (300 ppm) CFPP [° C] Polymer solution 1 -20 Polymer solution 2 -22 Polymer solution 3 -22 Polymer solution 4 -20 MDFI A -18 MDFI B -17 MDFI C -18 MDFI D -19

The following examples show that the copolymers of the invention are also useful as impact modifiers for cold flow improvers of the prior art. For this purpose, in each case 10% solutions of the polymers 6 and 7 were prepared in solvent naphtha.

2.5 Test Example 5

Used middle distillate: heating oil, Germany, CP = +0.5 ° C, CFPP = -3 ° C, CFPP target = -10 ° C, 90-20 = 157 ° C, 15.9% n-paraffins

The determined CFPP values (in ° C) of the additized middle distillate fuels are summarized in Table 6. Table 6 MDFI (200 ppm) CFPP [° C] MDFI B -4 MDFI B + Polymer Solution 6 (90:10) -12 MDFI B + polymer solution 7 (90:10) -15

2.6 Test Example 6

Used middle distillate: heating oil, Germany, CP = + 4.1 ° C, CFPP = + 2 ° C, CFPP target = - 12 ° C, 90-20 = 108 ° C, 24.6% n-paraffins

The determined CFPP values (in ° C) of the additized middle distillate fuels are summarized in Table 7. Table 7 MDFI (700 ppm) CFPP [° C] MDFI B -8th MDFI B + polymer solution 7 (90:10) -13

The test results summarized in Tables 2 to 5 demonstrate a surprisingly good performance of the copolymers according to the invention as cold flow improvers in middle distillate fuel compositions. With the additives according to the invention, it is now possible on the one hand to set comparable CFPP values as with conventional MDFIs, but at a lower metering rate, or to achieve improved (higher) CFPP values for the same metering. In addition, the test results summarized in Tables 6 and 7 demonstrate that the copolymers according to the invention are also capable of significantly increasing the effect of conventional MDFI on the CFPP value.

Claims (20)

Copolymer composed of monomers comprising M1, M2 and M3, where M1, M2 and M3 have the following general formulas:

wherein R ^{1 is} H or C ₁ -C ₄₀ hydrocarbyl; R ² , R ³ , R ⁴ and R ^{5 are the} same or different and are H, C ₁ -C ₄₀ -hydrocarbyl, -COOR ¹⁰ or -OCOR ¹⁰ , wherein at least one of R ² , R ³ , R ⁴ or R ^{5 is} -COOR ¹⁰ or -OCOR ¹⁰ ; R ⁶ , R ⁷ and R ^{8 are the} same or different and are H or C ₁ -C ₄ alkyl; R ^{9 is} aryl; and R ^{10 is} C ₁ -C ₄₀ hydrocarbyl; wherein the copolymer contains the monomers M1, M2 and M3 randomly polymerized. Copolymer according to Claim 1, in which the monomers M1, M2 and M3 are present in the copolymer in the following molar proportions: M1: 0.70 to 0.98 M2: 0.01 to 0.299 M3: 0.001 to 0.10 Copolymer according to one of the preceding claims, wherein in the monomer M2 one of the radicals R ² , R ³ , R ⁴ and R ^{5 is} -OCOR ¹⁰ . A copolymer according to claim 3, wherein monomer M2 is selected from vinyl esters of saturated aliphatic carboxylic acids. A copolymer according to claim 4, wherein monomer M2 is vinyl acetate. Copolymer according to one of the preceding claims, wherein monomer M1 is selected from ethylene, propylene and 1-butene. Copolymer according to one of the preceding claims, wherein in the monomer M3 R ^{9 is} phenyl which is optionally substituted by 1 to 4 C ₁ -C ₄ alkyl groups. A copolymer according to claim 7, wherein M3 is styrene, methylstyrene or dimethylstyrene. A copolymer according to any one of the preceding claims, which is an ethylene / vinyl acetate / styrene terpolymer. Use of a copolymer as defined in any one of the preceding claims as an additive for fuel oils and lubricants. Use according to claim 10, wherein the copolymer is used as a cold flow improver. A fuel oil composition comprising a major weight fraction of a middle distillate fuel boiling in the range of 120-500 ° C and a minor proportion by weight of at least one copolymer as defined in any one of claims 1 to 9. A fuel oil composition according to claim 12, wherein the middle distillate fuel comprises biodiesel (from animal or vegetable production) in proportions of 0-30% by weight. A fuel oil composition according to claim 12, wherein the middle distillate fuel is selected from diesel fuels, kerosene and fuel oil. A fuel oil composition according to claim 14, wherein the diesel fuel is obtainable by refining, coal gasification, gas liquefaction or biomass liquefaction, is a mixture of such products and optionally mixed with regenerative fuels. A fuel oil composition according to any one of claims 12 to 15, wherein the sulfur content of the mixture is at most 500 ppm. A lubricant composition comprising a major proportion by weight of a conventional lubricant and a minor proportion by weight of at least one copolymer as defined in any one of claims 1 to 9. Use or composition according to any one of claims 10 to 17, wherein the copolymer is used in combination with other conventional cold flow improvers and / or other lubricating or fuel oil additives. Use of a copolymer as defined in any one of claims 1 to 9 for improving the effect of conventional cold flow improvers. An additive package comprising at least one copolymer as defined in any one of claims 1 to 9 in combination with at least one other conventional lubricating or fuel oil additive.