EP3555244B1 - Polymere als dieselkraftstoffadditive für direkteinspritzende dieselmotoren - Google Patents

Polymere als dieselkraftstoffadditive für direkteinspritzende dieselmotoren Download PDF

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EP3555244B1
EP3555244B1 EP17807843.2A EP17807843A EP3555244B1 EP 3555244 B1 EP3555244 B1 EP 3555244B1 EP 17807843 A EP17807843 A EP 17807843A EP 3555244 B1 EP3555244 B1 EP 3555244B1
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use according
acid
group
esters
deposits
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EP3555244A1 (de
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Maxim Peretolchin
Ivette Garcia Castro
Aaron FLORES-FIGUEROA
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BASF SE
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BASF SE
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    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • 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
    • C10L1/1963—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 mono-carboxylic
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    • C10L1/00—Liquid carbonaceous fuels
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    • 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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    • C10L1/1985—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 polyethers, e.g. di- polygylcols and derivatives; ethers - esters
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    • C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
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    • C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
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    • C10L1/14—Organic compounds
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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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    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/04—Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
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    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/06—Use of additives to fuels or fires for particular purposes for facilitating soot removal
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    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/08—Use of additives to fuels or fires for particular purposes for improving lubricity; for reducing wear
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M149/00—Lubricating compositions characterised by the additive being a macromolecular compound containing nitrogen
    • C10M149/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M149/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amino group
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    • C10M149/00—Lubricating compositions characterised by the additive being a macromolecular compound containing nitrogen
    • C10M149/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M149/06—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amido or imido group
    • C—CHEMISTRY; METALLURGY
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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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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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
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    • C10L2300/00—Mixture of two or more additives covered by the same group of C10L1/00 - C10L1/308
    • C10L2300/20—Mixture of two components
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/086—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type polycarboxylic, e.g. maleic acid
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    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/109—Polyethers, i.e. containing di- or higher polyoxyalkylene groups esterified
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    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/06—Macromolecular compounds obtained by functionalisation op polymers with a nitrogen containing compound
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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
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    • C10N2040/00—Specified use or application for which the lubricating composition is intended
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    • C10N2070/00—Specific manufacturing methods for lubricant compositions

Definitions

  • the present invention relates to the use of certain polymers as a diesel fuel additive to reduce or prevent deposits in the fuel systems and in particular injection systems in direct-injection diesel engines, in particular in common-rail injection systems, to reduce the fuel consumption of direct-injection diesel engines, in particular diesel engines with common-rail Injection systems, and to minimize the power loss (power loss) in direct injection diesel engines, especially in diesel engines with common rail injection systems.
  • direct-injection diesel engines the fuel is injected through a multi-hole injection nozzle that reaches directly into the engine's combustion chamber and is finely distributed (nebulized), instead of being introduced into a pre-chamber or swirl chamber as in the classic (chamber) diesel engine.
  • the advantage of direct-injection diesel engines is their high performance for a diesel engine and yet low consumption. In addition, these engines achieve a very high torque even at low speeds.
  • the diesel fuel is pumped by a pump at pressures of up to 2000 bar into a high-pressure line, the common rail.
  • branch lines run to the various injectors, which inject the fuel directly into the combustion chamber.
  • There is always full pressure on the common rail which enables multiple injections or a special injection form.
  • the other injection systems on the other hand, only a smaller variation of the injection is possible.
  • Common rail injection is essentially divided into three groups: (1.) Pre-injection, which essentially achieves softer combustion, so that hard combustion noise ("knocking") is reduced and the engine runs smoothly; (2.) Main injection, which is responsible in particular for a good torque curve; and (3.) post-injection, which in particular ensures a low NO x value.
  • Pre-injection which essentially achieves softer combustion, so that hard combustion noise ("knocking") is reduced and the engine runs smoothly
  • (2.) Main injection which is responsible in particular for a good torque curve
  • (3.) post-injection which in particular ensures a low NO x value.
  • the fuel is usually not burned, but vaporized by residual heat in the cylinder.
  • the resulting exhaust gas/fuel mixture is transported to the exhaust system, where the fuel acts as a reducing agent for the nitrogen oxides NO x in the presence of suitable catalysts.
  • variable, cylinder-specific injection can have a positive effect on the pollutant emissions of the engine, eg the emission of nitrogen oxides (NO x ), carbon monoxide (CO) and, in particular, particles (soot).
  • NO x nitrogen oxides
  • CO carbon monoxide
  • particles particles
  • deposits can form on the injector openings that affect the injection behavior of the fuel negatively affect the fuel and thereby impair the performance of the engine, ie in particular reduce the performance, but in some cases also worsen the combustion.
  • the formation of deposits is increased by further structural developments of the injectors, in particular by changing the geometry of the nozzles (narrower, conical openings with a rounded outlet). In order for the engine and injectors to function optimally over the long term, such deposits in the nozzle openings must be prevented or reduced using suitable fuel additives.
  • IDID internal diesel injector deposits
  • 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.
  • the compounds according to the invention act against deposits not only in the injection system but also in the rest of the fuel system, here in particular against deposits in fuel filters and fuel pumps.
  • the object of the present invention is to provide a specific class of copolymer-based additives for use in modern diesel fuels.
  • copolymers are characterized in particular by the fact that they work against a wide variety of deposits that impair the performance of modern diesel engines.
  • the compounds according to the invention act, for example, against loss of performance both caused by the introduction of zinc and caused by the introduction of sodium into the diesel fuel. This essentially eliminates or avoids deposits in the spray channels and the injector tip.
  • the compounds according to the invention also act against internal diesel injector deposits (IDID) caused by Na, Ca and/or K ions (so-called Na, Ca or K soaps IDID) and/or polymers deposits.
  • IDID internal diesel injector deposits
  • Na, Ca and K soaps IDID are deposits that contain the relevant metal ions with any counterions.
  • the polymeric deposits on the other hand, are free of metal ions and can be traced back to high-molecular organic material that is either insoluble or insoluble in the fuel.
  • figure 1 shows the sequence of a one-hour engine test cycle according to CEC F-098-08.
  • 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 is understood as meaning methyl, ethyl, isopropyl , n-propyl, n-butyl, isobutyl , 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 acid 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 derivatives thereof.
  • 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 precisely one ⁇ -olefin having from at least 12 up to and including 30 carbon atoms.
  • 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 and including 28, particularly preferably up to and including 26 and very particularly preferably up to and including 24 carbon atoms.
  • the ⁇ -olefins can preferably be linear or branched, preferably linear, 1-alkenes.
  • Examples thereof 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, and mixtures thereof are preferred.
  • ⁇ -olefin (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.
  • 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 thereof 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 Mentioned specifically as ⁇ -olefins (B) are oligomers and polymers of propene, 1-butene, 2-butene, isobutene and mixtures thereof, especially oligomers and polymers of propene or isobutene or of mixtures of 1-butene and 2-butene.
  • the oligomers the trimers, tetramers, pentamers and hexamers and mixtures thereof are preferred.
  • 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 having from 4 to less than 12 or more than 30 carbon atoms. If the olefin (C) is an olefin having 12 to 30 carbon atoms, this olefin (C) has no double bond in the ⁇ position.
  • 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 mixtures thereof, limonene and norbornene.
  • olefins (C) are polymers of propene, 1-butene, 2-butene or isobutene containing more than 30 carbon atoms or olefin mixtures containing such, preferably 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 copolymerized form preferably have a high content of terminal ethylenic double bonds ( ⁇ -double bonds), for example at least 50 mol %, preferably at least 60 mole %, more preferably at least 70 mole % and most preferably at least 80 mole %.
  • ⁇ -double bonds terminal ethylenic double bonds
  • Suitable isobutene sources for the preparation of such isobutene-containing oligomers or polymers are both pure isobutene and isobutene-containing C4 hydrocarbon streams, for example C4 raffinates, in particular "raffinate 1", C4 cuts from isobutane -Dehydrogenation, C4 cuts from steam crackers and from FCC crackers (fluid catalysed cracking), provided they are largely freed from the 1,3-butadiene contained therein.
  • a C4 hydrocarbon stream from an FCC refinery unit is also known as a "b/b" stream.
  • Suitable isobutenic C4 hydrocarbon streams are, for example, the product stream of a propylene-isobutane co-oxidation or the product stream from a metathesis unit, which are generally used after customary purification and/or concentration.
  • Suitable C4 hydrocarbon streams typically contain less than 500 ppm, preferably less than 200 ppm, 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 isobutene, 10 to 50% by weight 1-butene, 10 to 40% by weight cis- and trans-2-butene and 2 to 35% by weight % Butanes;
  • the unbranched butenes in raffinate 1 are generally practically inert and only the isobutene is polymerized from 1 to 99% by weight, in particular from 1 to 90% by weight, particularly preferably from 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 co-oxidation or a product stream from a metathesis unit.
  • Said isobutenic monomer mixture can contain small amounts of contaminants, such as water, carboxylic acids or mineral acids, without critical losses in yield or selectivity occurring. It is expedient to avoid accumulation of these impurities 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 the isobutene-containing hydrocarbon mixture with olefinically unsaturated monomers which are copolymerizable with isobutene.
  • monomer mixtures of isobutene are to be copolymerized with suitable comonomers, contains the monomer mixture preferably at least 5% by weight, more preferably at least 10% by weight and in particular at least 20% by weight of isobutene, and preferably at most 95% by weight, more preferably at most 90% by weight and in particular at most 80% by weight % comonomers.
  • the substance mixture of the olefins (B) and optionally (C), averaged for their amounts has 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 usually no more than 60 carbon atoms, preferably no more than 55, more preferably no more than 50, most preferably no more than 45 and especially no 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 (neoheptanoic 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,
  • vinyl ethers (Db) are vinyl ethers of C 1 - to C 12 -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-ethyl-hexanol.
  • vinyl ethers of C 1 - to C 12 -alkanols preferably vinyl ethers of methanol, ethanol, isopropanol , n-propanol, n-butanol, isobutanol , sec- butanol, tert -butanol, n -Hexanol, n-
  • Preferred (meth)acrylic esters (Dc) are (meth)acrylic 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. Pentyl acrylate, 2-ethylhexyl acrylate and 2-propylheptyl acrylate are particularly preferred.
  • Examples of monomers (Dd) are allyl alcohols and allyl ethers of C 2 - to C 12 -alkanols, 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-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.
  • 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)) (total) is from 10:1 to 1:10, preferably from 8:1 to 1:8, particularly preferably from 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)) (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 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%.
  • the copolymer consists of the monomers (A) and (B).
  • reaction step (II) some of the anhydride or carboxylic acid ester functionalities present in the copolymer obtained from (I) are reacted with at least one compound (E) containing at least one alcohol group and/or at least one amino group.
  • reaction step (II) anhydride functionalities are reacted and carboxylic acid ester functionalities are left essentially intact.
  • Compounds (E) are those which have at least one alcohol group and/or at least one amino group, preferably either at least one alcohol group or at least one amino group.
  • Examples of alcohols (E1) as compounds (E) are those which have one to six hydroxyl groups, preferably one to four, particularly preferably one to three, very particularly preferably one or two and in particular exactly one hydroxyl group.
  • Examples of amines (E2) as compounds (E) are those which have one to six amino groups, preferably one to four, particularly preferably one to three, very particularly preferably one or two and in particular precisely one amino group.
  • amino alcohols (E3) which have at least one hydroxy group and at least one amino group, preferably exactly one hydroxy group and at least one amino group, particularly preferably exactly one hydroxy group and exactly one amino group.
  • the amino groups are primary or secondary amino groups, preferably primary amino groups. Tertiary amino groups are not included in compounds (E2) or (E3) since they do not react in reaction step (II).
  • Examples of monoalcohols are alkanols having 1 to 20 carbon atoms and their alkoxylates.
  • Alkanols having 1 to 20 carbon atoms are, for example, methanol, ethanol, isopropanol , n-propanol, n-butanol, isobutanol , sec -butanol, tert -butanol, n-hexanol, n-heptanol, n-octanol, n- Decanol, n-dodecanol (lauryl alcohol), 2-ethylhexanol, n-decanol, n-dodecanol, tridecanol, heptadecanol and eicosanol.
  • fatty alcohols preferably octyl alcohol (caprylic alcohol), nonyl alcohol (pelargonyl alcohol), decyl alcohol (capric alcohol), undecyl alcohol, dodecyl alcohol (lauryl alcohol), tridecyl alcohol, tetradecyl alcohol (myristyl alcohol), pentadecyl alcohol, hexadecyl alcohol (cetyl alcohol, palmityl alcohol), heptadecyl alcohol, octadecyl alcohol (stearyl alcohol), oleyl alcohol, elaidyl alcohol, linoleyl alcohol, linolenoyl alcohol, nonadecyl alcohol, eicosyl alcohol (arachyl alcohol) or mixtures thereof.
  • octyl alcohol caprylic alcohol
  • nonyl alcohol pelargonyl alcohol
  • decyl alcohol capric alcohol
  • undecyl alcohol dodecyl alcohol (lauryl alcohol)
  • R 1 is preferably methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, sec - butyl, tert -butyl, n-hexyl, n-heptyl, n-octyl, 2- ethylhexyl, n-decyl, 2-propylheptyl, n-dodecyl, tridecyl, n-tetradecyl, n-hexadecyl, heptadecyl, n-octadecyl or n-eicosyl.
  • R 1 is particularly preferably 2-ethylhexyl, 2-propylheptyl, stearyl, cetyl, lauryl, C 13 isomer mixtures and C 17 isomer mixtures.
  • the underlying alcohol R 1 -OH is a mixture of alcohols containing 13 carbon atoms, particularly preferably one that can be obtained by hydroformylation from a C 12 -olefin mixture, which in turn can be obtained by oligomerization of an olefin mixture is, which predominantly contains hydrocarbons having four carbon atoms.
  • This olefin mixture has a statistical average of 11 to 13 carbon atoms, preferably 11.1 to 12.9, more preferably 11.2 to 12.8, very preferably 11.5 to 12.5 and in particular 11.8 to 12.2 .
  • this alcohol R 1 —OH has an average degree of branching, measured as the ISO index, of from 2.8 to 3.7.
  • this alcohol R 1 -OH is obtained by a method as described in WO 00/02978 or WO 00/50543 .
  • the alcohol R 1 -OH on which it is based is a mixture of alcohols having 17 carbon atoms, particularly preferably one which can be obtained by hydroformylation from a C 16 -olefin mixture, which in turn can be obtained by oligomerization of an olefin mixture is available, which contains predominantly hydrocarbons having four carbon atoms.
  • this olefin mixture has from 15 to 17 carbon atoms, preferably from 15.1 to 16.9, more preferably from 15.2 to 16.8, very preferably from 15.5 to 16.5 and in particular from 15.8 to 16.2 .
  • this alcohol R 1 —OH has an average degree of branching, measured as the ISO index, of from 2.8 to 3.7.
  • this alcohol R 1 -OH is obtained by a method as described in WO 2009/124979 A1 , there in particular page 5, line 4 to page 16, line 29, and the examples from page 19, line 19 to page 21, line 25, which is hereby incorporated by reference into the present disclosure.
  • a C 17 -alcohol mixture having particularly advantageous performance properties can be prepared as the product of the transition metal-catalyzed oligomerization of olefins having 2 to 6 carbon atoms.
  • a C 16 -olefin mixture is first isolated from the product of the olefin oligomerization by distillation and only then is this C 16 -olefin mixture subjected to hydroformylation. It is thus possible to provide a more highly branched C 17 -alcohol mixture with particularly advantageous performance properties.
  • the alcohols can also carry tertiary amino groups, since these do not react in reaction step (II).
  • Preferred such alcohols are dimethylaminoethanolamine, dimethylaminopropanolamine, diethylaminoethanolamine, diethylaminopropanolamine and hydroxyethylmorpholine.
  • diols examples are ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,1-dimethylethane-1,2-diol, 2-butyl-2-ethyl-1,3-propanediol, 2-ethyl-1, 3-propanediol, 2-methyl-1,3-propanediol, neopentyl glycol, neopentyl glycol hydroxypivalate, 1,2-, 1,3- or 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol, bis-(4 -hydroxycyclohexane)isopropylidene, tetramethylcyclobutanediol, 1,2-, 1,3- or 1,4-cyclohexanediol, cyclooctanediol, norbornanediol, pinanediol
  • polyethylene glycol with a molecular weight of 106 to 678 g/mol poly-1,2-propanediol with a molecular weight of 134 to 888 g/mol, poly-1,3-propanediol with a molecular weight of 134 to 888 g/mol or poly-THF with a molar mass of 162 to 1098 g/mol.
  • triols and polyols are trimethylolbutane, trimethylolpropane, trimethylolethane, pentaerythritol, glycerol, ditrimethylolpropane, dipentaerythritol, sorbitol, mannitol, diglycerol, threitol, erythritol, adonitol (ribitol), arabitol (lyxitol), xylitol, dulcitol (galactitol), maltitol or isomalt .
  • Examples of primary or secondary monoamines as amines (E2) are monoamines having 6 to 200 carbon atoms, which can be monoalkylamines or dialkylamines, preferably monoalkylamines, preferably methylamine, ethylamine, isopropylamine , n-propylamine, n-butylamine, iso -butylamine, sec -butylamine, tert -butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-decylamine, n-dodecylamine, 2-ethylhexylamine, stearylamine, cetylamine, laurylamine, dimethylamine, diethylamine, Di-n-propylamine, di- iso -propylamine, di-n-butylamine, dihexylamine, dioctylamine
  • Preferred examples are fatty amines, i.e. octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine (stearylamine), oleylamine, elaidylamine, linoleylamine, linolenoylamine, nonadecylamine, eicosylamine or mixtures thereof.
  • the amines can also carry tertiary amino groups, since these do not react in reaction step (II).
  • Preferred such amines are 2-dimethylaminoethylamine, 3-dimethylaminopropylamine and N',N",N"-trimethyl diethylene triamine.
  • the radical R 3 in the amine (II) used is a polyisobutene polymer; the amines (II) are preferably obtainable by hydroformylation and amination of polyisobutene polymers.
  • the polyisobutene polymer preferably has a weight-average molecular weight of from 550 to 2300 g/mol, particularly preferably from 650 to 1500 g/mol, very particularly preferably from 850 to 1150 g/mol and in particular from 950 to 1050 g/mol.
  • the polyisobutene polymer which can be used for this purpose can be isobutene homo- or copolymers which preferably have a content of terminal vinylidene double bonds per polyisobutene chain end of at least 50 mol %. Such polyisobutene polymers have a higher reactivity.
  • Such homo- or copolymers are obtainable by polymerizing isobutene or an isobutene-containing monomer mixture in the presence of at least one Lewis acid suitable as a polymerization catalyst or of a complex composed of at least one Lewis acid and at least one donor and effective as a polymerization catalyst and in the presence of at least one initiator.
  • Lewis acid suitable as a polymerization catalyst or of a complex composed of at least one Lewis acid and at least one donor and effective as a polymerization catalyst and in the presence of at least one initiator.
  • Boron halides preferably boron trifluoride, are frequently and preferably used as the Lewis acid, but also iron halides, aluminum halides or alkylaluminum halides.
  • isobutene homopolymers are understood as meaning those polymers which, based on the polymer, are made up of at least 98 mol %, preferably at least 99 mol %, of isobutene.
  • isobutene copolymers are understood as meaning those polymers which contain more than 2 mol % of monomers in copolymerized form which differ from isobutene, for example linear butenes.
  • suitable isobutene sources include both pure isobutene and isobutene-containing C 4 hydrocarbon streams, for example C 4 raffinates, in particular "raffinate 1", C 4 cuts from isobutane dehydrogenation, C 4 cuts from steam crackers and from FCC crackers (fluid catalyzed cracking), provided they are largely freed from the 1,3-butadiene contained therein.
  • C 4 hydrocarbon stream from an FCC refinery unit is also known as a "b/b" stream.
  • Suitable isobutenic C 4 -hydrocarbon streams are, for example, the product stream of a propylene-isobutane co-oxidation or the product stream from a metathesis unit, which are generally used after conventional purification and/or concentration.
  • Suitable C 4 hydrocarbon streams typically 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 C 4 hydrocarbon streams mentioned is typically in the range from 40 to 60% by weight.
  • raffinate 1 generally consists essentially of 30 to 50% by weight isobutene, 10 to 50% by weight 1-butene, 10 to 40% by weight cis- and trans-2-butene and 2 to 35% by weight % butanes; in the polymerization process, the unbranched butenes in raffinate 1 are generally practically inert and only the isobutene is polymerized.
  • the monomer source used for the polymerization is a technical C 4 -hydrocarbon stream having an isobutene content of from 1 to 100% by weight, in particular from 5 to 99% by weight, in particular from 20 to 90% by weight. %, more preferably from 30 to 60% by weight, especially a raffinate 1 stream, a b/b stream from an FCC refinery unit, a product stream from a propylene-isobutane co-oxidation or a product stream from a metathesis unit.
  • amines are diamines, preferably 1,2-propanediamine, ethylenediamine, 2,2-dimethyl-1,2-ethanediamine, 1,3-propanediamine, 1,2-butanediamine, 1,4-butanediamine, 2 - Ethylhexane-1,3-diamine, 2,4-diethyloctane-1,3-diamine, 1,6-hexanediamine, or polyamines, preferably diethylenetriamine, triethylenetetramine, polyethyleneimines and polyethyleneamines.
  • the amine (E2) is an ethylenediamine or its oligomer, preferably it is selected from the group consisting of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and pentaethylenehexamine.
  • Conceivable alkanolamines (E3) are monoethanolamine, diethanolamine, monopropanolamine, dipropanolamine, 1,2-propanolamine, 1,3-propanolamine, 1,4-butanolamine, 1,6-hexanolamine and aminoethylethanolamine.
  • Component (E) is preferably monoalcohols, preferably those of the formula (I), monoamines, preferably those of the formula (II), or polyethyleneamines.
  • Hydrolysis in reaction step (III) occurs when an anhydride, preferably the anhydride of a dicarboxylic acid, is used as the derivative of monomer (A), whereas saponification or hydrolysis can occur when an ester is used as monomer (A).
  • the anhydride functionalities present in the copolymer after reaction step (II) are essentially completely hydrolyzed.
  • the amount of water corresponding to the desired degree of hydrolysis, based on the anhydride functionalities present, is added and the copolymer obtained from (I) is heated in the presence of the added water.
  • the reaction can be carried out under pressure to prevent water from escaping. Under these reaction conditions, the anhydride functionalities are usually selective implemented in the copolymer, whereas any carboxylic acid ester functionalities contained in the copolymer do not react, or at least react only to a minor extent.
  • the copolymer is reacted with an amount of strong base in the presence of water equal to the degree of saponification desired.
  • Hydroxides, oxides, carbonates or bicarbonates of alkali metals or alkaline earth metals can preferably be used as strong bases.
  • the copolymer obtained from (II) is then heated in the presence of the added water and the strong base.
  • 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, benzenesulfonic acids substituted or unsubstituted on the aromatic compound, sulfuric acid, nitric acid, hydrochloric acid or phosphoric acid; the use of acidic ion exchange resins is also conceivable.
  • the copolymer obtained from (II) is then heated in the presence of the added water and acid.
  • the copolymers obtained from step (III) still contain residues of acid anions, it may be preferable to remove these acid anions from the copolymer using an ion exchanger and preferably to exchange them for hydroxide ions or carboxylate ions, particularly preferably hydroxide ions. This is particularly the case when the acid anions contained in the copolymer are halides, contain sulfur or contain nitrogen.
  • the copolymer obtained from reaction step (III) 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 standards).
  • the number-average molecular weight Mn is usually from 0.5 to 10 kDa, preferably from 0.6 to 5, particularly preferably from 0.7 to 4, very particularly preferably from 0.8 to 3 and in particular from 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 reaction step (III) is preferably less than 5 mmol/g copolymer, particularly preferably less than 3, very particularly preferably less than 2 mmol/g copolymer and in particular less than 1 mmol/g.
  • the copolymers contain a high proportion of adjacent carboxylic acid groups, as determined by measuring adjacency. For this purpose, a sample of the copolymer is annealed for a period of 30 minutes at a temperature of 290° C. between two Teflon foils and an FTIR spectrum is recorded at a bubble-free point. The IR spectrum of Teflon is subtracted from the spectra obtained, 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%, very particularly preferably at least 25% and in particular at least 30%.
  • the fuel to which additives have been added with the above-mentioned copolymer can also be a gasoline fuel or, in particular, a middle distillate fuel; according to the invention, it is a diesel fuel.
  • the fuel can contain other customary additives to improve effectiveness and/or suppress wear.
  • the described copolymers are often used in the form of fuel additive mixtures, together with the usual additives: In the case of diesel fuels, these are primarily customary detergent additives, carrier oils, cold flow improvers, lubricity improvers, corrosion inhibitors other than the described copolymers, demulsifiers, dehazers, antifoams, cetane number improvers, combustion improvers, antioxidants or stabilizers, antistatic agents, metallocenes, metal deactivators , dyes and/or solvents.
  • additives In the case of diesel fuels, these are primarily customary detergent additives, carrier oils, cold flow improvers, lubricity improvers, corrosion inhibitors other than the described copolymers, demulsifiers, dehazers, antifoams, cetane number improvers, combustion improvers, antioxidants or stabilizers, antistatic agents, metallocenes, metal deactivators , dyes and/or solvents.
  • the invention encompasses the use of the above identified copolymers in additive packages containing at least one additive selected from the group consisting of detergent additives, carrier oils, cold flow improvers, lubricity improvers (lubricity improvers), corrosion inhibitors other than the described copolymers, demulsifiers, dehazers, antifoams, cetane number improvers, combustion improvers, antioxidants, stabilizers, antistatic agents, Metallocenes, metal deactivators, dyes and solvents to reduce the fuel consumption of direct-injection diesel engines, especially diesel engines with common-rail injection systems and/or to minimize power loss (power loss) in direct-injection diesel engines, especially in diesel engines with common-rail injection systems.
  • additives selected from the group consisting of detergent additives, carrier oils, cold flow improvers, lubricity improvers (lubricity improvers), corrosion inhibitors other than the described copolymers, demulsifiers, dehazers, antifoams, cetane number improvers,
  • lubricity improvers primarily lubricity improvers (friction modifiers), corrosion inhibitors other than the described copolymers, demulsifiers, dehazers, Antifoams, combustion improvers, antioxidants or stabilizers, antistatic agents, metallocenes, metal deactivators, dyes and/or solvents.
  • a further subject not according to the invention is the use of the above-mentioned copolymers in additive packages containing at least one additive selected from the group consisting of lubricity improvers (friction modifiers), corrosion inhibitors other than the described copolymers, demulsifiers, dehazers, antifoams, combustion improvers, antioxidants, stabilizers, antistatic agents, metallocenes, metal deactivators, dyes and solvents, to reduce of deposits in the intake system of a gasoline engine, such as in particular DISI and PFI (Port Fuel Injector) engines.
  • lubricity improvers corrosion modifiers
  • demulsifiers demulsifiers
  • dehazers dehazers
  • antifoams combustion improvers
  • combustion improvers antioxidants
  • stabilizers stabilizers
  • antistatic agents metallocenes
  • metal deactivators dyes and solvents
  • the hydrophobic hydrocarbon residue in the above detergent additives which provides sufficient solubility in fuel, has a number average molecular weight ( Mn ) of from 85 to 20,000, preferably from 113 to 10,000, more preferably from 300 to 5,000, more preferably from 300 to 3000, even more preferably from 500 to 2500 and in particular from 700 to 2500, especially from 800 to 1500.
  • Mn number average molecular weight
  • a typical hydrophobic hydrocarbon radical in particular in connection with the polar, in particular, polypropenyl, polybutenyl and polyisobutenyl radicals with a number-average molecular weight M n of preferably 300 to 5000, particularly preferably 300 to 3000, more preferably 500 to 2500, even more preferably 700 to 2500 and in particular 800 to 1500 in consideration.
  • Such additives based on highly reactive polyisobutene which are obtained 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 can be prepared, in particular from the EP-A 244 616 known.
  • the production route offers itself by chlorination and subsequent amination or by 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 e.g. B. ammonia, monoamines or the above polyamines can be used.
  • Corresponding additives based on polypropylene are in particular in the WO-A 94/24231 described.
  • Da monoamino groups containing additives
  • Da monoamino groups containing additives
  • Other particular monoamino groups (Da) containing additives are the compounds obtainable from polyisobutene epoxides by reaction with amines and subsequent dehydration and reduction of the amino alcohols, as they are particularly in DE-A 196 20 262 are described.
  • 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 having a total molecular weight of 500 to 20,000, all or part of the carboxyl groups to the alkali metal or alkaline earth metal salts and one remaining Rest of the carboxyl groups are reacted with alcohols or amines.
  • Such additives are in particular from EP-A 307 815 known.
  • Such additives are mainly used to prevent valve seat wear and, as in the WO-A 87/01126 described, are used with advantage in combination with conventional fuel detergents such as poly (iso) buteneamines 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 sulfosuccinate, as is found in particular in EP-A 639 632 is described.
  • Such additives serve mainly to prevent valve seat wear and can be used to advantage in combination with conventional fuel detergents such as poly(iso)buteneamines or polyetheramines.
  • Additives containing polyoxy-C 2 -C 4 -alkylene groups are preferably polyethers or polyetheramines, 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 the polyetheramines, are obtainable by subsequent reductive amination with ammonia, monoamines or polyamines.
  • Such products are particularly 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 have carrier oil properties. Typical examples of these are tridecanol or isotridecanol butoxylates, isononylphenol butoxylates and polyisobutenol butoxylates and propoxylates and the corresponding reaction products with ammonia.
  • Carboxylic acid ester groups (Dg) containing additives are preferably esters of mono-, di- or tricarboxylic acids with long-chain alkanols or polyols, especially those with a minimum viscosity of 2 mm 2 / s at 100 ° C, as in particular in the DE-A 38 38 918 are described.
  • Aliphatic or aromatic acids can be used as mono-, di- or tricarboxylic acids, and long-chain representatives having, for example, 6 to 24 carbon atoms are particularly suitable as ester alcohols or ester 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 hydroxyl 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 have free amine groups in addition to the amide function, and 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 reacting di- or polyamines with two succinic acid derivatives.
  • Such fuel additives are generally known and are 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.
  • the compounds according to the invention can be combined with quaternized compounds, as described in WO 2012/004300 , there preferably page 5, line 18 to page 33, line 5, particularly preferably of preparation example 1, which is hereby expressly incorporated by reference into the present disclosure.
  • the compounds according to the invention can be combined with quaternized compounds as described in the unpublished international application with the application number PCT/EP2014/061834 and the submission date June 6, 2014, preferably page 5, line 21 to page 47, line 34, particularly preferably of preparation examples 1 to 17.
  • the compounds according to the invention can be combined with quaternized compounds, as described in WO 11/95819 A1 , there preferably page 4, line 5 to page 13, line 26, particularly preferably preparation example 2.
  • the compounds according to the invention can be combined with quaternized compounds, as described in WO 11/110860 A1 , there preferably page 4, line 7 to page 16, line 26, particularly preferably of preparation examples 8, 9, 11 and 13.
  • the compounds according to the invention can be combined with quaternized compounds, as described in WO 06/135881 A2 , there preferably page 5, line 14 to page 12, line 14, particularly preferably examples 1 to 4.
  • the compounds according to the invention can be combined with quaternized compounds, as described in WO 10/132259 A1 , there preferably page 3, line 29 to page 10, line 21, particularly preferably example 3.
  • the compounds according to the invention can be combined with quaternized compounds, as described in WO 08/060888 A2 , there preferably page 6, line 15 to page 14, line 29, particularly preferably examples 1 to 4.
  • the compounds according to the invention can be combined with quaternized compounds, as described in GB 2496514A , there preferably paragraphs [00012] to [00039], particularly preferably examples 1 to 3.
  • the compounds according to the invention can be combined with quaternized compounds, as described in WO 2013 070503 A1 , there preferably paragraphs [00011] to [00039], particularly preferably examples 1 to 5.
  • 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.
  • One or more of the detergent additives mentioned can be added to the fuel in such an amount that the dosing 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 .-ppm, is.
  • Carrier oils used can be mineral or synthetic. Suitable mineral carrier oils are fractions obtained during petroleum processing, such as bright stock or base oils with viscosities such as those from the SN class 500 to 2000, but also aromatic hydrocarbons, paraffinic hydrocarbons and alkoxyalkanols. A fraction known as "hydrocrack oil” and obtained in the refining of mineral oil (vacuum distillate cut with a boiling range of about 360 to 500° C., obtainable from natural mineral oil which has been catalytically hydrogenated and isomerized and dewaxed under high pressure) can also be used. Mixtures of the mineral carrier oils mentioned above are also suitable.
  • suitable synthetic carrier oils are polyolefins (polyalphaolefins or polyinternal olefins), (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 -alkyl-cyclohexanols 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 the polyetheramines, are obtainable by subsequent reductive amination with ammonia, monoamines or polyamines.
  • Such products are particularly in the EP-A 310 875 , EP-A 356 725 , EP-A 700 985 and the US-A 4,877,416 described.
  • 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 and 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, such as those in particular DE-A 38 38 918 are described.
  • Aliphatic or aromatic acids can be used as mono-, di- or tricarboxylic acids, and long-chain representatives having, for example, 6 to 24 carbon atoms are particularly suitable as ester alcohols or ester polyols.
  • esters are adipates, phthalates, isophthalates, terephthalates and trimellitates of isooctanol, isononanol, isodecanol and isotridecanol, e.g. B. di-(n- or isotridecyl)phthalate.
  • Examples of particularly suitable synthetic carrier oils are alcohol-started polyethers having 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, z. B. 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 include 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 either in the form of the pure isomers or in the form of technical mixtures.
  • a particularly preferred alcohol is tridecanol.
  • 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.
  • 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 particular preference is given to 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.
  • Suitable synthetic carrier oils are alkoxylated alkyl phenols, as in the DE-A 10 102 913 are described.
  • Particular carrier oils are synthetic carrier oils, with the alcohol-initiated 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 which are able to improve the flow behavior of middle distillate fuels or diesel fuels in the cold. Appropriately, they must have sufficient oil solubility.
  • the cold flow improvers (middle distillate flow improvers", "MDFI") usually used with middle distillates of fossil origin, ie with conventional mineral diesel fuels, come into consideration for this.
  • MDFI middle distillate flow improvers
  • WASA wax anti-settling additive
  • 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 having 1 or 2, in particular having a carbon-carbon double bond.
  • the carbon-carbon double bond can be arranged both terminally ( ⁇ -olefins) and 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 also polymerized, these are preferably higher molecular weight than the abovementioned C 2 - to C 40 -olefin base monomers. 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 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 and structural isomers thereof.
  • Suitable carboxylic acid alkenyl esters are, for example, C 2 - to C 14 -alkenyl esters, for example the vinyl and propenyl esters, of carboxylic acids having 2 to 21 carbon atoms, the hydrocarbon radical of which can be linear or branched.
  • carboxylic acids with a branched hydrocarbon radical preference is given to those whose branching is in the ⁇ -position to the carboxyl group, the ⁇ -carbon atom particularly preferably being tertiary, ie the carboxylic acid being a so-called neocarboxylic acid.
  • the hydrocarbyl radical of the carboxylic acid is preferably linear.
  • carboxylic acid alkenyl 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, preference being given to the vinyl esters.
  • a particularly preferred carboxylic acid alkenyl ester is vinyl acetate;
  • Typical group (K1) copolymers resulting therefrom are the ethylene-vinyl acetate copolymers ("EVA”) used most frequently.
  • class (K1) copolymers are those which contain two or more different carboxylic acid alkenyl esters as copolymerized units, these differing in the alkenyl function and/or in the carboxylic acid group. Also suitable are copolymers which, in addition to the alkenyl carboxylic ester(s), contain at least one olefin and/or at least one (meth)acrylic ester as copolymerized units.
  • 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 suitable as class (K1) copolymers.
  • 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 other ethylenically unsaturated monomers are present in the copolymers of class (K1) in an amount of preferably 1 to 50% by weight, in particular 10 to 45% by weight and above all 20 to 40% by weight. %, based on the total copolymer, polymerized.
  • 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 class (K1) copolymers preferably have a number-average molecular weight M n of from 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, for example, by the copolymerization of 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 with at least 10 carbon atoms available.
  • 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 suitable comb polymers.
  • suitable comb polymers are, for example, those in the WO 2004/035715 and in " Comb-Like Polymers. Structure and Properties", NA Platé and VP Shibaev, J. Poly. Sci. Macromolecular Revs. 8, pp. 117-253 (1974 )" are described. Mixtures of comb polymers are also suitable.
  • Polyoxyalkylenes suitable as a component 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 EP-A 061 895 as well as in the U.S. 4,491,455 described. Particular polyoxyalkylene compounds are based on polyethylene glycols and polypropylene glycols having a number-average molecular weight of 100 to 5000. Polyoxyalkylene mono- and diesters of fatty acids having 10 to 30 carbon atoms, such as stearic acid or behenic acid, are also suitable.
  • Polar nitrogen compounds suitable as a component of class (K4) can be both ionic and nonionic 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 , where R 7 is a C 8 - bis C 40 hydrocarbon residue.
  • the nitrogen substituents can also be quaternized, ie in cationic form. Examples of such nitrogen compounds are ammonium salts and/or amides which can be obtained 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 are, for example, dioctadecylamine and methylbehenylamine.
  • Amine mixtures are also suitable for this purpose, in particular amine mixtures which can be obtained industrially, such as fatty amines or hydrogenated tallamines, as described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 6th edition, in the "Amines, aliphatic" chapter.
  • acids suitable for the reaction are 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) having at least one tertiary amino group with primary or secondary amines.
  • the poly(C 2 -C 20 -carboxylic acids) containing at least one tertiary amino group and on which this reaction product is based preferably contain at least 3 carboxyl groups, in particular 3 to 12, in particular 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 form 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 connected via hydrocarbon chains.
  • the component of class (K4) is preferably an oil-soluble reaction product based on poly(C 2 - to C 20 -carboxylic acids) having at least one tertiary amino group and having 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 denotes B 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 especially 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 especially 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, which may be bonded to one another.
  • These amines on which the oil-soluble reaction products of component (K4) are based are usually secondary amines and have the general formula HN(R 8 ) 2 , in which the two variables R 8 are each, independently of one another, 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, with regard to their relatively long-chain alkyl radicals, from naturally occurring fatty acids or from their derivatives.
  • the two radicals R 8 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 the ammonium salts; it is also possible for only a part to be present as amide structures and another part as ammonium salts. Preferably there are few or no free acid groups present.
  • the oil-soluble reaction products of component (K4) are preferably present entirely in the form of the amide structures.
  • Typical examples of such components (K4) are reaction products of nitrilotriacetic acid, ethylenediaminetetraacetic acid or propylene-1,2-diaminetetraacetic acid with in each case 0.5 to 1.5 mol per carboxyl group, in particular 0.8 to 1.2 mol per carboxyl group , dioleylamine, dipalmitinamine, dicoco fatty amine, distearylamine, dibehenylamine or especially 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, the latter being 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, the latter two being 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 in the WO 93/18115 are described.
  • Sulfocarboxylic acids, sulfonic acids or derivatives thereof suitable as cold flow improvers for the component of class (K5) are, for example, the oil-soluble carboxamides 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 in EP-A 261 957 to be discribed.
  • Poly(meth)acrylic acid esters suitable as cold flow improvers of the component of class (K6) are both homo- and copolymers of acrylic and methacrylic acid esters. Copolymers of at least two different (meth)acrylic acid esters, which differ in terms of the alcohol condensed in, are preferred. If appropriate, the copolymer also contains another, different, olefinically unsaturated monomer as copolymerized units. 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 C14 and C15 alcohols, the acid groups being neutralized with hydrogenated tallamine. Suitable poly (meth) acrylic acid esters are for example in WO 00/44857 described.
  • the cold flow improver or the mixture of different 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 especially from 100 to 700 wppm, for example from 200 to 500 wppm.
  • Suitable lubricity improvers are usually based on fatty acids or fatty acid esters. Typical examples are tall oil fatty acid, such as in WO 98/004656 described, and glycerol monooleate. Also the one in the U.S. 6,743,266 B2 reaction products described from natural or synthetic oils, for example triglycerides, and alkanolamines are suitable as such lubricity improvers.
  • Suitable corrosion inhibitors are, for example, succinic esters, especially with polyols, fatty acid derivatives, e.g (Ethyl Corporation).
  • demulsifiers are the alkali metal or alkaline earth metal salts of alkyl-substituted phenol and naphthalene sulfonates and the alkali metal or alkaline earth metal 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, Condensation products of ethylene oxide (EO) and propylene oxide (PO), e.g. also in the form of EO/PO block copolymers, polyethylene imines 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 antifoams are, for example, 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 improvers include aliphatic nitrates such as 2-ethylhexyl nitrate and cyclohexyl nitrate, and peroxides such as di-tert-butyl peroxide.
  • antioxidants examples include substituted phenols such as 2,6-di-tert-butylphenol and 6-di-tert-butyl-3-methylphenol and phenylenediamines such as N,N'-di-sec-butyl-p-phenylenediamine.
  • Suitable metal deactivators include salicylic acid derivatives such as N,N'-disalicylidene-1,2-propanediamine.
  • Suitable are, for example, 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.
  • solvents usually get into the diesel fuel together with the aforementioned additives and co-additives, which they are supposed to dissolve or dilute for better handling.
  • the additive according to the invention is outstandingly suitable as a fuel additive and can in principle be used in any fuel. It brings about a whole range of beneficial effects when operating internal combustion engines with fuels.
  • the quaternized additive is used in middle distillate fuels, in particular diesel fuels.
  • Another subject not according to the invention is therefore also fuels, in particular middle distillate fuels, with an additive to achieve advantageous effects in the operation of internal combustion engines, for example diesel engines, in particular direct-injection diesel engines, especially diesel engines with common rail injection systems, effective content of the quaternized additive according to the invention.
  • This effective content is generally from 10 to 5000 ppm by weight, preferably from 20 to 1500 ppm by weight, in particular from 25 to 1000 ppm by weight, in particular from 30 to 750 ppm by weight. in each case based on the total amount of fuel.
  • Middle distillate fuels such as diesel fuels or heating oils are preferably petroleum raffinates which usually have a boiling range of 100 to 400.degree. These are mostly distillates with a 95% point up to 360°C or even higher. However, this can also be so-called "ultra low sulfur diesel” or "city diesel", characterized by a 95% point of, for example, a maximum of 345° C. and a maximum sulfur content of 0.005% by weight or by a 95% point of for example 285°C and a maximum sulfur content of 0.001% by weight.
  • middle distillate fuels of fossil, vegetable or animal origin which are essentially hydrocarbon mixtures
  • biofuel oils biodiesel
  • middle distillate fuel Such mixtures are encompassed by the term "middle distillate fuel”. They are commercially available and usually contain the biofuel oils in minor amounts, typically in amounts of 1 to 30% by weight, in particular 3 to 10% by weight, based on the total amount of middle distillate of fossil, vegetable or animal origin and biofuel oil.
  • Biofuel oils are typically 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, in particular C 1 - to C 4 -alkyl esters, which are obtained by transesterification of the glycerides occurring in vegetable and/or animal oils and/or fats, in particular triglycerides, using lower alcohols, for example ethanol or, above all, methanol (“FAME”), are available.
  • 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”) and in particular rapeseed oil methyl ester (“RME”) .
  • the middle distillate fuels or diesel fuels are particularly preferably those with a low sulfur content, ie with a sulfur content of less than 0.05% by weight, preferably less than 0.02% by weight, in particular less than 0.005% by weight and especially less than 0.001% by weight sulphur.
  • the quaternized additive according to the invention is particularly suitable as a fuel additive in fuel compositions, in particular in diesel fuels, for overcoming the problems described at the outset in direct-injection diesel engines, especially in those with common-rail injection systems.
  • the mass average Mw and number average molecular weight Mn of the polymers were measured by gel permeation chromatography (GPC). GPC separation was performed using two PLge Mixed B columns (Agilent) in tetrahydrofuran at 35 °C. The calibration was carried out using a narrow-distribution polystyrene standard (PSS, Germany) with a molecular weight of 162-50400 Da. Hexylbenzene was used as a low molecular weight marker.
  • the olefin or the mixture of olefins with or without a solvent was initially taken in a reactor with an anchor stirrer. The mixture was heated to the indicated temperature under a stream of nitrogen and with stirring. To this was added the indicated free radical initiator (optionally diluted in the same solvent) and molten maleic anhydride (1 equivalent based on olefin monomer). The reaction mixture was stirred at the same temperature for the specified reaction time and then cooled. Water was then added (unless otherwise stated, 0.9 equivalent based on maleic anhydride) and the mixture was stirred either at 95° C. for 10-14 h or under pressure at 110° C. for 3 h.
  • the IDID engine test was used as a further test method, in which the exhaust gas temperatures of the cylinders at the cylinder outlet were determined during a cold start of the DW10 engine.
  • a direct-injection diesel engine with a common-rail system from the manufacturer Peugeot was used in accordance with test methods CEC F-098-08.
  • a commercially available B7 diesel fuel in accordance with EN 590 from Aral was used as the fuel.
  • 1 ppm by weight of sodium naphthenate and 20 ppm by weight of dodecenylsuccinic acid were added to this.
  • the engine was cooled down and restarted.
  • the exhaust gas temperature from each cylinder was recorded. The lower the differences between the determined exhaust gas temperatures, the lower the amount of IDID formed.
  • the IDID engine test described above was used as a further test method. Instead of a dirty up and clean up sequence, only a keep clean run with 1 ppm by weight of sodium naphthenate and 40 ppm by weight (based on the solids content) according to synthesis example 2 was added.
  • the performance measurement was performed as performed in CEC F-98-08. At the end of an 8 hour period, a 0.1% power loss was observed.
  • the compounds of the present invention are effective against deposits caused by metal deposits in direct injection engines.
  • the performance measurement was performed as performed in CEC F-98-08. A power loss of 0.6% was observed at the end of an 8 hour period.
  • the compounds of the present invention are effective against deposits caused by metal deposits in direct injection engines.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Combustion & Propulsion (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Liquid Carbonaceous Fuels (AREA)
EP17807843.2A 2016-12-15 2017-11-29 Polymere als dieselkraftstoffadditive für direkteinspritzende dieselmotoren Active EP3555244B1 (de)

Applications Claiming Priority (2)

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EP16204390 2016-12-15
PCT/EP2017/080838 WO2018108534A1 (de) 2016-12-15 2017-11-29 Polymere als dieselkraftstoffadditive für direkteinspritzende dieselmotoren

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EP (1) EP3555244B1 (pl)
CN (1) CN110088253B (pl)
ES (1) ES2948483T3 (pl)
MY (1) MY202420A (pl)
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WO2024061760A1 (de) 2022-09-23 2024-03-28 Basf Se Verminderung der kristallisation von paraffinen in kraftstoffen

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EP3555244A1 (de) 2019-10-23
MY202420A (en) 2024-04-28
PL3555244T3 (pl) 2023-11-06
US10947467B2 (en) 2021-03-16
CN110088253B (zh) 2022-03-18
WO2018108534A1 (de) 2018-06-21
CN110088253A (zh) 2019-08-02
US20200056109A1 (en) 2020-02-20
US11566196B2 (en) 2023-01-31
US20210163837A1 (en) 2021-06-03
ES2948483T3 (es) 2023-09-13

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