WO2004035715A1

WO2004035715A1 - Use of ether vinyl hydrocarbyl homopolymers for increasing effect of a cold flow improving agent

Info

Publication number: WO2004035715A1
Application number: PCT/EP2003/011309
Authority: WO
Inventors: Wolfgang Ahlers; Uwe Rebholz; Jan Van Trier
Original assignee: Basf Aktiengesellschaft
Priority date: 2002-10-14
Filing date: 2003-10-13
Publication date: 2004-04-29
Also published as: EP1554365A1; ATE430186T1; KR20050061537A; DE50311484D1; KR101092726B1; DE10247795A1; ES2323686T3; AU2003267442A1; CN1705734B; CN1705734A; EP1554365B1

Abstract

The invention relates to the use of ether vinyl hydrocarbyl homopolymers for increasing the effect of a cold flow improving agent with respect to combustible compounds and the use of an additive containing the same type polymer and an ordinary agent improving the cold flow in order to reduce the CFPP value( maximum temperature value of a gas oil filterability), thereby eventually reducing the CFPP 2 value and/or a suction value of a combustible compound.

Description

Use of hydrocarbyl vinyl ether homopolymers to improve the effect of cold flow improvers

description

The present invention relates to the use of hydrocarbyl vinyl ether homopolymers to improve the effect of cold flow improvers for fuel oil compositions. The invention 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.

Mineral oils and crude oils containing paraffinic waxes show a marked deterioration in the flow properties when the temperature is lowered. The reason for this lies in the crystallization of long-chain paraffins which occur from the temperature of the cloud point (cloud point) and form large platelet-shaped wax crystals. These wax crystals have a sponge-like structure and lead to the inclusion of other fuel components in the crystal composite.

The appearance of these crystals leads to a deterioration in the flow properties of the mineral oils and crude oils, which can lead to malfunctions during the extraction, transport, storage and / or use of the oils. For example, when the oils are transported through pipelines, deposits can form on the pipe walls, particularly in winter, and even lead to complete blockage. In the case of mineral oils, fuel filters in motor vehicle engines (fuel filters) and combustion systems can become clogged and clogged, thereby preventing safe metering of the fuels and possibly completely interrupting the fuel supply. At temperatures below the pour point (PP), there is no longer any fuel flow.

In order to remedy these problems, additives have been added to the mineral oils and crude oils in small concentrations for a long time, which often consist of a combination of nucleators with the actual cold flow improvers. Nucleators are substances that generate crystal nuclei that promote the formation of tiny crystals. Cold flow improvers have similar crystallization properties to the paraffins contained in mineral oil or crude oil, but prevent their growth. Furthermore, the crude and mineral oils are wax Anti-settling additives (WASA) added to prevent the tiny crystals from sinking into the oils.

Such additive fuels pass through fuel filters at significantly lower temperatures than non-additive fuels. The Cold Filter Plugging Point (CFPP; see EN 116, German version 1997) serves as a measure of the filterability of fuels at low temperatures. However, with certain fuel oils there are additional effects that worsen the effect of cold flow improvers. This includes the occurrence of a so-called CFPP2 point during the determination of the CFPP value according to EN116 above. This further CFPP (point) occurs when a filtered fuel oil flows back from the pipette of the analyzer (cf. EN 116 German version 1997, point 4, penultimate sentence, 2nd half sentence) and is reached when the pipette reaches the the next lower test temperature (reduced by 1 degree) is not yet completely empty. Furthermore, a so-called aspiration value (a temperature value) can be determined for individual fuel oils, which is expressed in the determination of the CFPP value according to EN 116 in the temporary increase in the filling time of the pipette, which then progressively returns before the actual CFPP value is reached decreases (see EN 116, German version 1997, points 10.1.9 and 10.2.6, note). In the case of fuels, this manifests itself in a significant decrease in the flow rate of the fuel through the fuel filter in a certain temperature range. Both CFPP2 and the aspiration value cause a reduction in fuel oil quality.

Numerous cold flow improvers are known from the prior art. For example, EP-A-0 360 419 describes additives for improving the cold flow properties of fuel compositions which contain homo- or copolymers of alkyl vinyl ethers and, if appropriate, other customary cold flow improvers.

DE-A-2 047 448 describes an additive mixture of polyvinyl ethers with ethylene-vinyl acetate copolymers to improve the pumpability of crude oils. The use in fuel oils is not described.

A disadvantage of the additives of the prior art is that they sometimes do not, or only slightly, reduce the CFPP value of fuel oils. In addition, the prior art does not describe any additives which have an effect on the CFPP2 and / or aspiration value of the fuel oils. The object of the present invention was therefore to further improve the effect of conventional cold flow improvers. In particular, the additive should improve the effect of the cold flow improvers on reducing the CFPP value of fuel oil compositions and, if appropriate, lead to a reduction or elimination of the CFPP2 values and / or to avoid aspiration effects.

The object was achieved by using a homopolymer of a hydrocarbyl vinyl ether to improve the effect of cold flow improvers for fuel oil compositions.

In the context of the present invention, hydrocarbyl is understood as a hydrocarbon radical which is bonded to the ether function of the vinyl ether via a carbon atom. The hydrocarbon radical can be, for example, an aliphatic radical, such as alkyl and alkenyl, which is optionally substituted by at least one aromatic and / or alicyclic radical, an alicyclic radical, such as cycloalkyl or cycloalkenyl, which may optionally be substituted by at least one aromatic and / or aliphatic Radical is substituted, or an aromatic radical which is optionally substituted with at least one aliphatic and / or alicyclic radical. The aliphatic and alicyclic radicals can be interrupted by at least one group 0, S, NR ⁵ , or CO. The hydrocarbon radical can furthermore be substituted by at least one radical such as OR ⁵ , SR ⁵ , NR ⁵ R ⁶ , COR ⁵ , COOR ⁵ or CONR ⁵ R ⁶ , the radicals R ⁵ and R ^{6 being} as defined below. - ■ ^• ■ ^•

The homopolymer of hydrocarbyl vinyl ether preferably has the following structural formula I:

wherein

R ¹ for C ¹ -C ₄ -alkyl, which is optionally interrupted by one or more groupings which are selected from CO, NR ⁵ , 0 and S, and / or by one or more Radicals which are selected from NR ⁵ R ⁶ , OR ⁵ , SR ⁵ , COR ⁵ , COOR ⁵ , CONR ⁵ R ⁶ and aryl, or are aryl,

R ² , R ³ and R ⁴ each independently represent H or C 1 -C ₄ -alk l,

R ⁵ and R ^{6 are} each independently of one another H or C 1 -C ₄ -alkyl and

n stands for a number from 2 to 3000.

In the above definition of the radicals R ¹ , R ² , R ³ and R ^4, -C 1 -C ₄ o-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, eggcosyl, docosyl, tricosyl, tetracosyl, pentac Hexacosyl, Heptacosyl, Octacosyl, Nonacosyl, Squalyl and the higher homologues as well as the corresponding positional isomers.

In the definition of R ⁵ and R ⁶ , 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 ¹ , aryl is preferably C ₆ -C ₄ -aryl, such as phenyl, naphthyl, anthracenyl and phenanthryl, the aryl radical being optionally by one or more radicals selected from C 1 -C ₄ o-alkyl, OR ⁵ , SR ⁵ , NR ⁵ R ⁶ , COOR ⁵ , CONR ⁵ R ^{6 "} 'and aryl.

R ¹ is preferably Cι-C ₄ -alkyl, particularly preferably Cι-C ₃ -alkyl and in particular C ₂ -C ₂₂ alkyl. The alkyl radical is preferably not very branched or linear, in particular linear. Furthermore, the alkyl radical is neither interrupted nor substituted by the groups listed above.

R ² , R ³ and R ⁴ are preferably H.

Preferred compounds of the formula I also have a number-average molecular weight Mn in the range from about 1000 to 20,000, in particular 2,000 to 20,000, preferably 3,000 to 15,000.

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 at least one further ethylenically unsaturated monomer a), the monomer is preferably selected from alkenyl carboxylic acid esters, (meth) acrylic acid esters and olefins.

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

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

Suitable alkenyl carboxylic acid esters are, for example, the vinyl and propenyl esters of carboxylic acids having 2 to 20 carbon atoms, the hydrocarbon radical of which can be linear or branched. Among these, the vinyl esters are preferred. Among the carboxylic acids with branched hydrocarbon radical, those are preferred whose branch is in the α position to the carboxyl group, the α carbon atom being particularly preferably tertiary, ie the carboxylic acid being a so-called neocarboxylic acid. However, the hydrocarbon residue of the carboxylic acid is preferably linear. Examples of suitable alkenyl carboxylic acid esters are vinyl acetate, vinyl propiona, vinyl butyrate, vinyl neopentanoate, vinyl hexanoate, vinyl neononanoate, vinyl neodecanoate and the corresponding propenyl esters, with the vinyl esters being preferred. A particularly preferred alkenyl carboxylic acid ester is vinyl acetate.

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

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

The ethylenically unsaturated monomer is copolymerized in the copolymer in an amount of preferably 1 to 30 mol%, particularly preferably 1 to 25 mol% and in particular 5 to 20 mol%, based on the total copolymer.

The copolymer a) preferably has a number average molecular weight M _n of 500 to 20,000, particularly preferably of 1,000 to 15,000.

Comb polymers b) are, for example, those described in "Comb-Like Polymers. Structure and Properties", N.A. Plat and V.P. Shibaev, J. Poly. Be. Macromolecular Revs. 8, pages 117 to 253 (1974). Of the compounds described there, comb polymers of the formula II are suitable, for example

wherein D 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 ester, such as vinyl acetate, and then esterifying the anhydride or acid function with an alcohol having at least 10 carbon atoms available. Further preferred comb polymers are copolymers of a-olefins and esterified ^~ comonomers, for example esterified copolymers of styrene and maleic anhydride or esterified copolymers of styrene and fumaric acid. Mixtures of comb polymers are also suitable. Comb polymers can also be polyfumarates or polymaleates.

Suitable polyoxyalkylenes c) are, for example, polyoxyalkylene esters, ethers, esters / ethers and mixtures thereof. The polyoxyalkylene compounds preferably contain at least one, particularly preferably at least two linear alkyl groups with 10 to 30 carbon atoms and a polyoxyalkylene group with a molecular weight of up to 5000. The alkyl group of the polyoxyalkylene radical preferably contains 1 to 4 carbon atoms. Such polyoxyalkylene compounds are described, for example, in EP-A-0 061 895 and in US 4,491,455, which are hereby incorporated by reference in their entirety. Preferred polyoxyalkylene esters, ethers and esters / ethers have the general formula III

wherein

R ⁹ and R ¹⁰ each independently represent R ¹¹ , RH-CO-, _R ¹¹ _0-CO (CH ₂ ) _z - or R ^H -0-CO (CH ₂ ) _z -CO-,

R ^{11 represents} linear C ₁ -C ₃ -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 and R ^{10 are} R ¹¹ and the other stands for R ^{1: 1} -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 stand for a radical R —CO— are diesters of fatty acids with 10 to; Carbon atoms, preferably stearic or behenic acid.

The polar nitrogen compounds d), suitably öllös lent are _'can both ionically and non-be nonionic and preferably have at least one, more preferably at least 2 substituents of the formula> NR ¹² wherein R ¹² is a C ₈ -C ₄ o -Carbon residue stands. 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 a linear Cs-C ₄ o-alkyl radical. Suitable primary amines are, for example, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tetradecylamine and the higher linear homologues. Suitable secondary amines are, for example, dioctadecylamine and methylbehenylamine. Amine mixtures, in particular amine mixtures accessible on a large industrial scale, such as fatty amines or hydrogenated tallamines, as described, for example, in Ull ann's Encyclopedia of Industrial Chemistry, 6th edition, 2000 electronic release, chapter "Airlines, aliphatic", are also suitable. the. 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 stand for a C ₉ -C ₄ o-hydrocarbon residue which may be replaced by one or more groups selected from 0, S, NR ⁵ and CO , interrupted and / or 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 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, hydrindenes 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, norbornene, bicyclooctane and bicyclooctene.

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

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

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

_ in what

Y for S0 ₃ - (NR ¹⁵ ₃ R ¹⁶ ) ⁺ , S0 ₃ - (NHRl ⁵ ₂ Rl6) ⁺ , S0 ₃ - (NH ₂ R ¹⁵ Rl6) +, S0 ₃ - (NH ₃ R ¹ 6) + or S0 ₂ NR ¹⁵ R ¹⁶ stands,

X for Y, CONR ¹⁵ R ¹⁷ , C0 ₂ - (NR ¹⁵ ₃ Rl ⁷ ) +, C0 ₂ - (NHRl ⁵ ₂ R ¹⁷ ) +, Rl ⁸ -COORl ⁷ , NR ¹⁵ COR ¹⁷ , Rl ⁸ OR ¹⁷ , R ¹⁸ OCOR ¹⁷ , R ¹⁸ Rl ⁷ , N (COR ¹⁵ ) R ¹⁷ or Z- (NR ¹⁵ ₃ R ¹⁷ ) +,

wherein

R ^{15 represents} a hydrocarbon radical,

R ¹⁶ and R ^{17 represent} alkyl, alkoxyalkyl or polyalkoxyalkyl with at least 10 carbon atoms in the main chain,

R ^{18 represents} Cό-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 sulfo or sulfonic acids and- their 'derivatives are described in EP-A-0261957, which is incorporated in its entirety by reference.

Suitable poly (meth) acrylic acid esters f) are both homo- and copolymers of acrylic and methacrylic acid esters. Copolymers of at least two mutually different (meth) acrylic acid esters which differ with respect to the condensed alcohol are preferred. If appropriate, the copolymer contains a further, different olefinically unsaturated mono- polymerized. 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 cis alcohols, the 5 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.

10 Preferably, copolymers of ethylene with at least one further ethylenically unsaturated monomer a) are used as cold flow improvers. With regard to preferred copolymers, reference is made to the statements made above.

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

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

The heating oils are, for example, low-sulfur or high-sulfur petroleum refines or stone or brown coal

25 leather distillates, which usually have a boiling range of 150 to 400 ° C. The heating oils 1 are preferably 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 at most 0.005% by weight, and INS

30 special of at most 0.001% by weight.

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

35 360 ° C or beyond. However, these can also be so-called “ultra low sulfur diesel” or “city diesel”, characterized by a 95% point of, for example, a maximum of 345 ° C. and one

■ •• - ■ Sulfur content of a maximum of 0.005% by weight or by one

95% point of, for example, 285 ° C and a sulfur content of

40 maximum 0.001% by weight. In addition to the diesel fuels obtainable by refining, those which are obtainable by coal gasification or gas liquefaction ("gas to liquid" (GTL) fuels) are suitable. Mixtures of the aforementioned diesel fuels with regenerative fuels, such as

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

The hydrocarbyl vinyl ether hemopolymer (activity improver) is preferably used in a proportion, based on the total amount of the fuel oil composition, which per se has essentially no influence on the cold flow properties of the fuel oil compositions. The activity enhancer is particularly preferably used in an amount of 0.0001 to 0.005% by weight, in particular 0.0001 to 0.001% by weight, based on the total amount of the fuel oil composition.

The weight ratio of effect improver to cold flow improver is preferably 1: 1 to 1: 500, particularly preferably 1: 4 to 1: 500, even more preferably 1: 9 to 1: 500, in particular 1:19 to 1: 500 and especially 1:24 up to 1: 200.

Another object of the present invention is the use of an additive mixture comprising

i) as component A at least one homopolymer of a hydrocarbyl vinyl ether and

ii) as component B at least one conventional cold flow improver

to reduce the CFPP of a fuel oil composition and, if necessary, also to reduce the CFPP2 and / or to avoid aspiration effects.

The statements made above on the suitable and preferred hydrocarbyl vinyl ether homopolymers, cold flow improvers and fuel oil compositions apply accordingly.

Another object of the present invention is the use of an additive mixture comprising i) as component A at least one homopolymer of a hydrocarbyl vinyl ether and

ii) as component B at least one conventional cold flow improver

with a weight ratio of component A to component B of 1: 1 to 1: 500 for the additive of fuel oil compositions.

Here, too, reference is made to the statements made above regarding hydrocarbyl vinyl ether homopolymers, cold flow improvers and fuel oil compositions.

The additive mixtures used according to the invention preferably serve to improve the cold flow properties of fuel oil compositions, such as, for example, lowering the cloud point, the pour point, the viscosity and in particular the CFPP value.

The present invention furthermore relates to an additive mixture comprising

a) at least one component A as defined above unc

b) at least one component B as defined above,

wherein the weight ratio of component A to component is 1: 5 to 1: 500. - - - -

The statements made above regarding the suitable and preferred hydrocarbyl vinyl ether homopolymers and cold flow improvers also apply here.

The weight ratio of component A to component B is preferably 1: 9 to 1: 500, particularly preferably 1:15 to 1: 500, even more preferably 1:20 to 1: 500 and especially 1:24 to 1: 200.

The present invention also relates to a fuel oil composition comprising a major amount of a hydrocarbon fuel and an effective amount of an additive mixture as defined above and optionally at least one further customary additive. Reference is hereby made to the statements made above on fuel oil compositions and additive mixtures.

Finally, the subject of the present application is an additive concentrate containing an additive mixture as defined above and at least one diluent and optionally at least one further additive.

Suitable diluents are, for example, fractions obtained in petroleum processing, such as kerosene, naphtha or

Bright floor. 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 ^R, and mixtures of these solvents and diluents.

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

Suitable additives which may be present in the fuel or concentrate according to the invention in addition to the additive mixtures according to the invention, in particular for diesel fuels and heating oils, include detergents, corrosion inhibitors, dehazers, demulsifiers, antifoams ("antifoam"), antioxidants, metal deactivators, multifunctional stabilizers, cetane number improvers, combustion improvers, dyes, markers, solubilizers, antistatic agents, lubricity improvers, additives other than the abovementioned which improve the cold properties, such as flow improvers ("MDFI"), paraffin dispersants ("WASA") and the combination of the latter two Additives ("WAFI").

The use of hydrocarbyl vinyl ether homopolymers leads to an improved effect of conventional cold flow improvers on the cold flow properties of fuel oil compositions, in particular to a more effective reduction in the CFPP value. As a result, the cold flow improvers can be used in significantly smaller quantities than previously required.

The following examples illustrate the invention without, however, restricting it. Examples

To investigate the cold flow behavior of fuel oil compositions, six different middle distillates were mixed with different cold flow improvers alone or in a mixture with hydrocarbyvinyl ether homopolymers and the CFPP value determined in accordance with EN 116.

The following middle distillates were used 10

Middle distillate A (Q8): CP = 2.4 ° C; CFPP = -1 o _C; ^' d = 855g / cm ³ ; n-paraffin content = 21%; Initial boiling point = 166 ° C, 20% point = 219 ° C; 90% point = 349 ° C; End of boiling = 380 ° C

15 middle distillate B (Nerefco): CP = -4.2 ° C; CFPP = -5 ° C; 88% HOB; 12% LCO

Middle distillate C (Nerefco): CP = 2.0 ° C; CFPP = 1.0 ° C; 80% HOB; 10% HGO; 10% LCO 20

Middle distillate D (Total Fina Elf France): CP = 2 ° C; CFPP = -6 ° C; d = 855g / cm ³ ; Initial boiling point = 155 ° C, 20% point = 202 ° C; 90% point = 350 ° C; End of boiling = 375 ° C

25 middle distillate E (Nerefco): CFPP = 2 ° C; 8% HGO; 8% LCO

Middle distillate F (Total Fina Elf France): CFPP = 0 ° C

LCO = Light cycle oil 30 HGO = Heavy gas oil

HOB = Heating oil blend

The following polymers were used as cold flow improvers (MDFI): 35

MDFI 1: ethylene-vinyl acetate-based polymer mixture (Keroflux 3283)

MDFI 2: ethylene-vinyl acetate-based polymer mixture (Keroflux ES 40 6103)

MDFI 3: ethylene-vinyl acetate-based polymer mixture (Keroflux ES 6305)

45 MDFI 4: ethylene-vinyl acetate-based polymer mixture (Keroflux ES 6309) MDFI 5: ethylene-vinyl acetate-based polymer mixture (Keroflux ES 6100)

MDFI 6: ethylene-vinyl acetate-based polymer mixture (Keroflux ES 5 6204)

MDFI 7: ethylene-vinyl acetate-based polymer mixture (Keroflux ES 6203)

0 MDFI 8: ethylene-vinyl acetate-based polymer mixture (Keroflux ES 6205)

MDFI 9: ethylene-vinyl acetate-based polymer mixture (Keroflux ES 6310) 5

The following polyvinyl ethers (PVE) were used to improve the effect:

PVE 1: 40% by weight solution of polyoctadecyl vinyl ether (M _n = 3525; 0 M _w = 12208) in Solvesso 150

PVE 2: 10% by weight solution of polyoctadecyl vinyl ether / polystyrene vinyl ether mixture (85/15) in Solvesso 150

5 PVE 3: 10% by weight solution of polyoctadecyl vinyl ether (M _n = 352! M _w = 12208) in Solvesso 150

PVE 4: 10% by weight solution of polyoctadecyl vinyl ether (M _n = 10785; * M _w = 43125) in Solvesso 150 0

The effect improvers PVE 1 to 4 were used in an amount of 1 to 4% by weight of pure substance, based on the amount of cold flow improver.

5 The table below shows the CFPP values of middle distillates, which were additized on the one hand only with cold flow improvers and on the other hand with the mixture of cold flow improvers and polyvinyl ethers according to the invention;

0

5

17

* CFPP2 value

"-": not determined

The CFPP values were determined in accordance with EN 116. For this purpose, a commercially available automatic CFPP analysis device, e.g. available from WalterHerzog GmbH, Lauda-Koenigshofen, Germany, type MP842. Also compare the operating instructions for determining the CFPP 2 value.

As the above test results show, the addition of hydrocarbyl vinyl ether homopolymers to conventional cold flow improvers leads to a lowering of the CFPP value with much lower doses of the cold flow improvers. In addition, as the comparison of experiments 38 and 39 shows, no CFPP2 value is observed.

Claims

claims

1. Use of a homopolymer of a hydrocarbyl vinyl ether to improve the effect of a cold flow improver for fuel oil compositions.

2. Use of an additive mixture comprising

i) as component A at least one homopolymer of a hydrocarbyl vinyl ether 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 an aspiration value.

Use of an additive mixture comprising

i) as component A at least one homopolymer of a hydrocarbyl vinyl ether and

ii) as component B at least one conventional cold flow improver

with a weight ratio of component A to component E of 1: 1 to 1: 500 for the additive of fuel oil compositions.

4. Use according to one of the preceding claims, wherein the effect improver is used in a proportion based on the total amount of the fuel oil composition which has essentially no influence on the CFPP value of the fuel oil composition additized with the cold flow improver.

5. Use according to any one of the preceding claims, wherein the fuel oil composition is selected from heating oils and diesel fuels.

6. Use according to any one of the preceding claims, wherein the fuel oil composition comprises petroleum middle distillate.

7. Use according to one of the preceding claims, wherein the fuel oil composition has a sulfur content of less than 500 ppm (0.05 wt .-%).

5 8. Use according to any one of the preceding claims, wherein the fuel oil composition has a proportion of regenerative fuel.

9, Use according to any one of the preceding claims, wherein the

10 homopolymer of hydrocarbyl vinyl ether has the following structural formula:

20 where

R ¹ for -CC ₄ o-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

25 radicals which are selected from NR ⁵ R ⁶ , OR ⁵ , SR ⁵ , COR ⁵ , COOR ⁵ , CONR ⁵ R ⁵ and aryl, or are substituted for aryl,

R ² , R ³ and R ^{4 are} each independently of one another H or

30 are C ₄ -C ₄ alkyl,

35 n stands for a number from 2 to 3000.

10. Use according to claim 9, wherein R ² , R ³ and R ^{4 is} H and R ^{1 is} -C-C ₄ o-Al yl. ... ^• .-

40 11. Use according to one of the preceding claims, wherein the cold flow improver is selected from

a) copolymers of ethylene with at least one further ethylenically unsaturated monomer;

45 b) comb polymers other than hydrocarbyl vinyl ether homopolymers;

c) polyoxyalkylenes; 5 d) polar nitrogen compounds;

e) sulfocarboxylic acids or sulfonic acids or their derivatives;

10 f) poly (meth) acrylic acid esters.

12. Use according to claim 11, wherein the cold flow improver "is selected from copolymers of ethylene and at least

15 another ethylenically unsaturated monomer which is selected from alkenyl carboxylic acid esters, (meth) acrylic acid esters and olefins.

13. Use according to claim 12, wherein the unsaturated monomer 20 is an alkenyl carboxylic acid ester.

14. Use according to claim 13, wherein the alkenyl carboxylic acid ester is polymerized in an amount of 10 to 50% by weight, based on the total amount of the copolymerized monomers

25 is.

15. Use according to one of claims 13 or 14, wherein the alkenyl carboxylic acid ester is vinyl acetate.

16. Use according to one of the preceding claims, to improve the cold flow properties of the fuel oil compositions.

17. Additive mixture comprising 35 a) at least one component A as defined above and

b) at least one component B as defined above, "

40 wherein the weight ratio of component A to component B is about 1: 5 to 1: 500.

18. A fuel oil composition containing a major amount of a hydrocarbon fuel and an effective amount of one

45 additive mixture as defined in one of claims 1 to 15 or 17 and optionally at least one other conventional additive.

19. The fuel oil composition of claim 18, wherein the fuel is diesel fuel, heating oil, or kerosene.

20. Fuel oil composition according to Anspueh 19, the diesel fuel being obtainable by refining, coal gasification or gas liquefaction, or is a mixture of such fuels and optionally mixed with regenerative fuels.

21. Fuel oil composition according to one of claims 19 or 20, wherein the diesel fuel has a sulfur content of at most 500 ppm.

22. Additive concentrate containing an additive mixture as defined in claim 17 and at least one diluent and optionally at least one further additive.