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  • C10L10/00—Use of additives to fuels or fires for particular purposes
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  • C10L1/183—Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom
  • C10L1/1832—Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom mono-hydroxy
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  • C10L1/00—Liquid carbonaceous fuels
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  • C10L1/192—Macromolecular compounds
  • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • C10L1/196—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof
  • C10L1/1966—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof poly-carboxylic
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  • C10L1/192—Macromolecular compounds
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  • C10L1/197—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid
  • C10L1/1973—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid mono-carboxylic
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  • C10L1/00—Liquid carbonaceous fuels
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  • C10L1/18—Organic compounds containing oxygen
  • C10L1/192—Macromolecular compounds
  • C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
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  • C10L1/00—Liquid carbonaceous fuels
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  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
  • C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
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  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
  • C10L1/223—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond having at least one amino group bound to an aromatic carbon atom
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  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
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  • C10L1/232—Organic compounds containing nitrogen containing nitrogen in a heterocyclic ring
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  • C10L1/00—Liquid carbonaceous fuels
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  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/232—Organic compounds containing nitrogen containing nitrogen in a heterocyclic ring
  • C10L1/233—Organic compounds containing nitrogen containing nitrogen in a heterocyclic ring containing nitrogen and oxygen in the ring, e.g. oxazoles
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  • C10L1/00—Liquid carbonaceous fuels
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  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/234—Macromolecular compounds
  • C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
  • C10L1/2362—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing nitrile groups
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  • C10L1/234—Macromolecular compounds
  • C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
  • C10L1/2364—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing amide and/or imide groups
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  • C10L1/00—Liquid carbonaceous fuels
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  • C10L1/234—Macromolecular compounds
  • C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
  • C10L1/2366—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing amine groups
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  • C10L1/234—Macromolecular compounds
  • C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
  • C10L1/2368—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing heterocyclic compounds containing nitrogen in the ring
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  • C10L1/00—Liquid carbonaceous fuels
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  • C10L1/234—Macromolecular compounds
  • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
  • C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)
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  • C10L2200/00—Components of fuel compositions
  • C10L2200/04—Organic compounds
  • C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
  • C10L2200/0438—Middle or heavy distillates, heating oil, gasoil, marine fuels, residua
  • C10L2200/0446—Diesel
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  • C10L2200/00—Components of fuel compositions
  • C10L2200/04—Organic compounds
  • C10L2200/0461—Fractions defined by their origin
  • C10L2200/0469—Renewables or materials of biological origin
  • C10L2200/0476—Biodiesel, i.e. defined lower alkyl esters of fatty acids first generation biodiesel
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  • C10L2230/00—Function and purpose of a components of a fuel or the composition as a whole
  • C10L2230/08—Inhibitors
  • C10L2230/081—Anti-oxidants
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  • C10L2230/00—Function and purpose of a components of a fuel or the composition as a whole
  • C10L2230/22—Function and purpose of a components of a fuel or the composition as a whole for improving fuel economy or fuel efficiency
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  • C10L2270/00—Specifically adapted fuels
  • C10L2270/02—Specifically adapted fuels for internal combustion engines
  • C10L2270/026—Specifically adapted fuels for internal combustion engines for diesel engines, e.g. automobiles, stationary, marine

Definitions

• the present invention relates to compositions for improving the stability of fuels containing biofuel oils, as well as fuels containing biofuel oils additives therewith, especially diesel fuels.
• Quaternary nitrogen compounds are known to be effective as additives in fuels, especially diesel fuels, and to remove deposits.
• WO 18/114348 describes the improvement of the thermal stability of diesel fuels containing fatty acid alkyl esters with copolymers, as in WO 15/113681 Quaternary nitrogen compounds are generally described here as additives to fuels, but it is not recognized that these quaternary nitrogen compounds are a cause for the reduction of the thermal stability of the fuels.
• the object of the present invention is to improve the stability, especially the thermal stability, of fuels, especially diesel fuels, especially those containing biofuel oils, in the presence of quaternary nitrogen compounds.
• diesel fuels require a thermal or oxidation stability of at least 20 hours, measured as text according to DIN EN 15751.
• FAME fatty acid methyl esters
• Fuel decomposition occurs at locations where the fuel is exposed to oxygen and/or elevated temperature, often catalyzed by metal surfaces. Such conditions often exist within the high-pressure injection system, where elevated temperatures of up to 120 °C and higher can be reached.
• injection system is understood to mean the part of the fuel system in motor vehicles from the fuel pump up to and including the injector outlet.
• fuel system is understood to mean the components of motor vehicles that are in contact with the respective fuel, preferably the area from the tank up to and including the injector outlet.
• One embodiment of the present invention is that the compounds according to the invention act against deposits not only in the injection system, but also in the rest of the fuel system, in particular against deposits in fuel filters and pumps.
• Such copolymers have been found to be effective in improving the stability of fuels containing quaternary nitrogen compounds, particularly diesel fuels, and especially diesel fuels containing biofuel oils.
• the use according to the invention improves the stability of such fuels against oxidation or against thermal stress or against both.
• the copolymers are combined with at least one antioxidant, preferably at least one antioxidant selected from the group consisting of phenols and diarylamines, particularly preferably at least one phenol, very particularly preferably at least one sterically hindered phenol.
• at least one antioxidant selected from the group consisting of phenols and diarylamines, particularly preferably at least one phenol, very particularly preferably at least one sterically hindered phenol.
• copolymers are particularly characterized by their effectiveness against oxidation and/or thermal stress on fuels, which cause various deposits in the fuel and/or injection system that impair the performance of modern diesel engines.
• the monomer (A) is at least one, preferably one to three, particularly preferably one or two and very particularly preferably exactly one ethylenically unsaturated, preferably ⁇ , ⁇ -ethylenically unsaturated mono- or dicarboxylic acid or derivatives thereof, preferably a dicarboxylic acid or derivatives thereof, particularly preferably the anhydride of a dicarboxylic acid, very particularly preferably maleic anhydride.
• the derivatives are preferably anhydrides in monomeric form or di-C 1 -C 4 -alkyl esters, particularly preferably anhydrides in monomeric form.
• C 1 -C 4 alkyl means methyl, ethyl, iso -propyl, n-propyl, n-butyl, iso -butyl, sec -butyl and tert -butyl, preferably methyl and ethyl, particularly preferably methyl.
• the ⁇ , ⁇ -ethylenically unsaturated mono- or dicarboxylic acid is a mono- or dicarboxylic acid or its derivatives in which the carboxyl group or, in the case of dicarboxylic acids, at least one carboxyl group, preferably both carboxyl groups, are conjugated with the ethylenically unsaturated double bond.
• Examples of ethylenically unsaturated mono- or dicarboxylic acids that are not ⁇ , ⁇ -ethylenically unsaturated 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.
• ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acids are acrylic acid, methacrylic acid, crotonic acid and ethylacrylic acid, preferably acrylic acid and methacrylic acid, referred to in this document as (meth)acrylic acid for short, and particularly preferably acrylic acid.
• Particularly preferred derivatives of ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acids are methyl acrylate, ethyl acrylate, n-butyl acrylate and methyl methacrylate.
• dicarboxylic acids examples include maleic acid, fumaric acid, itaconic acid (2-methylenebutanedioic acid), citraconic acid (2-methylmaleic acid), glutaconic acid (pent-2-ene-1,5-dicarboxylic acid), 2,3-dimethylmaleic acid, 2-methylfumaric acid, 2,3-dimethylfumaric acid, methylenemalonic acid and tetrahydrophthalic acid, preferably maleic acid and fumaric acid and particularly preferably maleic acid and its derivatives.
• the monomer (A) is maleic anhydride.
• the monomer (B) is at least one, preferably one to four, particularly preferably one to three, very particularly preferably one or two and in particular exactly one ⁇ -olefin having at least 12 up to 30 carbon atoms inclusive.
• the ⁇ -olefins (B) preferably have at least 14, particularly preferably at least 16 and very particularly preferably at least 18 carbon atoms.
• the ⁇ -olefins (B) preferably have up to 28, particularly preferably up to 26 and very particularly preferably up to 24 carbon atoms inclusive.
• the ⁇ -olefins can preferably be linear or branched, preferably linear 1-alkenes.
• Examples are 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonodecene, 1-eicosene, 1-docosene, 1-tetracosene, 1-hexacosene, of which 1-octadecene, 1-eicosene, 1-docosene and 1-tetracosene, as well as mixtures thereof, are preferred.
• ⁇ -olefins (B) are those olefins which are oligomers or polymers of C 2 - to C 12 -olefins, preferably of C 3 - to C 10 -olefins, particularly preferably of C 4 - to C 6 -olefins.
• examples of these are ethene, propene, 1-butene, 2-butene, isobutene, pentene isomers and hexene isomers, preference being given to ethene, propene, 1-butene, 2-butene and isobutene.
• ⁇ -olefins (B) are oligomers and polymers of propene, 1-butene, 2-butene, isobutene, and mixtures thereof, particularly oligomers and polymers of propene or isobutene or of mixtures of 1-butene and 2-butene.
• oligomers trimers, tetramers, pentamers and hexamers and mixtures thereof are preferred.
• At least one, preferably one to four, particularly preferably one to three, very particularly preferably one or two and in particular exactly one further aliphatic or cycloaliphatic Olefin (C) other than (B) may be polymerized into the copolymer of the invention.
• the olefins (C) can be olefins with a terminal ( ⁇ -) double bond or those with a non-terminal double bond, preferably with an ⁇ -double bond.
• the olefin (C) is preferably an olefin with 4 to less than 12 or more than 30 carbon atoms. If the olefin (C) is an olefin with 12 to 30 carbon atoms, this olefin (C) does not have an ⁇ -position double bond.
• Examples of aliphatic olefins (C) are 1-butene, 2-butene, isobutene, pentene isomers, hexene isomers, heptene isomers, octene isomers, nonene isomers, decene isomers, undecene isomers and mixtures thereof.
• cycloaliphatic olefins are cyclopentene, cyclohexene, cyclooctene, cyclodecene, cyclododecene, ⁇ - or ⁇ -pinene and their mixtures, limonene and norbornene.
• olefins (C) are polymers of propene, 1-butene, 2-butene or isobutene having more than 30 carbon atoms or olefin mixtures containing such, preferably of isobutene or olefin mixtures containing such, particularly preferably having an average molecular weight M w in the range from 500 to 5000 g/mol, preferably 650 to 3000, particularly preferably 800 to 1500 g/mol.
• the oligomers or polymers containing isobutene in polymerized form preferably have a high content of terminally arranged ethylenic double bonds ( ⁇ -double bonds), for example at least 50 mol%, preferably at least 60 mol%, particularly preferably at least 70 mol% and very particularly preferably at least 80 mol%.
• both pure isobutene and isobutene-containing C4 hydrocarbon streams are suitable as isobutene sources, for example C4 raffinates, in particular "raffinate 1", C4 cuts from isobutane dehydrogenation, C4 cuts from steam crackers and from FCC crackers (fluid catalyzed cracking), provided they are largely freed of the 1,3-butadiene contained therein.
• a C4 hydrocarbon stream from an FCC refinery unit is also known as a "b/b" stream.
• Suitable isobutene-containing C4 hydrocarbon streams are, for example, the product stream from a propylene-isobutane cooxidation or the product stream from a metathesis unit, which are generally used after conventional purification and/or concentration.
• Suitable C4 hydrocarbon streams generally contain less than 500 ppm, preferably less than 200 ppm, of butadiene.
• the presence of 1-butene and of cis- and trans-2-butene is largely uncritical.
• the isobutene concentration in the C4 hydrocarbon streams mentioned is in the range from 40 to 60% by weight.
• raffinate 1 generally consists essentially of 30 to 50% by weight of isobutene, 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 butanes; in the polymerization process according to the invention, the unbranched butenes in the raffinate 1 are generally practically inert and only the isobutene is polymerized.
• the monomer source for the polymerization used is a technical C4 hydrocarbon stream having an isobutene content of 1 to 100% by weight, in particular 1 to 99% by weight, especially 1 to 90% by weight, particularly preferably 30 to 60% by weight, in particular a raffinate 1 stream, a b/b stream from an FCC refinery unit, a product stream from a propylene-isobutane cooxidation or a product stream from a metathesis unit.
• water as the sole or additional initiator has proven particularly useful when using a raffinate 1 stream as an isobutene source, particularly when polymerizing at temperatures of -20°C to +30°C, in particular 0°C to +20°C.
• temperatures of -20°C to +30°C, in particular 0°C to +20°C the use of an initiator can be dispensed with when using a raffinate 1 stream as an isobutene source.
• the isobutene-containing monomer mixture mentioned can contain small amounts of contaminants such as water, carboxylic acids or mineral acids without causing critical losses in yield or selectivity. It is expedient to avoid an accumulation of these contaminants by removing such pollutants from the isobutene-containing monomer mixture, for example by adsorption on solid adsorbents such as activated carbon, molecular sieves or ion exchangers.
• monomer mixtures of isobutene or of the isobutene-containing hydrocarbon mixture can also be reacted with olefinically unsaturated monomers which are copolymerizable with isobutene.
• the monomer mixture preferably contains at least 5% by weight, particularly preferably at least 10% by weight and in particular at least 20% by weight of isobutene, and preferably at most 95% by weight, particularly preferably at most 90% by weight and in particular at most 80% by weight of comonomers.
• the mixture of olefins (B) and optionally (C) has, on average based on their molar amounts, at least 12 carbon atoms, preferably at least 14, particularly preferably at least 16 and very particularly preferably at least 17 carbon atoms.
• the upper limit is less relevant and is generally not more than 60 carbon atoms, preferably not more than 55, particularly preferably not more than 50, most particularly preferably not more than 45 and in particular not more than 40 carbon atoms.
• vinyl esters (Da) are vinyl esters of C 2 - to C 12 -carboxylic acids, preferably vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pentanoate, vinyl hexanoate, vinyl octanoate, vinyl 2-ethylhexanoate, vinyl decanoate, and vinyl esters of Versatic acids 5 to 10, preferably vinyl esters of 2,2-dimethylpropionic acid (pivalic acid, Versatic acid 5), 2,2-dimethylbutyric acid (neohexanoic acid, Versatic acid 6), 2,2-dimethylpentanoic acid (neoheptanic acid, Versatic acid 7), 2,2-dimethylhexanoic acid (neooctanoic acid, Versatic acid 8), 2,2-dimethylheptanoic acid (neononanoic acid, Versatic acid 9) or 2,2-dimethyloctanoic acid (neodecanoic acid, Versatic acids
• vinyl ethers (Db) are vinyl ethers of C 1 - to C 12 -alkanols, preferably vinyl ethers of methanol, ethanol, iso -propanol, n-propanol, n-butanol, iso -butanol, sec -butanol, tert -butanol, n-hexanol, n-heptanol, n-octanol, n-decanol, n-dodecanol (lauryl alcohol) or 2-ethylhexanol.
• Preferred (meth)acrylic acid esters (Dc) are (meth)acrylic acid esters of C 5 - to C 12 -alkanols, preferably of n-pentanol, n-hexanol, n-heptanol, n-octanol, n-decanol, n-dodecanol (lauryl alcohol), 2-ethylhexanol or 2-propylheptanol. Particularly preferred are pentyl acrylate, 2-ethylhexyl acrylate and 2-propylheptyl acrylate.
• Examples of monomers (Dd) are allyl alcohols and allyl ethers of C 2 - to C 12 -alkanols, preferably allyl ethers of methanol, ethanol, iso -propanol, n-propanol, n-butanol, iso -butanol, sec -butanol, tert -butanol, n-hexanol, n-heptanol, n-octanol, n-decanol, n-dodecanol (lauryl alcohol) or 2-ethylhexanol.
• Examples of vinyl compounds (De) of heterocycles containing at least one nitrogen atom are N-vinylpyridine, N-vinylimidazole and N-vinylmorpholine.
• Preferred monomers (D) are (Da), (Db), (Dc), (De) and/or (Df), particularly preferably (Da), (Db) and/or (Dc), very particularly preferably (Da) and/or (Dc) and in particular (Dc).
• the incorporation ratio of the monomers (A) and (B) and optionally (C) and optionally (D) in the copolymer obtained from reaction step (I) is generally as follows:
• the molar ratio of (A) / ((B) and (C)) (in total) is generally from 10:1 to 1:10, preferably 8:1 to 1:8, particularly preferably 5:1 to 1:5, very particularly preferably 3:1 to 1:3, in particular 2:1 to 1:2 and especially 1.5:1 to 1:1.5.
• the molar incorporation ratio of maleic anhydride to monomers ((B) and (C)) (in total) is about 1:1.
• maleic anhydride in a slight excess over the ⁇ -olefin, for example 1.01 - 1.5:1, preferably 1.02 - 1.4:1, particularly preferably 1.05 - 1.3:1, very particularly preferably 1.07 - 1.2:1 and in particular 1.1 - 1.15:1.
• the molar ratio of the obligate monomer (B) to the monomer (C), if present, is generally from 1:0.05 to 10, preferably from 1:0.1 to 6, particularly preferably from 1:0.2 to 4, very particularly preferably from 1:0.3 to 2.5 and especially 1:0.5 to 1.5.
• no optional monomer (C) is present in addition to monomer (B).
• the proportion of one or more of the monomers (D), if present, based on the amount of the monomers (A), (B) and optionally (C) (in total) is generally 5 to 200 mol%, preferably 10 to 150 mol%, particularly preferably 15 to 100 mol%, very particularly preferably 20 to 50 mol% and in particular 0 to 25 mol%.
• no optional monomer (D) is present.
• the copolymer consists of the monomers (A) and (B).
• a second reaction step (II) the anhydride or carboxylic acid ester functionalities contained in the copolymer obtained from (I) are partially or completely hydrolyzed and/or saponified.
• the anhydride functionalities contained in the copolymer after reaction step (II) are essentially completely hydrolyzed.
• the amount of water corresponding to the desired degree of hydrolysis is added based on the anhydride functionalities present and the copolymer obtained from (I) is heated in the presence of the added water.
• a temperature of preferably 20 to 150°C is sufficient for this, preferably 60 to 100°C.
• the reaction can be carried out under pressure to prevent the escape of water. Under these reaction conditions, the anhydride functionalities in the copolymer are generally reacted selectively, whereas any carboxylic acid ester functionalities present in the copolymer do not react or at least react only to a minor extent.
• the copolymer is reacted with an amount of a strong base in the presence of water that corresponds to the desired degree of saponification.
• Hydroxides, oxides, carbonates or hydrogen carbonates of alkali or alkaline earth metals can preferably be used as strong bases.
• the copolymer obtained from (I) is then heated in the presence of the added water and the strong base.
• a temperature of preferably 20 to 130°C is sufficient, preferably 50 to 110°C. If necessary, the reaction can be carried out under pressure.
• the acids used are preferably mineral, carboxylic, sulfonic or phosphorus-containing acids with a pKa value of not more than 5, particularly preferably not more than 4.
• acetic acid formic acid, oxalic acid, salicylic acid, substituted succinic acids, aromatic-substituted or unsubstituted benzenesulfonic acids, sulfuric acid, nitric acid, hydrochloric acid or phosphoric acid; the use of acidic ion exchange resins is also conceivable.
• the copolymer obtained from (I) is then heated in the presence of the added water and the acid.
• a temperature of preferably 40 to 200°C is sufficient, preferably 80 to 150°C. If necessary, the reaction can be carried out under pressure.
• the copolymers obtained from step (II) still contain residues of acid anions, it may be preferable to remove these acid anions from the copolymer using an ion exchanger and to exchange them preferably for hydroxide ions or carboxylate ions, particularly preferably hydroxide ions. This is particularly the case if the acid anions contained in the copolymer are halides, sulfur-containing or nitrogen-containing.
• the copolymer obtained from reaction step (II) generally has a weight-average molecular weight Mw of 0.5 to 20 kDa, preferably 0.6 to 15, particularly preferably 0.7 to 7, very particularly preferably 1 to 7 and in particular 1.5 to 54 kDa (determined by gel permeation chromatography with tetrahydrofuran and polystyrene as standard).
• the number average molecular weight Mn is usually from 0.5 to 10 kDa, preferably 0.6 to 5, particularly preferably 0.7 to 4, very particularly preferably 0.8 to 3 and in particular 1 to 2 kDa (determined by gel permeation chromatography with tetrahydrofuran and polystyrene as standard).
• the polydispersity is generally from 1 to 10, preferably from 1.1 to 8, particularly preferably from 1.2 to 7, very particularly preferably from 1.3 to 5 and in particular from 1.5 to 3.
• the content of free acid groups in the copolymer after passing through reaction step (II) is preferably from 1 to 8 mmol/g copolymer, particularly preferably from 2 to 7 and very particularly preferably from 3 to 7 mmol/g copolymer.
• the copolymers contain a high proportion of neighboring carboxylic acid groups, which is determined by measuring the adjacency. For this purpose, a sample of the copolymer is heated between two Teflon foils at a temperature of 290 °C for 30 minutes and an FTIR spectrum is recorded at a bubble-free point. The IR spectrum of Teflon is subtracted from the resulting spectra, the layer thickness is determined and the content of cyclic anhydride is determined.
• the adjacency is at least 10%, preferably at least 15%, particularly preferably at least 20%, most preferably at least 25% and in particular at least 30%.
• Quaternary nitrogen compounds reduce the stability of fuels containing such quaternary nitrogen compounds, especially their thermal stability.
• quaternary nitrogen compounds is to be interpreted broadly and includes those compounds in which at least one, preferably exactly one, nitrogen atom in the compound is tetravalent and thus carries a positive charge. Preferably, there are four bonds between the nitrogen and one carbon atom. Less preferred are therefore those compounds with a tetravalent nitrogen atom in which there is at least one bond between a nitrogen and a hydrogen atom, i.e. quaternization as a result of protonation.
• quaternary nitrogen compounds includes not only ammonium ions, but also those compounds in which the basic nitrogen atom is linked via a multiple bond or is part of a cyclic or aromatic system. Examples of these are quaternized nitrogen compounds in which the nitrogen compound has a pyrrole, pyridine, imidazole, imidazoline, pyrazole, benzimidazole, indole, quinoline, isoquinoline, purine, pyrimidine, oxazole, thiazole or 1,4-thiazine as a substructure.
• the quaternary nitrogen compounds are preferably nitrogen compounds that are obtainable in the presence of acid or acid-free by reaction with at least one quaternizing reagent, preferably obtainable by addition of an oxygen- or nitrogen-containing group that is reactive with an anhydride group and additionally at least one quaternizable amino group to a polycarboxylic acid anhydride and subsequent quaternization.
• the quaternary nitrogen atom is connected to other radicals, preferably to organic radicals, via four electron pair bonds.
• Preferred quaternary nitrogen compounds are ammonium compounds as well as morpholinium, piperidinium, piperazinium, pyrrolidinium, imidazolinium or pyridinium cations.
• the organic radicals R 1 to R 5 are preferably unsubstituted.
• the anion has multiple negative charges, e.g. when anions of di- or polybasic acids are used.
• the stoichiometric ratio of ammonium ions to anions corresponds to the ratio of positive and negative charges.
• the carbon atoms can be interrupted by one or more oxygen and/or sulfur and/or one or more substituted or unsubstituted imino groups and can optionally be substituted by C 6 -C 12 aryl, C 5 -C 12 cycloalkyl or a five- or six-membered, oxygen-, nitrogen-, sulfur- or nitrogen-containing heterocycle, or two of the radicals can together form an unsaturated, saturated or aromatic ring which can be interrupted by one or more oxygen and/or sulfur and/or one or more substituted or unsubstituted imino groups and can optionally be substituted, where said radicals can each be substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatom and/or heterocycles.
• Two of the radicals R 1 to R 4 can together form an unsaturated, saturated or aromatic ring, preferably a five-, six- or six-membered ring, including the nitrogen atom of the ammonium ion.
• ammonium ion can be a morpholinium, piperidinium, piperazinium, pyrrolidinium, imidazolinium or pyridinium cation.
• C 1 -C 20 alkyl which can optionally be substituted with functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and/or heterocycles, is e.g. methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, 2,4,4-trimethylpentyl, decyl, dodecyl, tetradecyl, heptadecyl, octadecyl, eicosyl, 1,1-dimethylpropyl, 1,1-dimethylbutyl, 1,1,3,3-tetramethylbutyl, benzyl, 1-phenylethyl, 2-phenylethyl, ⁇ , ⁇ -dimethylbenzyl,
• C 2 -C 20 alkyl which is interrupted by one or more oxygen and/or sulfur and/or one or more substituted or unsubstituted imino groups, e.g. 5-hydroxy-3-oxa-pentyl, 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-trioxapentadecyl, 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-4,8-dio
• two radicals together form a ring, they can together form 1,3-propylene, 1,4-butylene, 1,5-pentylene, 2-oxa-1,3-propylene, 1-oxa-1,3-propylene, 2-oxa-1,3-propylene, 1-oxa-1,3-propenylene, 1-aza-1,3-propenylene, 1-C 1 -C 4 -alkyl-1-aza-1,3-propenylene, 1,4-buta-1,3-dienylene, 1-aza-1,4-buta-1,3-dienylene or 2-aza-1,4-buta-1,3-dienylene.
• the number of oxygen and/or sulfur atoms and/or imino groups is not limited. In general, there are no more than five in the radical, preferably no more than four and particularly preferably no more than three.
• Substituted and unsubstituted imino groups can be, for example, imino, methylimino, iso-propylimino, n-butylimino or tert-butylimino.
• the radicals R 1 to R 5 are preferably C 2 -C 18 alkyl or C 6 -C 12 aryl, particularly preferably C 4 -C 16 alkyl or C 6 -C 12 aryl, and very particularly preferably C 4 -C 16 alkyl or C 6 aryl.
• the radicals R 1 to R 5 can be saturated or unsaturated, preferably saturated.
• Preferred radicals R 1 to R 5 are composed exclusively of carbon and hydrogen atoms.
• R 1 to R 4 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, heptadecyl, octadecyl, eicosyl, 1,1-dimethylpropyl, 1,1-dimethylbutyl, 1,1,3,3-tetramethylbutyl, benzyl, 1-phenylethyl, 2-phenylethyl, ⁇ , ⁇ -dimethylbenzyl, benzhydryl, p-tolylmethyl or 1-(p-butylphenyl)ethyl.
• At least one, preferably exactly one of the radicals R 1 to R 4 is selected from the group consisting of 2-hydroxyethyl, hydroxyprop-1-HI, hydroxyprop-2-yl, 2-hydroxybutyl and 2-hydroxy-2-phenylethyl.
• the radical R 5 is a polyolefin homo- or copolymer, preferably a polypropylene, polybutene or polyisobutene radical with a number average molecular weight (M n ) of 85 to 20,000, eg 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.
• M n number average molecular weight
• Bev are polypropenyl, polybutenyl and polyisobutenyl radicals, eg with an M n of 350 to 5,000, 350 to 3,000, 500 to 2,500, 700 to 2,500 and 800 to 1,500 g/mol.
• anions A - are the anions of acetic acid, propionic acid, butyric acid, 2-ethylhexanoic acid, trimethylhexanoic acid, 2-propylheptanoic acid, isononanoic acid, versatic acids, decanoic acid, undecanoic acid, dodecanoic acid, saturated or unsaturated fatty acids having 12 to 24 carbon atoms or mixtures thereof, also salicylic acid, oxalic acid mono-C 1 -C 4 alkyl esters, phthalic acid mono-C 1 -C 4 alkyl esters, C 12 -C 100 alkyl and alkenyl succinic acid, especially dodecenyl succinic acid, hexadecenyl succinic acid, eicosenyl succinic acid and polyisobutenyl succinic acid. Further examples are methyl carbonates, ethyl carbonates, n-butyl carbonates, 2-hydroxyethyl carbon
• the nitrogen compounds are quaternized in the presence of an acid or in an acid-free reaction and are obtainable by addition of a compound which contains at least one oxygen- or nitrogen-containing group which is reactive with an anhydride group and additionally at least one quaternizable amino group to a polycarboxylic acid anhydride and subsequent quaternization, especially with an epoxide, as described in WO 2012/004300 , or with a carboxylic acid ester, e.g. dimethyl oxalate or methyl salicylate.
• Suitable compounds which contain at least one oxygen- or nitrogen-containing group are particularly polyamines which contain at least one primary or secondary amino group and at least one tertiary amino group, preferably N,N-dimethyl-1,3-propanediamine, N,N-dimethyl-1,2-ethanediamine or N,N,N'-trimethyl-1,2-ethanediamine.
• Useful polycarboxylic acid anhydrides are particularly dicarboxylic acid anhydrides, such as succinic anhydride, which carries a relatively long-chain hydrocarbyl substituent, preferably those with a number-average molecular weight Mn of the hydrocarbyl substituent of 200 to 10,000, in particular of 350 to 5,000.
• Such quaternized nitrogen compounds are, for example, the reaction product obtainable at 40 °C of polyisobutenesuccinic acid, in which the polyisobutenyl radical has a Mn of 1000, with 3-(dimethylamino)propylamine, to form a reaction mixture containing polyisobutenylsuccinic acid monoamide, which is subsequently quaternized with dimethyl oxalate or methyl salicylate or with styrene oxide or propylene oxide in the absence of free acid.
• quaternary ammonium compounds satisfy the formula where in this formula PIB stands for a polyisobutenyl radical having a number-average molecular weight M n of 550 to 2300, preferably 650 to 1500 and particularly preferably 750 to 1300 g/mol, and R stands for hydroxy-C 1 - to C 4 -alkyl, preferably 2-hydroxypropyl.
• PIB stands for a polyisobutenyl radical having a number-average molecular weight M n of 550 to 2300, preferably 650 to 1500 and particularly preferably 750 to 1300 g/mol
• R stands for hydroxy-C 1 - to C 4 -alkyl, preferably 2-hydroxypropyl.
• quaternary ammonium compounds satisfy the formula where in this formula R a and R b independently of one another represent C 1 -C 20 alkyl or hydroxy-C 1 -C 4 alkyl, preferably R a represents C 1 -C 20 alkyl, preferably ethyl, n-butyl, n-octyl, n-dodecyl, tetradecyl or hexadecyl, and R b represents hydroxy-C 1 -C 4 alkyl, preferably 2-hydroxypropyl, A - represents an anion, preferably carboxylate R 5 COO - or a carbonate R 5 O-COO - as defined above, particularly preferably the anions of C 12 -C 100 alkyl and alkenyl succinic acid, in particular dodecenyl succinic acid, hexadecenyl succinic acid, eicosenyl succinic acid, and polyisobut
• the quaternary nitrogen compounds are generally added to the fuel in amounts of 10 to 1000, preferably 15 to 500, particularly preferably 20 to 250 ppm by weight.
• the effect of the quaternary nitrogen compounds, e.g. against deposits, is known.
• the stabilizing effect of the copolymer on the fuel is enhanced by at least one antioxidant selected from the group consisting of phenols and diarylamines, preferably at least one phenol.
• Antioxidants are usually understood by experts to be compounds that capture radicals.
• phenols are alkylphenols, for example o-, m- or p-cresol (methylphenol), 2-tert-butyl-4-methylphenol, 6-tert-butyl-2,4-dimethylphenol, 2,6-di-tert-butyl-4-methylphenol, 2-tert-butylphenol, 4-tert-butylphenol, 2,4-di-tert-butylphenol, 2-methyl-4-tert-butylphenol, 4-tert-butyl-2,6-dimethylphenol, or 2,2'-methylene-bis-(6-tert-butyl-4-methylphenol), 4,4'-oxydiphenyl, 3,4-methylenedioxydiphenol (sesamol), 3,4-dimethylphenol, hydroquinone, pyrocatechol (1,2-dihydroxybenzene), 2-(1'-methylcyclohex-1'-yl)-4,6-dimethylphenol, 2- or 4-(1'-phenyl-eth-1'-yl
• -butyl-4'-hydroxy-2'-methyl-phen-1'-yl)butane aminophenols, such as para-aminophenol, 3-diethylaminophenol, nitrosophenols, such as para-nitrosophenol, p-nitroso-o-cresol, alkoxyphenols, for example 2-methoxyphenol (guaiacol, catechol monomethyl ether), 2-ethoxyphenol, 2-Isopropoxyphenol, 4-methoxyphenol (hydroquinone monomethyl ether), mono- or di-tert-butyl-4-methoxyphenol, 3,5-di-tert-butyl-4-hydroxyanisole, 3-hydroxy-4-methoxybenzyl alcohol, 2,5-dimethoxy-4-hydroxybenzyl alcohol (syringa alcohol), 4-hydroxy-3-methoxybenzaldehyde (vanillin), 4-hydroxy-3-ethoxybenzaldehyde (ethylvanillin), 3-hydroxy-4-methoxybenzaldehyde (is
• phenols which have exactly one phenolic hydroxy group on the aromatic ring and particularly preferably those which have any substituent, preferably an alkyl group, in the ortho position, very particularly preferably in the ortho and para positions to the phenolic hydroxy group.
• Such phenols can also be components of a polyphenolic system with several phenol groups such as pentaerythritol tetrakis [ ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (e.g. Irganox ® 1010), Irganox ® 1330, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (e.g. Irganox ® 3114), all products of BASF.
• pentaerythritol tetrakis [ ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] e.g. Irganox ® 1010
• Irganox ® 1330 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenz
• Corresponding products are available, for example, under the trade names Irganox ® (BASF), Sumilizer ® from Sumitomo, Lowinox ® from Great Lakes, Cyanox ® from Cytec.
• Irganox ® BASF
• Sumilizer ® from Sumitomo
• Lowinox ® from Great Lakes
• Cyanox ® from Cytec.
• thiodiethylene bis[3-[3,5-di-tert.-butyl-4-hydroxyphenyl]propionate] (Irganox ® 1035) and 6,6'-di-tert.-butyl-2,2'-thiodi-p-cresol (eg Irganox ® 1081), both products of BASF.
• BHT 2,6-di-tert-butyl-4-methylphenol
• Irganox ® 1135 isooctyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate
• Irganox ® 1076 isooctadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate
• pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate CAS No. 6683-19-8 ; e.g. Irganox ® 1010).
• At least one sterically hindered phenol and/or aminophenol, preferably at least one sterically hindered phenol, is added to the fuel.
• alkyl radicals having 1 to 20 carbon atoms alkenyl radicals having 2 to 20 carbon atoms and alkyl radicals having 4 to 16 carbon atoms correspond to the definitions and individuals listed for the diphenylamines.
• Preferred radicals R 10 , R 11 and R 12 are independently of one another methyl, ethyl, iso -propyl, iso- butyl, tert -butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-decyl, 2-propylheptyl, n-dodecyl, n-tetradecyl or n-hexadecyl, particular preference being given to methyl, iso -propyl, tert -butyl and 2-ethylhexyl and very particular preference being given to methyl and tert-butyl.
• R 12 can additionally preferably be hydrogen, 2-(methoxycarbonyl)ethyl, 2-(ethoxycarbonyl)ethyl, 2-(n-butyloxycarbonyl)ethyl, 2-(tert-butyloxycarbonyl)ethyl, 2-(n-octyloxycarbonyl)ethyl or 2-(2'-ethylhexyloxycarbonyl)ethyl.
• Preferred sterically hindered phenols are 2,6-di tert. butyl phenol, 2-tert.-butyl-4-methylphenol, 6-tert.-butyl-2,4-dimethyl-phenol, 2,6-di-tert.-butyl-4-methylphenol, 2-tert.-butylphenol, 4-tert.-butylphenol, 2,4-di-tert.-butylphenol, 2-methyl-4-tert.-butylphenol, 4-tert.-butyl-2,6-dimethylphenol, 2-tert-butyl-6-methylphenol, 2,4,6-tris-tert-butylphenol, 2,6-di-tert.-butylphenol, 2,4-di-tert.-butylphenol, 2,6-dimethylphenol, 2,6-di-tert-butyl-p-cresol, 3-(3',5'-di- tert .-butyl-4'-hydroxyphenyl)propi
• aminophenols the amino and phenolic hydroxy groups can be in ortho, meta or para position relative to each other, preferably ortho or para.
• the amino group can be unsubstituted in the form of an -NH 2 group, or mono- or disubstituted, preferably disubstituted.
• the substituents can be the same or different, preferably they are C 1 - to C 4 -alkyl or hydroxy-C 1 - to C 4 -alkyl.
• aminophenols examples include 2-aminophenol, 3-aminophenol, 4-aminophenol, 3-diethylaminophenol, 3-methyl-4-aminophenol, 2-methyl-5-hydroxyethylaminophenol, 6-methyl-3-aminophenol, ethyl p-aminophenol, 4-methyl-2-aminophenol, 3-phenylaminophenol
• alkyl radical having 1 to 20 carbon atoms, for example methyl, ethyl, iso -propyl, n-propyl, n-butyl, iso -butyl, sec -butyl, tert -butyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-decyl, 2-propylheptyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl or n-eicosyl.
• it is an alkyl radical having 4 to 16 carbon atoms. Examples of this are the individuals having 4 to 16 carbon atoms listed above.
• methyl, ethyl, iso -propyl, iso -butyl, tert -butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-decyl, 2-propylheptyl, n-dodecyl, n-tetradecyl or n-hexadecyl particular preference is given to methyl, iso -propyl, tert -butyl and 2-ethylhexyl.
• Alkenyl radicals having 2 to 20 carbon atoms are vinyl, allyl, isopropenyl, octenyl, decenyl, dodecenyl, tetradecenyl, hexadecenyl and octadecenyl.
• hydroxyalkyl radicals containing 1 to 4 carbon atoms are hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 2-hydroxypropyl and 2-hydroxyprop-2-yl.
• R 21 and R 20 independently of one another are hydrogen, methyl, isopropyl, tert-butyl, 2-ethylhexyl, hydroxymethyl or 2-hydroxyprop-2-yl.
• R 21 and R 20 are the same.
• Preferred diphenylamines are diphenylamine, dinaphthylamine, 4,4'-di(dimethylbenzyl)diphenylamine ( CAS-10081-67-1 ), 4-hydroxydiphenylamine ( CAS-122-37-2 ), 4-methoxy-2-methyldiphenylamine ( CAS-41317-15-1 ), alkylated diphenylamines, reaction product of diphenylamine with 2,4,4-trimethylpentene ( CAS-68411-46-1 , Irganox ® L57), reaction product of styrene with diphenylmethane ( CAS-68442-68-2 ), p-aminodiphenylamine ( CAS-101-54 -), 4-isopropylaminodiphenylamine ( CAS-101-72-4 ), bis(nonyl)diphenylamine (reaction product of diphenylamine with nonene, bis(4-(1,1,3,3-tetramethyl
• diphenylamine or N-phenylnaphthylamine can be reacted with isobutene, diisobutene, nonene, styrene, ⁇ -methylstyrene or propylene tetramer using suitable catalysts, giving mixtures of mono- and disubstituted products as particularly preferred diphenylamines.
• Reaction products from the reaction of diphenylamine with mixtures of the olefins mentioned can also be used.
• reaction product of diphenylamine with 2,4,4-trimethylpentene (CAS-68411-46-1 , Irganox ® L57) and butylated, octylated diphenylamine (Naugalube ® 640).
• the fuel additived with the copolymer according to the invention is a gasoline fuel or in particular a middle distillate fuel, especially a diesel fuel, very particularly a diesel fuel containing at least one biofuel oil, in particular a diesel fuel containing at least one fatty acid alkyl ester (FAME).
• a gasoline fuel or in particular a middle distillate fuel especially a diesel fuel, very particularly a diesel fuel containing at least one biofuel oil, in particular a diesel fuel containing at least one fatty acid alkyl ester (FAME).
• a particular embodiment of the present invention is that the combination of copolymer and optional antioxidant can stabilize a diesel fuel containing quaternary nitrogen compounds and fatty acid alkyl esters even under the conditions prevailing in the injection system, i.e. under high pressure, preferably up to 1500 bar, and at temperatures up to 120 °C.
• a method for stabilizing a diesel fuel containing quaternary nitrogen compounds and fatty acid alkyl esters in the injection system of a diesel engine at a pressure of up to 1500 bar and at temperatures of up to 120 °C with the aid of at least one copolymer according to the invention, optionally together with at least one antioxidant represents a preferred embodiment.
• the fuel may contain other common additives.
• the copolymers described are often used in the form of fuel additive mixtures, together with common additives: In the case of diesel fuels, these are primarily common detergent additives, carrier oils, cold flow improvers, lubricity improvers, corrosion inhibitors other than the copolymers described, demulsifiers, dehazers, antifoam agents, cetane number improvers, combustion improvers, antioxidants or stabilizers, antistatic agents, metallocenes, metal deactivators, dyes and/or solvents.
• the hydrophobic hydrocarbon radical in the above detergent additives which ensures sufficient solubility in the fuel, has a number-average molecular weight (M n ) of 85 to 20,000, preferably 113 to 10,000, particularly preferably 300 to 5,000, more preferably 300 to 3,000, even more preferably 500 to 2,500 and in particular 700 to 2,500, especially 800 to 1,500.
• M n number-average molecular weight
• a typical hydrophobic hydrocarbon radical in particular in combination with the polar, in particular polypropenyl, polybutenyl and polyisobutenyl radicals with a number-average molecular weight M n of preferably 300 to 5,000, particularly preferably 300 to 3,000, more preferably 500 to 2,500, even more preferably 700 to 2,500 and especially 800 to 1,500 come into consideration.
• Such additives based on highly reactive polyisobutene which can be prepared from the polyisobutene, which can contain up to 20% by weight of n-butene units, by hydroformylation and reductive amination with ammonia, monoamines or polyamines such as dimethylaminopropylamine, ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine, are particularly suitable for use in the EP-A 244 616 known.
• the additives are made from polybutene or polyisobutene with predominantly central double bonds (mostly in the ⁇ - and ⁇ -position)
• the production route is through chlorination and subsequent amination or through oxidation of the double bond with air or ozone to the carbonyl or carboxyl compound and subsequent amination under reductive (hydrogenating) conditions.
• Amines such as ammonia, monoamines or the above-mentioned polyamines can be used for amination.
• Corresponding additives based on polypropene are particularly popular in the WO-A 94/24231 described.
• Da monoamino groups
• These reaction products are generally mixtures of pure nitropolyisobutenes (e.g. ⁇ , ⁇ -dinitropolyisobutene) and mixed hydroxynitropolyisobutenes (e.g. ⁇ -nitro- ⁇ -hydroxypolyisobutene).
• Additives containing carboxyl groups or their alkali metal or alkaline earth metal salts (Dd) are preferably copolymers of C 2 - to C 40 -olefins with maleic anhydride with a total molecular weight of 500 to 20,000, whose carboxyl groups are completely or partially converted to the alkali metal or alkaline earth metal salts and a remaining residue of the carboxyl groups is converted with alcohols or amines.
• Such additives are particularly suitable for EP-A 307 815
• Such additives mainly serve to prevent valve seat wear and can, as described in the WO-A 87/01126 described, can be used advantageously in combination with conventional fuel detergents such as poly(iso)-butenamines or polyetheramines.
• Additives containing sulfonic acid groups or their alkali metal or alkaline earth metal salts are preferably alkali metal or alkaline earth metal salts of an alkyl sulfosuccinic ester, as he particularly in the EP-A 639 632 Such additives serve primarily to prevent valve seat wear and can be used advantageously in combination with conventional fuel detergents such as poly(iso)butene amines or polyether amines.
• Additives containing polyoxy-C 2 -C 4 -alkylene groups are preferably polyethers or polyetheramines, which are obtainable by reacting C 2 - to C 60 -alkanols, C 6 - to C 30 -alkanediols, mono- or di-C 2 - to C 30 -alkylamines, C 1 - to C 30 -alkylcyclohexanols or C 1 - to C 30 -alkylphenols with 1 to 30 mol of ethylene oxide and/or propylene oxide and/or butylene oxide per hydroxyl group or amino group and, in the case of polyetheramines, by subsequent reductive amination with ammonia, monoamines or polyamines.
• Such products are used in particular in the EP-A 310 875 , EP-A 356 725 , EP-A 700 985 and US-A 4 877 416 described.
• polyethers such products also fulfill carrier oil properties. Typical examples are tridecanol or isotridecanol butoxylates, isononylphenol butoxylates and polyisobutenol butoxylates and propoxylates as well as the corresponding reaction products with ammonia.
• Additives containing carboxylic acid ester groups (Dg) are preferably esters of mono-, di- or tricarboxylic acids with long-chain alkanols or polyols, in particular those with a minimum viscosity of 2 mm 2 /s at 100 °C, as used in particular in the DE-A 38 38 918 Aliphatic or aromatic acids can be used as mono-, di- or tricarboxylic acids, and long-chain representatives with, for example, 6 to 24 carbon atoms are particularly suitable as ester alcohols or polyols.
• esters are adipates, phthalates, isophthalates, terephthalates and trimellitates of isooctanol, isononanol, isodecanol and isotridecanol. Such products also fulfill carrier oil properties.
• the groups with hydroxy and/or amino and/or amido and/or imido groups are, for example, carboxylic acid groups, acid amides of monoamines, acid amides of di- or polyamines which, in addition to the amide function, also have free amine groups, succinic acid derivatives with an acid and an amide function, carboxylic acid imides with monoamines, carboxylic acid imides with di- or polyamines which, in addition to the imide function, also have free amine groups, or diimides which are formed by the reaction of di- or polyamines with two succinic acid derivatives.
• Such fuel additives are generally known and described, for example, in documents (1) and (2).
• reaction products of alkyl- or alkenyl-substituted succinic acids or Derivatives thereof with amines are preferably the reaction products of polyisobutenyl-substituted succinic acids or derivatives thereof with amines.
• reaction products with aliphatic polyamines such as in particular ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine and hexaethyleneheptamine, which have an imide structure.
• Additives containing groups (Di) produced by Mannich reaction of substituted phenols with aldehydes and mono- or polyamines are preferably reaction products of polyisobutene-substituted phenols with formaldehyde and mono- or polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine or dimethylaminopropylamine.
• Such "polyisobutene Mannich bases” are particularly useful in the EP-A 831 141 described.
• One or more of the detergent additives mentioned can be added to the fuel in such an amount that the dosage rate of these detergent additives is preferably 25 to 2500 ppm by weight, in particular 75 to 1500 ppm by weight, especially 150 to 1000 ppm by weight.
• Carrier oils used can be mineral or synthetic in nature.
• Suitable mineral carrier oils are fractions arising from petroleum processing, such as brightstock or base oils with viscosities such as those from class SN 500 to 2000, but also aromatic hydrocarbons, paraffinic hydrocarbons and alkoxyalkanols.
• a fraction known as "hydrocrack oil” arising from the refining of mineral oil is also usable (vacuum distillate cut with a boiling range of around 360 to 500 °C, obtainable from natural mineral oil catalytically hydrogenated and isomerized under high pressure and dewaxed). Mixtures of the above-mentioned mineral carrier oils are also suitable.
• suitable synthetic carrier oils are polyolefins (polyalphaolefins or polyinternalolefins), (poly)esters, (poly)alkoxylates, polyethers, aliphatic polyetheramines, alkylphenol-started polyethers, alkylphenol-started polyetheramines and carboxylic acid esters of long-chain alkanols.
• suitable polyethers or polyetheramines are preferably compounds containing polyoxy-C 2 - to C 4 -alkylene groups, which are obtained by reacting C 2 - to C 60 -alkanols, C 6 - to C 30 -alkanediols, mono- or di-C 2 - to C 30 -alkylamines, C 1 - to C 30 -alkylcyclohexanols or C 1 - to C 30 -alkylphenols with 1 to 30 mol of ethylene oxide and/or propylene oxide and/or butylene oxide per hydroxyl group or amino group and, in the case of polyetheramines, by subsequent reductive amination with ammonia, monoamines or polyamines.
• poly-C 2 - to C 6 -alkylene oxide amines or functional derivatives thereof can be used as polyetheramines.
• Typical examples of these are tridecanol or isotridecanol butoxylates, isononylphenol butoxylates and polyisobutenol butoxylates and propoxylates as well as the corresponding reaction products with ammonia.
• carboxylic acid esters of long-chain alkanols are in particular esters of mono-, di- or tricarboxylic acids with long-chain alkanols or polyols, as they are used in particular in DE-A 38 38 918
• Aliphatic or aromatic acids can be used as mono-, di- or tricarboxylic acids, and long-chain representatives with, for example, 6 to 24 carbon atoms are particularly suitable as ester alcohols or polyols.
• Typical representatives of esters are adipates, phthalates, isophthalates, terephthalates and trimellitates of isooctanol, isononanol, isodecanol and isotridecanol, e.g. di-(n- or isotridecyl)phthalate.
• Examples of particularly suitable synthetic carrier oils are alcohol-started polyethers with about 5 to 35, preferably about 5 to 30, particularly preferably 10 to 30 and in particular 15 to 30 C 3 - to C 6 -alkylene oxide units, e.g. propylene oxide, n-butylene oxide and isobutylene oxide units or mixtures thereof, per alcohol molecule.
• suitable starter alcohols are long-chain alkanols or phenols substituted with long-chain alkyl, where the long-chain alkyl radical is in particular a straight-chain or branched C 6 - to C 18 -alkyl radical.
• Particular examples are tridecanol and nonylphenol.
• Particularly preferred alcohol-started polyethers are the reaction products (polyetherification products) of monohydric aliphatic C 6 - to C 18 -alcohols with C 3 - to C 6 -alkylene oxides.
• monohydric aliphatic C 6 -C 18 alcohols are hexanol, heptanol, octanol, 2-ethylhexanol, nonyl alcohol, decanol, 3-propylheptanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, octadecanol and their constitutional and positional isomers.
• the alcohols can be used both in the form of the pure isomers and in the form of technical mixtures.
• a particularly preferred alcohol is tridecanol.
• Examples of C 3 - to C 6 -alkylene oxides are propylene oxide, such as 1,2-propylene oxide, butylene oxide, such as 1,2-butylene oxide, 2,3-butylene oxide, isobutylene oxide or tetrahydrofuran, pentylene oxide and hexylene oxide.
• Particularly preferred among these are C 3 - to C 4 -alkylene oxides, ie propylene oxide such as 1,2-propylene oxide and butylene oxide such as 1,2-butylene oxide, 2,3-butylene oxide and isobutylene oxide.
• Butylene oxide is used in particular.
• Suitable synthetic carrier oils are alkoxylated alkylphenols, as used in DE-A 10 102 913 are described.
• Special carrier oils are synthetic carrier oils, with the alcohol-started polyethers described above being particularly preferred.
• the carrier oil or the mixture of different carrier oils is added to the fuel in an amount of preferably 1 to 1000 ppm by weight, particularly preferably 10 to 500 ppm by weight and in particular 20 to 100 ppm by weight.
• suitable cold flow improvers are all organic compounds that are able to improve the flow behavior of middle distillate fuels or diesel fuels in the cold. They must be sufficiently oil-soluble.
• the cold flow improvers (“middle distillate flow improvers", "MDFI") that are usually used for middle distillates of fossil origin, i.e. for common mineral diesel fuels, are suitable for this.
• MDFI middle distillate flow improvers
• organic compounds can also be used that, when used in common diesel fuels, partly or predominantly have the properties of a wax anti-settling additive ("WASA"). They can also act partly or predominantly as nucleators.
• WASA wax anti-settling additive
• mixtures of organic compounds that act as MDFI and/or as WASA and/or as nucleators can also be used.
• Suitable C 2 - to C 40 -olefin monomers for the copolymers of class (K1) are, for example, those having 2 to 20, in particular 2 to 10 carbon atoms and having 1 to 3, preferably 1 or 2, in particular one carbon-carbon double bond.
• the carbon-carbon double bond can be arranged either terminally ( ⁇ -olefins) or internally.
• ⁇ -olefins particularly preferably ⁇ -olefins having 2 to 6 carbon atoms, for example propene, 1-butene, 1-pentene, 1-hexene and especially ethylene.
• the at least one further ethylenically unsaturated monomer is preferably selected from carboxylic acid alkenyl esters, (meth)acrylic acid esters and other olefins.
• olefins are polymerized in, these are preferably higher molecular weight ones than the C 2 to C 40 olefin base monomers mentioned above. If, for example, ethylene or propene is used as the olefin base monomer, C 10 to C 40 ⁇ -olefins are particularly suitable as further olefins. In most cases, further olefins are only polymerized in if monomers with carboxylic acid ester functions are also used.
• Suitable (meth)acrylic acid esters are, for example, esters of (meth)acrylic acid with C 1 - to C 20 -alkanols, in particular C 1 - to C 10 -alkanols, especially with methanol, ethanol, propanol, isopropanol, n-butanol, sec-butanol, isobutanol, tert-butanol, pentanol, hexanol, heptanol, octanol, 2-ethylhexanol, nonanol and decanol as well as structural isomers thereof.
• Suitable carboxylic acid alkenyl esters are, for example, C 2 - to C 14 -alkenyl esters, eg the vinyl and propenyl esters, of carboxylic acids having 2 to 21 carbon atoms, whose hydrocarbon radical can be linear or branched. Vinyl esters are preferred among these.
• carboxylic acids with a branched hydrocarbon radical those are preferred whose branch is in the ⁇ -position to the carboxyl group, the ⁇ -carbon atom being particularly preferably tertiary, ie the carboxylic acid is a so-called neocarboxylic acid.
• the hydrocarbon radical of the carboxylic acid is preferably linear.
• alkenyl carboxylic acid esters examples include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, 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; typical copolymers of group (K1) resulting therefrom are the most frequently used ethylene-vinyl acetate copolymers ("EVA").
• copolymers of class (K1) are those which contain two or more different carboxylic acid alkenyl esters in copolymerized form, whereby these differ in the alkenyl function and/or in the carboxylic acid group. Also suitable are copolymers which, in addition to the carboxylic acid alkenyl ester(s), contain at least one olefin and/or at least one (meth)acrylic acid ester in copolymerized form.
• Terpolymers of a C 2 - to C 40 - ⁇ -olefin, a C 1 - to C 20 -alkyl ester of an ethylenically unsaturated monocarboxylic acid having 3 to 15 carbon atoms and a C 2 - to C 14 -alkenyl ester of a saturated monocarboxylic acid having 2 to 21 carbon atoms are also suitable as copolymers of class (K1).
• Such terpolymers are in the WO 2005/054314 described.
• a typical terpolymer of this type is composed of ethylene, 2-ethylhexyl acrylate and vinyl acetate.
• the at least one or the further ethylenically unsaturated monomers are polymerized into the copolymers of class (K1) in an amount of preferably 1 to 50% by weight, in particular 10 to 45% by weight and especially 20 to 40% by weight, based on the total copolymer.
• the majority by weight of the monomer units in the copolymers of class (K1) thus generally comes from the C 2 to C 40 base olefins.
• the copolymers of class (K1) preferably have a number-average molecular weight M n of 1000 to 20,000, particularly preferably from 1000 to 10,000 and in particular from 1000 to 8000.
• Typical comb polymers of component (K2) are obtainable, for example, by copolymerizing maleic anhydride or fumaric acid with another ethylenically unsaturated monomer, for example with an ⁇ -olefin or an unsaturated ester such as vinyl acetate, and subsequent esterification of the anhydride or acid function with an alcohol having at least 10 carbon atoms.
• Other suitable comb polymers are copolymers of ⁇ -olefins and esterified comonomers, for example esterified copolymers of styrene and maleic anhydride or esterified copolymers of styrene and fumaric acid.
• Suitable comb polymers can also be polyfumarates or polymaleates.
• Homo- and copolymers of vinyl ethers are also suitable comb polymers.
• Comb polymers suitable as components of class (K2) are, for example, those which are in the WO 2004/035715 and in " Comb-Like Polymers. Structure and Properties", NA Plate and VP Shibaev, J. Poly. Sci. Macromolecular Revs. 8, pages 117 to 253 (1974 )". Mixtures of comb polymers are also suitable.
• Polyoxyalkylenes suitable as components of class (K3) are, for example, polyoxyalkylene esters, polyoxyalkylene ethers, mixed polyoxyalkylene ester ethers and mixtures thereof. These polyoxyalkylene compounds preferably contain at least one, preferably at least two linear alkyl groups each having 10 to 30 carbon atoms and a polyoxyalkylene group having a number-average molecular weight of up to 5000. Such polyoxyalkylene compounds are, for example, in the EP-A 061 895 as well as in the US 4 491 455 described. Special polyoxyalkylene compounds are based on polyethylene glycols and polypropylene glycols with a number-average molecular weight of 100 to 5000. Polyoxyalkylene mono- and diesters of fatty acids with 10 to 30 carbon atoms, such as stearic acid or behenic acid, are also suitable.
• Polar nitrogen compounds suitable as components of class (K4) can be either ionic or non-ionic in nature and preferably have at least one, in particular at least two substituents in the form of a tertiary nitrogen atom of the general formula >NR 7 , in which R 7 is a C 8 - to C 40 -hydrocarbon radical.
• the nitrogen substituents can also be quaternized, i.e. in cationic form. Examples of such Nitrogen compounds are ammonium salts and/or amides which are obtainable by reacting at least one amine substituted by at least one hydrocarbon radical with a carboxylic acid having 1 to 4 carboxyl groups or with a suitable derivative thereof.
• the amines preferably contain at least one linear C 8 - to C 40 -alkyl radical.
• Primary amines suitable for preparing the polar nitrogen compounds mentioned are, for example, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tetradecylamine and the higher linear homologues; secondary amines suitable for this purpose are, for example, dioctadecylamine and methylbehenylamine.
• Amine mixtures are also suitable for this purpose, in particular amine mixtures which are accessible on an industrial scale, such as fatty amines or hydrogenated tall amines, as are used, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 6th edition, in the chapter "Amines, aliphatic " 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.
• the component of class (K4) is an oil-soluble reaction product of poly(C 2 - to C 20 -carboxylic acids) containing at least one tertiary amino group with primary or secondary amines.
• the poly(C 2 - to C 20 -carboxylic acids) containing at least one tertiary amino group on which this reaction product is based preferably contain at least 3 carboxyl groups, in particular 3 to 12, especially 3 to 5 carboxyl groups.
• the carboxylic acid units in the polycarboxylic acids preferably have 2 to 10 carbon atoms, in particular they are acetic acid units.
• the carboxylic acid units are linked in a suitable manner to the polycarboxylic acids, usually via one or more carbon and/or nitrogen atoms. They are preferably attached to tertiary nitrogen atoms, which in the case of several nitrogen atoms are linked via hydrocarbon chains.
• the component of class (K4) is an oil-soluble reaction product based on poly(C 2 - to C 20 -carboxylic acids) having at least one tertiary amino group of the general formula IIa or IIb in which the variable A is a straight-chain or branched C 2 - to C 6 -alkylene group or the grouping of the formula III and the variable B denotes a C 1 to C 19 alkylene group.
• the compounds of the general formula IIa and IIb have in particular the properties of a WASA.
• the preferred oil-soluble reaction product of component (K4) in particular that of the general formula IIa or IIb, is an amide, an amide ammonium salt or an ammonium salt in which none, one or more carboxylic acid groups are converted into amide groups.
• Straight-chain or branched C 2 - to C 6 -alkylene groups of the variable A are, for example, 1,1-ethylene, 1,2-propylene, 1,3-propylene, 1,2-butylene, 1,3-butylene, 1,4-butylene, 2-methyl-1,3-propylene, 1,5-pentylene, 2-methyl-1,4-butylene, 2,2-dimethyl-1,3-propylene, 1,6-hexylene (hexamethylene) and in particular 1,2-ethylene.
• the variable A preferably comprises 2 to 4, in particular 2 or 3, carbon atoms.
• C 1 - to C 19 -alkylene groups of the variable B are, for example, 1,2-ethylene, 1,3-propylene, 1,4-butylene, hexamethylene, octamethylene, decamethylene, dodecamethylene, tetradecamethylene, hexadecamethylene, octadecamethylene, nonadecamethylene and in particular methylene.
• the variable B preferably comprises 1 to 10, in particular 1 to 4, carbon atoms.
• the primary and secondary amines as reaction partners for the polycarboxylic acids to form component (K4) are usually monoamines, in particular aliphatic monoamines. These primary and secondary amines can be selected from a large number of amines which carry hydrocarbon radicals, optionally linked to one another.
• These amines underlying the oil-soluble reaction products of component (K4) are usually secondary amines and have the general formula HN(R 8 ) 2 , in which the two variables R 8 independently of one another each represent straight-chain or branched C 10 - to C 30 -alkyl radicals, in particular C 14 - to C 24 -alkyl radicals. These longer-chain alkyl radicals are preferably straight-chain or only slightly branched.
• the secondary amines mentioned are derived from naturally occurring fatty acids or their derivatives with regard to their longer-chain alkyl radicals.
• the two R 8 radicals are preferably the same.
• the secondary amines mentioned can be bound to the polycarboxylic acids by means of amide structures or in the form of ammonium salts; only a portion can be present as amide structures and another portion as ammonium salts. Preferably, only a few or no free acid groups are present. Preferably, the oil-soluble reaction products of component (K4) are present entirely in the form of amide structures.
• Typical examples of such components (K4) are reaction products of nitrilotriacetic acid, ethylenediaminetetraacetic acid or propylene-1,2-diaminetetraacetic acid, each with 0.5 to 1.5 moles per carboxyl group, in particular 0.8 to 1.2 moles per carboxyl group, dioleylamine, dipalmitinamine, dicoconut fatty amine, distearylamine, dibehenylamine or in particular ditallow fatty amine.
• a particularly preferred component (K4) is the reaction product of 1 mole of ethylenediaminetetraacetic acid and 4 moles of hydrogenated ditallow fatty amine.
• component (K4) are the N,N-dialkylammonium salts of 2-N',N'-dialkylamidobenzoates, for example the reaction product of 1 mole of phthalic anhydride and 2 moles of ditallow fatty amine, where the latter may be hydrogenated or non-hydrogenated, and the reaction product of 1 mole of an alkenylspirobislactone with 2 moles of a dialkylamine, for example ditallow fatty amine and/or tallow fatty amine, where the latter two may be hydrogenated or non-hydrogenated.
• component of class (K4) are cyclic compounds with tertiary amino groups or condensates of long-chain primary or secondary amines with carboxylic acid-containing polymers, as described in the WO93/18115 are described.
• Sulfocarboxylic acids, sulfonic acids or their derivatives suitable as cold flow improvers for the component of class (K5) are, for example, the oil-soluble carboxylic acid amides and carboxylic acid esters of ortho-sulfobenzoic acid in which the sulfonic acid function is present as a sulfonate with alkyl-substituted ammonium cations, as described in the EP-A 261 957 to be discribed.
• Poly(meth)acrylic acid esters suitable as cold flow improvers for the component of class (K6) are both homo- and copolymers of acrylic and methacrylic acid esters. Preference is given to copolymers of at least two different (meth)acrylic acid esters which differ in terms of the condensed alcohol.
• the copolymer optionally contains another, different olefinically unsaturated monomer in copolymerized form.
• the weight-average molecular weight of the polymer is preferably 50,000 to 500,000.
• a particularly preferred polymer is a copolymer of methacrylic acid and methacrylic acid esters of saturated C 14 and C 15 alcohols, the acid groups being neutralized with hydrogenated tallamine. Suitable poly(meth)acrylic acid esters are described, for example, in WO 00/44857 described.
• the cold flow improver or the mixture of various cold flow improvers is added to the middle distillate fuel or diesel fuel in a total amount of preferably 10 to 5000 ppm by weight, particularly preferably 20 to 2000 ppm by weight, more preferably 50 to 1000 ppm by weight and in particular 100 to 700 ppm by weight, e.g. 200 to 500 ppm by weight.
• Suitable lubricity improvers or friction modifiers are usually based on fatty acids or fatty acid esters. Typical examples are tall oil fatty acids, as used in WO 98/004656 described, and glycerol monooleate.
• the US 6 743 266 B2 The reaction products described above from natural or synthetic oils, for example triglycerides, and alkanolamines are suitable as lubricity improvers.
• Suitable corrosion inhibitors are, for example, succinic acid esters, especially with polyols, fatty acid derivatives, e.g. oleic acid esters, oligomerized fatty acids, substituted ethanolamines and products sold under the trade name RC 4801 (Rhein Chemie Mannheim, Germany), Irgacor ® L12 (BASF SE) or HiTEC 536 (Ethyl Corporation).
• succinic acid esters especially with polyols, fatty acid derivatives, e.g. oleic acid esters, oligomerized fatty acids, substituted ethanolamines and products sold under the trade name RC 4801 (Rhein Chemie Mannheim, Germany), Irgacor ® L12 (BASF SE) or HiTEC 536 (Ethyl Corporation).
• Suitable demulsifiers are, for example, the alkali or alkaline earth salts of alkyl-substituted phenol and naphthalene sulfonates and the alkali or alkaline earth salts of fatty acids, as well as neutral compounds such as alcohol alkoxylates, e.g. alcohol ethoxylates, phenol alkoxylates, e.g. tert-butylphenol ethoxylate or tert-pentylphenol ethoxylate, fatty acids, alkylphenols, condensation products of ethylene oxide (EO) and propylene oxide (PO), e.g. also in the form of EO/PO block copolymers, polyethyleneimines or polysiloxanes.
• EO ethylene oxide
• PO propylene oxide
• Suitable dehazers are, for example, alkoxylated phenol-formaldehyde condensates, such as the products available under the trade names NALCO 7D07 (Nalco) and TOLAD 2683 (Petrolite).
• Suitable antifoaming agents include polyether-modified polysiloxanes, such as the products available under the trade names TEGOPREN 5851 (Goldschmidt), Q 25907 (Dow Corning) and RHODOSIL (Rhone Poulenc).
• Suitable cetane number improvers include aliphatic nitrates such as 2-ethylhexyl nitrate and cyclohexyl nitrate as well as peroxides such as di-tert-butyl peroxide.
• Suitable metal deactivators include salicylic acid derivatives such as N,N'-disalicylidene-1,2-propanediamine.
• Suitable solvents include non-polar organic solvents such as aromatic and aliphatic hydrocarbons, for example toluene, xylenes, "white spirit” and products sold under the trade names SHELLSOL (Royal Dutch/Shell Group) and EXXSOL (ExxonMobil), as well as polar organic solvents, for example alcohols such as 2-ethylhexanol, decanol and isotridecanol.
• non-polar organic solvents such as aromatic and aliphatic hydrocarbons, for example toluene, xylenes, "white spirit” and products sold under the trade names SHELLSOL (Royal Dutch/Shell Group) and EXXSOL (ExxonMobil)
• polar organic solvents for example alcohols such as 2-ethylhexanol, decanol and isotridecanol.
• solvents usually end up in diesel fuel together with the aforementioned additives and co-additives, which are
• the additive according to the invention is outstandingly suitable as a fuel additive and can in principle be used in any fuel. It has a whole series of advantageous effects when operating internal combustion engines with fuels.
• the additive is preferably used in middle distillate fuels, especially diesel fuels, especially in diesel fuels containing biofuel oils.
• the present invention therefore also relates to diesel fuels containing at least one biofuel oil and at least one copolymer as described above, and optionally at least one further additive.
• the present invention further relates to a method for operating a diesel engine with such a fuel according to the invention, in particular direct-injection diesel engines, especially diesel engines with common rail injection systems.
• This effective content (dosage rate) of the copolymer in the fuel is generally 5 to 5000 ppm by weight, preferably 6 to 1000 ppm by weight, in particular 8 to 500 ppm by weight, especially 10 to 200 ppm by weight, in each case based on the total amount of fuel.
• the use according to the invention relates in principle to any fuels, preferably diesel and gasoline fuels, especially diesel fuels, very particularly in diesel fuels containing biofuel oils, in particular diesel fuels containing at least one fatty acid alkyl ester (FAME).
• fuels preferably diesel and gasoline fuels, especially diesel fuels, very particularly in diesel fuels containing biofuel oils, in particular diesel fuels containing at least one fatty acid alkyl ester (FAME).
• Middle distillate fuels such as diesel fuels or heating oils are preferably petroleum raffinates, which usually have a boiling range of 100 to 400°C. These are usually distillates with a 95% point of up to 360°C or even higher. However, these can also be so-called “ultra low sulphur diesel” or "city diesel", characterized by a 95% point of, for example, a maximum of 345°C and a sulphur content of a maximum of 0.005% by weight or by a 95% point of, for example, 285°C and a sulphur content of a maximum of 0.001% by weight.
• mineral middle distillate fuels or diesel fuels obtainable through refining
• those obtainable through coal gasification or gas liquefaction [“gas to liquid” (GTL) fuels] or through biomass liquefaction [“biomass to liquid” (BTL) fuels] are also suitable.
• Mixtures of the above-mentioned middle distillate fuels or diesel fuels with renewable fuels such as biodiesel or bioethanol are also suitable.
• middle distillate fuels of fossil, vegetable or animal origin which are essentially hydrocarbon mixtures
• biofuel oils biodiesel
• middle distillate fuel Such mixtures are covered by the term "middle distillate fuel”.
• biofuel oils are commercially available and usually contain the biofuel oils in minor amounts, typically in amounts of 1 to 50% by weight, preferably 2 to 30% by weight and in particular 3 to 10% by weight, based on the total amount of middle distillate of fossil, vegetable or animal origin and biofuel oil.
• Fuels are also conceivable which contain a larger proportion of biofuel oils or even consist of them, for example more than 50% by weight, preferably at least 60% by weight, particularly preferably at least 70% by weight, very particularly preferably at least 80% by weight and even 100% by weight (B100).
• Biofuel oils are generally based on fatty acid esters, preferably essentially on alkyl esters of fatty acids derived from vegetable and/or animal oils and/or fats.
• Alkyl esters are usually understood to mean lower alkyl esters, preferably C 1 to C 4 alkyl esters, particularly preferably methyl or ethyl esters and very particularly preferably methyl esters, which are obtainable by transesterification of the glycerides, in particular triglycerides, found in vegetable and/or animal oils and/or fats using lower alcohols, for example ethanol or especially methanol ("FAME").
• Typical lower alkyl esters based on vegetable and/or animal oils and/or fats that are used as biofuel oil or components thereof are, for example, sunflower methyl ester, palm oil methyl ester (“PME”), soybean oil methyl ester (“SME”), animal fat methyl ester (“FME”) or tallow methyl ester (“TME”), methyl esters from recovered vegetable oils, processed used cooking oils and frying fats, so-called used vegetable oil (“UVO”) or waste vegetable oil (“WVE”) or used cooking oil methyl ester (“UCOME”), tall oil methyl ester and in particular rapeseed oil methyl ester (“RME”).
• PME palm oil methyl ester
• SME soybean oil methyl ester
• FME animal fat methyl ester
• TME tallow methyl ester
• UVO used vegetable oil
• WVE waste vegetable oil
• UCOME used cooking oil methyl ester
• middle distillate fuels or diesel fuels with a low sulphur content i.e. with a sulphur content of less than 0.05 wt.%, preferably less than 0.02 wt.%, in particular less than 0.005 wt.% and especially less than 0.001 wt.% sulphur.
• All commercially available petrol compositions can be considered as petrol.
• a typical example is the commercially available Eurosuper base fuel according to EN 228.
• petrol compositions that meet the specification according to WO 00/47698 possible areas of application for the present invention are also commercially available.
• the present invention further provides a process for increasing the thermal and/or oxidation stability, in particular the oxidation stability of fuels, preferably diesel fuels, particularly preferably diesel fuels containing at least one biofuel oil, measured in the form of DIN EN 15751:2014-06 by at least one hour, preferably by at least two hours, particularly preferably by at least three hours, wherein at least 10 ppm by weight, preferably at least 20 ppm by weight based on the fuel, of at least one of the copolymers described is added to the fuel, mixed and the mixture thus obtained is subjected to a thermal and/or oxidative stress.
• fuels preferably diesel fuels, particularly preferably diesel fuels containing at least one biofuel oil, measured in the form of DIN EN 15751:2014-06 by at least one hour, preferably by at least two hours, particularly preferably by at least three hours, wherein at least 10 ppm by weight, preferably at least 20 ppm by weight based on the fuel, of at least one of the copolymers
• Component 1 Succinic acid amide quaternized with propylene oxide in 2-ethylhexanol based on polyisobutene succinic anhydride (PIBSA1000) and 3-dimethylamino-1-propylamine, prepared analogously to Preparation Example 1 of WO 12/004300 A1 .
• PIBSA1000 polyisobutene succinic anhydride
• 3-dimethylamino-1-propylamine prepared analogously to Preparation Example 1 of WO 12/004300 A1 .
• Component 2 N,N-dimethylhexadecylamine (nC 16 H 33 NMe 2 ) quaternized with propylene oxide in the presence of polyisobutene succinic acid (based on PIB1000) in 2-ethylhexanol. CAS-112-69-6 ), prepared according to Example 6 of WO 2014/195464 A1 .
• Polyacid Copolymer of maleic anhydride and a mixture of C 20 -C 24 olefins, fully hydrolyzed, prepared according to Synthesis Example 2 of WO 2015/113681 A1 with the molecular weight indicated there.
• a B7 diesel fuel in accordance with DIN EN590 with soy methyl ester as FAME was tested for its thermal stability using the test in accordance with DIN EN 15751:2014-06 in a Rancimat ® device, model Metrohm 873 Biodiesel Ranzimat, from Metrohm AG, Herisau, Switzerland.
• the amounts of additives specified in the table (in mg/kg) were added to 7.5 g of the fuel and the test was carried out in accordance with DIN EN 15751:2014-06 by passing an air stream of 10 liters per hour through the sample heated to 110 °C.
• the stream containing the volatile components is passed into 60 ml of demineralized water and the conductivity is determined.
• a sudden increase in electrical conductivity indicates the end of the induction time (in hours) specified in the table.

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• 2022
  • 2022-12-06 EP EP22211629.5A patent/EP4382588A1/fr not_active Withdrawn

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