New mixtures for improving the stability of additive packages

Abstract

The present invention relates to the use of mixtures of certain olefin-carboxylic acid copolymers (A) with at least one additive having a cleaning action, preferably at least one quaternary nitrogen compound (B), and optionally further fuel additives for improving the stability of the additive package for fuel, especially fuel oil and gasoline fuel.

Description

[0001] This invention relates to the use of a mixture of certain olefin-carboxylic acid copolymers (A) with at least one additive having a cleaning effect, preferably at least one quaternary nitrogen compound (B), and optionally other fuel additives, for improving the stability of fuel (especially fuel oil and gasoline fuel) additive packages.

[0002] Fuel additive mixtures (also known as fuel additive packages or additive packs), especially when they contain components with different densities, polarities, solubilities, and / or crystallization temperatures, may form precipitates, separated phases, or stratification during storage, particularly upon cooling. Fuel additive stability is required, especially in the case of modern additive packs containing highly polar quaternary ammonium compounds. This stability is achieved through solubilizers or stabilizers.

[0003] WO 15 / 113681 discloses the use of olefin-carboxylic acid copolymers, wherein the copolymers contain at least one free carboxylic acid side group, as fuel additives or lubricant additives or as corrosion inhibitors, see, for example, WO 15 / 114029. Therefore, it is desirable to have such copolymers in fuels to prevent the formation of deposits or to remove existing deposits or to rely on corrosion inhibition.

[0004] Unpublished European patent application No. 20208827.4, filed on November 20, 2020, and unpublished PCT application No. PCT / EP2021 / 081447, filed on November 12, 2021, respectively disclose the use of a mixture of components (A) and (B) for improving or facilitating the separation of water from fuel.

[0005] The stabilizing activity of such copolymers has not been reported or has become apparent in WO 15 / 113681.

[0006] Therefore, one object of the present invention is to provide an additive package with improved stratification stability, especially when a quaternary ammonium compound is part of the package.

[0007] As used herein, "stability" refers to a low tendency for the additive package or its components to separate into layers, especially at lower temperatures, and to storage stability, preferably after several days, e.g., at least three days, more preferably several weeks, e.g., at least four weeks, and even more preferably several months, e.g., at least two months. The phrase "solubilizing" is used synonymously. Indications of separation may include, for example, the formation of separate liquid or solid phases, the formation of precipitates, and turbidity.

[0008] The term “stability” as used in this article does not imply stability against the decomposition of the additive package or components, such as due to oxidation or thermal stress.

[0009] Therefore, the use of mixtures of certain olefin-carboxylic acid copolymers (A) as defined above with at least one additive with a cleaning effect selected from quaternary nitrogen compounds (B) and polyisobutylene succinimide (G) for improving the stability of fuel additive packages or their components has been discovered.

[0010] Sufficient amounts of component (A) are able to stabilize fuel additive packages or their components, especially component (B), at lower temperatures, such as as low as 0°C, preferably as low as -10°C, more preferably as low as -20°C, and even at lower temperatures for longer periods of time.

[0011] Compound (A)

[0012] The olefin-carboxylic acid copolymer (A) is a copolymer that can be obtained through the following steps.

[0013] - In the first reaction step (I), the following substances are copolymerized.

[0014] (Aa) At least one olefinically unsaturated monocarboxylic acid or dicarboxylic acid or its derivatives, preferably a dicarboxylic acid.

[0015] (Ab) at least one α-olefin having at least 12 and at most 30 carbon atoms,

[0016] (Ac) optionally includes at least one other aliphatic or cycloaliphatic olefin having at least 4 carbon atoms and different from (Ab), and

[0017] (Ad) optionally one or more copolymerizable monomers other than monomers (Aa), (Ab) and (Ac), selected from...

[0018] (Ada) vinyl ester,

[0019] (Adb) vinyl ether,

[0020] (Adc) (meth)acrylates of alcohols having at least 5 carbon atoms

[0021] (Add) Allyl alcohol or its ether

[0022] (Ade)N-vinyl compounds, selected from vinyl compounds containing at least one nitrogen atom in a heterocyclic ring, N-vinylamides, or N-vinyl lactams.

[0023] (Adf) olefinic unsaturated aromatic compounds.

[0024] (Adg)α,β-olefinic unsaturated nitrile

[0025] (Adh)(methyl)acrylamide and

[0026] (Adi) allylamine,

[0027] Subsequently

[0028] - In a second optional reaction step (II), the anhydride or carboxylic acid ester functional groups present in the copolymer obtained by (I) are partially or completely hydrolyzed and / or saponified, the second reaction step being carried out at least when the copolymer obtained by reaction step (I) does not contain any free carboxyl functional groups.

[0029] Description of copolymer (A)

[0030] The monomer (Aa) is at least one, preferably one to three, more preferably one or two, and most preferably exactly one olefinic unsaturated, preferably α,β-olefinic unsaturated monocarboxylic acid or dicarboxylic acid or its derivatives, preferably dicarboxylic acid or its derivatives.

[0031] Derivatives should be understood as meaning

[0032] - The corresponding acid anhydride in monomeric or polymeric form.

[0033] - Mono- or dialkyl esters, preferably mono- or di-C1-C4-alkyl esters, more preferably mono- or dimethyl esters or the corresponding mono- or diethyl esters, and

[0034] - A mixture of esters, preferably a mixture of esters with different C1-C4 alkyl components, more preferably a mixture of methyl ethyl esters.

[0035] Preferably, the derivative is a monomeric acid anhydride or a di-C1-C4-alkyl ester, more preferably a monomeric acid anhydride.

[0036] In the context of this document, C1-C4 alkyl should be understood to mean methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, sec-butyl, and tert-butyl, preferably methyl and ethyl, more preferably methyl.

[0037] Examples of α,β-olefinic unsaturated monocarboxylic acids or dicarboxylic acids are those monocarboxylic acids or dicarboxylic acids or their derivatives, wherein the carboxyl group, or in the case of dicarboxylic acids, at least one carboxyl group, preferably two carboxyl groups, is / is conjugated with an olefinic unsaturated double bond.

[0038] Examples of non-α,β-ene unsaturated olefinic monocarboxylic acids or dicarboxylic acids are cis-5-norbornene-endo-2,3-dicarboxylic anhydride, exo-3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride, and cis-4-cyclohexene-1,2-dicarboxylic anhydride.

[0039] Examples of α,β-olefinic unsaturated monocarboxylic acids are acrylic acid, methacrylic acid, crotonic acid and ethylacrylic acid, preferably acrylic acid and methacrylic acid, referred to herein simply as (meth)acrylic acid, and more preferably acrylic acid.

[0040] Particularly preferred derivatives of α,β-olefinic unsaturated monocarboxylic acids are methyl acrylate, ethyl acrylate, n-butyl acrylate, and methyl methacrylate.

[0041] Examples of dicarboxylic acids include maleic acid, fumaric acid, itaconic acid (2-methylenesuccinic acid), citraconic acid (2-methylmaleic acid), pentenic acid (pent-2-ene-1,5-dicarboxylic acid), 2,3-dimethylmaleic acid, 2-methylfumaric acid, 2,3-dimethylfumaric acid, methylene malonic acid, and tetrahydrophthalic acid, with maleic acid and fumaric acid being preferred, and maleic acid and its derivatives being more preferred.

[0042] More specifically, the monomer (Aa) is maleic anhydride.

[0043] The monomer (Ab) is at least one, preferably one to four, more preferably one to three, even more preferably one or two, and most preferably exactly one α-olefin having at least 12 and at most 30 carbon atoms. The α-olefin (Ab) preferably has at least 14, more preferably at least 16, and most preferably at least 18 carbon atoms. Preferably, the α-olefin (Ab) has at most 28, more preferably at most 26, and most preferably at most 24 carbon atoms.

[0044] Preferably, the α-olefin can be one or more straight-chain or branched, preferably straight-chain 1-olefins.

[0045] Examples of these are 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecaene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecaene, 1-eicosene, 1-docosahexane, 1-tetradecene, 1-hexadecene, preferably 1-octadecene, 1-eicosene, 1-docosahexane and 1-tetradecene, and mixtures thereof.

[0046] Other examples of α-olefins (Ab) are those olefins that are C2 to C3. 12 Olefins, preferably C3 to C 10 Oligomers or polymers of olefins, more preferably C4 to C6 olefins. Examples include ethylene, propylene, 1-butene, 2-butene, isobutene, pentene isomers and hexene isomers, with ethylene, propylene, 1-butene, 2-butene and isobutene being preferred.

[0047] Examples of α-olefins (Abs) mentioned include oligomers and polymers of propylene, 1-butene, 2-butene, isobutene, and mixtures thereof, particularly oligomers and polymers of propylene or isobutene or mixtures of 1-butene and 2-butene. Among the oligomers, trimers, tetramers, pentamers, and hexamers, and mixtures thereof are preferred.

[0048] In addition to olefins (Ab), at least one, preferably one to four, more preferably one to three, or even more preferably one or two, particularly exactly one other aliphatic or cycloaliphatic olefin (Ac) may be incorporated into the copolymer of the present invention by polymerization, wherein the olefin (Ac) has at least four carbon atoms and is different from (Ab).

[0049] The olefin (Ac) can be an olefin having a terminal (α-) double bond or those having a non-terminal double bond, preferably having an α-double bond. The olefin (Ac) preferably comprises olefins having 4 to less than 12 or more than 30 carbon atoms. If the olefin (Ac) is an olefin having 12 to 30 carbon atoms, then the olefin (Ac) does not have an α-double bond.

[0050] Examples of aliphatic olefins (Ac) include 1-butene, 2-butene, isobutene, pentene isomers, hexene isomers, heptenene isomers, octene isomers, nonene isomers, decene isomers, undecene isomers, and mixtures thereof.

[0051] Examples of cycloaliphatic alkenes (Ac) include cyclopentene, cyclohexene, cyclooctene, cyclodecene, cyclododecene, α- or β-pinene and mixtures thereof, limonene and norbornene.

[0052] Other examples of olefins (Ac) are polymers of propylene, 1-butene, 2-butene, or isobutene, or mixtures of olefins containing the latter, having more than 30 carbon atoms, preferably polymers of isobutene or mixtures of olefins containing the latter, more preferably polymers with an average molecular weight M. w The concentration is 500 to 5000 g / mol, preferably 650 to 3000 g / mol, and more preferably 800 to 1500 g / mol.

[0053] Preferably, the oligomer or polymer containing isobutylene in a copolymeric form has a high content of terminal olefinic double bonds (α-double bonds), for example at least 50 mol%, preferably at least 60 mol%, more preferably at least 70 mol%, and most preferably at least 80 mol%.

[0054] To prepare oligomers or polymers containing isobutylene in a copolymeric form, suitable sources of isobutylene are pure isobutylene or isobutylene-containing C4 hydrocarbon streams, such as C4 raffinate, especially "raffinate 1," the C4 cut from isobutane dehydrogenation, C4 fractions from steam crackers and FCC crackers (fluid catalytic cracking), provided they are substantially free of 1,3-butadiene present therein. C4 hydrocarbon streams from FCC refinery units are also referred to as "b / b" streams. Other suitable isobutylene-containing C4 hydrocarbon streams are, for example, product streams from propylene-isobutane co-oxidation or product streams from metathesis units, which are typically used after routine purification and / or concentration. Suitable C4 hydrocarbon streams typically contain less than 500 ppm, preferably less than 200 ppm, of butadiene. The presence of 1-butene, as well as cis- and trans-2-butene, is essentially negligible. Typically, the concentration of isobutylene in the C4 hydrocarbon stream is 40% to 60% by weight. For example, raffinate 1 typically consists essentially of 30% to 50% by weight of isobutylene, 10% to 50% by weight of 1-butene, 10% to 40% by weight of cis- and trans-2-butene, and 2% to 35% by weight of butane; during polymerization, the linear butene in raffinate 1 is typically practically inert, and only isobutylene is polymerized.

[0055] In a preferred embodiment, the monomer source for polymerization is an industrial C4 hydrocarbon stream containing isobutylene of 1% to 100% by weight, particularly 1% to 99% by weight, particularly 1% to 90% by weight, more preferably 30% to 60% by weight; particularly raffinate stream, b / b stream from an FCC refining unit, product stream from propylene-isobutane co-oxidation, or product stream from a metathesis unit.

[0056] In particular, when raffinate stream 1 is used as the isobutylene source, it has been found useful to use water as a standalone initiator or as an additional initiator, especially when the polymerization reaction is carried out at temperatures ranging from -20°C to +30°C, particularly from 0°C to +20°C. However, when raffinate stream 1 is used as the isobutylene source, an initiator can be eliminated at temperatures ranging from -20°C to +30°C, particularly from 0°C to +20°C.

[0057] The isobutylene-containing monomer mixture may contain small amounts of impurities, such as water, carboxylic acids, or inorganic acids, without causing any significant loss of yield or selectivity. It is appropriate to avoid the accumulation of these impurities by removing them from the isobutylene-containing monomer mixture, for example, by adsorption onto solid adsorbents such as activated carbon, molecular sieves, or ion exchangers.

[0058] Although less preferred, a monomer mixture of isobutylene or a hydrocarbon mixture containing isobutylene may be converted with an olefinically unsaturated monomer that can copolymerize with isobutylene. If isobutylene is to be copolymerized with a monomer mixture of suitable comonomers, the monomer mixture contains preferably at least 5% by weight, more preferably at least 10% by weight, and especially at least 20% by weight of isobutylene, and preferably at most 95% by weight, more preferably at most 90% by weight, and especially at most 80% by weight of comonomers.

[0059] In a preferred embodiment, the mixture of olefin (Ab) and optionally (Ac) has an average of at least 12 carbon atoms, preferably at least 14, more preferably at least 16, and most preferably at least 17 carbon atoms on a molar basis.

[0060] For example, the average carbon atom count of a 2:3 mixture of dodecene and tetradecene is 0.4 x 22 + 0.6 x 14 = 17.2.

[0061] The upper limit is not very relevant and is generally no more than 60 carbon atoms, preferably no more than 55, more preferably no more than 50, even more preferably no more than 45, and especially no more than 40 carbon atoms.

[0062] The optional monomer (Ad) is at least one monomer, preferably one to three, more preferably one or two, and most preferably exactly one selected from the following monomers:

[0063] (Ada) vinyl ester,

[0064] (Adb) vinyl ether,

[0065] (Adc) (meth)acrylates of alcohols having at least 5 carbon atoms

[0066] (Add) Allyl alcohol or its ether

[0067] (Ade)N-vinyl compounds, selected from vinyl compounds containing at least one nitrogen atom in a heterocyclic ring, N-vinylamides, or N-vinyl lactams.

[0068] (Adf) olefinic unsaturated aromatic compounds and

[0069] (Adg)α,β-olefinic unsaturated nitrile

[0070] (Adh)(methyl)acrylamide and

[0071] (Adi)allylamine.

[0072] Examples of vinyl esters (Ada) are C2- to C3-. 12Vinyl esters of carboxylic acids, preferably vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate, vinyl hexanoate, vinyl octanoate, vinyl 2-ethylhexanoate, vinyl decanoate, and vinyl esters of 5 to 10 versatic acids, preferably vinyl esters of 2,2-dimethylpropionic acid (neovaleric acid, versatic acid 5), 2,2-dimethylbutyric acid (neovaleric acid, versatic acid 6), 2,2-dimethylvaleric acid (neovaleric acid, versatic acid 7), 2,2-dimethylhexanoic acid (neovaleric acid, versatic acid 8), 2,2-dimethylheptanoic acid (neovaleric acid, versatic acid 9), or 2,2-dimethyloctanoic acid (neovaleric acid, versatic acid 10).

[0073] Examples of vinyl ethers (Adb) are C1- to C2-. 12 Vinyl ethers of alkanols, preferably vinyl ethers of methanol, ethanol, isopropanol, n-propanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-hexanol, n-heptanol, n-octanol, n-decanol, n-dodecanol (lauryl alcohol) or 2-ethylhexanol.

[0074] Preferred (meth)acrylates (Adc) are C5- to C6-. 12 (Meth)acrylates of alkanols, preferably (meth)acrylates of n-pentanol, n-hexanol, n-heptanol, n-octanol, n-decanol, n-dodecyl alcohol (laurate), 2-ethylhexanol, or 2-propylheptanol. Particularly preferred are pentyl acrylate, 2-ethylhexyl acrylate, and 2-propylheptanol acrylate.

[0075] Examples of monomers (Add) are allyl alcohol and C2-to-C2-additions. 12 Allyl ethers of alkyl alcohols, preferably allyl ethers of methanol, ethanol, isopropanol, n-propanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-hexanol, n-heptanol, n-octanol, n-decanol, n-dodecyl alcohol (lauryl alcohol) or 2-ethylhexanol.

[0076] Examples of vinyl compounds (Ade) containing a heterocycle of at least one nitrogen atom are N-vinylpyridine, N-vinylimidazolium and N-vinylmorpholine.

[0077] The preferred compound (Ade) is N-vinylamide or N-vinyllactam.

[0078] Examples of N-vinylamide or N-vinyllactam (Ade) are N-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone and N-vinylcaprolactam.

[0079] Examples of olefinically unsaturated aromatic hydrocarbons (Adf) are styrene and α-methylstyrene.

[0080] Examples of α,β-olefinic unsaturated nitrile (Adg) are acrylonitrile and methacrylonitrile.

[0081] Examples of (meth)acrylamide (Adh) are acrylamide and methacrylamide.

[0082] Examples of allylamines (Adi) are allylamine, dialkylallylamine and trialkylallyl ammonium halide.

[0083] Preferred monomers (Ad) are (Ada), (Adb), (Adc), (Ade) and / or (Adf), more preferably (Ada), (Adb) and / or (Adc), even more preferably (Ada) and / or (Adc), and especially (Adc).

[0084] The proportions of monomers (Aa) and (Ab), and optionally (Ac) and optionally (Ad), incorporated into the polymer obtained from reaction step (I) are typically as follows:

[0085] The molar ratio of (Aa) to ((Ab) and (Ac)) (total) is typically 10:1 to 1:10, preferably 8:1 to 1:8, more preferably 5:1 to 1:5, even more preferably 3:1 to 1:3, particularly 2:1 to 1:2, and especially 1.5:1 to 1:1.5. In preferred specific cases where maleic anhydride is the monomer (Aa), the molar incorporation ratio of maleic anhydride to the monomers ((Ab) and (Ac)) (total) is about 1:1.

[0086] The molar ratio of the essential monomer (Ab) to the monomer (Ac) (if present) is typically 1:0.05 to 10, preferably 1:0.1 to 6, more preferably 1:0.2 to 4, even more preferably 1:0.3 to 2.5, especially 1:0.5 to 1.5.

[0087] In a preferred embodiment, there is no optional monomer (Ac) other than monomer (Ab).

[0088] The proportion of one or more monomers (Ad) (if present) is typically 5 to 200 mol%, preferably 10 to 150 mol%, more preferably 15 to 100 mol%, even more preferably 20 to 50 mol%, and especially 0 to 25 mol%, based on the amount of monomers (Aa), (Ab) and optionally (Ac) (total).

[0089] In a preferred embodiment, there is no optional monomer (Ad).

[0090] In the second reaction step (II), the anhydride or carboxylic acid ester functional groups present in the copolymer obtained by (I) are partially or completely hydrolyzed and / or saponified.

[0091] If the copolymer obtained by reaction step (I) does not contain free carboxylic acid groups, reaction step (II) is necessary.

[0092] Hydrolysis of acid anhydride groups is superior to saponification of ester groups.

[0093] Preferably, 10% to 100%, more preferably at least 20%, more preferably at least 30%, even more preferably at least 50%, and especially at least 75% and particularly at least 85% of the presence of anhydride or carboxylic acid ester functional groups are hydrolyzed and / or saponified.

[0094] For hydrolysis, based on the presence of anhydride functional groups, an amount of water corresponding to the desired level of hydrolysis is added, and the copolymer obtained from (I) is heated in the presence of the added water. Typically, a temperature of 20 to 150°C is sufficient to achieve the desired effect, preferably 60 to 100°C. If desired, the reaction can be carried out under pressure to prevent water escape. Under these reaction conditions, generally, the anhydride functional groups in the copolymer are selectively converted, while any carboxylic acid ester functional groups present in the copolymer, if reacted, react at least to a lesser extent.

[0095] For saponification, in the presence of water, the copolymer is reacted with a certain amount of strong base corresponding to the desired level of saponification.

[0096] The strong base used can preferably be a hydroxide, oxide, carbonate or bicarbonate of an alkali metal or alkaline earth metal.

[0097] The copolymer obtained from (I) is then heated in the presence of added water and a strong base. Typically, a temperature of 20 to 130°C is sufficient to achieve this, preferably 50 to 110°C. If desired, the reaction can be carried out under pressure.

[0098] The functional groups of carboxylic acid esters can also be hydrolyzed with water in the presence of an acid. The acid used is preferably an inorganic acid, carboxylic acid, sulfonic acid, or phosphoric acid with a pKa of not more than 5, more preferably not more than 4.

[0099] Examples include acetic acid, formic acid, oxalic acid, salicylic acid, substituted succinic acid, aromatic substituted or unsubstituted benzenesulfonic acid, sulfuric acid, nitric acid, hydrochloric acid, or phosphoric acid; acidic ion exchange resins may also be considered.

[0100] In a preferred embodiment of the acid anhydride, particularly maleic anhydride as the monomer (Aa), such an anhydride portion is partially or completely hydrolyzed, especially completely hydrolyzed, while the ester groups potentially present in the copolymer remain intact. In this case, saponification does not occur in step (II).

[0101] The copolymer obtained from (I) is then heated in the presence of added water and acid. Typically, a temperature of 40 to 200°C is sufficient for this purpose, preferably 80 to 150°C. If desired, the reaction can be carried out under pressure.

[0102] If the copolymer obtained from step (II) still contains acidic anionic residues, these acidic anions can preferably be removed from the copolymer by means of an ion exchanger and preferably exchanged for hydroxide or carboxylate ions, more preferably hydroxide ions. This is especially true when the acidic anions present in the copolymer are halides or contain sulfur or nitrogen.

[0103] The copolymers obtained from reaction step (II) typically have a weight-average molecular weight Mw of 0.5 to 20 kDa, preferably 0.6 to 15, more preferably 0.7 to 7, even more preferably 1 to 7, and especially 1.5 to 4 kDa (determined by gel permeation chromatography using tetrahydrofuran and polystyrene as standards).

[0104] The number-average molecular weight Mn is typically 0.5 to 10 kDa, preferably 0.6 to 5, more preferably 0.7 to 4, even more preferably 0.8 to 3, and especially 1 to 2 kDa (determined by gel permeation chromatography using tetrahydrofuran and polystyrene as standards).

[0105] The polydispersity is typically 1 to 10, preferably 1.1 to 8, more preferably 1.2 to 7, even more preferably 1.3 to 5, and especially 1.5 to 3.

[0106] The content of acid groups in the copolymer is preferably 1 to 8 mmol / g copolymer, more preferably 2 to 7.5, and even more preferably 3 to 7 mmol / g copolymer.

[0107] In a preferred embodiment, the copolymer contains a high proportion of adjacent carboxylic acid groups, which is determined by measuring their adjacency. For this purpose, the copolymer sample is heat-treated between two layers of polytetrafluoroethylene (PTFE) film at 290°C for 30 minutes, and FTIR spectra are recorded at bubble-free locations. The IR spectrum of PTFE is subtracted from the obtained spectrum to determine the layer thickness and the cyclic anhydride content.

[0108] In a preferred embodiment, the adjacency is at least 10%, preferably at least 15%, more preferably at least 20%, even more preferably at least 25%, and especially at least 30%.

[0109] The olefin-carboxylic acid copolymer (A) is applied in the form of a free acid, i.e., in the presence of COOH groups, or in the form of an anhydride, which can be an intramolecular anhydride or an intermolecular anhydride linking two dicarboxylic acid molecules together, preferably in the form of a free acid. To a lesser extent, some carboxyl functional groups may be present in the form of salts, such as alkali metal salts or basic metal salts, or ammonium salts or substituted ammonium salts, depending on the pH of the liquid phase. Preferably, at least 50% of all carboxylic acid groups are utilized as COOH- groups in the form of a free acid, more preferably at least 66%, very preferably at least 75%, even more preferably at least 85%, and especially at least at least 95%. A single olefin-carboxylic acid copolymer (A) or a mixture of different olefin-carboxylic acid copolymers (A) can be used.

[0110] According to the present invention, compared with the same composition without component (A), a mixture of olefin-carboxylic acid copolymer (A) and at least one additive having a cleaning effect exhibits improved storage stability of the added additive package, wherein the additive having a cleaning effect is selected from...

[0111] - Quaternary nitrogen compounds (B) and

[0112] - Polyisobutylene succinimide (G), preferably at least one quaternary nitrogen compound or nitrogen-containing compound (B).

[0113] Typically, storage stability is checked for several weeks, such as 6 or 8 weeks or even longer, at different temperatures (e.g., -20°C or -10°C, room temperature, 40°C). Sometimes, the storage stability of additive samples stored at different temperatures (i.e., 1 week at -20°C, then 1 week at 0°C, etc.) is checked. In the context of this invention, a fuel additive package is considered stable if it can be stored at room temperature for at least 8 weeks and / or at -20°C for at least 8 weeks without stratification of components after being warmed to room temperature. Of course, fuel additive packages can also be stable under other storage conditions not explicitly mentioned herein, such as +40°C.

[0114] In the context of this invention, at least one quaternary nitrogen component (B) refers to a nitrogen compound that is quaternized in the presence of an acid or in an acid-free manner, preferably obtained by adding a compound comprising at least one oxygen-containing or nitrogen-containing group that can react with an acid anhydride and optionally at least one quaternizable amino group to a polycarboxylic acid anhydride compound and subsequently quaternizing it.

[0115] In most cases, the quaternary nitrogen component (B) is an ammonium compound; however, in the context of this article, morpholinium, piperidinium, piperazineium, pyrrolidineium, imidazolineium, or pyridinium cations are also included in the phrase “quaternary nitrogen component”.

[0116] Quaternary ammonium compound (B) is preferably of formula

[0117] + NR 1 R 2 R 3 R 4 A -

[0118] in

[0119] A - Representing anion, preferably carboxylate R. 5 COO - Or carbonate R 5 O-COO - ,

[0120] and

[0121] R 1 R 2 R 3 R 4 and R 5 Each is an organic residue, substituted or unsubstituted, having 1 to 100 carbon atoms, preferably unsubstituted, having 1 to 100, more preferably 1 to 75, even more preferably 1 to 30, most preferably 1 to 25, and especially 1 to 20 carbon atoms, of straight-chain or branched alkyl, alkenyl, or hydroxyalkyl residues.

[0122] R 5 Optionally, it is a substituted or unsubstituted cycloalkyl or aryl group having 5 to 20, preferably 5 to 12, carbon atoms.

[0123] Anions may also carry multiple negative charges. For example, if an anion of a dicarboxylic acid is used, the stoichiometric ratio of ammonium ions to anions corresponds to the ratio of positive to negative charges.

[0124] This also applies to salts with cations containing more than one ammonium ion, such as those with substituents connecting two or more ammonium ions.

[0125] In organic residues, the carbon atom can be interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imine atoms, and can be C6-C. 12 -Aryl, C5-C 12 - A cycloalkyl or five- or six-membered, oxygen-, nitrogen- and / or sulfur-containing heterocyclic ring, or two of them together, forming an unsaturated ring, a saturated ring, or an aromatic ring, said ring may be interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups, wherein the mentioned groups may each be substituted by a functional group, aryl, alkyl, aryloxy, alkoxy, halogen, heteroatom, and / or heterocyclic ring.

[0126] Residue R 1To R 4 The two components can together form an unsaturated ring, a saturated ring, or an aromatic ring, preferably a five-membered ring, a six-membered ring, or a seven-membered ring (including the nitrogen atom of the ammonium ion).

[0127] In this case, the ammonium cation can be a morpholinium, piperidinium, piperazineium, pyrrolidineium, imidazolineium, or pyridinium cation.

[0128] In these definitions

[0129] C1-C atoms that can be substituted with functional groups, aryl groups, alkyl groups, aryloxy groups, alkoxy groups, halogens, heteroatoms, and / or heterocycles 20-alkyl groups include, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, 2,4,4-trimethylpentyl, decyl, dodecyl, tetradecyl, heptadecanyl, octadecyl, eicosyl, 1,1-dimethylpropyl, 1,1-dimethylbutyl, 1,1,3,3-tetramethylbutyl, benzyl, 1-phenylethyl, 2-phenylethyl, α,α-dimethylbenzyl, diphenylmethyl, p-tolylmethyl, 1-(p-butylphenyl)ethyl, p-chlorobenzyl, 2,4-dichlorobenzyl, p-methoxy Benzyl, m-ethoxybenzyl, 2-cyanoethyl, 2-cyanopropyl, 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-butoxycarbonylpropyl, 1,2-di-(methoxycarbonyl)ethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-butoxyethyl, diethoxymethyl, diethoxyethyl, 1,3-dioxolane-2-yl, 1,3-dioxolane-2-yl, 2-methyl-1,3-dioxolane-2-yl, 4-methyl-1,3-dioxolane-2-yl, 2-isopropoxyethyl, 2-butoxypropyl, 2-octyloxy Ethyl, chloromethyl, 2-chloroethyl, trichloromethyl, trifluoromethyl, 1,1-dimethyl-2-chloroethyl, 2-methoxyisopropyl, 2-ethoxyethyl, butylthiomethyl, 2-dodecylthioethyl, 2-phenylthioethyl, 2,2,2-trifluoroethyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 4-hydroxybutyl, 6-hydroxyhexyl, 2-aminoethyl, 2-aminopropyl, 3-aminopropyl, 4-aminobutyl, 6-aminohexyl, 2-methylaminoethyl, 2-methylaminopropyl, 3-methylaminopropyl, 4-methylaminobutyl 6-Methylaminohexyl, 2-dimethylaminoethyl, 2-dimethylaminopropyl, 3-dimethylaminopropyl, 4-dimethylaminobutyl, 6-dimethylaminohexyl, 2-hydroxy-2,2-dimethylethyl, 2-phenoxyethyl, 2-phenoxypropyl, 3-phenoxypropyl, 4-phenoxybutyl, 6-phenoxyhexyl, 2-methoxyethyl, 2-methoxypropyl, 3-methoxypropyl, 4-methoxybutyl, 6-methoxyhexyl, 2-ethoxyethyl, 2-ethoxypropyl, 3-ethoxypropyl, 4-ethoxybutyl or 6-ethoxyhexyl, and

[0130] C2-C interrupted by one or more oxygen atoms and / or sulfur atoms and / or one or more substituted or unsubstituted imine groups 20The alkyl group is, for example, 5-hydroxy-3-oxapentyl, 8-hydroxy-3,6-dioxaoctyl, 11-hydroxy-3,6,9-trioxaundecyl, 7-hydroxy-4-oxaheptyl, 11-hydroxy-4,8-dioxaundecyl, 15-hydroxy-4,8,12-trioxapentadecanyl, 9-hydroxy-5-oxanonyl, 14-hydroxy-5,10-oxatetradecyl, 5-methoxy-3-oxapentyl, 8-methoxy-3,6-dioxaoctyl, 11-methoxy-3,6,9-trioxaundecyl, 7-methoxy-4-oxaheptyl, 11-methoxy The compounds are 4,8-dioxaundecyl, 15-methoxy-4,8,12-trioxapentadecanyl, 9-methoxy-5-oxanonyl, 14-methoxy-5,10-oxatetradecyl, 5-ethoxy-3-oxapentyl, 8-ethoxy-3,6-dioxaoctyl, 11-ethoxy-3,6,9-trioxaundecyl, 7-ethoxy-4-oxaheptyl, 11-ethoxy-4,8-dioxaundecyl, 15-ethoxy-4,8,12-trioxapentadecanyl, 9-ethoxy-5-oxanonyl, or 14-ethoxy-5,10-oxatetradecyl.

[0131] If two groups form a ring, they can together be 1,3-propylidene, 1,4-butylidene, 1,5-pentylidene, 2-oxa-1,3-propylidene, 1-oxa-1,3-propylidene, 2-oxa-1,3-propylidene, 1-oxa-1,3-propenyne, 1-aza-1,3-propenyne, 1-C1-C4-alkyl-1-aza-1,3-propenyne, 1,4-but-1,3-dieneyl, 1-aza-1,4-but-1,3-dieneyl, or 2-aza-1,4-but-1,3-dieneyl.

[0132] The number of oxygen and / or sulfur atoms and / or imino groups is not limited in any way. Generally, there are no more than 5 groups, preferably no more than 4, and very particularly preferably no more than 3.

[0133] In addition, there is usually at least one carbon atom between any two heteroatoms, preferably at least two carbon atoms.

[0134] The substituted and unsubstituted imino groups can be, for example, imino, methylimino, isopropylimino, n-butylimino, or tert-butylimino.

[0135] also,

[0136] The functional group can be carboxyl, formamide, hydroxyl, di(C1-C4-alkyl)amino, C1-C4-alkoxycarbonyl, cyano, or C1-C4-alkoxy.

[0137] C6-C atoms that can be substituted with functional groups, aryl groups, alkyl groups, aryloxy groups, alkoxy groups, halogens, heteroatoms, and / or heterocycles 12 -The aryl group can be, for example, phenyl, tolyl, xylyl, α-naphthyl, β-naphthyl, 4-diphenyl, chlorophenyl, dichlorophenyl, trichlorophenyl, difluorophenyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, isopropylphenyl, tert-butylphenyl, dodecylphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexoxyphenyl, methylnaphthyl, isopropylnaphthyl, chloronaphthyl, ethoxynaphthyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-dimethoxyphenyl, 2,6-dichlorophenyl, 4-bromophenyl, 2- or 4-nitrophenyl, 2,4- or 2,6-dinitrophenyl, 4-dimethylaminophenyl, 4-acetylphenyl, methoxyethylphenyl, or ethoxymethylphenyl.

[0138] C5-C atoms that can be substituted with functional groups, aryl groups, alkyl groups, aryloxy groups, alkoxy groups, halogens, heteroatoms, and / or heterocycles 12 -The cycloalkyl group is, for example, cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, diethylcyclohexyl, butylcyclohexyl, methoxycyclohexyl, dimethoxycyclohexyl, diethoxycyclohexyl, butylthiocyclohexyl, chlorocyclohexyl, dichlorocyclohexyl, dichlorocyclopentyl, or a saturated or unsaturated bicyclic system, such as norbornyl or norbornenyl.

[0139] Five- or six-membered heterocycles containing oxygen, nitrogen, and / or sulfur are, for example, furanyl, thiophene, pyrrole, pyridyl, indolyl, benzoxazolyl, dioxacyclopentyl, dioxy, benzimidazolyl, benzothiazolyl, dimethylpyridyl, methylquinolinyl, dimethylpyrrole, methoxyfuranyl, dimethoxypyridyl, difluoropyridyl, methylthiophene, isopropylthiophene, or tert-butylthiophene.

[0140] C1 to C4 alkyl groups are, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, or tert-butyl.

[0141] Residue R 1 To R 5 C2-C is preferred. 18 -alkyl or C6-C 12 -Aryl, more preferably C4-C 16 -alkyl or C6-C 12 -Aryl, and even more preferably C4-C 16 -alkyl or C6-aryl.

[0142] Residue R 1 To R 5 It can be saturated or unsaturated, but saturated is preferred.

[0143] Preferred residue R 1 To R 5 It contains no heteroatoms other than hydrogen and carbon.

[0144] R 1 To R 4 Preferred examples are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, 2,4,4-trimethylpentyl, 2-propylheptyl, decyl, dodecyl, tetradecyl, heptadecanyl, octadecyl, eicosyl, 1,1-dimethylpropyl, 1,1-dimethylbutyl, 1,1,3,3-tetramethylbutyl, benzyl, 1-phenylethyl, 2-phenylethyl, α,α-dimethylbenzyl, diphenylmethyl, p-tolylmethyl, or 1-(p-butylphenyl)ethyl.

[0145] In a preferred embodiment, residue R 1 To R 4 At least one of them is selected from 2-hydroxyethyl, hydroxypropyl-1-yl, hydroxypropyl-2-yl, 2-hydroxybutyl or 2-hydroxy-2-phenylethyl.

[0146] In one implementation, R 5 It is a polyolefin homopolymer or polyolefin copolymer, preferably polypropylene, polybutene or polyisobutylene residues, with a number average molecular weight (M n The number average molecular weight is 85 to 20,000, for example 113 to 10,000, or 200 to 10,000, or 350 to 5,000, for example 350 to 3,000, 500 to 2,500, 700 to 2,500, or 800 to 1,500. Polypropylene-based, polybutene-based, and polyisobutylene-based are preferred, for example, a number average molecular weight M. n The values ​​are 3500 to 5000, 350 to 3000, 500 to 2500, 700 to 2500 and 800 to 1500 g / mol.

[0147] A - Preferred examples include the following anions: acetic acid, propionic acid, butyric acid, 2-ethylhexanoic acid, trimethylhexanoic acid, 2-propylheptanoic acid, isononanoic acid, tert-carbonic acid, decanoic acid, undecanoic acid, dodecanoic acid, saturated or unsaturated fatty acids having 12 to 24 carbon atoms or mixtures thereof, salicylic acid, mono-C1-C4-alkyl oxalate, mono-C1-C4-alkyl phthalate, C 12 -C 100 -alkyl-succinic acid and C 12 -C 1001-Alkenyl succinic acids, especially dodecenyl succinic acid, hexadecenyl succinic acid, eicosenoyl succinic acid, and polyisobutylene succinic acid. Other examples are methyl carbonate, ethyl carbonate, n-butyl carbonate, 2-hydroxyethyl carbonate, and 2-hydroxypropyl carbonate.

[0148] In a preferred embodiment, the nitrogen compound quaternized in the presence of an acid or in an acid-free manner can be obtained by adding a compound comprising at least one oxygen-containing or nitrogen-containing group reactive to an acid anhydride and optionally at least one quaternizable amino group to a polycarboxylic anhydride compound and subsequently quaternizing it in the absence of a free acid, particularly with epoxides, such as styrene oxide or propylene oxide, as described in WO 2012 / 004300, or with carboxylic esters, such as dimethyl oxalate or methyl salicylate. Suitable compounds having at least one oxygen-containing or nitrogen-containing group reactive to an acid anhydride and optionally at least one quaternizable amino group are, in particular, polyamines having at least one primary or secondary amine group and at least one tertiary amine group, especially N,N-dimethyl-1,3-propanediamine, N,N-dimethyl-1,2-ethylenediamine, or N,N,N'-trimethyl-1,2-ethylenediamine. Useful polycarboxylic anhydrides, especially dicarboxylic acids such as succinic acid, have relatively long-chain hydrocarbon substituents with a number-average molecular weight M of the hydrocarbon substituents. n Preferably, the value is 200 to 10,000, particularly 350 to 5,000. Such quaternized nitrogen compounds are, for example, polyisobutylene succinic anhydride obtained at 40°C (wherein the polyisobutylene typically has an M of 1000). n The reaction product of 3-(dimethylamino)propylamine constitutes polyisobutylene succinic acid monoamide and is subsequently quaternized with dimethyl oxalate or methyl salicylate or with styrene oxide or propylene oxide in the absence of free acid.

[0149] Other nitrogen compounds suitable as quaternized compounds of compound (B) are described in

[0150] WO 2006 / 135881 A1, page 5, line 13 to page 12, line 14;

[0151] WO 10 / 132259A1, page 3, line 28 to page 10, line 25;

[0152] WO 2008 / 060888 A2, page 6, line 15 to page 14, line 29;

[0153] WO 2011 / 095819 A1, page 4, line 5 to page 9, line 29;

[0154] GB 2496514 A, paragraphs

[00012] to

[00041] ;

[0155] WO 2013 / 117616 A1, page 3, line 34 to page 11, line 2;

[0156] WO 14 / 202425A2, page 3, line 14 to page 5, line 9;

[0157] WO 14 / 195464A1, page 15, line 31 to page 45, line 26, and page 75, lines 1 to 4;

[0158] WO 15 / 040147A1, page 4, line 34 to page 5, line 18, and page 19, line 11 to page 50, line 10;

[0159] WO 14 / 064151A1, page 5, line 14 to page 6, line 17, and page 16, line 10 to page 18, line 12;

[0160] WO 2013 / 064689 A1, page 18, line 16 to page 29, line 8; and

[0161] WO 2013 / 087701 A1, page 13, line 25 to page 19, line 30.

[0162] WO 13 / 000997A1, page 17, line 4 to page 25, line 3.

[0163] WO 12 / 004300, page 5, lines 20-30; page 8, line 1 to page 10, line 10; and page 19, line 29 to page 28, line 3.

[0164] Each of them is incorporated into this article by way of citation.

[0165] In one embodiment, the quaternized ammonium compound (B) has the following formula:

[0166]

[0167] Where in this formula

[0168] PIB represents the number-average molecular weight M. n The polyisobutylene residues are 550 to 2300, preferably 650 to 1500, and more preferably 750 to 1300 g / mol.

[0169] R represents C1- to C4-alkyl or hydroxy-C1- to C4-alkyl, preferably methyl or 2-hydroxypropyl, and

[0170] A - Representing anion, preferably carboxylate R as defined above. 5 COO- Or carbonate R 5 O-COO - More preferably, acetate, salicylate or methyl oxalate.

[0171] In another preferred embodiment, the quaternized ammonium compound (B) has the following formula:

[0172]

[0173] Where in this formula

[0174] PIB represents the number-average molecular weight M. n The polyisobutylene residues are 550 to 2300, preferably 650 to 1500, and more preferably 750 to 1300 g / mol.

[0175] R represents hydroxy-C1- to C4-alkyl, preferably 2-hydroxypropyl.

[0176] In another embodiment, the quaternized compound (B) has the following formula:

[0177]

[0178] Where in this formula

[0179] PIB represents its number-average molecular weight M. n The polyisobutylene residues are 550 to 2300, preferably 650 to 1500, and more preferably 750 to 1300 g / mol.

[0180] R represents C1- to C4-alkyl or hydroxy-C1- to C4-alkyl, preferably methyl, and

[0181] A - Representing anion, preferably carboxylate R as defined above. 5 COO - Or carbonate R 5 O-COO - More preferably, salicylate or methyl oxalate.

[0182] In another embodiment, the quaternized ammonium compound (B) has the following formula:

[0183]

[0184] In this formula,

[0185] R a Representing C1-C 20 -alkyl group, preferably C9- to C10- 17 -alkyl, more preferably representing undecyl, tridecyl, pentadecyl or heptadecyl.

[0186] R b Representing hydroxy-C1- to C4-alkyl, preferably 2-hydroxypropyl or 2-hydroxybutyl, and

[0187] A - Representing anion, preferably carboxylate R. 5 COO - As defined above, the carboxyl group R of a more preferred fatty acid 5 COO - Especially A - It is acetate, 2-ethylhexanoate, oleate or polyisobutylene succinate.

[0188] In one embodiment, the quaternized ammonium compound (B) has the following formula:

[0189]

[0190] In this formula,

[0191] For X, i = 1 to n and 1 to m i The terms are independently selected from -CH2-CH2-O-, -CH2-CH(CH3)-O-, -CH(CH3)-CH2-O-, -CH2-C(CH3)2-O-, -C(CH3)2-CH2-O-, -CH2-CH(C2H5)-O-, -CH(C2H5)-CH2-O-, and -CH(CH3)-CH(CH3)-O-; preferably selected from -CH2-CH(CH3)-O-, -CH(CH3)-CH2-O-, -CH2-C(CH3)2-O-, -C(CH3)2-CH2-O-, -CH2-CH(C2H5)-O-, and -CH(C2H5)-CH2 -O- and -CH(CH3)-CH(CH3)-O-; more preferably selected from -CH2-CH(CH3)-O-, -CH(CH3)-CH2-O-, -CH2-C(CH3)2-O-, -C(CH3)2-CH2-O-, -CH2-CH(C2H5)-O- and -CH(C2H5)-CH2-O-; even more preferably selected from -CH2-CH(C2H5)-O-, -CH(C2H5)-CH2-O-, -CH2-CH(CH3)-O- and -CH(CH3)-CH2-O-; and especially selected from -CH2-CH(CH3)-O- and -CH(CH3)-CH2-O-,

[0192] m and n are independent positive integers, provided that the sum of (m+n) is 2 to 50, preferably 5 to 40, more preferably 10 to 30, and especially 15 to 25.

[0193] R represents C1- to C4-alkyl, preferably methyl, and

[0194] A - Representing an anion, preferably a carboxylate R as defined above. 5 COO - Or carbonate R 5 O-COO - More preferably, salicylate or methyl oxalate.

[0195] In another preferred embodiment, the quaternized ammonium compound (B) has the following formula:

[0196]

[0197] Where in this formula

[0198] R a and R b Each represents C1-C independently. 20 -alkyl or hydroxy-C1- to C4-alkyl, preferably R a Representing C1-C 20 -alkyl, preferably ethyl, n-butyl, n-octyl, n-dodecyl, tetradecyl or hexadecyl, and R b Representing hydroxy-C1- to C4-alkyl, preferably 2-hydroxypropyl,

[0199] A - The anion is represented, preferably the carboxylate group R as defined above. 5 COO - Or carbonate R 5 O-COO - C is preferred 12 -C 100 -alkyl- and -alkenyl succinic acids, especially dodecenyl succinic acid, hexadecenyl succinic acid, eicoseneyl succinic acid and polyisobutyleneyl succinic acid.

[0200] Polyisobutylene succinimide (G) is of the following formula:

[0201]

[0202] Where in this formula

[0203] PIB represents the number-average molecular weight M. n The polyisobutylene residues are 550 to 2300, preferably 650 to 1500, and more preferably 750 to 1300 g / mol, and n represents a positive integer of 2 to 6, preferably 2 to 5, and more preferably 3 or 4.

[0204] Among additives with cleaning properties, quaternary nitrogen compounds (B) are superior to polyisobutylene succinimide (G).

[0205] Fuel oil and gasoline fuels are typically used in conjunction with at least one emulsifying agent as an additive component (C), said component (C) being selected from...

[0206] (C1) Alkoxylated copolymers of ethylene oxide, propylene oxide, butane oxide, styrene oxide and / or other oxides, such as epoxy resins;

[0207] (C2) Alkoxylated phenolic resin.

[0208] The defogger components (C1) and (C2) are typically commercially available products, for example, under brand names. Demisting products such as Tolad2898, 9360K, 9348, 9352K, 9327, or 286K are available from Baker Petrolite.

[0209] In another preferred embodiment of the invention, the fuel oil further comprises at least one cetane number improver as additive component (D). The cetane number improver used is typically an organic nitrate ester. Such organic nitrate esters are particularly nitrate esters of unsubstituted or substituted aliphatic or alicyclic alcohols, typically having up to about 10 carbon atoms, particularly 2 to 10. The alkyl groups in these nitrate esters can be straight-chain or branched, saturated or unsaturated. Typical examples of such nitrate esters are methyl nitrate, ethyl nitrate, n-propyl nitrate, isopropyl nitrate, allyl nitrate, n-butyl nitrate, isobutyl nitrate, sec-butyl nitrate, tert-butyl nitrate, n-pentyl nitrate, isopentyl nitrate, 2-pentyl nitrate, 3-pentyl nitrate, tert-pentyl nitrate, n-hexyl nitrate, n-heptyl nitrate, sec-heptyl nitrate, n-octyl nitrate, 2-ethylhexyl nitrate, sec-octyl nitrate, n-nonyl nitrate, n-decyl nitrate, cyclopentyl nitrate, cyclohexyl nitrate, methylcyclohexyl nitrate, and isopropylcyclohexyl nitrate, as well as formula R. a R b Branched decyl nitrate of CH-CH2-O-NO2, wherein R a It is a n-propyl or isopropyl group, R b It is a straight-chain or branched alkyl group having 5 carbon atoms, as described in WO 2008 / 092809. Also suitable are, for example, nitrate esters of alkoxy-substituted aliphatic alcohols, such as 2-ethoxyethyl nitrate, 2-(2-ethoxy-ethoxy)ethyl nitrate, 1-methoxypropyl nitrate, or 4-ethoxybutyl nitrate. Also suitable are diol nitrate esters, such as 1,6-hexamethylene dinitrate. Among the mentioned categories of cetane number improvers, primary amyl nitrate, primary hexyl nitrate, octyl nitrate, and mixtures thereof are preferred. Most preferably, 2-ethylhexyl nitrate is present in the fuel oil as the sole cetane number improver or as a mixture with other cetane number improvers.

[0210] In the context of this invention, fuel oil preferably refers to middle distillate fuels, particularly diesel fuel. However, heating oil, jet fuel, and kerosene should also be included. Diesel fuel or middle distillate fuel is typically mineral oil raffinate with a boiling range typically ranging from 100 to 400°C. These are typically distillates with a 95% distillation point as high as 360°C or even higher. However, these can also be so-called “ultra-low sulfur diesel” or “city diesel,” characterized by a 95% distillation point, for example, not exceeding 345°C and a sulfur content not exceeding 0.005% by weight, or a 95% distillation point, for example, 285°C and a sulfur content not exceeding 0.001% by weight. In addition to diesel fuels that can be obtained through refining, those whose main component is relatively long-chain paraffin, which can be obtained synthetically through coal gasification or gas liquefaction [“gas liquefaction (GTL) fuels”], are also suitable. Also suitable are mixtures of the above-mentioned diesel fuels with renewable fuels (biofuel oils) such as biodiesel or bioethanol. Of particular interest are diesel fuels with low sulfur content, i.e., sulfur content 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.

[0211] In a preferred embodiment, the olefin-carboxylic acid copolymer (A) is used together with the above-described components (B) or (G), (C) (if desired), and (D) (if desired) in a fuel oil, said fuel oil having the following composition:

[0212] (a) 0.1 to 100% by weight, preferably 0.1 to less than 100% by weight, especially 10 to 95% by weight, and particularly 30 to 90% by weight of at least one fatty acid ester-based biofuel oil, and

[0213] (b) 0 to 99.9% by weight, preferably greater than 0 to 99.9% by weight, especially 5 to 90% by weight, and particularly 10 to 70% by weight, of a middle fraction of fossil and / or synthetic and / or plant and / or animal origin, which is essentially a mixture of hydrocarbons and is free of fatty acid esters.

[0214] The olefin-carboxylic acid copolymer (A) can also be used in fuel oils together with the above-mentioned components (B) or (G), (C) (if applicable), (D) (if applicable), which consist only of intermediate fractions of fossil and / or synthetic and / or plant and / or animal origins, which are essentially hydrocarbon mixtures and do not contain fatty acid esters.

[0215] Fuel oil component (a) is also commonly referred to as "biodiesel". This preferably comprises essentially alkyl esters of fatty acids derived from oils and / or fats of plants and / or animals. Alkyl esters generally refer to lower alkyl esters, especially C1- to C4-alkyl esters, which can be obtained by transesterification of glycerides, especially triglycerides, present in oils and / or fats of plants and / or animals, with the aid of lower alcohols such as ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, or especially methanol ("FAME").

[0216] Examples of vegetable oils that can be converted into the corresponding alkyl esters and thus used as a base component of biodiesel include castor oil, olive oil, peanut oil, palm kernel oil, coconut oil, mustard oil, cottonseed oil, and especially sunflower oil, palm oil, soybean oil, and rapeseed oil. Other examples include oils obtainable from wheat, jute, sesame, and shea tree nut; peanut oil, jatropha oil, and flaxseed oil can also be used. The extraction of these oils and their conversion into alkyl esters are known in the prior art or can be inferred from it.

[0217] Used vegetable oils, such as deep fat fryer oil, can also be converted into alkyl esters after proper cleaning, and thus used as a base component of biodiesel.

[0218] Vegetable fats can also be used as a source of biodiesel in principle, but their role is smaller.

[0219] Examples of animal oils and fats that can be converted into the corresponding alkyl esters and thus used as a basic component of biodiesel include fish oil, beef tallow, pork tallow, and similar fats and oils obtained as waste in slaughterhouses or when utilizing farm animals or wild animals.

[0220] The saturated or unsaturated parent fatty acids of the oils and / or fats of the plant and / or animal (which typically have 12 to 22 carbon atoms and may have other functional groups, such as hydroxyl groups appearing in alkyl esters), particularly lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, trans oleic acid, erucic acid, and / or ricinoleic acid.

[0221] Typical lower alkyl esters of plant and / or animal-based oils and / or fats used as biodiesel or biodiesel components are found to be, for example, sunflower methyl ester, palm oil methyl ester (“PME”), soybean oil methyl ester (“SME”), and especially rapeseed oil methyl ester (“RME”).

[0222] However, monoglycerides, diglycerides, and especially triglycerides, such as castor oil, or mixtures of these glycerides, can also be used as biodiesel or as components for biodiesel.

[0223] In the context of this invention, fuel oil component (b) should be understood to refer to the aforementioned middle distillate fuels, especially diesel fuels, particularly those with a boiling point of 120 to 450°C.

[0224] In another preferred embodiment, the olefin-carboxylic acid copolymer (A) is used together with the above-described components (B) or (G), (C) and (D) (if desired) in a fuel oil having at least one of the following properties:

[0225] (α) Sulfur content less than 50 mg / kg (equivalent to 0.005% by weight), especially less than 10 mg / kg (equivalent to 0.001% by weight);

[0226] The maximum content of (β) polycyclic aromatic hydrocarbons is 8% by weight;

[0227] (γ) 95% distillation point (volume / volume) not exceeding 360°C.

[0228] The polycyclic aromatic hydrocarbons (PAHs) in β should be understood to refer to PAHs as defined in standard EN 12916. They are determined according to that standard.

[0229] The amount of olefin-carboxylic acid copolymer (A) described in the context of this invention in the fuel oil is typically 1 to 1000 ppm by weight, preferably 2 to 500 ppm by weight, more preferably 3 to 300 ppm by weight, most preferably 5 to 200 ppm by weight, for example 10 to 100 ppm by weight.

[0230] The amount of cleaning additive (B) or (G) or a mixture of such cleaning additives in the fuel oil is typically 1 to 500 ppm by weight, preferably 2 to 250 ppm by weight, more preferably 3 to 100 ppm by weight, most preferably 4 to 75 ppm by weight, for example 5 to 50 ppm by weight.

[0231] One or more demisters (if present) as additive component (C) are typically present in fuel oil at a content of 0.5 to 100 ppm by weight, preferably 1 to 50 ppm by weight, more preferably 1.5 to 40 ppm by weight, most preferably 2 to 30 ppm by weight, for example 3 to 20 ppm by weight.

[0232] The content of cetane number improver (D) or a mixture of cetane number improvers in fuel oil is typically 10 to 10,000 ppm by weight, preferably 20 to 5,000 ppm by weight, more preferably 50 to 2,500 ppm by weight, most preferably 100 to 1,000 ppm by weight, for example 150 to 750 ppm by weight.

[0233] The subject of this invention also includes a fuel additive concentrate suitable for fuel oils, particularly diesel fuels, comprising...

[0234] (A) 0.01 to 40% by weight, preferably 0.05 to 20% by weight, more preferably 0.1 to 10% by weight, of an olefin-carboxylic acid copolymer containing at least one hydrocarbon substituent of 10 to 3000 carbon atoms;

[0235] (B) / (G) 5 to 40% by weight, preferably 10 to 35% by weight, more preferably 15 to 30% by weight of at least one compound (B) or (G);

[0236] (C) 0 to 5% by weight, preferably 0.01 to 5% by weight, more preferably 0.02 to 3.5% by weight, and most preferably 0.05 to 2% by weight of at least one demister, selected from...

[0237] (C1) Alkoxylated copolymers of ethylene oxide, propylene oxide, butane oxide, styrene oxide, and / or other oxides, such as epoxy resins.

[0238] (C2) Alkoxylated phenolic resin;

[0239] (D) 0 to 75% by weight, preferably 5 to 75% by weight, more preferably 10 to 70% by weight, at least one cetane number improver;

[0240] (E) 0 to 50% by weight, preferably 5 to 50% by weight, more preferably 10 to 40% by weight of at least one solvent or diluent.

[0241] In each case, the sum of components (A), (B), (C), (D), and (E) is 100%.

[0242] In addition to olefin-carboxylic acid copolymers (A) and components (B) and (C) (if included) and / or (D) as coadditives, the fuel oil, such as diesel fuel, or the mixture of the biofuel oil with fossil, synthetic, plant, or animal-derived middle fractions, may contain other conventional additive components in their usual amounts, particularly cold flow improvers, corrosion inhibitors, other demulsifiers, defoamers, antioxidants and heat stabilizers, metal passivators, antistatic agents, lubrication improvers, dyes (labeling) and / or diluents and solvents. The fuel additive concentrate may also contain certain of the aforementioned coadditives in their usual amounts, such as corrosion inhibitors, additional demulsifiers, defoamers, antioxidants and heat stabilizers, metal passivators, antistatic agents, and lubrication improvers.

[0243] Suitable cold flow improvers as other auxiliary additives include, for example, copolymers of ethylene with at least one other unsaturated monomer, particularly ethylene-vinyl acetate copolymers.

[0244] Suitable corrosion inhibitors as other auxiliary additives include, for example, succinates, especially with polyols; fatty acid derivatives such as oleate, oligomeric fatty acids and substituted ethanolamines.

[0245] Other demulsifiers suitable as auxiliary additives include, for example, alkali metal and alkaline earth metal salts of alkyl-substituted phenol sulfonates and naphthalene sulfonates, as well as alkali metal and alkaline earth metal salts of fatty acids, and alcohol alkoxylates, such as alcohol ethoxylates, phenol alkoxylates, such as tert-butylphenol ethoxylate or tert-amylphenol ethoxylate, fatty acids themselves, alkylphenols, condensation products of ethylene oxide and propylene oxide, such as ethylene oxide-propylene oxide block copolymers, polyethyleneimine, and polysiloxanes.

[0246] Suitable defoamers as other auxiliary additives include, for example, polyether-modified polysiloxanes.

[0247] Suitable antioxidants as other co-additives include, for example, substituted phenols, such as 2,6-di-tert-butylphenol and 2,6-di-tert-butyl-3-methylphenol, and phenylenediamines, such as N,N'-di-sec-butyl-p-phenylenediamine.

[0248] Suitable metal passivating agents as other auxiliary additives include, for example, salicylic acid derivatives, such as N,N'-disalicylicyl-1,2-propanediamine.

[0249] Suitable lubrication improvers as other auxiliary additives include, for example, glyceryl monooleate.

[0250] Suitable solvents and diluents for component (E), especially for diesel performance packages, are, for example, non-polar organic solvents, particularly aromatic and aliphatic hydrocarbons, such as toluene, xylene, "petroleum solvents (white spirit)," and those with the name [missing information]. (Manufactured by Royal Dutch / Shell Group) (Manufactured by ExxonMobil) and industrial solvent mixtures with SolventNaphtha. Polar organic solvents are also useful in this paper, particularly in blends with the nonpolar solvents mentioned, especially alcohols such as 2-ethylhexanol, decanol, and isothietol.

[0251] In another preferred embodiment of the invention, the gasoline fuel may further comprise at least one substantially nitrogen-free carrier oil selected from synthetic carrier oils and mineral oils as an additive component (F). The carrier oil of component (F) may be a synthetic oil or a mineral oil; for the purposes of this invention, refined petroleum is also understood to be a mineral oil.

[0252] The amount of carrier oil in component (F) is typically from about 50 to about 2,000 ppm by weight of gasoline fuel, preferably from 100 to 800 ppm by weight of gasoline fuel. Preferably, the ratio of carrier oil (F) to additive component (B) or additive component (G) is from 0.35:1 to 10:1, typically from 0.4:1 to 2:1.

[0253] Examples of suitable mineral carrier oils are those with a viscosity grade of solvent neutral (SN) 500 to 2000, as well as aromatic hydrocarbons and alkanes and alkoxyalkanols. Another useful mineral carrier oil is a fraction known as "hydrocracked oil," which is obtained from refined mineral oils (boiling point of about 360 to 500 °C; available from natural mineral oils that have been isomerized, free of paraffin components, and catalytically hydrogenated under high pressure).

[0254] Examples of synthetic carrier oils that can be used in this invention are olefin polymers with a number-average molecular weight of 400 to 1,800 g / mol, based on poly-α-olefins or poly-intraolefins, particularly those based on polybutene or polyisobutylene (hydrogenated or non-hydrogenated). Other examples of suitable synthetic carrier oils are polyesters, polyalkoxylates, polyethers, alkylphenol-initiated polyethers, and carboxylic acids of long-chain alkanols.

[0255] Examples of suitable polyethers that can be used in this invention are compounds containing polyoxy-C2-C4-alkylene, especially polyoxy-C3-C4-alkylene, which can be made possible by reducing the C1-C... 30 -Alkanols, C2-C 60 -Alkanediol, C1-C 30 -alkylcyclohexanol or C1-C 30 - Alkylphenols with 1 to 30 moles of ethylene oxide and / or propylene oxide and / or butane per hydroxyl group, particularly with 1 to 30 moles of propylene oxide and / or butane per hydroxyl group. Compounds of this type are described, for example, in EP-A 310 875, EP-A 356 725, EP-A 700 985 and US-A 4,877,416.

[0256] Typical examples of suitable polyethers are tridecaneol propoxylate, tridecaneol butoxylate, isotriadecaneol butoxylate, 2-propylheptanol propoxylate, 2-propylheptanol butoxylate, heptadecanol propoxylate, isohexadecanol propoxylate, heptadecanol butoxylate, isohexadecanol butoxylate, isononylphenol butoxylate, polyisobutylene alcohol butoxylate, and polyisobutylene alcohol propoxylate. In a preferred embodiment, the carrier oil component (F) comprises at least one obtained from C1- to C2-C4. 30 -Alkanols, especially C6- to C6-alkanols 18-Alkanols, or C2-to-C 60 -Alkanediols, especially C8-polyethers-to-C 24 - Alkanediols and a total of 1 to 30 moles, especially 5 to 30 moles, of propylene oxide and / or butane oxide. Other synthetic carrier oils and / or mineral carrier oils may be present in small amounts in component (F).

[0257] In the context of this invention, gasoline fuel refers to a liquid hydrocarbon distillate fuel that boils within the gasoline range. It applies in principle to all types of gasoline, including both "light" and "heavy" gasoline varieties. Gasoline fuel may also contain a certain amount of other fuels, such as ethanol.

[0258] Typically, gasoline fuels usable according to the present invention also exhibit one or more of the following characteristics:

[0259] The aromatic content of gasoline fuel is preferably no more than 50% by volume, more preferably no more than 35% by volume. The preferred range for aromatic content is 1 to 45% by volume, and particularly 5 to 35% by volume.

[0260] The sulfur content of gasoline fuel is preferably no more than 100 ppm by weight, more preferably no more than 10 ppm by weight. The preferred range for sulfur content is 0.5 to 150 ppm by weight, particularly 1 to 10 ppm by weight.

[0261] The olefin content of the gasoline fuel is no more than 21% by volume, preferably no more than 18% by volume, and more preferably no more than 10% by volume. The preferred range for the olefin content is 0.1% to 21% by volume, particularly 2% to 18% by volume.

[0262] The benzene content of the gasoline fuel does not exceed 1.0% by volume, preferably not exceeding 0.9% by volume. The preferred range for the benzene content is 0 to 1.0% by volume, and more preferably 0.05% to 0.9% by volume.

[0263] The oxygen content of the gasoline fuel shall not exceed 45% by weight, preferably 0 to 45% by weight, most preferably 0.1 to 3.7% by weight (Category I) or most preferably 3.7 to 45% by weight (Category II). The aforementioned Category II gasoline fuel is a mixture of lower alcohols such as methanol or especially ethanol (preferably from natural sources such as plants) with mineral oil-based gasoline (i.e., gasoline typically prepared from crude oil). An example of such gasoline is "E 85," a mixture of 85% by volume ethanol and 15% by volume mineral oil-based gasoline. Fuels containing 100% lower alcohols, especially ethanol, are also suitable.

[0264] In the first category of gasoline fuels mentioned in the previous paragraph, the content of alcohols, especially lower alcohols and ethers, is usually low. Typical maximum contents are 3 vol% methanol, 5 vol% ethanol, 10 vol% isopropanol, 7 vol% tert-butanol, 10 vol% isobutanol, and 15 vol% ethers containing 5 or more carbon atoms in their molecules.

[0265] For example, gasoline fuels with an aromatic content not exceeding 38% by volume, an olefin content not exceeding 21% by volume, a sulfur content not exceeding 50 ppm by weight, a benzene content not exceeding 1.0% by volume, and an oxygen content of 0.1 to 2.7% by weight may be used.

[0266] The summer vapor pressure of gasoline fuel typically does not exceed 70 kPa, preferably not exceeding 60 kPa (at 37°C).

[0267] The research octane rating (“RON”) of gasoline fuel is typically between 90 and 100. The corresponding engine octane rating (“MON”) is typically between 80 and 90.

[0268] The above characteristics are determined by conventional methods (DIN EN 228).

[0269] In the context of this invention, the amount of the olefin-carboxylic acid copolymer (A) contained in the gasoline fuel is typically 1 to 1000 ppm by weight, preferably 5 to 500 ppm by weight, more preferably 3 to 300 ppm by weight, and most preferably 5 to 200 ppm by weight, for example 10 to 100 ppm by weight.

[0270] Additives (B) with cleaning properties or mixtures of multiple such additives with cleaning properties are typically present in gasoline fuels in amounts of 1 to 500 ppm by weight, preferably 2 to 250 ppm by weight, more preferably 3 to 100 ppm by weight, most preferably 4 to 50 ppm by weight, for example 5 to 30 ppm by weight.

[0271] In the case of an additive (G) having a cleaning effect or a mixture of multiple such additives having a cleaning effect, the additive is typically present in gasoline fuel in an amount of 1 to 500 ppm by weight, preferably 1 to 500 ppm by weight, more preferably 1 to 300 ppm by weight, more preferably 1 to 250 ppm by weight, and most preferably 2 to 150 ppm by weight.

[0272] One or more demisting agents (if present) as additive component (C) are typically present in gasoline fuel in an amount of 0.5 to 100 ppm by weight, preferably 1 to 50 ppm by weight, more preferably 1.5 to 40 ppm by weight, most preferably 2 to 30 ppm by weight, for example 3 to 20 ppm by weight.

[0273] One or more carrier oils (F) (if present) are typically present in gasoline fuel in amounts of 10 to 3,000 ppm by weight, preferably 20 to 1,000 ppm by weight, more preferably 50 to 700 ppm by weight, most preferably 70 to 500 ppm by weight, for example 150 to 300 ppm by weight.

[0274] The subject of this invention also includes a fuel additive concentrate suitable for gasoline fuel, comprising...

[0275] (A) 0.01 to 40% by weight, preferably 0.05 to 20% by weight, more preferably 0.1 to 10% by weight, of an olefin-carboxylic acid copolymer of 10 to 3000 carbon atoms, comprising at least one hydrocarbon substituent;

[0276] (B) / (G) 5 to 40% by weight, preferably 10 to 35% by weight, more preferably 15 to 30% by weight of at least one compound (B) or (G);

[0277] (C) 0 to 5% by weight, preferably 0.01 to 5% by weight, more preferably 0.02 to 3.5% by weight, and most preferably 0.05 to 2% by weight of at least one of the following demisters.

[0278] (C1) Alkoxylated copolymers of ethylene oxide, propylene oxide, butane oxide, styrene oxide, and / or other oxides, such as epoxy resins.

[0279] (C2) Alkoxylated phenolic resin;

[0280] (E) 0 to 80% by weight, preferably 5 to 50% by weight, more preferably 10 to 40% by weight of at least one solvent or diluent;

[0281] (F) 2 to 50% by weight, preferably 10 to 50% by weight, more preferably 25 to 45% by weight, of at least one substantially nitrogen-free carrier oil selected from synthetic carrier oils and mineral carrier oils.

[0282] In each case, the sum of components (A), (B) or (G), (C), (D), (E) and (F) is 100%.

[0283] Unless otherwise stated, the quantities given throughout refer to the pure components excluding, for example, solvents.

[0284] In addition to olefin-carboxylic acid copolymers (A) and components (B) or (G) and (C) (if present) and / or (F) as auxiliary additives, the gasoline fuel may contain other conventional additive components in its conventional amounts, particularly corrosion inhibitors, other demulsifiers, antioxidants and heat stabilizers, metal passivators, antistatic agents, friction modifiers, dyes (markers) and / or diluents, and solvents such as component (E) as defined above. The gasoline fuel additive concentrate may also contain certain of the aforementioned auxiliary additives, such as corrosion inhibitors, other demulsifiers, defoamers, antioxidants and heat stabilizers, metal passivators, antistatic agents, and friction modifiers, in their conventional amounts.

[0285] Another object of the present invention is a method for improving the stability of a cleaning agent additive in a fuel additive package by applying at least one olefin-carboxylic acid copolymer (A) to the fuel additive package, said fuel additive package comprising at least one cleaning agent selected from the group consisting of:

[0286] - Quaternary nitrogen compounds (B) and

[0287] - Polyisobutylene succinimide (G).

[0288] The following examples are intended to illustrate the invention but not to limit it. Example

[0289] Additive formulations (by weight percentage) (gasoline additive formulations)

[0290] <![CDATA[Cleaning agent a) > 26.65 26.60 26.56 <![CDATA[carrier oil b) > 14.73 14.71 14.69 <![CDATA[Quaternary ammonium cleaner c) > 9.40 9.39 9.38 <![CDATA[Oleic acid d) > 10.97 10.96 10.94 Solvesso 150 31.98 31.93 31.88 2-Ethylhexanol 6.27 6.26 6.25 <![CDATA[Component (A) e) > -- 0.16 0.31

[0291] a) The cleaning agent is polyisobutyleneamine, with a molecular weight of approximately 1000 g / mol. PIBA 03 was purchased from BASF.

[0292] b) Carrier oil: According to WO 00 / 02978, C 13 - Alkyl alcohol propoxylate, with a molecular weight Mn of approximately 1300 g / mol

[0293] c) Quaternary ammonium salt cleaner: The reaction product of hexadecyl dimethylamine and propylene oxide, with hydrolyzed polyisobutylene succinic acid as the balancing ion, as described in Example 6 of the synthesis (using a 50% by weight 2-ethylhexanol solution).

[0294] d) Oleic acid as a friction modifier

[0295] e) C 20 To C24 A hydrolytic copolymer of a mixture of α-olefin and maleic anhydride, Mn: 1500 g / mol, Mw: 3200 g / mol, used as a 40% solution in Solvesso, as described in Synthesis Example 2, EP 3099720B1.

[0296] Application testing

[0297] Store 100ml of formulations 1 to 3 at -20℃ for 3 days.

[0298] 1) Check the turbidity of the sample immediately after storage. Figure 1 (From left to right), the results are as follows:

[0299] Example 1 (most turbid) > Example 2 (less turbid) > Example 3 (least turbid)

[0300] 2) Then heat the sample to room temperature and check its turbidity. Figure 2 (From left to right), the results are as follows:

[0301] Example 1 (slightly turbid) > Example 2 (clear) > Example 3 (clear)

[0302] Because the formulation of Example 1 remained turbid even after being stored at -20°C for 3 days, and this turbidity persisted even after being warmed to room temperature, it did not meet the stability criteria. In contrast, the formulations of Examples 2 and 3 remained stable at -20°C for more than 8 weeks.

[0303] Additive formulations (by weight) (diesel additive formulations)

[0304] <![CDATA[Quaternary ammonium cleaner (B) a) > <![CDATA[ 21.9 ]]> <![CDATA[ 21.9 ]]> tall oil fatty acids <![CDATA[ 8.8 ]]> <![CDATA[ 8.8 ]]> Defoamer (containing Si) <![CDATA[ 1.8 ]]> <![CDATA[ 1.8 ]]> defogger <![CDATA[ 1.8 ]]> <![CDATA[ 1.8 <!-- 19 -->]]> 2-Ethylhexyl nitrate <![CDATA[ 65.7 ]]> <![CDATA[ 64.8 ]]> <![CDATA[Component (A) b) > <![CDATA[ -- ]]> <![CDATA[ 0.9 ]]>

[0305] a) The cleaning agent polyisobutylene succinic acid, converted from DMAPA and PO, has a molecular weight of approximately 1200 g / mol. See Example 1 of WO 2012 / 004300, with a polymer content of 50% in 50% solvent.

[0306] b) C 20 To C 24 A hydrolytic copolymer of a mixture of α-olefin and maleic anhydride, Mn: 1500 g / mol, Mw: 3200 g / mol, as described in Example 2 of EP 3099720 B1.

[0307] Application testing

[0308] Store 100 ml of formulations 4 and 5 at -30°C for 7 days. After this storage period, check the turbidity of the samples:

[0309] Example 4 (turbidity, precipitate)

[0310] Example 5 (No turbidity, no sediment)

[0311] Since the comparative formulation of Example 4 showed precipitation and turbidity after being stored at -30°C for 7 days, it was significantly less stable than that of Example 5 of the present invention.

Claims

1. The use of an olefin-carboxylic acid copolymer (A) having a number-average molecular weight (Mn) of 0.5 to 10 kDa—determined by gel permeation chromatography using tetrahydrofuran and polystyrene as standards—with at least one additive having a cleaning effect for improving the stability of fuel additive packages for fuel oils, wherein the olefin-carboxylic acid copolymer (A) is obtained by the following steps: - In the first reaction step (I), the following substances are copolymerized: (Aa) At least one olefinically unsaturated monocarboxylic acid or dicarboxylic acid or its anhydride. (Ab) At least one α-alkene having at least 12 and at most 30 carbon atoms, (Ac) optionally at least one other aliphatic or cycloaliphatic olefin having at least 4 carbon atoms and different from (Ab), and (Ad) There are no one or more copolymerizable monomers other than monomers (Aa), (Ab), and (Ac), which are selected from... (Ada) vinyl ester, (Adb) vinyl ether, (Adc) (meth)acrylates of alcohols having at least 5 carbon atoms. (Add) Allyl alcohol or its ether, (Ade) N-vinyl compounds, selected from vinyl compounds containing at least one nitrogen atom in a heterocyclic ring, N-vinylamides, or N-vinyl lactams. (Adf) olefinic unsaturated aromatic compounds, (Adg) α,β-olefinic unsaturated nitrile, (Adh) (methyl)acrylamide and (Adi) allylamine, Subsequently - In a second optional reaction step (II), the anhydride or carboxylic acid ester functional groups present in the copolymer obtained by (I) are partially or completely hydrolyzed and / or saponified, the second reaction step being carried out at least when the copolymer obtained by reaction step (I) does not contain any free carboxylic acid functional groups. The at least one additive with cleaning properties is selected from... - Quaternary nitrogen compounds (B) and - Polyisobutylene succinimide (G) The amount of the olefin-carboxylic acid copolymer (A) is 0.01 to 40% by weight, and the amount of the at least one cleaning additive is 5 to 40% by weight, based on the weight of the fuel additive package.

2. The use according to claim 1, wherein the fuel additive package is used for diesel and gasoline fuels.

3. The use according to claim 1, wherein the monomer (Aa) is at least one olefinically unsaturated dicarboxylic acid or its anhydride.

4. The use according to claim 1, wherein the monomer (Aa) is maleic anhydride.

5. The use according to claim 1 or 4, wherein the monomer (Ab) is one or more straight-chain or branched 1-olefins.

6. The use according to any one of claims 1 to 4, wherein (Ac) is not present in the copolymer.

7. The use according to any one of claims 1 to 4, wherein the quaternary nitrogen compound (B) has the formula + NR 1 R 2 R 3 R 4 A - in A - Represents anion. and R 1 R 2 R 3 R 4 Each is an organic residue, substituted or unsubstituted, having 1 to 100 carbon atoms, which are independent of each other.

8. The use according to claim 7, wherein A - Represents carboxylate R 5 COO - or carbonate R 5 O-COO - , where R 5 Organic residues, whether substituted or unsubstituted, have 1 to 100 carbon atoms.

9. The use according to claim 7, wherein R 1 R 2 R 3 R 4 Each is an unsubstituted straight-chain or branched alkyl, alkenyl, or hydroxyalkyl residue having 1 to 100 carbon atoms.

10. The use according to claim 7, wherein R 1 R 2 R 3 R 4 Each is an unsubstituted straight-chain or branched alkyl, alkenyl, or hydroxyalkyl residue having 1 to 75 carbon atoms.

11. The use according to claim 7, wherein R 1 R 2 R 3 R 4 Each is an unsubstituted straight-chain or branched alkyl, alkenyl, or hydroxyalkyl residue having 1 to 30 carbon atoms.

12. The use according to claim 7, wherein R 1 R 2 R 3 R 4 Each is an unsubstituted straight-chain or branched alkyl, alkenyl, or hydroxyalkyl residue having 1 to 25 carbon atoms.

13. The use according to claim 7, wherein R 1 R 2 R 3 R 4 Each is an unsubstituted straight-chain or branched alkyl, alkenyl, or hydroxyalkyl residue having 1 to 20 carbon atoms.

14. The use according to claim 8, wherein R 5 It is a substituted or unsubstituted cycloalkyl or aryl residue having 5 to 20 carbon atoms.

15. The use according to claim 8, wherein R 5 It is a substituted or unsubstituted cycloalkyl or aryl residue having 5 to 12 carbon atoms.

16. The use according to any one of claims 1 to 4, wherein the quaternary nitrogen compound (B) is formed by adding a compound comprising at least one oxygen-containing or nitrogen-containing group reactive to an acid anhydride and at least one quaternizable amino group to a polycarboxylic acid anhydride compound, and subsequently quaternizing it in the presence of an acid or in the absence of an acid, using an epoxide or a carboxylic acid ester.

17. The use according to claim 16, wherein quaternization is carried out in the absence of free acid.

18. The use according to claim 16, wherein the epoxide is styrene oxide or propylene oxide.

19. The use according to claim 16, wherein the carboxylic ester is dimethyl oxalate or methyl salicylate.

20. The use according to any one of claims 1 to 4, wherein said quaternary nitrogen compound (B) has the following formula: Where in this formula PIB represents polyisobutylene residues with a number-average molecular weight (Mn) of 550 to 2300 g / mol. R represents C1- to C4-alkyl or hydroxy-C1- to C4-alkyl, and A - Represents anions.

21. The use according to claim 20, wherein PIB represents polyisobutylene residues with a number-average molecular weight Mn of 650 to 1500 g / mol.

22. The use according to claim 20, wherein PIB represents polyisobutylene residues with a number-average molecular weight Mn of 750 to 1300 g / mol.

23. The use according to claim 20, wherein R represents methyl or 2-hydroxypropyl.

24. The use according to claim 20, wherein A - Represents carboxylate R 5 COO - or carbonate R 5 O-COO - , where R 5 Organic residues, whether substituted or unsubstituted, have 1 to 100 carbon atoms.

25. The use according to claim 20, wherein A - It represents acetate or salicylate.

26. The use according to claim 20, wherein A - It represents methyl oxalate.

27. The use according to claim 24, wherein R 5 It is a substituted or unsubstituted cycloalkyl or aryl residue having 5 to 20 carbon atoms.

28. The use according to claim 24, wherein R 5 It is a substituted or unsubstituted cycloalkyl or aryl residue having 5 to 12 carbon atoms.

29. The use according to any one of claims 1 to 4, wherein the quaternary nitrogen compound (B) is of the following formula: Where in this formula PIB represents polyisobutylene residues with a number-average molecular weight (Mn) of 550 to 2300 g / mol. R represents hydroxyl-C1- to C4-alkyl.

30. The use according to claim 29, wherein PIB represents polyisobutylene residues with a number-average molecular weight Mn of 650 to 1500 g / mol.

31. The use according to claim 29, wherein PIB represents polyisobutylene residues with a number-average molecular weight Mn of 750 to 1300 g / mol.

32. The use according to claim 29, wherein R represents 2-hydroxypropyl.

33. The use according to any one of claims 1 to 4, wherein said quaternary nitrogen compound (B) has the following formula: Where in this formula PIB represents polyisobutylene residues with a number-average molecular weight (Mn) of 550 to 2300 g / mol. R represents C1- to C4-alkyl or hydroxy-C1- to C4-alkyl, and A - Represents anions.

34. The use according to claim 33, wherein PIB represents polyisobutylene residues with a number-average molecular weight Mn of 650 to 1500 g / mol.

35. The use according to claim 33, wherein PIB represents polyisobutylene residues with a number-average molecular weight Mn of 750 to 1300 g / mol.

36. The use according to claim 33, wherein R represents methyl.

37. The use according to claim 33, wherein A - Represents carboxylate R 5 COO - or carbonate R 5 O-COO - , where R 5 Organic residues, whether substituted or unsubstituted, have 1 to 100 carbon atoms.

38. The use according to claim 33, wherein A - It represents salicylate.

39. The use according to claim 33, wherein A - It represents methyl oxalate.

40. The use according to claim 37, wherein R 5 It is a substituted or unsubstituted cycloalkyl or aryl residue having 5 to 20 carbon atoms.

41. The use according to claim 37, wherein R 5 It is a substituted or unsubstituted cycloalkyl or aryl residue having 5 to 12 carbon atoms.

42. The use according to any one of claims 1 to 4, wherein the quaternary nitrogen compound (B) is of the following formula: Where in this formula R a Representing C1-C 20 -alkyl R b Represents hydroxy-C1- to C4-alkyl, and A - Represents anions.

43. The use according to claim 42, wherein R a Representing C9 to C 17 -alkyl.

44. The use according to claim 42, wherein R a It represents undecyl, tridecyl, pentadecyl, or heptadecanyl.

45. The use according to claim 42, wherein R b It represents 2-hydroxypropyl or 2-hydroxybutyl.

46. ​​The use according to claim 42, wherein A - Represents carboxylate R 5 COO - , where R 5 Organic residues, whether substituted or unsubstituted, have 1 to 100 carbon atoms.

47. The use according to claim 46, wherein R 5 COO - It is the carboxyl group of fatty acids.

48. The use according to claim 42, wherein A - It is acetate, 2-ethylhexanoate, oleate or polyisobutylene succinate.

49. The use according to claim 46, wherein R 5 It is a substituted or unsubstituted cycloalkyl or aryl residue having 5 to 20 carbon atoms.

50. The use according to claim 46, wherein R 5 It is a substituted or unsubstituted cycloalkyl or aryl residue having 5 to 12 carbon atoms.

51. The use according to any one of claims 1 to 4, wherein said quaternary nitrogen compound (B) has the following formula: Where in this formula For X i = 1 to n and 1 to m i They are independently selected from -CH2-CH2-O-, -CH2-CH(CH3)-O-, -CH(CH3)-CH2-O-, -CH2-C(CH3)2-O-, -C(CH3)2-CH2-O-, -CH2-CH(C2H5)-O-, -CH(C2H5)-CH2-O- and -CH(CH3)-CH(CH3)-O-. m and n are independent positive integers, provided that the sum (m+n) is between 2 and 50. R represents C1- to C4-alkyl, and A - Represents anions.

52. The use according to claim 51, wherein for X = 1 to n and 1 to m i They are independently selected from -CH2-CH(CH3)-O-, -CH(CH3)-CH2-O-, -CH2-C(CH3)2-O-, -C(CH3)2-CH2-O-, -CH2-CH(C2H5)-O-, -CH(C2H5)-CH2-O- and -CH(CH3)-CH(CH3)-O-.

53. The use of claim 51, wherein for X = 1 to n and 1 to m i They are independently selected from -CH2-CH(CH3)-O-, -CH(CH3)-CH2-O-, -CH2-C(CH3)2-O-, -C(CH3)2-CH2-O-, -CH2-CH(C2H5)-O- and -CH(C2H5)-CH2-O-.

54. The use of claim 51, wherein for X = 1 to n and 1 to m i They are independently selected from -CH2-CH(C2H5)-O-, -CH(C2H5)-CH2-O-, -CH2-CH(CH3)-O- and -CH(CH3)-CH2-O-.

55. The use of claim 51, wherein for X = 1 to n and 1 to m i They are independently selected from -CH2-CH(CH3)-O- and -CH(CH3)-CH2-O-.

56. The use according to claim 51, wherein the sum (m+n) is 5 to 40.

57. The use according to claim 51, wherein the sum (m+n) is 10 to 30.

58. The use according to claim 51, wherein the sum (m+n) is 15 to 25.

59. The use according to claim 51, wherein R represents methyl.

60. The use according to claim 51, wherein A - Represents carboxylate R 5 COO - or carbonate R 5 O-COO - , where R 5 Organic residues, whether substituted or unsubstituted, have 1 to 100 carbon atoms.

61. The use according to claim 51, wherein A - It represents salicylate.

62. The use according to claim 51, wherein A - It represents methyl oxalate.

63. The use according to claim 60, wherein R 5 It is a substituted or unsubstituted cycloalkyl or aryl residue having 5 to 20 carbon atoms.

64. The use according to claim 60, wherein R 5 It is a substituted or unsubstituted cycloalkyl or aryl residue having 5 to 12 carbon atoms.

65. The use according to any one of claims 1 to 4, wherein the quaternary nitrogen compound (B) has the following formula: Where in this formula R a and R b Each represents C1-C independently. 20 -alkyl or hydroxy-C1- to C4-alkyl, A - Represents anions.

66. The use according to claim 65, wherein R a Represents ethyl, n-butyl, n-octyl, n-dodecyl, tetradecyl, or hexadecyl.

67. The use according to claim 65, wherein R b It represents 2-hydroxypropyl.

68. The use according to claim 65, wherein A - Represents carboxylate R 5 COO - or carbonate R 5 O-COO - , where R 5 Organic residues, whether substituted or unsubstituted, have 1 to 100 carbon atoms.

69. The use according to claim 65, wherein A - Representing C 12 -C 100 -alkyl- and -alkenyl succinic acids.

70. The use according to claim 65, wherein A - It represents dodecenylsuccinate, hexadecenylsuccinate, eicoseneylsuccinate, and polyisobutyleneylsuccinate.

71. The use according to claim 68, wherein R 5 It is a substituted or unsubstituted cycloalkyl or aryl residue having 5 to 20 carbon atoms.

72. The use according to claim 68, wherein R 5 It is a substituted or unsubstituted cycloalkyl or aryl residue having 5 to 12 carbon atoms.

73. The use according to any one of claims 1 to 4, wherein the polyisobutylene succinimide (G) has the following formula: Where in this formula PIB represents polyisobutylene residues with a number-average molecular weight (Mn) of 550 to 2300 g / mol. n represents a positive integer from 2 to 6.

74. The use according to claim 73, wherein PIB represents polyisobutylene residues with a number-average molecular weight Mn of 650 to 1500 g / mol.

75. The use according to claim 73, wherein PIB represents polyisobutylene residues with a number-average molecular weight Mn of 750 to 1300 g / mol.

76. The use according to claim 73, wherein n represents 2 to 5.

77. The use according to claim 73, wherein n represents 3 or 4.

78. The use according to any one of claims 1 to 4, wherein the mixture of (A) and (B) or (G) is applied together with at least one anti-misting agent as an additive component (C), said additive component (C) being selected from... (C1) Alkoxylated copolymers of ethylene oxide, propylene oxide, butane oxide, styrene oxide and / or other oxides; (C2) Alkoxylated phenolic resin.

79. The use according to claim 78, wherein (C1) is an epoxy resin.

80. The use according to any one of claims 1 to 4, wherein the mixture of (A) and (B) or (G) is applied together with at least one organic nitrate as an additive cetane number improver (D).

81. A method for improving the stability of a cleaning additive in a fuel additive package by applying at least one olefin-carboxylic acid copolymer (A) with a number-average molecular weight Mn of 0.5 to 10 kDa—determined by gel permeation chromatography using tetrahydrofuran and polystyrene as standards. The olefin-carboxylic acid copolymer (A) is obtained through the following steps: - In the first reaction step (I), the following substances are copolymerized: (Aa) At least one olefinically unsaturated monocarboxylic acid or dicarboxylic acid or its anhydride. (Ab) At least one α-alkene having at least 12 and at most 30 carbon atoms, (Ac) optionally at least one other aliphatic or cycloaliphatic olefin having at least 4 carbon atoms and different from (Ab), and (Ad) There are no one or more copolymerizable monomers other than monomers (Aa), (Ab), and (Ac), which are selected from... (Ada) vinyl ester, (Adb) vinyl ether, (Adc) (meth)acrylates of alcohols having at least 5 carbon atoms. (Add) Allyl alcohol or its ether, (Ade) N-vinyl compounds, selected from vinyl compounds containing at least one nitrogen atom in a heterocyclic ring, N-vinylamides, or N-vinyl lactams. (Adf) olefinic unsaturated aromatic compounds, (Adg) α,β-olefinic unsaturated nitrile, (Adh) (methyl)acrylamide and (Adi) allylamine, Subsequently - In a second optional reaction step (II), the anhydride or carboxylic acid ester functional groups present in the copolymer obtained by (I) are partially or completely hydrolyzed and / or saponified, the second reaction step being carried out at least when the copolymer obtained by reaction step (I) does not contain any free carboxylic acid functional groups. The additive package contains at least one additive with cleaning properties, selected from... - Quaternary nitrogen compounds (B) and - Polyisobutylene succinimide (G) The olefin-carboxylic acid copolymer (A) is 0.01 to 40% by weight, and the at least one cleaning additive is 5 to 40% by weight, based on the weight of the fuel additive package.

82. The use according to claim 81, wherein the monomer (Aa) is at least one olefinically unsaturated dicarboxylic acid or its anhydride.

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