DE10254640A1 - Use of homopolymers of ethylenically unsaturated esters to improve the effect of cold flow improvers - Google Patents

Abstract

The present invention relates to the use of homopolymers of ethylenically unsaturated esters to improve the effect of cold flow improvers for fuel oil compositions. The compound further relates to the use of an additive which comprises such a polymer and a customary cold flow improver for reducing the CFPP value and, if appropriate, furthermore for reducing the CFPP2 value and / or the aspiration value of a fuel oil composition.

Description

The present invention relates to the use of homopolymers of ethylenically unsaturated Esters to improve the effectiveness of cold flow improvers for fuel oil compositions. The compound further relates to the use of an additive, which is such a polymer and a conventional cold flow improver includes, to reduce the CFPP value and possibly continue to reduce the CFPP2 value and / or the aspiration value a fuel oil composition.

Containing paraffinic waxes mineral oils and crude oils show a marked deterioration when the temperature drops the flow properties. The cause of this lies in the from the temperature of the cloud point (cloud point) occurring longer-chain crystallization Paraffins, the big one platelet-shaped wax crystals form. These wax crystals have a sponge-like structure and lead to include others Fuel components in the crystal composite.

The appearance of these crystals leads to Deterioration of flow properties of mineral oils and crude oils, which causes malfunctions in the extraction, transport, storage and / or use of the oils can. So it can occur when transporting the oils due to pipes, especially in winter, to deposits on the pipe walls and even complete Constipation come. Mineral oils can cause constipation and bonding of fuel filters in motor vehicle engines (fuel filters) and combustion plants come, which ensures a safe dosage of the Fuel is prevented and under certain circumstances a complete interruption of the fuel supply entry. At temperatures below the pour point (pour point, PP) finally does not find any More fuel flow instead.

To fix these problems continues one has been around for a long time the mineral oils and crude oils Additives in small concentrations too, often from a combination of nucleators with the actual cold flow improvers. nucleators are substances that generate crystal nuclei that prevent the formation of tiny crystals favor. cold flow improvers have similar ones Prevent crystallization properties such as the paraffins contained in mineral oil or crude oil however their growth. Furthermore, the crude and mineral oils are wax Anti Settling Additive (WASA) added to the sinking of the tiny crystals in the oils prevent.

Such additive fuels pass through fuel filters at significantly lower temperatures as non-additive fuels. As a measure of the filterability of fuels the cold filter plugging point is used at low temperatures (CFPP; see EN 116, German version 1997). However, with certain fuel oils additional Effects that worsen the effect of cold flow improvers. This counts the occurrence of a so-called CFPP2 point during the determination of the CFPP Value according to ENI16 above. This further CFPP point occurs when one flows back filtered fuel oil from the pipette of the analyzer (see EN 116 German version 1997, point 4, penultimate sentence, 2. Half sentence) and is reached when the pipette reaches the next lower Test temperature (reduced by 1 degree) is not yet completely empty. Furthermore is for individual fuel oils a so-called aspiration value (a temperature value) can be determined, the in determining the CFPP value according to EN 116 in the temporary increase the filling time of the Pipette expresses that subsequently progressively again before reaching the actual CFPP value decreases (see EN 116, German version 1997, points 10.1.9 and 10.2.6, Annotation). Expresses itself in the case of fuels this in a significant decrease in the flow rate of the Fuel through the fuel filter in a certain temperature range. Both CFPP2 and aspiration value cause a decrease in Fuel oil quality.

Numerous cold flow improvers are known from the prior art. So describes the GB 1,154,966 Homo- or copolymers of monoolefinically unsaturated compounds with a linear saturated group with at least 18 carbon atoms as pour point depressants for fuels. Examples include vinyl and allyl esters of long-chain monocarboxylic acids, (meth) acrylic acid esters of long-chain alcohols and dicarboxylic acid esters of long-chain alcohols.

The GB 1,161,188 describes homo- and copolymers of ethylenically unsaturated compounds with aliphatic hydrocarbon side chains with at least 14 carbon atoms as cold flow improvers for crude oils.

WO 99/27037 describes copolymers various (meth) acrylic acid esters as a cold flow improver for beet oil methyl ester.

The DE 2 022 588 describes polymer mixtures which contain components A and B in a ratio of 5: 1 to 1: 5. Component A comprises homo- or copolymers which have long-chain, essentially linear paraffin side chains. Homopolymers of unsaturated esters are not mentioned. Component B comprises copolymers of ethylene with ethylenically unsaturated compounds. The mixtures are used as pour point depressants for residual fuels such as heavy fuel oil and crude oil. An influence on the CFPP value is not described.

A disadvantage of the additives of State of the art is that they sometimes have the CFPP value of fuel oils do not reduce or reduce it only slightly. The booth also describes no additives which have an effect on the CFPP2 and / or Aspiration value of the fuel oils own (see above).

Another disadvantage of the cold flow improver The state of the art is that they are at low temperatures not in fuel oil to solve. unresolved or not completely dissolved However, additives have a positive effect on Improvement of the cold flow properties of oils not enough. To solve this problem, mixing and storage tanks as well as pipelines heated, which, however, involves considerable energy consumption is.

Object of the present invention it was, therefore, the effect more common cold flow improvers continue to improve. In particular, the additive should have the effect the cold flow improver on reducing the CFPP of fuel oil compositions improve and, if necessary, reduce or eliminate them CFPP2 values and / or to avoid aspiration effects to lead (so.). Moreover the additive should effectively mix in the cold flow improvers into the fuel oils enable even at low temperatures.

The task was solved by the use of a homopolymer of an ethylenically unsaturated Esters to improve the effect of cold flow improvers for fuel oil compositions.

worin
R¹ für COOR⁵ oder (CH₂)_mOCOR⁶ steht,
R² und R³ jeweils unabhängig voneinander für H oder C₁-C₄-Alkyl stehen oder gemeinsam mit den Kohlenstoffatomen, an die sie gebunden sind, einen 5- bis 7-gliedrigen carbo- oder heterocyclischen Ring bilden,
R⁴ für H oder C₁-C₄-Alkyl oder für COOR⁵ steht,
R⁵ für C₁-C₁₀-Alkyl, das gegebenenfalls durch eine oder mehrere Gruppierungen, die ausgewählt sind unter CO, NR⁵, O und S, unterbrochen, und/oder durch einen oder mehrere Reste, die ausgewählt sind unter NR⁷R⁸, OR⁷, SR⁷, COR⁷, COOR⁷, CONR⁷R⁸, Aryl oder Heterocyclyl substituiert ist,
R⁶ für H oder R⁵ steht,
R⁷ und R⁸ jeweils unabhängig voneinander für H oder C₁-C₄-Alkyl stehen,
n für eine Zahl von 2 bis 3000 steht und
m für 0 oder 1 steht.The homopolymer of the ethylenically unsaturated ester preferably has the following structural formula I:

wherein
R ^{1 represents} COOR ⁵ or (CH ₂ ) _m OCOR ⁶ ,
R ² and R ³ each independently represent H or C ₁ -C ₄ alkyl or together with the carbon atoms to which they are attached form a 5- to 7-membered carbo- or heterocyclic ring,
R ^{4 represents} H or C ₁ -C ₄ alkyl or COOR ⁵ ,
R ⁵ for C ₁ -C ₁₀ alkyl, which is optionally interrupted by one or more groupings which are selected from CO, NR ⁵ , O and S, and / or by one or more radicals which are selected from NR ⁷ R ⁸ , OR ⁷ , SR ⁷ , COR ⁷ , COOR ⁷ , CONR ⁷ R ⁸ , aryl or heterocyclyl,
R ^{6 represents} H or R ⁵ ,
R ⁷ and R ⁸ each independently represent H or C ₁ -C ₄ alkyl,
n stands for a number from 2 to 3000 and
m stands for 0 or 1.

In the above definition of the radicals R ⁵ and R ⁶ , C ₁ -C ₄₀ alkyl is in particular methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, Octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, undec Homologues and the corresponding positional isomers.

In the definition of R ² , R ³ and R ⁴ , C ₁ -C ₄ alkyl is in particular methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl.

In the definition of R ⁵ and R ⁶ , aryl preferably represents C ₆ -C ₁₄ aryl, such as phenyl, naphthyl, anthracenyl and phenanthryl, the aryl radical optionally being replaced by one or more radicals selected from C ₁ -C ₄₀ - Alkyl, OR ⁷ , SR ⁷ , NR ⁷ R ⁸ , COOR ⁷ , CONR ⁷ R ⁸ and aryl. Heterocyclyl preferably represents a 5- to 7-membered saturated or unsaturated heterocyclic radical having 1 to 4 heteroatoms, which are selected from O, N and S, which is optionally condensed with a further heterocycle or carbocycle. In particular, it stands for pyrrolidine, tetrahydrofuran, piperidine, morpholine, pyrrole, furan, thiophene, pyrazole, imidazole, oxazole, thiazole, pyridine, pyran, pyrimidine, pyridazine, pyrazine, coumarone, indole and quinoline.

R ⁵ preferably represents C ₁ -C ₃₀ alkyl, particularly preferably C ₁ -C ₂₄ alkyl, such as C ₈ -C ₂₂ alkyl. The alkyl radical is preferably not very branched or linear, in particular linear. Furthermore, the alkyl radical is preferably either unsubstituted or substituted by OH, NH ₂ or SH.

R ⁶ preferably represents H or C ₁ -C ₃₀ alkyl, particularly preferably H or C ₁ -C ₂₄ alkyl, for example C ₈ -C ₂₂ alkyl. The alkyl radical is preferably not very branched or linear, in particular linear. In addition, the alkyl radical is preferably not interrupted or substituted by the groups listed above.

R ² and R ³ are preferably H.

R ⁴ preferably represents H or COOR ⁵ , the above statements relating to the preferred radicals R ⁵ correspondingly applying. In particular, R ⁴ stands for H.

Preferred compounds of the formula I also point a number average molecular weight Mn in the range of about 1000 to 40,000, particularly preferably from 5,000 to 35,000 and in particular from 10,000 to 30,000.

Examples of suitable ethylenically unsaturated esters are the vinyl, propenyl and allyl esters of formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, oenanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachic acid, behenic acid, lignoceric acid and ceric acid melissinic, the vinyl esters being preferred; also the esters of acrylic acid, methacrylic acid, crotonic acid, maleic acid and fumaric acid with methanol, ethanol, ethylene glycol, propanol, propanediol, butanol, Butanediol, pentanol, hexanol, octanol, 2-ethylhexanediol, nonanol, Decanol, lauryl alcohol, myristyl alcohol, stearyl alcohol, arachidyl alcohol or behenyl alcohol, the esters of acrylic and methacrylic acid being preferred are.

• a) Copolymeren von Ethylen mit wenigstens einem weiteren ethylenisch ungesättigten Monomer;
• b) Kammpolymeren;
• c) Polyoxyalkylenen;
• d) polaren Stickstoffverbindungen;
• e) Sulfocarbonsäuren oder Sulfonsäuren oder deren Derivaten; und
• f) Poly(meth)acrylsäureestern.

The cold flow improvers are preferably selected from

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

In the copolymers of ethylene with that is at least one further ethylenically unsaturated monomer a) Monomer preferably selected under alkenyl carboxylic acid esters, (Meth) Acrylsäureestern and olefins.

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

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

Suitable alkenyl carboxylic acid esters are for example the vinyl and Propenyl ester of carboxylic acids with 2 to 20 carbon atoms, the hydrocarbon residue of which is linear or can be branched.

Among these, the vinyl esters are preferred. Among the carboxylic acids with branched hydrocarbon radical are preferred those whose Branching in the α position to the carboxyl group, the α-carbon atom being particularly preferred tertiary is, d. H. the carboxylic acid a so-called neocarboxylic acid is. However, the hydrocarbon residue of the carboxylic acid is preferred linear.

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

This is particularly preferred ethylenically unsaturated Monomer selected among alkenyl carboxylic acid esters.

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

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

The copolymer a) preferably has a number average molecular weight Mn of 500 to 30,000, especially preferably from 1,000 to 30,000 and in particular from 1,000 to 10,000, on.

worin
D für R⁷, COOR⁷, OCOR⁷, R⁸, COOR⁷ oder OR⁷ steht,
E für H, CH₃, D oder R⁸ steht,
G für H oder D steht,
J für H, R⁸, R⁸COOR⁷, Aryl oder Heterocyclyl steht,
K für H, COOR⁸, OCOR⁸, OR⁸ oder COOH steht,
L für H, R⁸ COOR⁸, OCOR⁸, COOH oder Aryl steht,
R⁷ für einen Kohlenwasserstoffrest mit wenigstens 10 Kohlenstoffatomen, vorzugsweise mit 10 bis 30 Kohlenstoffatomen, steht,
R⁸ für einen Kohlenwasserstoffrest mit wenigstens einem Kohlenstoffatom, vorzugsweise mit 1 bis 30 Kohlenstoffatomen, steht,
m für einen Molenbruch im Bereich von 1,0 bis 0,4 steht und
n für einen Molenbruch im Bereich von 0 bis 0,6 steht.Comb polymers b) are, for example, those described in "Comb-Like Polymers. Structure and Properties", NA Platé and VP Shibaev, J. Poly. Sci. Macromolecular Revs. 8, pages 117 to 253 (1974). Of the compounds described there, comb polymers of the formula II are suitable, for example

wherein
D represents R ⁷ , COOR ⁷ , OCOR ⁷ , R ⁸ , COOR ⁷ or OR ⁷ ,
E represents H, CH ₃ , D or R ⁸ ,
G represents H or D,
J represents H, R ⁸ , R ⁸ COOR ⁷ , aryl or heterocyclyl,
K represents H, COOR ⁸ , OCOR ⁸ , OR ⁸ or COOH,
L represents H, R ⁸ COOR ⁸ , OCOR ⁸ , COOH or aryl,
R ^{7 represents} a hydrocarbon radical with at least 10 carbon atoms, preferably with 10 to 30 carbon atoms,
R ^{8 represents} a hydrocarbon radical with at least one carbon atom, preferably with 1 to 30 carbon atoms,
m stands for a mole fraction in the range from 1.0 to 0.4 and
n stands for a mole fraction in the range from 0 to 0.6.

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

worin
R⁹ und R¹⁰ jeweils unabhängig voneinander für R¹¹, R¹¹-CO-, R¹¹-O-CO(CH₂)_z- oder R¹¹-O-CO(CH₂)_z-CO- stehen,
R¹¹ für lineares C₁-C₃₀-Alkyl steht,
y für eine Zahl von 1 bis 4 steht,
x für eine Zahl von 2 bis 200 steht, und
z für eine Zahl von 1 bis 4 steht.Suitable polyoxyalkylenes c) are, for example, polyoxyalkylene esters, ethers, esters / ethers and mixtures thereof. The polyoxyalkylene compounds preferably contain at least one, particularly preferably at least two linear alkyl groups with 10 to 30 carbon atoms and a polyoxyalkylene group with a molecular weight of up to 5000. The alkyl group of the polyoxyalkylene radical preferably contains 1 to 4 carbon atoms. Such polyoxyalkylene compounds are for example in the EP-A-0 061 895 as well as in the US 4,491,455 described, to which reference is hereby made in full. Preferred polyoxyalkylene esters, ethers and esters / ethers have the general formula III

wherein
R ⁹ and R ¹⁰ each independently represent R ¹¹ , R ¹¹ -CO-, R ¹¹ -O-CO (CH ₂ ) _z - or R ¹¹ -O-CO (CH ₂ ) _z -CO-,
R ^{11 represents} linear C ₁ -C ₃₀ alkyl,
y represents a number from 1 to 4,
x represents a number from 2 to 200, and
z represents a number from 1 to 4.

Preferred polyoxyalkylene compounds of the formula III, in which both R ⁹ and R ^{10 are} R ¹¹ , are polyethylene glycols and polypropylene glycols with a number average molecular weight of 100 to 5000. Preferred polyoxyalkylenes of the formula III, in which one of the radicals R ^{9 is} R ¹¹ and the other represents R ¹¹ -CO- are polyoxyalkylene esters of fatty acids with 10 to 30 carbon atoms, such as stearic acid or behenic acid. Preferred polyoxyalkylene compounds in which both R ⁹ and R ^{10 represent} a radical R ¹¹ -CO- are diesters of fatty acids having 10 to 30 carbon atoms, preferably stearic or behenic acid.

The polar nitrogen compounds d), which are suitably oil-soluble, can be both ionic and non-ionic and preferably have at least one, particularly preferably at least 2, substituents of the formula> NR ¹² , in which R ^{12 is} a C ₈ -C ₄₀ -hydrocarbon radical. The nitrogen substituents can also be quaternized, that is to say in cationic form. An example of such nitrogen compounds are ammonium salts and / or amides which can be obtained by reacting at least one amine substituted with at least one hydrocarbon radical with a carboxylic acid having 1 to 4 carboxyl groups or with a suitable derivative thereof. The amines preferably contain at least one linear one C ₈ -C ₄₀ alkyl group. Suitable primary amines are, for example, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tetradecylamine and the higher linear homologues. Suitable secondary amines are, for example, dioctadecylamine and methylbehenylamine. Amine mixtures, in particular amine mixtures which are commercially available, such as fatty amines or hydrogenated tallamines, as described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 6th edition, 2000 electronic release, chapter "Amines, aliphatic", are also suitable. Acids suitable for the reaction are, for example, cyclohexane-1,2-dicarboxylic acid, cyclohexene-1,2-dicarboxylic acid, cyclopentane-1,2-dicarboxylic acid, naphthalenedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid and succinic acids substituted with long-chain hydrocarbon radicals.

Another example of polar nitrogen compounds are ring systems which carry at least two substituents of the formula -A-NR ¹³ R ¹⁴ , in which A stands for a linear or branched aliphatic hydrocarbon group, which may be replaced by one or more groups selected from O, S , NR and CO, is interrupted, and R ¹³ and R ^{14 represent} a C ₉ -C ₄₀ hydrocarbon radical which is optionally interrupted and / or by one or more groups which are selected from O, S, NR ⁵ and CO is substituted by one or more substituents selected from OH, SH and NR ⁵ R ⁶ , where R ⁵ and R ^{6 are} as defined above. A is preferably a methylene or polymethylene group having 2 to 20 methylene units. Examples of suitable radicals R ¹³ and R ¹⁴ are 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 2-ketopropyl, ethoxyethyl and propoxypropyl. The cyclic system can be both homocyclic, heterocyclic, condensed polycyclic or uncondensed polycyclic systems. The ring system is preferably carbo- or heteroaromatic, in particular carboaromatic. Examples of such polycyclic ring systems are condensed benzoid structures, such as naphthalene, anthracene, phenanthrene and pyrene, condensed nonbenzoic structures, such as azulene, indene, hydrindens and fluorene, uncondensed polycycles, such as diphenyl, heterocycles, such as quinoline, indole, dihydroindole, benzofuran, Coumarin, isocoumarin, benzthiophene, carbazole, diphenylene oxide and diphenylene sulfide, non-aromatic or partially saturated ring systems, such as decalin, and three-dimensional structures, such as α-pinene, camphene, bornylene, norbonane, norbones, bicyclooctane and bicyclooctene.

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

The polar nitrogen compounds mentioned here are in WO 00/44857 and in the references mentioned therein described, to which reference is hereby made in full.

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

worin
Y für SO₃ ^–(NR¹⁵ ₃R¹⁶)⁺, SO₃ ^–(NHR¹⁵ ₂R¹⁶)⁺, SO₃ ^–(NH₂R¹⁵R¹⁶), SO₃ ^–(NH₃R¹⁶) oder SO₂NR¹⁵R¹⁶ steht,
X für Y, CONR¹⁵R¹⁷, CO₂ ^–(NR¹⁵ ₃R¹⁷)⁺, CO₂ ^–(NHR¹⁵ ₂R¹⁷)⁺, R¹⁸-COOR¹⁷, NR¹⁵COR¹⁷, R¹⁸OR¹⁷, R¹⁸OCOR¹⁷, R¹⁸R¹⁷, N(COR¹⁵)R¹⁷ oder Z^–(NR¹⁵ ₃R¹⁷)⁺ steht,
worin
R¹⁵ für einen Kohlenwasserstoffrest steht,
R¹⁵ und R¹⁷ für Alkyl, Alkoxyalkyl oder Polyalkoxyalkyl mit wenigstens 10 Kohlenstoffatomen in der Hauptkette stehen,
R¹⁸ für C₀-C₅-Alkylen steht,
Z- für ein Anionenäquivalent steht und
A und B für Alkyl, Alkenyl oder zwei substituierte Kohlenwasserstoffreste stehen oder gemeinsam mit den Kohlenstoffatomen, an die sie gebunden sind, ein aromatisches oder cycloaliphatisches Ringsystem bilden.Suitable sulfocarboxylic acids / sulfonic acids or their derivatives e) are, for example, those of the general formula IV

wherein
Y for SO ₃ ^- (NR ¹⁵ ₃ R ¹⁶ ) ⁺ , SO ₃ ^- (NHR ¹⁵ ₂ R ¹⁶ ) ⁺ , SO ₃ ^- (NH ₂ R ¹⁵ R ¹⁶ ), SO ₃ ^- (NH ₃ R ¹⁶ ) or SO ₂ NR ¹⁵ R ¹⁶ stands,
X for Y, CONR ¹⁵ R ¹⁷ , CO ₂ ^- (NR ¹⁵ ₃ R ¹⁷ ) ⁺ , CO ₂ ^- (NHR ¹⁵ ₂ R ¹⁷ ) ⁺ , R ¹⁸ -COOR ¹⁷ , NR ¹⁵ COR ¹⁷ , R ¹⁸ OR ¹⁷ , R ¹⁸ OCOR ¹⁷ , R ¹⁸ R ¹⁷ , N (COR ¹⁵ ) R ¹⁷ or Z ^- (NR ¹⁵ ₃ R ¹⁷ ) ⁺ ,
wherein
R ^{15 represents} a hydrocarbon radical,
R ¹⁵ and R ^{17 represent} alkyl, alkoxyalkyl or polyalkoxyalkyl with at least 10 carbon atoms in the main chain,
R ^{18 represents} C ₀ -C ₅ alkylene,
Z- stands for an anion equivalent and
A and B represent alkyl, alkenyl or two substituted hydrocarbon radicals or together with the carbon atoms to which they are attached form an aromatic or cycloaliphatic ring system.

Such sulfocarboxylic acids or sulfonic acids and their derivatives are in the EP-A-0 261 957 described, to which reference is hereby made in full.

Suitable poly (meth) acrylic acid esters f) are both homo- and copolymers of acrylic and methacrylic acid esters, the homopolymers being different from the compounds of the formula I used according to the invention. Copolymers of at least two mutually different (meth) acrylic acid esters which differ with respect to the condensed alcohol are preferred. Optionally, the copolymer contains another, different olefinically unsaturated monomer copolymerized. The weight average molecular weight of the polymer is preferably 50,000 to 500,000 a particularly preferred polymer is a copolymer of methacrylic acid and methacrylic acid esters of saturated C ₁₄ and C ₁₅ alcohols, the acid groups being neutralized with hydrogenated tallamine. Suitable poly (meth) acrylic acid esters are described, for example, in WO 00/44857, to which reference is hereby made in full.

Preferably used as a cold flow improver Copolymers of ethylene with at least one other ethylenically unsaturated Monomer a). In terms of of preferred copolymers is based on the statements made above directed.

Mixtures of copolymers are also suitable a) with at least one of the cold flow improvers b) to f).

Under fuel oil compositions understood fuel is preferred. Suitable fuels are petrol and middle distillates, such as diesel fuels, heating oil or kerosene, being diesel fuel and heating oil are preferred.

The heating oils are, for example low-sulfur or high-sulfur petroleum refines or stone or Lignite distillates, which are usually have a boiling range of 150 to 400 ° C. Preferably acts heating oils low-sulfur heating oils, for example those with a sulfur content of at most 0.1% by weight, preferably at most 0.05% by weight, particularly preferably of at most 0.005% by weight, and in particular of at most 0.001% by weight. As an example for heating oil be especially heating oil for domestic oil firing systems or heating oil EL called. The quality requirements for such Fuel oils are specified, for example, in DIN 51-603-1 (see also Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, vol. A12, p. 617 ff., Whereupon herewith expressly Is referred to).

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

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

The homopolymer of ethylenically unsaturated Ester (activity improver) is preferably used in a proportion, based on the total amount of fuel oil composition used, the for seen essentially no influence on the cold flow properties of fuel oil compositions has. The effect improver is particularly preferred in one Amount from 0.0001 to 0.005% by weight, in particular from 0.0001 to 0.001 % By weight, based on the total amount of the fuel oil composition, is used.

The weight ratio of effectiveness improver for cold flow improvers is preferably 1: 1 to 1: 500, particularly preferably 1: 5 to 1 : 500, stronger preferably 1: 6 to 1: 500, still more preferably 1:10 to 1 : 500, in particular 1:20 to 1: 500 and especially 1:20 to 1 : 350, e.g. B. 1: 20, 1: 80, 1: 100, 1: 200 or 1: 300.

• i) als Komponente A wenigstens ein Homopolymer eines ethylenisch ungesättigten Esters und
• ii) als Komponente B wenigstens einen üblichen Kaltfließverbesserer

zur Verringerung des CFPP-Werts einer Brennstoffölzusammensetzung und gegebenenfalls außerdem zur Verringerung des CFPP2-Werts und/oder zur Vermeidung von Aspirationseffekten (s.o.).Another object of the present invention is the use of an additive mixture comprising

• i) as component A at least one homopolymer of an ethylenically unsaturated ester and
• ii) as component B at least one conventional cold flow improver

to reduce the CFPP value of a fuel oil composition and possibly also to reduce the CFPP2 value and / or to avoid aspiration effects (see above).

The statements made above to the suitable and preferred homopolymers of ethylenically unsaturated Esters, cold flow improvers and fuel oil compositions apply here correspondingly.

• i) als Komponente A wenigstens ein Homopolymer eines ethylenisch ungesättigten Esters und
• ii) als Komponente B wenigstens einen üblichen Kaltfließverbesserer

zur Additivierung von Brennstoffölzusammensetzungen.Another object of the present invention is the use of an additive mixture comprising

• i) as component A at least one homopolymer of an ethylenically unsaturated ester and
• ii) as component B at least one conventional cold flow improver

for the additives of fuel oil compositions.

The weight ratio of component is preferably A to component B from 1: 1 to 1: 500, particularly preferably 1: 5 to 1: 500, stronger preferably 1: 6 to 1: 500, still more preferably 1:10 to 1: 500, in particular 1:20 to 1: 500 and especially 1:20 to 1: 350, z. B. 1: 20, 1: 80, 1: 100, 1: 200 or 1: 300.

Again, the above made executions to homopolymers of ethylenically unsaturated esters, cold flow improvers and fuel oil compositions directed.

The ones used according to the invention are preferably used Additive mixtures to improve the cold flow properties of fuel oil compositions, such as lowering the cloud point, the pour point, the viscosity and especially the CFPP value.

• a) wenigstens eine Komponente A gemäß obiger Definition und
• b) wenigstens eine Komponente B gemäß obiger Definition,

The present invention furthermore relates to an additive mixture comprising

• a) at least one component A as defined above and
• b) at least one component B as defined above,

The above statements apply here as well versions to the suitable and preferred homopolymers of ethylenically unsaturated Esters and cold flow improvers.

The weight ratio is preferably from Component A to component B 1: 1 to 1: 500, particularly preferred 1: 5 to 1: 500, stronger preferably 1: 6 to 1: 500, still more preferably 1:10 to 1 : 500, in particular 1:20 to 1: 500 and especially 1:20 to 1 : 350, e.g. B. 1: 20, 1: 80, 1: 100, 1: 200 or 1: 300.

It is also the subject of the present Invention a fuel oil composition containing a major amount of a hydrocarbon fuel and an effective amount of an additive mixture as defined above and optionally at least one other customary additive.

On the statements made above to fuel oil compositions and additive mixtures are hereby referred.

Finally, the subject of the present Application for an additive concentrate containing one as defined above Additive mixture and at least one diluent and optionally at least one other additive.

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

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

Suitable additives in the fuel according to the invention or concentrate in addition to the additive mixtures according to the invention could be, especially for Diesel fuels and heating oils, include detergents, corrosion inhibitors, dehazers, demulsifiers, Anti-foaming agents ("Antifoam"), antioxidants, Metal deactivators, multifunctional stabilizers, cetane number improvers, Combustion improvers, dyes, markers, solubilizers, antistatic agents, lubricity, different from those mentioned above improving the cold properties Additives such as nucleators, flow improvers ("MDFI"), paraffin dispersants ("WASA") and the combination of the last two additives mentioned ("WAFI").

The use of homopolymers ethylenically unsaturated Ester (active ingredient improver) leads for an improved effect more common cold flow improvers on the cold flow properties of fuel oil compositions, in particular for a more effective reduction in CFPP. As a result, the cold flow improvers are used in significantly smaller quantities than previously required. In addition, the Effect improver to improve the solubility of conventional cold flow improvers in the fuel compositions at low temperatures.

The following examples illustrate the invention, but without restricting it.

Example 1: Investigation the cold flow properties

To investigate the cold flow behavior of fuel oil compositions different middle distillates with different cold flow improvers alone or in a mixture with homopolymers of ethylenically unsaturated Ester added and the CFPP value determined according to EN 116.

The following middle distillates were used
Middle distillate A (GO 2, BP Grangemouth): CP = 0 ° C; CFPP = -5 ° C; d = 852 kg / m ³ ; IBP = 177 ° C; FBP = 376 ° C; 90-20 = 92 ° C;
Middle distillate B (GO, BP Grangemouth): CP = 0 ° C; CFPP = -3 ° C; d = 854 kg / m ³ ; IBP = 187 ° C; FBP = 376 ° C; 90-20 = 93 ° C;
Middle distillate C (Nerefco): CP = 2 ° C; CFPP = 1 ° C; 80% HOB; 10 HGO; 10% LCO;
Middle distillate D (Total Fina Elf): CP = 2 ° C; CFPP = 0 ° C; d = 841 kg / m ³ ; IBP = 155 ° C; FBP = 375 ° C; 90-20 = 148 ° C;
Middle distillate E (PKN Orlen): CP = -3.4 ° C; d = 836 kg / m ³ ; IBP = 164 ° C; FBP = 360 ° C; 90-20 = 115 ° C; CFPP target: –25 ° C;
Middle distillate F (Nerefco): CFPP = 2 ° C; 84% HOB; 8% HGO; 8% LCO;
Middle distillate G (Total Elf Fina): CFPP = 0 ° C;
Middle distillate H (Nerefco): HO with 8% LCO and 8% HGO
IBP = initial boiling point;
FBP = final boiling point;
LCO = light cycle oil
HGO = heavy gas oil
HOB = Heating oil blend

The following polymers were used as cold flow improvers (MDFI):
MDFI 1: ethylene-vinyl acetate based polymer blend (Keroflux ES 6100)
MDFI 2: ethylene-vinyl acetate based polymer mixture (Keroflux ES 6204)
MDFI 3: ethylene-vinyl acetate based polymer mixture (Keroflux ES 6305)
MDFI 4: ethylene-vinyl acetate based polymer blend (Keroflux ES 6103)

The following polymeric esters (PE) were used to improve the effect:
PE 1: polyacrylate with C ₁₆ / C ₁₈ / C ₂₀ / C ₂₂ alcohol components; M _n = 28049; M _w = 55288; PID (M _w / M _n ) = 1.97; 10% by weight solution in toluene
PE 2: polyacrylate with C ₁₈ / C ₂₀ / C ₂₂ alcohol components; M _n = 17188; M _w = 32936; PID (M _w / M _n ) = 1.91; 10% by weight solution in toluene
PE 3: polyacrylate with C ₁₈ / C ₂₀ / C ₂₂ alcohol components; M _n = 22723; M _w = 46752; PID (M _w / M _n ) = 2.06; 10% by weight solution in toluene
PE 4: polyvinyl stearate; M _w = 90000; 50% by weight solution in toluene

The following are examples the CFPP values of middle distillates are listed, on the one hand only with cold flow improvers and on the other hand with the mixture of cold flow improvers according to the invention and polyvinyl ethers were added.

Example 1.1 Middle distillate: A

In the case of moving only with MDFI 1 Middle distillate A aspiration occurs (experiment No. 1). One repeats the experiment (experiment No. 2), one observes one essentially poor CFPP. However, if the combination according to the invention is used from MDFI 1 with PE 2, no more aspiration is observed. Also corresponds the retry attempt (trial No. 4) the first attempt (trial No. 3), d. H. the CFPP value is reproducibly reduced.

Example 1.2 Middle Distillate B

In the case of moving only with MDFI 1 Middle distillate B aspiration occurs (Experiment No. 5). One repeats the experiment (experiment No. 6), one observes one essentially poor CFPP. However, if the combination according to the invention is used from MDFI 1 with PE 2, no more aspiration is observed. Also corresponds the repeat attempt (attempt no. 8) the first attempt (attempt No. 7), d. H. the CFPP value is reproducibly reduced.

Example 1.3 Middle Distillate C

Example 1.4 Middle Distillate D

Example 1.5

Middle distillate E

A CFPP value of –25 ° C should be reached here become.

Example 1.6 Middle Distillate F

The one treated only with MDFI 3 Middle distillate F had a CFPP 2 effect (experiment no. 19). By encore the composition of the invention of MDFI 3 with PE 1 or 2 prevented the occurrence of CFPP 2 become.

Example 1.7 Middle distillate G

Example 1.8 Middle Distillate H

The CFPP values were determined according to EN 116. For this purpose a commercially available automatic CFPP Analyzers, such as. available by WalterHerzog GmbH, Lauda-Königshofen, Germany, type MP 842, used. Also compare the operating instructions to determine the CFPP 2 value.

Like the test results above show leads the addition of homopolymers of ethylenically unsaturated esters to conventional ones Cold flow improvers contribute to a lowering of the CFPP value much lower doses of the cold flow improver. Besides, will prevents the occurrence of aspiration and CFPP 2.

Example 2: Investigation of solubility the cold flow improver in fuels

The mixing behavior of MDFI 1 was in different fuels at two different temperatures certainly. For this, the additive (MDFI 1 or MDFI 1 with active improver PE) added to the fuel at 5 ° C, the vessel once pivoted and connect the CFPP value is determined. The other was the additive in the fuel given, the mixture was heated at 45 ° C for 15 minutes and then was the CFPP value is determined. The results are in the table below listed.

As can be seen from the table leaves, unfolds the cold flow improver MDFI 1 alone is not fully effective. With the addition of the effect improver on the other hand, the full effectiveness is also lower when mixed in Temperature reached.

Claims (23)

Use of a homopolymer of an ethylenic unsaturated Esters to improve the effect of a cold flow improver for fuel oil compositions. Use of an additive mixture comprising i) as component A at least one homopolymer of an ethylenically unsaturated Esters and ii) as component B at least one usual cold flow improvers to Additization of fuel oil compositions. Use of an additive mixture comprising i) as component A at least one homopolymer of an ethylenically unsaturated Esters and ii) as component B at least one usual cold flow improvers to Reducing the CFPP of a fuel oil composition and, if necessary Moreover to reduce CFPP2 and / or to avoid aspiration. Use according to one of the preceding claims, wherein the effect enhancer in a proportion based on the total quantity the fuel oil composition is used for have essentially no effect on the CFPP value of those with the cold flow improver additive fuel oil composition has. Use according to any one of the preceding claims, wherein the fuel oil composition is selected from heating oils and diesel fuels. Use according to one of the preceding claims, wherein the fuel oil composition petroleum middle distillates includes. Use according to one of the preceding claims, wherein the fuel oil composition has a sulfur content of less than 500 ppm (0.05% by weight). Use according to one of the preceding claims, wherein the fuel oil composition has a share of renewable fuel. Use according to one of the preceding claims, wherein the homopolymer of the ethylenically unsaturated ester has the following structural formula I:

where R ^{1 is} COOR ⁵ or (CH ₂ ) _m OCOR ⁶ , R ² and R ³ each independently represent H or C ₁ -C ₄ alkyl, or a 5 together with the carbon atoms to which they are attached - Form to 7-membered carbocyclic or heterocyclic ring, R ^{4 is} H or C ₁ -C ₄ alkyl or COOR ⁵ , R ^{5 is} C ₁ -C ₄₀ alkyl, which may be replaced by one or more groups are selected from CO, NR ⁵ , O and S, interrupted, and / or by one or more radicals which are selected from NR ⁷ R ⁸ , OR ⁷ , SR ⁷ , COR ⁷ , COOR ⁷ , CONR ⁷ R ⁸ , aryl and heterocyclyl, is substituted, R ^{6 represents} H or R ⁵ , R ⁷ and R ⁸ each independently represent H or C ₁ -C ₄ alkyl, n represents a number from 2 to 3000 and m represents 0 or 1 stands. Use according to claim 9, wherein R ² and R ^{3 are} H. Use according to one of the preceding claims, wherein the cold flow improver is selected under a) copolymers of ethylene with at least one other ethylenically unsaturated monomer; b) comb polymers; c) polyoxyalkylenes; d) polar nitrogen compounds; e) sulfocarboxylic acids or sulfonic acids or their derivatives; f) poly (meth) acrylic acid esters. Use according to claim 11, wherein the cold flow improver selected is among copolymers of ethylene and at least one other ethylenically unsaturated Monomers that selected is among alkenyl carboxylic acid esters, acrylsäureestern (meth) and olefins. Use according to claim 12, wherein the ethylenic unsaturated Monomer an alkenyl carboxylic acid ester is. Use according to one of claims 12 or 13, wherein the ethylenic unsaturated Monomer in an amount of 10 to 50 wt .-%, based on the total amount of the copolymerized monomers is copolymerized. Use according to one of claims 13 or 14, wherein the alkenyl carboxylic acid ester Is vinyl acetate. Use according to one of the preceding claims, for Improvement of the cold flow properties of fuel oil compositions. Additive mixture, comprising a) at least one Component A according to the above Definition and b) at least one component B according to the above Definition. Additive mixture according to claim 17, wherein the weight ratio of Component A to component B is 1: 5 to 1: 500. Fuel oil composition, containing a major amount of a hydrocarbon fuel and an effective amount of an additive mixture as defined in any of the Expectations 1 to 15, 17 or 18 and optionally at least one other usual Additive. Fuel oil composition of claim 19, wherein the fuel is diesel fuel, heating oil or kerosene. Fuel oil composition of claim 20, wherein the diesel fuel by refining, Coal gasification or gas liquefaction available is, or is a mixture of such fuels and optionally with regenerative fuels is mixed. Fuel composition according to one of claims 20 or 21, the diesel fuel having a sulfur content of at most 500 ppm. Additive concentrate containing an additive mixture as defined in one of the claims 17 or 18 and at least one diluent and optionally at least one other additive.