WO2013064689A1 - Polyétheramines quaternaires et leur utilisation en tant qu'additifs dans des carburants et des lubrifiants - Google Patents

Polyétheramines quaternaires et leur utilisation en tant qu'additifs dans des carburants et des lubrifiants Download PDF

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WO2013064689A1
WO2013064689A1 PCT/EP2012/071844 EP2012071844W WO2013064689A1 WO 2013064689 A1 WO2013064689 A1 WO 2013064689A1 EP 2012071844 W EP2012071844 W EP 2012071844W WO 2013064689 A1 WO2013064689 A1 WO 2013064689A1
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alkyl
fuel
quaternized
general formula
additive
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PCT/EP2012/071844
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German (de)
English (en)
Inventor
Markus Hansch
Harald BÖHNKE
Ludwig Völkel
Marc Walter
Wolfgang Grabarse
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Basf Se
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Priority to BR112014010671A priority Critical patent/BR112014010671A2/pt
Priority to ES12780216T priority patent/ES2726102T3/es
Priority to AU2012331073A priority patent/AU2012331073B2/en
Priority to CA2854421A priority patent/CA2854421C/fr
Priority to CN201280065791.5A priority patent/CN104024385B/zh
Priority to KR1020147015015A priority patent/KR102033606B1/ko
Priority to EP12780216.3A priority patent/EP2773729B1/fr
Priority to MX2014005325A priority patent/MX2014005325A/es
Priority to PL12780216T priority patent/PL2773729T3/pl
Publication of WO2013064689A1 publication Critical patent/WO2013064689A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • 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
    • C10L1/22—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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • 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
    • C10L1/22—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
    • C10L1/2225—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates hydroxy containing
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • 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
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • C10L1/2227—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond urea; derivatives thereof; urethane
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • 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
    • C10L1/22—Organic compounds containing nitrogen
    • 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)
    • C10L1/2387—Polyoxyalkyleneamines (poly)oxyalkylene amines and derivatives thereof (substituted by a macromolecular group containing 30C)
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • 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
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/04—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M133/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M133/08—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2215/042—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/04—Molecular weight; Molecular weight distribution
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/04—Detergent property or dispersant property
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/54—Fuel economy
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/252—Diesel engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/252—Diesel engines
    • C10N2040/253—Small diesel engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2070/00—Specific manufacturing methods for lubricant compositions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2070/00—Specific manufacturing methods for lubricant compositions
    • C10N2070/02—Concentrating of additives

Definitions

  • the present invention relates to novel quaternized polyetheramines and their preparation, Furthermore, the present invention relates to the use of these compounds as a fuel and lubricant additive. More particularly, the invention relates to the use of these quaternized nitrogen compounds as a fuel additive to reduce or prevent deposits in the injection systems of direct injection diesel engines, particularly in common rail injection systems, to reduce fuel consumption of direct injection diesel engines, particularly diesel engines with common rail injection systems. and to minimize the power loss in direct injection diesel engines, especially in diesel engines with common rail injection systems.
  • the invention also relates to additive packages containing these polyetheramines; as well as with it additized fuels and lubricants. Furthermore, the invention relates to the use of these quaternized nitrogen compounds as an additive for gasoline fuels, in particular for improving the intake system cleanliness of gasoline engines.
  • direct-injection diesel engines the fuel is injected through a directly into the combustion chamber-reaching multi-hole injection nozzle of the engine and finely distributed (nebulized), instead of being introduced as in the classic (chamber) diesel engine in a vortex or vortex chamber.
  • the advantage of direct-injection diesel engines lies in their high performance for diesel engines and yet low consumption. In addition, these engines achieve a very high torque even at low speeds.
  • the conventional distributor injection pump the unit-injector system and the common-rail system
  • the diesel fuel is pumped from a pump with pressures up to 2000 bar into a high-pressure line, the common rail.
  • spur lines run to the various injectors, which inject the fuel directly into the combustion chamber.
  • the full pressure is always applied to the common rail, which allows a multiple injection or a special injection form.
  • the other injection systems only a smaller variation of the injection is possible.
  • Injection in the common rail is essentially subdivided into three groups: (1) pre-injection, which essentially achieves softer combustion, so that hard combustion noises ("nails") are reduced and engine running appears quiet; (2.) main injection, which is responsible in particular for a good torque curve; and (3) post-injection which provides, in particular, a low NCv value.
  • pre-injection which essentially achieves softer combustion, so that hard combustion noises ("nails") are reduced and engine running appears quiet
  • main injection which is responsible in particular for a good torque curve
  • post-injection which provides, in particular, a low NCv value.
  • the fuel is not burned in the rule, but evaporated by residual heat in the cylinder.
  • the resulting exhaust gas / fuel mixture is transported to the exhaust system, where the fuel in the presence of suitable catalysts acts as a reducing agent for the nitrogen oxides NO x .
  • the pollutant emissions of the engine eg the emission of nitrogen oxides (NO x ), carbon monoxide (CO) and particulate matter (soot) can be positively influenced in the common-rail injection system.
  • NO x nitrogen oxides
  • CO carbon monoxide
  • particulate matter particulate matter
  • Fuel metering systems are contaminated by impurities caused by dust particles from the air, unburned hydrocarbon residues from the combustion chamber and the crankcase ventilation gases directed into the gasifier. These residues shift the air-fuel ratio at idle and in the lower part-load range, making the mixture leaner, incomplete combustion and, in turn, increasing the proportion of unburned or partially combusted hydrocarbons in the exhaust gas and increasing gasoline consumption. It is known that to avoid these disadvantages, fuel additives are used for keeping valves and carburetors or injection systems of gasoline engines clean (cf., for example: M. Rossenbeck in Catalysts, Surfactants, Mineral Oil Additives, Ed. J. Falbe, U. Hasserodt, S. 223, G. Thieme Verlag, Stuttgart 1978). Depending on the mode of action but also on the preferred site of action of such detergent additives, a distinction is made today between two generations.
  • the first additive generation was only able to prevent the formation of deposits in the intake system, but not to remove existing deposits, whereas the modern second generation additives can do both (keep-clean and clean-up effect) and especially also because of their excellent thermal stability at higher temperature zones, namely at the intake valves.
  • Such detergents which can originate from a large number of chemical substance classes, such as, for example, polyalkeneamines, polyetheramines, polybutene-Mannich bases or polybutene succinimides, are generally used in combination with carrier oils and in some cases further additive components, for example corrosion inhibitors and demulsifiers.
  • the carrier oils perform a solvent or wash function in combination with the detergents.
  • Carrier oils are usually high-boiling, viscous, thermostable liquids which coat the hot metal surface and thereby prevent the formation or deposition of impurities on the metal surface.
  • Detergent-effect fuel additives of the younger generation often have quaternized nitrogen groups.
  • quaternized ammonium salts prepared by condensation of a hydrocarbyl-substituted acylating agent and an oxygen- or nitrogen-containing compound having a tertiary amino group, followed by quaternization by means of hydrocarbyl epoxide in combination with stoichiometric amounts of an acid, in particular acetic acid.
  • additives are used especially as diesel fuel additives to reduce power loss.
  • Polyalkene-substituted quaternized amines, such as in particular quaternized polyisobuteneamines, and their use as detergent additives to reduce inlet valve deposits and as lubricant additives for internal combustion engines are described in US 2008/01 13890.
  • No. 6,331,648 B1 relates to specific quaternary etheramine compounds which contain a 1-ethyl-1,3-propylene unit incorporated between the alkoxylate chain and quaternary nitrogen.
  • the use of these compounds as corrosion inhibitors or detergent additives in gasoline and diesel fuels is speculated, but without demonstrating their usefulness.
  • EP 182 669 A1 describes halogenated or sulfur-containing alkoxylated quaternary ammonium compounds of the general structure
  • R i represents an alkylene oxide block.
  • R i represents an alkylene oxide block.
  • Preferred anions A- are chloride, methylsulfate and ethylsulfate.
  • US 4 564 372, US 4 581 151, US 4 600 409 and WO 1985/000620 relate to alkyl halides quaternized, ie halogen-containing, polyoxyalkyleneamine salts in which polyoxyalkylene unit and amine moiety via different linker groups, in particular amine linkers of Type - C (0) -NH-. Use as dispersants and corrosion inhibitors in fuels is postulated, but without actually demonstrating specific functions experimentally.
  • the additives according to the invention are superior to the known additives according to the prior art in several respects and can be used simultaneously in diesel and gasoline fuels. They are distinguished by their advantageous cleaning and retention effect on various components of internal combustion engines, such as on diesel engine injectors but also on intake valves and injectors of gasoline engines, and prevent the formation of combustion chamber deposits or eliminate ready formed combustion chamber deposits of internal combustion engines. In addition, they prevent the formation of deposits in fuel filters or eliminate already formed filter contaminants.
  • FIG. 1 shows the injector cleanliness achievable with additives according to the invention after a test operation with a direct-injection gasoline engine (1 b and 1 c) in comparison to operation with non-additized fuel (1 a).
  • FIG. 2 shows the sequence of a one-hour engine test cycle according to CEC F-098-08. Detailed description of the invention:
  • a fuel or lubricant composition in particular a fuel composition, comprising, in a majority of a conventional fuel or lubricant, an effective amount of at least one quaternized nitrogen compound-containing reaction product, or a quaternized nitrogen compound-containing partial fraction thereof obtained from the reaction product, wherein the reaction product is available through implementation
  • quaternizing agent which converts the at least one tertiary amino group into a quaternary ammonium group.
  • R 3 and R 4 are identical or different and are H, alkyl, alkylaryl or aryl.
  • a fuel or lubricant composition according to any one of the preceding embodiments, wherein the quaternizing agent is selected from among Alky- lenoxiden optionally in combination with acid; aliphatic or aromatic mono- or polycarboxylic acid esters, in particular mono- or dialkylcarboxylic acid esters; cyclic non-aromatic or aromatic mono- or polycarboxylic acid esters; dialkyl; alkyl sulfates; alkyl halides; Alkylaryl halides; in particular halogen and sulfur-free quaternizing agents, such as alkylene oxides in combination with acid, such as a carboxylic acid; aliphatic or aromatic mono- or polycarboxylic acid esters, in particular mono- or dialkylcarboxylic acid esters; cyclic non-aromatic or aromatic mono- or polycarboxylic acid esters and dialkyl carbonates; and mixtures thereof.
  • a fuel or lubricant composition comprising, in a majority of a conventional fuel
  • R 1 and R 2 are identical or different and represent alkyl, alkenyl, hydroxyalkyl, hydroxyalkynyl, aminoalkyl or aminoalkenyl, or R 1 and R 2 together represent alkylene, oxyalkylene or aminoalkylene;
  • R 3 and R 4 are identical or different and are H, alkyl, alkylaryl, or aryl;
  • R5 is a radical introduced by quaternization, in particular alkyl, hydroxyalkyl, arylalkyl or hydroxyarylalkyl;
  • R 6 is alkyl, alkenyl, optionally mono- or polyunsaturated cycloalkyl, aryl, in each case optionally substituted, for example with at least one hydroxyl radical or alkyl radical, or interrupted by at least one heteroatom;
  • A is a straight-chain or branched alkylene radical which is optionally interrupted by one or more heteroatoms, such as N, O and S;
  • n stands for an integer value of 1 to 50 and
  • X- represents an anion, in particular an anion resulting from the quaternization reaction.
  • R 3 and R 4 are identical or different and represent H, Ci-C6 alkyl or phenyl;
  • R5 is a quaternized radical selected from C 1 -C 6 -alkyl, hydroxy-C 1 -C 6 -alkyl or -CH 2 CH (OH) aryl;
  • R 6 is C 1 -C 20 alkyl, e.g. C10-C20, Cn-C2o or Ci2-C2o-alkyl or aryl or alkylaryl, wherein alkyl is in particular C1-C20- stands;
  • A is a straight-chain or branched C 2 -C 6 -alkylene radical which is optionally interrupted by one or more heteroatoms, such as N, O and S; n for an integer value of 1 to 30 and
  • X- represents an anion resulting from the quaternization reaction.
  • Fuel composition according to one of the preceding embodiments selected from diesel fuels, gasoline fuels, biodiesel fuels and alkanol-containing gasolines.
  • Quaternized nitrogen compound as defined in one of the preceding embodiments in particular selected from halogen-free and sulfur-free.
  • R 5 is alkyl or aryl and X has the meaning given above, or with an alkylene oxide of the formula
  • R6 has the meanings given above, with an epoxide of the general formula III
  • R 3 and R 4 have the meanings given above, alkoxylated, to give a polyether of the formula Ib-1; R 6 -O-CH (R 3 ) -CH (R 4 ) -O-CH (R 3 ) -CH (R 4 ) OH (Ib-1); in which R 3 , R 4 and FS, A, X and n have the abovementioned meanings b) subsequently the polyether of the formula Ib-1 thus obtained with an amine of the general formula in which R1 and R2 have the meanings given above,
  • the alkyl of the formula (Ib-2) is optionally alkylated, if R 1 and / or R 2 are H and then c) the product from stage b) quaternized to obtain a reaction product comprising at least one compound of general formula Ib, wherein the quaternization is carried out for example with a compound of general formula IV
  • R 5 is alkyl or aryl and X has the meaning given above, or with an alkylene oxide of the formula
  • Quaternized nitrogen compound obtainable by a process according to embodiment 10 or 11, in particular in halogen- and sulfur-free form.
  • I DID Internal Diesel Injector Deposits
  • Additive concentrate containing in combination with further diesel or Otto fuel additives, in particular diesel fuel additives, at least one quaternized nitrogen compound as defined in embodiment 8 or prepared according to one of embodiments 9 or 10.
  • the quaternizing agent is not an aromatic carboxylic acid ester, such as e.g. Salicylates.
  • the quaternizing agent is selected from compounds of the formulas (1) or (2) described herein.
  • the quaternized (nitrogen) substituent is especially alkyl (especially C1-C6 alkyl), or hydroxyarylalkyl (such as 2-hydroxy-2-phenylethyl).
  • the polyether substituent has no aryl or aralkyl groups.
  • the quaternized nitrogen compound is a compound of formula (Ia) or (Ib).
  • halogen-free or sulfur-free means the absence of inorganic or organic halogen-containing or sulfur-containing compounds and / or their corresponding ions, such as halide anion and sulfur-containing anions, in particular sulfates.
  • Halogen-free or “sulfur-free” in particular includes the absence of stoichiometric amounts of halogen-containing or sulfur-containing compounds or anions. Substoichiometric amounts of halogen-containing or sulfur-containing compounds or anions are present, for example, in molar ratios of less than 1: 0.1, or less 1 .
  • Halogen-free or sulfur-free includes in particular the complete absence of halogen-containing or sulfur-containing compounds and / or their corresponding ions, such as halide anion and sulfur-containing anions, in particular sulfates.
  • Carboxylic acids include, in particular, organic carboxylic acids, in particular monocarboxylic acids of the RCOOH type, in which R represents a short-chain hydrocarbyl radical, for example a lower alkyl or C 1 -C 4 -alkylcarboxylic acid.
  • Quadraturear nitrogen groups or amino groups include in particular primary, secondary and tertiary amino groups.
  • hydrocarbyl is to be interpreted broadly and includes both cyclic aromatic or non-aromatic, as well as long-chain or short-chain, straight or branched hydrocarbon radicals having 1 to 50 carbon atoms, which may additionally heteroatoms,
  • hydrocarbyl includes, for example, the alkyl, alkenyl, aryl, alkylaryl, cycloalkenyl, or cycloalkyl radicals and their substituted analogs as defined below ,
  • Alkyl or “lower alkyl” in particular represents saturated, straight-chain or branched hydrocarbon radicals having 1 to 4, 1 to 6, 1 to 8, 1 to 10, 1 to 14 or 1 to 20 carbon atoms, such as. Methyl, ethyl, n -propyl, 1-methylethyl, n-butyl, 1 - Methyl-propyl, 2-methylpropyl, 1,1-dimethylethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1, 1 - Dimethylpropyl, 1, 2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2,2-dimethylbutyl, 1, 1-
  • Hydroxyalkyl is in particular the mono- or polysubstituted, in particular monohydroxylated, analogs of the above-mentioned alkyl radicals, for example the monohydroxylated analogs of the above straight-chain or branched alkyl radicals, for example the linear hydroxyalkyl groups, for example those having a primary (terminal) hydroxyl group, such as hydro - xymethyl, 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, or those with non-terminal hydroxyl groups, such as 1-hydroxyethyl, 1- or 2-hydroxypropyl, 1- or 2-hydroxybutyl or 1-, 2- or 3- hydroxybutyl.
  • Alkenyl is mono- or polysubstituted, in particular monounsaturated, straight-chain or branched hydrocarbon radicals having 2 to 4, 2 to 6, 2 to 8 2 to 10 or 2 or to 20 carbon atoms and a double bond in any position, for example C2-C6 alkenyl such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1 Methyl 2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl -1 -butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-2-butenyl, 2-methyl-2-but
  • aminoalkyl and “aminoalkenyl” are in particular the mono- or polysubstituted, in particular simply aminated, analogs of the above alkyl or alkenyl radicals, or analogs of the above hydroxyalkyl, where the OH group has been replaced by an amino group.
  • Alkylene stands for straight-chain or mono- or poly-branched hydrocarbon bridging groups having 1 to 10 carbon atoms, such as, for example, C 1 -C 6 -alkylene groups selected from -CH 2 -, - (CH 2 ) 2 -, - (CH 2 ) 3 , - (CH 2 ) 4-, - (CH 2 ) 2 -CH (CH 3 ) -, -CH 2 -CH (CH 3 ) - CH 2 -, (CH 2 ) 4 -, - (CH 2 ) 5 -, - (CH 2 ) 6 , - (CH 2 ) 7 -, -CH (CH 3 ) -CH 2 -CH 2 -CH (CH 3 ) - or - CH (CH 3 ) -CH 2 -CH 2 - CH 2 -CH (CH 3 ) - or C 1 -C 4 -alkylene groups selected from -CH 2 -, - (CH 2 ) 2
  • Oxyalkylene radicals correspond to the definition of the above straight-chain or mono- or polysubstituted alkylene radicals having 2 to 10 carbon atoms, the coal chain being interrupted by an oxygen heteroatom 1 or more times, in particular 1 times.
  • Aminoalkylene correspond to the definition of the above straight-chain or mono- or polysubstituted alkylene radicals having 2 to 10 carbon atoms, wherein the coal chain is interrupted by a nitrogen group (in particular - NH group) 1 or more times, in particular 1 times.
  • Non-limiting examples are: -CH 2 -NH-CH 2 -, - (CH 2 ) 2 -NH- (CH 2 ) 2-, - (CH 2 ) 3 -NH- (CH 2 ) 3-, or - CH 2 -NH- (CH 2 ) 2 -, - (CH 2 ) 2 -NH- (CH 2 ) 3 -, -CH 2 -NH- (CH 2 ) 3 .
  • cycloalkyl means carbocyclic radicals of 3 to 20 carbon atoms, such as C 3 -C 2 cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; preference is given to cyclopentyl, cyclohexyl, cycloheptyl and also cyclopropylmethyl, cyclopropylethyl, cyclobutylmethyl, cyclobutylethyl, cyclopentylmethyl, cyclopentylethyl, cyclohexylmethyl or C 3 -C 7 -cycloalkyl, such as cyclopropyl, cyclobutyl, Cyclopentyl, cyclohexyl,
  • Cycloalkenyl or mono- or polyunsaturated cycloalkyl in particular represents monocyclic, mono- or polyunsaturated hydrocarbon groups having 5 to 8, preferably up to 6 carbon ring members, such as the monounsaturated radicals cyclopenten-1-yl, cyclopenten-3-yl, cyclohexene -1 -yl, cyclohexen-3-yl and cyclohexyl-4-yl;
  • Aryl denotes mononuclear or polynuclear, preferably mononuclear or dinuclear, optionally substituted aromatic radicals having 6 to 20, for example 6 to 10, ring carbon atoms, for example phenyl, biphenyl, naphthyl, such as 1- or 2-naphthyl, tetracyclic hydronaphthyl, fluorenyl, indenyl and phenanthrenyl These aryl radicals may optionally carry 1, 2, 3, 4, 5 or 6 identical or different substituents.
  • Alkylaryl stands for the in any position of the ring one or more times, in particular 1- or 2-fold, alkyl-substituted analogs of the above aryl radicals, wherein aryl also has the abovementioned meanings, such as CrC 4 alkyl-phenyl, wherein the C 1 -C 4 -alkyl radicals can be in any desired ring position.
  • Substituents for radicals specified herein are especially selected from keto groups, -COOH, -COO-alkyl, -OH, -SH, -CN, amino, -NO 2 , alkyl, or alkenyl groups.
  • Mn number average molecular weight
  • R 1 and R 2 are identical or different and are alkyl, alkenyl, hydroxyalkyl, hydroxyalkenyl, aminoalkyl or aminoalkenyl, or R 1 and R 2 together represent alkylene, oxyalkylene or aminoalkylene; and A is a straight-chain or branched alkylene or alkenylene radical which is optionally interrupted by one or more heteroatoms, such as N, O and S;
  • Suitable quaternizing agents are, in principle, all compounds suitable as such.
  • the quaternizing agent is in particular selected from alkylene oxides, if appropriate in combination with acid; aliphatic or aromatic carboxylic acid esters, in particular dialkyl carboxylates; alkanoates; cyclic non-aromatic or aromatic carboxylic acid esters; dialkyl; alkyl sulfates; Alkyl halides; alkylaryl halides; and mixtures thereof.
  • the quaternization of the at least one quaternizable tertiary nitrogen atom takes place with at least one quaternizing agent selected from epoxides, in particular hydrocarbyl epoxides.
  • the R a radicals contained therein are identical or different and represent H or a hydrocarbyl radical.
  • the hydrocarbyl radical may have at least 1 to 14 carbon atoms.
  • these are aliphatic or aromatic radicals, such as, for example, linear or branched C 1 -C 6 -alkyl radicals or aromatic radicals, such as phenyl or C 1 -C 4 -alkylphenyl.
  • Suitable hydrocarbyl epoxides are, for example, aliphatic and aromatic alkylene oxides, in particular C 2-6 -alkylene oxides, such as ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 2-methyl-1,2-propene oxide (isobutene oxide ), 1,2-pentenoxide, 2,3-pentenoxide, 2-methyl-1,2-butene oxide, 3-methyl-1,2-butene oxide, 1,2-hexene oxide, 2,3-hexene oxide, 3,4- Hexene oxide, 2-methyl-1,2-pentenoxide, 2-ethyl-1,2-butene oxide, 3-methyl-1,2-pentene oxide, 1,2-decene oxide, 1,2-dodecene oxide or 4-methyl-1, 2-pentene; Tetra-decane oxide; hexadecene; and also aromatic-substituted ethylene oxides, such as optionally substituted styrene oxide, in particular
  • epoxides as quaternizing these are in the presence or absence of free acids, especially in the presence or absence of free protic acids, such as especially with C-12 monocarboxylic acids, such as formic acid, acetic acid or propionic acid or C2-i2-dicarboxylic acids such as oxalic acid or adipic acid; or in the presence or absence of sulfonic acids, such as benzenesulfonic acid or toluenesulfonic acid or aqueous mineral acids, such as sulfuric acid or hydrochloric acid.
  • the quaternization product thus produced is thus either "acidic" or "acid-free" within the meaning of the present invention.
  • alkyl esters of a cycloaromatic or cycloaliphatic mono- or polycarboxylic acid in particular a mono- or dicarboxylic acid
  • alkyl esters of a cycloaromatic or cycloaliphatic mono- or polycarboxylic acid in particular a mono- or dicarboxylic acid
  • an aliphatic polycarboxylic acid in particular dicarboxylic acid
  • the quaternization of the at least one quaternizable tertiary nitrogen atom is carried out with at least one quaternizing agent selected from a) compounds of general formula 1 wherein
  • Ri is a lower alkyl radical
  • R 2 is an optionally substituted mononuclear aryl or cycloalkyl radical, the substituent being selected from OH, NH 2 , NO 2 , C (O) OR 3 ; RiaOC (O) -, wherein Ri a has the meanings given above for R 1, and R 3 is H or R 1; or
  • Ri and Ria independently represent a lower alkyl radical
  • A represents hydrocarbylene (such as alkylene or alkenylene).
  • Particularly suitable quaternizing agents are the lower alkyl esters of oxalic acid, such as dimethyl oxalate and diethyl oxalate.
  • Ri is a d, C2 or C3 alkyl radical
  • R 2 is a substituted phenyl radical, where the substituent for HO or an ester radical of the formula R i a OC (O) - which is in the para, meta or in particular ortho position to the radical R i OC (O) - on the aromatic ring ,
  • Particularly suitable quaternizing agents are the lower alkyl esters of salicylic acid, such as methyl salicylate, ethyl salicylate, n- and i-propyl salicylate, and n-, i- or tert-butyl salicylate.
  • An "anion resulting from the quaternization reaction" X- is, for example, a halide such as a chloride or bromide, a sulfate radical ((SO4) 2 " ), or the anionic radical of a mono- or polyhydric, aliphatic or aromatic carboxylic acid, or the anionic one Rest ROC (0) 0- resulting from the quaternization of a dialkyl carbonate.
  • a halide such as a chloride or bromide
  • anionic radical of a mono- or polyhydric, aliphatic or aromatic carboxylic acid or the anionic one Rest ROC (0) 0- resulting from the quaternization of a dialkyl carbonate.
  • the quaternizable nitrogen compound is selected from hydroxyalkyl substituted mono- or polyamines having at least one quaternizable, primary, secondary or tertiary amino group and at least one hydroxyl group attachable to a polyether radical.
  • the quaternizable nitrogen compound is selected from hydroxyalkyl-substituted primary, secondary, tertiary or quaternary monoamines and hydroxyalkyl-substituted primary, secondary, tertiary or quaternary diamines.
  • hydroxyalkyl-substituted mono- or polyamines are those which are endowed with at least one, such as 1, 2, 3, 4, 5 or 6, hydroxyalkyl substituents Ala may be examples of "hydroxyalkyl-substituted monoamines" N-hydroxyalkyl-monoamines, ⁇ , ⁇ -dihydroxyalkyl-monoamines and ⁇ , ⁇ , ⁇ -trihydroxyalkyl-monoamines, wherein the hydroxyalkyl groups are the same or different and are also as defined above.
  • Hydroxyalkyl stands in particular for 2-hydroxyethyl, 3-hydroxypropyl or 4-hydroxybutyl.
  • hydroxyalkyl-substituted polyamines and especially “hydroxyalkyl-substituted diamines” may be mentioned: (N-hydroxyalkyl) alkylenediamines, ⁇ , ⁇ -dihydroxyalkylalkylenediamines wherein the hydroxyalkyl groups are the same or different and are also as defined above.
  • Hydroxyalkyl stands in particular for 2-hydroxyethyl, 3-hydroxypropyl or 4-hydroxybutyl
  • Alkylene stands in particular for ethylene, propylene or butylene.
  • amino alcohols of the general formula I I can be alkoxylated in a manner known in principle, giving alkoxylated amines of the general formula Ia-1.
  • C2-C6-alkylene oxides for example ethylene oxide, propylene oxide, or butylene oxide. Preference is given in each case to the 1, 2-alkylene oxides.
  • the alkoxylation may be a base-catalyzed alkoxylation.
  • the amino alcohols (II) can be mixed in a pressure reactor with alkali metal hydroxides, preferably potassium hydroxide or with alkali metal alkoxides such as sodium thylate.
  • alkali metal hydroxides preferably potassium hydroxide
  • alkali metal alkoxides such as sodium thylate.
  • the catalyst can be neutralized by addition of acid (eg acetic acid or phosphoric acid) and can be filtered off if necessary.
  • acid eg acetic acid or phosphoric acid
  • the basic catalyst can also be neutralized by adding commercial Mg silicates, which are then filtered off.
  • the alkoxylation can also be carried out in the presence of a solvent. This may be, for example, toluene, xylene, dimethylformamide or ethylene carbonate.
  • the alkoxylation of the amino alcohols can also be carried out by other methods, for example by acid-catalyzed alkoxylation.
  • DMC catalysts double metal cyanide catalysts
  • Suitable DMC catalysts are disclosed, for example, in DE 102 43 361 A1, in particular sections [0029] to [0041], and the literature cited therein.
  • Zn-Co type catalysts can be used.
  • the aminoalcohol can be admixed with the catalyst, the mixture can be dehydrated as described above and reacted with the alkylene oxides as described. It is usually not more than 1000 ppm catalyst used with respect to the mixture, and the catalyst can remain in the product due to this small amount.
  • the amount of catalyst can typically be less than 1000 ppm, for example 250 ppm and less.
  • the alkoxylation can alternatively be carried out by reaction of the compounds (IV) and (V) with cyclic carbonates such as ethylene carbonate.
  • the polyethers thus obtained can then by reductive amination with ammonia, primary amines or secondary amines (VI I) by conventional methods in continuous or batch processes using customary hydrogenation or amination catalysts such as those based on catalytically active ingredients the elements Ni, Co, Cu, Fe, Pd, Pt, Ru, Rh, Re, Al, Si, Ti, Zr, Nb, Mg, Zn, Ag, Au, Os, Ir, Cr, Mo ,, W or combinations of these elements with one another, are reacted in conventional amounts to the corresponding polyetheramines (Ib-2).
  • customary hydrogenation or amination catalysts such as those based on catalytically active ingredients the elements Ni, Co, Cu, Fe, Pd, Pt, Ru, Rh, Re, Al, Si, Ti, Zr, Nb, Mg, Zn, Ag, Au, Os, Ir, Cr, Mo ,, W or combinations of these elements with one another, are reacted in conventional amounts to the corresponding polyetheramine
  • the reaction can be carried out without solvent or at high polyether viscosities in the presence of a solvent, preferably in the presence of branched aliphatics such as isododecane.
  • the amine component (VII) is generally used in excess, for example in 2 to 100-fold excess, preferably 10 to 80-fold excess used.
  • the reaction is carried out at pressures of 10 to 600 bar over a period of 10 Minutes to 10 hours.
  • the catalyst is separated by filtration, excess amine component (VII) is evaporated off and the reaction water is distilled off azeotropically or under a gentle stream of nitrogen.
  • the resulting polyetheramine (Ib-2) have primary or secondary amine functionality (R 1 and / or R 2 is H), this can subsequently be converted into a polyether amine having a tertiary amine function (R 1 and R 2 not equal to H).
  • the alkylation can be carried out in a manner known in principle by reaction with alkylating agents.
  • alkylating agents such as, for example, alkyl halides, alkylaryl halides, dialkyl sulfates, alkylene oxides, if appropriate in combination with acid, are suitable; aliphatic or aromatic carboxylic acid esters, in particular dialkylcarboxylates; alkanoates; cyclic non-aromatic or aromatic carboxylic esters; Dialkyl carbonates; and mixtures thereof.
  • the reactions to the tertiary polyetheramine can also take place by reductive amination by reaction with a carbonyl compound such as formaldehyde in the presence of a reducing agent.
  • Suitable reducing agents are formic acid or hydrogen in the presence of a suitable heterogeneous or homogeneous hydrogenation catalyst.
  • the reactions can be carried out without solvent or in the presence of solvents.
  • Suitable solvents are, for example, H 2 O, alkanols, such as methanol or ethanol, or 2-ethylhexanol, aromatic solvents, such as toluene, xylene or solvent mixtures of the Solvesso series, or aliphatic solvents, in particular mixtures of branched aliphatic solvents.
  • the reactions are carried out at temperatures of 10 ° C to 300 ° C at pressures of 1 to 600 bar over a period of 10 minutes to 10 hours.
  • the reducing agent is used at least stoichiometrically, preferably in excess, in particular in 2- to 10-fold excess.
  • reaction product thus formed (polyetheramine Ib-1 or Ib-2) can theoretically be further purified or the solvent removed. Usually, however, this is not absolutely necessary, so that the reaction product can be converted into the next synthesis step, the quaternization, without further purification.
  • the reaction product or reaction mixture from stage a) above is mixed with at least one epoxide compound of the above formula (IVa), in particular in the required stoichiometric amounts, in order to achieve the desired quaternization.
  • the acid is preferably also added in stoichiometric amounts.
  • Per equivalent of quaternizable tertiary nitrogen atom can be e.g. Use 0.1 to 2.0 equivalents, or 0.5 to 1, 25 equivalents of quaternizing agent.
  • approximately equimolar amounts of the epoxide are used to quaternize a tertiary amine group.
  • higher amounts are required to quaternize a secondary or primary amine group.
  • Suitable acids are especially carboxylic acids such as acetic acid.
  • carboxylic acids such as acetic acid.
  • the reaction time may be in the range of a few minutes or a few hours, e.g. about 10 minutes to about 24 hours.
  • the reaction may be carried out at about 0.1 to 20 bar, e.g. 1 to 10 bar pressure.
  • the pressure is usually determined by the vapor pressure of the alkylene oxide used at the respective reaction temperature.
  • an inert gas atmosphere such as e.g. Nitrogen, appropriate.
  • the reactants may be presented in a suitable organic aliphatic or aromatic solvent or a mixture thereof for epoxidation, or there may still be a sufficient proportion of solvent from reaction step a).
  • suitable organic aliphatic or aromatic solvent or a mixture thereof for epoxidation or there may still be a sufficient proportion of solvent from reaction step a).
  • Typical examples are e.g. Solvesso series solvent, toluene or xylene.
  • alkanols are suitable as solvents or as cosolvents in a mixture with the abovementioned solvents, such as, for example, methanol, ethanol, propanol, 2-ethylhexanol or 2-propylheptanol.
  • the reaction product or reaction mixture from the above stage a) is admixed with at least one alkylating agent of the formula (IV), especially in the stoichiometric amounts required to achieve the desired quaternization.
  • at least one alkylating agent of the formula (IV) especially in the stoichiometric amounts required to achieve the desired quaternization.
  • at least one alkylating agent of the formula (IV) can be used per equivalent of quaternizable tertiary nitrogen atom.
  • approximately equimolar amounts of the alkylating agent are used to quaternize a tertiary amine group.
  • higher amounts are required to quaternize a secondary or primary amine group.
  • Particularly suitable quaternizing agents are methyl salicylate, dimethyl oxalate, dimethyl phthalate and dimethyl carbonate.
  • the reaction may optionally be accelerated by the addition of catalytic or stoichiometric amounts of an acid.
  • Suitable acids are, for example, proton donors, such as aliphatic or aromatic carboxylic acids or fatty acids.
  • Lewis acids such as boron trifluoride, ZnC, MgC, AlC or FeC, are suitable.
  • the acid can be used in amounts of 0.01 to 50% by weight, for example in the range 0, 1 to 10% by weight.
  • reaction time can be in the range of a few minutes or a few hours, such as about 10 minutes to about 24 hours.
  • the reaction can be carried out at about 0.1 to 20 bar, such as 0.5 to 10 bar pressure.
  • the reaction can be carried out at atmospheric pressure.
  • an inert gas atmosphere such as nitrogen, is useful.
  • the reactants may be presented in a suitable organic aliphatic or aromatic solvent or mixture thereof for quaternization, or there may still be a sufficient amount of solvent from reaction step a). Typical examples are, for example, solvents of the Solvesso series, toluene or xylene.
  • alkanols are suitable as solvents or as cosolvents in a mixture with the abovementioned solvents, such as, for example, methanol, ethanol, propanol, butanol, 2-ethylhexanol or 2-propylheptanol.
  • work-up of the reaction mixture The final reaction product thus formed can theoretically be further purified or the solvent removed. Usually, however, this is not absolutely necessary, so that the reaction product can be used without further purification as an additive, if appropriate after mixing with further additive components (see below).
  • the acid used can be removed by filtration, neutralization or extraction from the reaction product.
  • an excess of alkylating agent may be removed by distillation or by filtration.
  • the fuel additized with the quaternized additive according to the invention is a gasoline fuel or in particular a middle distillate fuel, especially a diesel fuel.
  • the fuel may contain other conventional additives to improve the effectiveness and / or wear suppression.
  • suitable co-additives are listed in the following section:
  • detergent additives are preferably amphiphilic substances which have at least one hydrophobic hydrocarbon radical with a number-average molecular weight (M n ) of from 85 to 20 000 and at least one polar group selected from:
  • the hydrophobic hydrocarbon radical in the above detergent additives which provides sufficient solubility in the fuel has a number average molecular weight (M n ) of 85 to 20,000, preferably 1 13 to 10,000, more preferably 300 to 5,000, more preferably 300 to 3,000, more preferably from 500 to 2,500, and especially from 700 to 2,500, especially from 800 to 1,500.
  • M n number average molecular weight
  • polypropenyl, polybutenyl and polyisobutenyl radicals having a number average molecular weight M n of preferably from 300 to 5,000, more preferably from 300 to 3,000, more preferably from 500 to 2,500 are even more preferred 700 to 2,500 and especially 800 to 1, 500.
  • Such additives based on highly reactive polyisobutene, which from the polyisobutene, the up to 20 wt .-% n Can be prepared by hydroformylation and reductive amination with ammonia, monoamines or polyamines such as dimethylaminopropylamine, ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethyl-enpentamine are known in particular from EP-A 244 616 known.
  • Other particular monoamino (Da) containing additives are the polyisobutene epoxides by reaction with amines and subsequent dehydration and reduction of the amino alcohols available compounds, as described in particular in DE-A 196 20 262.
  • these reaction products are mixtures of pure nitropolyisobutenes (for example ⁇ , ⁇ -dinitropolyisobutene) and mixed hydroxynitropolyisobutenes (for example ⁇ -nitro- ⁇ -hydroxypolyisobutene).
  • Carboxyl groups or their alkali metal or alkaline earth metal salts (Dd) containing additives are preferably copolymers of C2 to C4o-olefins with maleic anhydride having a total molecular weight of 500 to 20,000, the carboxyl groups wholly or partially to the alkali metal or alkaline earth metal salts and a remainder of the Carboxyl groups are reacted with alcohols or amines.
  • Such additives are known in particular from EP-A 307 815.
  • Such additives are primarily used to prevent valve seat wear and, as described in WO-A 87/01 126, can be advantageously used in combination with conventional fuel detergents such as poly (iso) buteneamines or polyetheramines.
  • Sulfonic acid groups or their alkali metal or alkaline earth metal salts (De) containing additives are preferably alkali metal or alkaline earth metal salts of a Sulfobern- steinklaklalesters, as described in particular in EP-A 639 632.
  • Such additives are mainly used to prevent valve seat wear and can be used with advantage in combination with conventional fuel detergents such as poly (iso) butenines or polyetheramines.
  • Polyoxy-C2-C4-alkylene (Df) containing additives are preferably lyether or polyetheramines, which by reaction of C2 to C6o-alkanols, C6 to C3o-alkanediols, mono- or D1-C2 to C3o-alkylamines, C 1 -C 30 -alkylcyclohexanols or C 1 -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 are available.
  • Such products are described in particular in EP-A 310 875, EP-A 356 725, EP-A 700 985 and US-A 4,877,416.
  • polyethers such products also meet carrier oil properties. Typical examples of these are tridecanol or Isotridecanolbutoxylate, isononylphenol butoxylates and Polyisobutenolbutoxylate and propoxylates and the corresponding reaction products with ammonia.
  • Carboxylic ester groups (Dg) containing additives are preferably esters of mono-, di- or tricarboxylic acids with long-chain alkanols or polyols, especially those having a minimum viscosity of 2 mm 2 / s at 100 ° C, as described in particular in DE-A 38 38 918 are described.
  • mono-, di- or tricarboxylic acids it is possible to use aliphatic or aromatic acids, especially suitable ester alcohols or polyols are long-chain representatives having, for example, 6 to 24 C atoms.
  • esters are adipates, phthalates, isophthalates, terephthalates and trimellitates of iso-octanol, iso-nonanol, iso-decanol and of isotridecanol. Such products also fulfill carrier oil properties.
  • the groupings having 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, in addition to the amide function, still have free amine groups, succinic acid derivatives with an acid and an amide function, carboximides with monoamines, carboximides with di- or polyamines which, in addition to the imide function, still have free amine groups, or diimides which are formed by reacting di- or polyamines with two succinic acid derivatives.
  • the further detergent additive according to the present invention is used only up to a maximum of 100% of the amount by weight of compounds having betaine structure.
  • Such fuel additives are well known and described, for example, in documents (1) and (2). Preference is given to the reaction products of alkyl- or alkenyl-substituted succinic acids or derivatives thereof with amines and particularly preferably to the reaction products of polyisobutenyl-substituted succinic acids or derivatives thereof with amines.
  • reaction products with aliphatic polyamines in particular ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine and hexaethyleneheptamine, which have an imide structure.
  • Mannich reaction of substituted phenols with aldehydes and mono- or polyamines generated moieties containing (di) additives 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 described in particular in EP-A 831 141.
  • One or more of said detergent additives may be added to the fuel in such an amount that the dosage rate of these detergent additives is preferably from 25 to 2500 ppm by weight, in particular from 75 to 1500 ppm by weight, especially from 150 to 1000% by weight . ppm. B2) carrier oils
  • Co-used carrier oils may be mineral or synthetic.
  • Suitable mineral carrier oils are fractions obtained in petroleum processing, such as bright stock or base oils having viscosities such as from class SN 500 to 2000, but also aromatic hydrocarbons, paraffinic hydrocarbons and alkoxyalkanols.
  • Also useful is a fraction known as "hydrocrack oil” and obtained in the refining of mineral oil (vacuum distillate cut having a boiling range of about 360 to 500 ° C, available from high pressure catalytically hydrogenated and isomerized and dewaxed natural mineral oil).
  • mineral oil vacuum distillate cut having a boiling range of about 360 to 500 ° C, available from high pressure catalytically hydrogenated and isomerized and dewaxed natural mineral oil.
  • mixtures of the abovementioned mineral carrier oils are also suitable.
  • suitable synthetic carrier oils are polyolefins (polyalphaolefins or polyinternalolefins), (poly) esters, poly) alkoxylates, polyethers, aliphatic polyetheramines, alkylphenol-initiated polyethers, alkylphenol-initiated 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 prepared by reacting C 2 - to C 6 -alkanols, C 6 - to C 3 -oxanediols, mono- or C 1 - to C 20 -alkylamines, C 1 -C 30 -alkylcyclohexanols or C 1 -C 30 -alkylphenols with 1 to 30 mol of ethylenoxide and / or propylene oxide and / or butylene oxide per hydroxyl group or amino group and, in the case of the polyetheramines, by subsequent reductive amination with ammonia, monoamines or polyamines are available.
  • P0IV-C2 to C6 alkylene oxide amines or functional derivatives thereof may be used as the polyether amines.
  • these are tridecanol or Isotridecanolbutoxylate, Isononylphenolbutoxylate and Polyisobutenolbutoxylate 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, as described in particular in DE-A 38 38 918.
  • mono-, di- or tricarboxylic acids it is possible to use aliphatic or aromatic acids, especially suitable ester alcohols or polyols are long-chain representatives having, for example, 6 to 24 carbon atoms.
  • suitable representatives of the esters are adipates, phthalates, isophthalates, terephthalates and trimellitates of isooctanol, isononanol, isodecanol and of isotridecanol, eg. B.
  • di- (n- or isotridecyl) phthalate di- (n- or isotridecyl) phthalate.
  • suitable carrier oil systems are described, for example, in DE-A 38 26 608, DE-A 41 42 241, DE-A 43 09 074, EP-A 452 328 and EP-A 548 617.
  • particularly suitable synthetic carrier oils are alcohol-started polyethers having from about 5 to 35, preferably about 5 to 30, particularly preferably 10 to 30 and in particular 15 to 30 C3 to C6 alkylene oxide units, for.
  • suitable starter alcohols are long-chain alkanols or long-chain alkyl-substituted phenols, where the long-chain alkyl radical is, in particular, a straight-chain or branched C 6 - to C 18 -alkyl radical.
  • Specific examples include tridecanol and nonylphenol.
  • Particularly preferred alcohol-started polyethers are the reaction products (polyetherification products) of monohydric C6- to Cis-aliphatic alcohols with C3- to C6-alkylene oxides.
  • monohydric C6-C18 aliphatic alcohols are hexanol, heptanol, octanol, 2-ethylhexanol, nonyl alcohol, decanol, 3-propylheptanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, octadecanol and their constitution and positional isomers.
  • the alcohols can be used both in the form of pure isomers and 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.
  • particularly preferred are C 3 -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.
  • 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.
  • Further suitable synthetic carrier oils are alkoxylated alkylphenols,
  • Particular carrier oils are synthetic carrier oils, 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 from 1 to 1000 ppm by weight, more preferably from 10 to 500 ppm by weight and in particular from 20 to 100 ppm by weight.
  • Suitable cold flow improvers are in principle all organic compounds which are able to improve the flow behavior of middle distillate fuels or diesel fuels in the cold. Conveniently, they must have sufficient oil solubility.
  • middle distillates of fossil origin ie for conventional mineral diesel fuels
  • used cold flow improvers (“middle distillate flow improvers", "MDFI") come into consideration.
  • MDFI middle distillate flow improvers
  • WASA wax anti-settling additive
  • the cold flow improver is selected from:
  • (K6) poly (meth) acrylic acid esters. Mixtures of different representatives from one of the respective classes (K1) to (K6) as well as mixtures of representatives from different classes (K1) to (K6) can be used.
  • Suitable C2 to C4o-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 having a carbon-carbon double bond. In the latter case, the carbon-carbon double bond can be arranged both terminally (a-olefins) and internally.
  • ⁇ -olefins preference is given to ⁇ -olefins, more preferably ⁇ -olefins having 2 to 6 carbon atoms, for example propene, 1-butene, 1-pentene, 1-hexene and, above all, ethylene.
  • the at least one further ethylenically unsaturated monomer is preferably selected from carboxylic alkenyl esters, (meth) acrylic esters and further olefins.
  • further olefins are polymerized in, these are preferably higher molecular weight than the abovementioned C 2 - to C 4 -olefin base monomers. If, for example, ethylene or propene is used as the olefin base monomer, suitable further olefins are, in particular, C 10 -C 4 -olefins. Other olefins are polymerized in most cases only when monomers with carboxylic acid ester functions are used.
  • Suitable (meth) acrylic esters are, for example, esters of (meth) acrylic acid with Cr to C 2 alkanols, in particular C 1 to C 1 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 alkenyl esters are, for example, C 2 - to C 6 -alkenyl esters, for example the vinyl and propenyl esters, of carboxylic acids having 2 to 21 carbon atoms, whose hydrocarbon radical may be linear or branched. Preferred among these are the vinyl esters.
  • carboxylic acids with a branched hydrocarbon radical preference is given to those whose branching is in the ⁇ -position to the carboxyl group, wherein the ⁇ -carbon atom is particularly preferably tertiary, ie the carboxylic acid is a so-called neocarboxylic acid.
  • the hydrocarbon radical of the carboxylic acid is linear.
  • carboxylic 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, the vinyl esters being preferred.
  • a particularly preferred carboxylic acid alkenyl ester is vinyl acetate; typical resulting copolymers of group (K1) are the most commonly used ethylene-vinyl acetate copolymers ("EVA"). Particularly advantageous ethylene-vinyl acetate copolymers and their preparation are described in WO 99/29748.
  • copolymers of class (K1) are those which contain two or more different carboxylic acid alkenyl esters in copolymerized form, these differing 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.
  • Such terpolymers are described in WO 2005/054314.
  • a typical such terpolymer 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 from 1 to 50% by weight, in particular from 10 to 45% by weight and especially from 20 to 40% by weight. %, based on the total copolymer, copolymerized.
  • the majority by weight of the monomer units in the copolymers of class (K1) thus usually comes from the C2 to C 4 o-based olefins.
  • the copolymers of class (K1) preferably have a number-average molecular weight Mn 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 available with 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 may also be polyfumarates or polymaleinates.
  • homopolymers and copolymers of vinyl ethers are suitable comb polymers.
  • Comb polymers suitable as a component of class (K2) are, for example, those described in WO 2004/035715 and in "Comb-Like Polymers, Structure and Properties", NA Plate and VP Shibaev, J. Poly. Be. Macromolecular Revs.
  • Polyoxyalkylenes suitable as a component of class (K3) are, for example, oxyalkylene esters, polyoxyalkylene ethers, mixed polyoxyalkylene ester ethers and mixtures thereof , 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 described for example in EP-A 061 895 and in US 4 491 455.
  • 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 suitable.
  • Polar nitrogen compounds suitable as a component of class (K4) may be both of ionic and nonionic nature and preferably have at least one, in particular at least two, substituents in the form of a tertiary nitrogen radical. atom of the general formula> NR 7 , in which R 7 is a Cs to C4o hydrocarbon radical.
  • the nitrogen substituents may also be quaternized, that is in cationic form. Examples of such nitrogen compounds are ammonium salts and / or amides obtainable by reacting at least one amine substituted with at least one hydrocarbyl radical with a carboxylic acid having 1 to 4 carboxyl groups or with a suitable derivative thereof.
  • the amines contain at least one linear Cs to C4o-alkyl radical.
  • suitable primary amines for the preparation of said polar nitrogen compounds are octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tetradecylamine and the higher linear homologues
  • suitable secondary amines for this purpose are, for example, dioctadecylamine and methylbehenylamine.
  • amine mixtures in particular industrially available amine mixtures such as fatty amines or hydrogenated tallamines, as described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 6th edition, in the chapter "Amines, aliphatic".
  • Suitable acids 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 by long-chain hydrocarbon radicals.
  • the component of class (K4) is an oil-soluble reaction product of at least one tertiary amino group-containing poly (C 2 - to C 20 -carboxylic acids) with primary or secondary amines.
  • the poly (C 2 - to C 20 -carboxylic acids) which have at least one tertiary amino group and are based on this reaction product 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 suitably linked to the polycarboxylic acids, usually via one or more carbon and / or nitrogen atoms. Preferably, they are attached to tertiary nitrogen atoms, which are connected in the case of several nitrogen atoms 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) of general formula IIa or IIb having at least one tertiary amino group HOOC.
  • DD OOH poly (C 2 - to C 20 -carboxylic acids) of general formula IIa or IIb having at least one tertiary amino group HOOC.
  • variable A is a straight-chain or branched C 2 - to C 6 -alkylene group or the grouping of the formula III
  • CH2-CH2- and the variable B denotes a C to Cig-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 general formula IIa or IIb, is an amide, an amide ammonium salt or an ammonium salt in which no, 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 ethylene, 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.
  • Cr to Ci9-alkylene groups of the variables B are before, for example, 1, 2-ethylene, 1, 3-propylene, 1, 4-butylene, hexamethylene, octamethylene, decamethylene, dodecamethylene, tetradecamethylene, hexadecamethylene, octadecamethylene, Nonadecamethylen and especially methylene.
  • the variable B 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 the component (K4) are usually monoamines, in particular aliphatic monoamines. These primary and secondary amines may be selected from a variety of amines bearing hydrocarbon radicals, optionally linked together. Most of these amines which are the oil-soluble reaction products of component (K4) are 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 Cu - to C24-alkyl radicals mean. These longer-chain alkyl radicals are preferably straight-chain or only slightly branched. As a rule, the abovementioned secondary amines are derived with regard to their longer-chain alkyl radicals from naturally occurring fatty acid or from its derivatives. Preferably, the two radicals R 8 are the same.
  • the abovementioned secondary amines can be bound to the polycarboxylic acids by means of amide structures or in the form of the ammonium salts, and only one part can be present as amide structures and another part as ammonium salts. Preferably, only a few or no free acid groups are present. Preferably, the oil-soluble reaction products of component (K4) are completely 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) include the N, N-dialkylammonium salts of 2-N ', ⁇ '-dialkylamidobenzoates, for example the reaction product of 1 mole of phthalic anhydride and 2 moles of Ditaigfettamin, the latter may be hydrogenated or unhydrogenated , and the reaction product of 1 mole of a Alkenylspirobislac- tons with 2 moles of a dialkylamine, for example, Ditaigfettamin and / or tallow fatty amine, the latter two may be hydrogenated or unhydrogenated, called.
  • N, N-dialkylammonium salts of 2-N ', ⁇ '-dialkylamidobenzoates for example the reaction product of 1 mole of phthalic anhydride and 2 moles of Ditaigfettamin, the latter may be hydrogenated or unhydrogenated
  • component of the class (K4) are cyclic compounds having tertiary amino groups or condensates of long-chain primary or secondary amines with carboxylic acid-containing polymers, as described in WO 93/181 15.
  • Sulfocarboxylic acids, sulfonic acids or their derivatives which are suitable as cold flow improvers of 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 sulfonate with alkyl-substituted ammonium cations, as described in EP -A 261 957.
  • suitable poly (meth) acrylic esters are both homo- and copolymers of acrylic and methacrylic esters.
  • Preferred are copolymers of at least two mutually different (meth) acrylic acid esters, which differ with respect to the fused alcohol.
  • the copolymer contains a further, different of which olefinically unsaturated monomer copolymerized.
  • the weight-average molecular weight of the polymer is preferably 50,000 to 500,000.
  • a particularly preferred polymer is a copolymer of methacrylic acid and methacrylic acid esters of saturated C14 and Cis alcohols wherein the acid groups are neutralized with hydrogenated tallamine.
  • Suitable poly (meth) acrylic esters are described, for example, in WO 00/44857.
  • the middle distillate fuel or diesel fuel is the cold flow improver or the mixture of various cold flow improvers in a total amount of preferably 10 to 5000 ppm by weight, more preferably from 20 to 2000 ppm by weight, stronger preferably from 50 to 1000 ppm by weight and in particular from 100 to 700 ppm by weight, for example from 200 to 500 ppm by weight, added.
  • Suitable lubricity improvers are usually based on fatty acids or fatty acid esters. Typical examples are tall oil fatty acid, as described, for example, in WO 98/004656, and glycerol monooleate.
  • the reaction products of natural or synthetic oils, for example triglycerides, and alkanolamines described in US Pat. No. 6,743,266 B2 are also suitable as such lubricity improvers.
  • Corrosion inhibitors are e.g. Succinic 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) or HiTEC 536 (Ethyl Corporation).
  • Suitable corrosion inhibitors are e.g. Succinic 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) or HiTEC 536 (Ethyl Corporation).
  • Suitable demulsifiers are e.g. 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, for example, the products NALCO 7D07 (Nalco) and TOLAD 2683 (Petrolite) available under the trade name. B8) antifoam
  • Suitable antifoams are e.g. Polyether-modified polysiloxanes, such as, for example, the TEGOPREN 5851 (Goldschmidt), Q 25907 (Dow Corning) and RHODOSIL (Rhone Poulenc) products available under the tradename.
  • Polyether-modified polysiloxanes such as, for example, the TEGOPREN 5851 (Goldschmidt), Q 25907 (Dow Corning) and RHODOSIL (Rhone Poulenc) products available under the tradename.
  • Cetane number improvers are e.g. aliphatic nitrates such as 2-ethylhexyl nitrate and cyclohexyl nitrate and peroxides such as di-tert-butyl peroxide.
  • antioxidants are e.g. 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 are e.g. Salicylic acid derivatives such as N, N'-disalicylidene-1, 2-propanediamine.
  • Suitable are, for example, nonpolar organic solvents such as aromatic and aliphatic hydrocarbons, for example toluene, xylenes, "white spirit" and products marketed under the trade name SHELLSOL (Royal Dutch / Shell Group) and EXXSOL (Exxon Mobil), and polar organic solvents, For example, alcohols such as 2-ethylhexanol, decanol and isotridecanol. Such solvents usually enter the diesel fuel together with the abovementioned additives and coadditives, which they are intended to dissolve or dilute for better handling.
  • C) fuels The additive of the invention is outstandingly suitable as a fuel additive and can be used in principle in any fuels. It has a number of beneficial effects on the operation of internal combustion engines with fuels.
  • the present invention therefore also fuels, especially middle distillate fuels, with an effective as an additive to achieve beneficial effects in the operation of internal combustion engines, such as diesel engines, especially direct injection diesel engines, especially of diesel engines with common rail injection systems, effective content on 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, especially 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 fuel oils
  • mineral middle distillate mineral fuels or diesel fuels available through refining
  • those produced by coal gasification or gas liquefaction [GTL] or by biomass to liquid (BTL) fuels are also included. are available, suitable. Also suitable are mixtures of the abovementioned middle distillate fuels or diesel fuels with regenerative fuels, such as biodiesel or bioethanol.
  • biofuel oils are commercially available and usually contain the biofuel oils in minor amounts, typically in amounts of 1 to 30 wt .-%, in particular from 3 to 10 wt .-%, based on the total amount of middle distillate of fossil, vegetable or animal origin and biofuel.
  • Biofuel oils are generally based on fatty acid esters, preferably substantially on alkyl esters of fatty acids derived from vegetable and / or animal oils and / or fats.
  • Alkyl esters are usually lower alkyl esters, especially C 1 to C 4 alkyl esters, understood by transesterification of occurring in vegetable and / or animal oils and / or fats glycerides, especially triglycerides, by means of lower alcohols, for example ethanol or especially methanol (“ FAME ”) are available.
  • Typical lower alkyl esters based on vegetable and / or animal oils and / or fats which 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 especially 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 of less than 0.005% by weight and especially less than 0.001% by weight of sulfur.
  • gasoline fuels are all commercially available gasoline fuel compositions into consideration.
  • a typical representative here is the market-standard basic fuel of Eurosuper according to EN 228.
  • gasoline compositions of the specification according to WO 00/47698 are also possible fields of use for the present invention.
  • the quaternized additive according to the invention is particularly suitable as a fuel additive in fuel compositions, especially in diesel fuels, to overcome the initially described problems in direct injection diesel engines, especially in those with common rail injection systems.
  • test methods mentioned below are part of the general disclosure of the application and are not limited to the specific exemplary embodiments.
  • the Keep Clean Test is based on the CEC Test Procedure F-098-08 Issue 5.
  • the same test setup and motor type (PEUGEOT DW10) are used as in the CEC procedure.
  • Test run times The test period was 12h without shutdown periods. The one-hour test cycle from CEC F-098-08 shown in FIG. 2 was traversed 12 times.
  • the initial power P0, KC [kW] is calculated from the measured torque at 4000 rpm full load directly after the test start and warm-up of the engine.
  • the procedure is described in issue 5 of the test procedure (CEC F-98-08).
  • the same test setup and the PEUGEOT DW10 motor type are used.
  • the final power (Pend, KC) is determined in the 12th cycle in stage 12, (see table, Figure 2). Again, the operating point is 4000 / min full load. Pend, KC [kW] is calculated from the measured torque.
  • the power loss in the KC test is calculated as follows:
  • the DU-CU test is based on the CEC test procedure F-098-08 Issue 5. The procedure is described in issue 5 of the test procedure (CEC F-98-08). The same test setup and the PEUGEOT DW10 motor type are used.
  • the DU - CU test consists of two separate tests that are run one behind the other.
  • the first test is for deposit formation (DU), the second for deposit removal (CU).
  • DU deposit formation
  • CU deposit removal
  • powerloss power loss
  • the engine is not operated for at least 8 hours and cooled to ambient temperature. Thereafter, the CU fuel is used to start the CU without removing and cleaning the injectors. Deposits and powerloss ideally go back in the CU test history. Change and special features:
  • the test period was 12h for the DU and 12h for the CU.
  • the engine was operated in the DU and CU test without shutdown phases.
  • the one-hour test cycle from CEC F-098-08 shown in FIG. 2 was traversed 12 times in each case.
  • the initial power PO, du [kW] is calculated from the measured torque at 4000 rpm full load directly after the test start and warm-up of the engine. The procedure is also described in Issue 5 of the test procedure.
  • the final power (Pend, du) is determined on the 12th cycle in step 12 (see table above). Again, the operating point is 4000 / min full load. Pend, du [kW] is calculated from the measured torque.
  • the power loss in the DU is calculated as follows
  • the initial power PO.cu [kW] is calculated from the measured torque at 4000 / min full load directly after the test start and warm-up of the engine in the CU. The procedure is also described in Issue 5 of the test procedure.
  • the final power (Pend, cu) is determined in the 12th cycle in stage 12, (see table Figure 2). Again, the operating point is 4000 / min full load. Pend, cu [kW] is calculated from the measured torque.
  • the power loss in the CU test is calculated as follows (negative number in the power loss in the cu test means performance increase)
  • the fuel used was a commercial diesel fuel from Craigrmann (RF-06-03).
  • RF-06-03 commercial diesel fuel from Garrmann (RF-06-03).
  • 1 ppm by weight zinc in the form of a zinc didodecanoate solution was added to artificially stimulate the formation of deposits on the injectors.
  • the formation of deposits inside the injector was characterized by the cylinder exhaust gas temperature variations at the cylinder exit during cold start of the DW10 engine.
  • the test is performed as a dirty-up clean-up test (DU-CU).
  • DU-CU is based on the CEC Test Procedure F-098-08 Issue 5.
  • the DU - CU test consists of two separate tests that are run one behind the other.
  • the first test is for deposit formation (DU), the second for deposit removal (CU).
  • a cold start of the engine is carried out after a shutdown phase of at least eight hours followed by a 10-minute idle period.
  • the CU fuel is used to start the CU without removing and cleaning the injectors.
  • the engine will be cold-start followed by a 10-minute idle run. The evaluation is done by comparing the temperature curves for the individual cylinders after a cold start of the du and the CU run.
  • the IDID test indicates internal deposit formation in the injector.
  • the characteristic used in this test is the exhaust gas temperature of the individual cylinders. For an injector system Without IDID, the exhaust gas temperatures of the cylinders increase evenly. If the IDID is available, the exhaust gas temperatures of the individual cylinders do not increase uniformly and deviate from one another.
  • the temperature sensors are located behind the cylinder head outlet in the exhaust manifold. Significant deviations of the individual cylinder temperatures (eg> 20 ° C) indicate the presence of internal injector deposits (IDID).
  • the tests (DU and CU) are carried out with 8h running time.
  • the one-hour test cycle from the CEC F-098-08 is passed through 8 times in each case.
  • the test is terminated prematurely.
  • N, N-dimethylethanolamine * 15 PO (A) In an autoclave, N, N-dimethylethanolamine (76.7 g) is treated with potassium ferric butylate (4.1 g). It is rinsed three times with N2, a pre-pressure of approximately 1.3 bar N2 is set and the temperature is raised to 130.degree. 1, 2-Propylene oxide (750 g) is metered in over a period of 10 h so that the temperature remains between 129 ° C-131 ° C. The mixture is then 6 h at 130 ° C stirred, rinsed with N 2, cooled to 60 ° C and the reactor emptied.
  • N N-dimethylethanolamine (47.1 g) is added with potassium feri-butylate (5.0 g). It is rinsed three times with N2, a pre-pressure of approximately 1.3 bar N2 is set and the temperature is increased to 140.degree. 1, 2-butylene oxide (953 g) is metered over a period of 9 h so that the temperature remains between 138 ° C-141 ° C. The mixture is then stirred for 6 h at 140 ° C, rinsed with N2, cooled to 60 ° C and the reactor emptied. Excess butylene oxide is removed on a rotary evaporator in vacuo. The basic crude product is neutralized using commercially available Mg silicates, which are then filtered off. 1000 g of the product are obtained in the form of a yellow oil (TBN 28, 1 mg KOH / g, D 1, 12).
  • Synthesis Example 3 N, N-Dimethylethanolamine * 15 PO quaternized with dimethyl oxalate
  • Synthesis Example 4 N, N-Dimethylethanolamine * 25 BuO quaternized with dimethyl oxalate (II)
  • Polyetheramine (B) 400 g) from Synthesis Example 2 is dissolved in Solvent Naphtha Heavy (436 g), added with styrene oxide (24.0 g) and acetic acid (12.0 g) and then at 80 ° C for 8 h touched. After cooling to room temperature, 870 g of the product are obtained.
  • 1 H NMR analysis of the quaternized polyetheramine solution thus obtained in Solvent Naphtha Heavy shows the quaternization.
  • Polyetheramine (A) (305 g) from Synthesis Example 1 is dissolved in 2-ethylhexanol (341 g) in a 21-liter autoclave, and acetic acid (18.3 g) is added. It is rinsed three times with N2, a pre-pressure of about 1 .3 bar N2 set and the temperature increased to 130 ° C. 1, 2-propylene oxide (17.7 g) is metered. The mixture is then stirred for 5 h at 130 ° C, rinsed with N2, cooled to 40 ° C and the reactor emptied. Excess propylene oxide is removed on a rotary evaporator in vacuo. This gives 675 g of the product in the form of an orange oil.
  • polyetheramine (A) (518 g) from Synthesis Example 1 is dissolved in 2-ethylhexanol (570 g) and treated with conc. Acetic acid (30 g) was added. It will be three times flushed with N2, a pre-pressure of about 1 .3 bar N2 set and the temperature increased to 130 ° C. Ethylene oxide (22 g) is added. The mixture is then stirred for 5 h at 130 ° C, rinsed with N2, cooled to 40 ° C and the reactor emptied. This gives 1 1 16 g of the product in the form of an orange oil.
  • 1 H-NMR analysis of the resulting solution of the quaternized polyetheramine in 2-ethylhexanol shows the quaternization.
  • the preparation of the polyether from isotridecanol N and 1, 2-butylene oxide in a molar ratio of 1:22 is carried out by known methods by DMC catalysis, such as, for example. described in EP1591466A.
  • the polyetheramine (D) (400 g) from Synthesis Example 9 is treated under ice bath cooling with formic acid (65.3 g, 85% in H2O).
  • the reaction mixture is then heated to a temperature of 45 ° C and formaldehyde solution (44.9 g, 36.5% in H 2 O) is added dropwise at this temperature, wherein the liberated carbon dioxide is discharged from the reaction vessel.
  • the reaction mixture is stirred for 16 h at a temperature of 80 ° C.
  • the reaction mixture is then cooled to room temperature, admixed with hydrochloric acid (37%, 35.4 g) and stirred at room temperature for 1 h.
  • the additives are used either as a pure substance (as synthesized in the above preparation examples) or in the form of an additive package.
  • the FR value is a parameter detected by the engine control, which correlates with the duration of fuel injection into the combustion chamber. The more pronounced the formation of deposits in the injector nozzles, the longer the injection duration or higher the FR value. Conversely, the FR value remains constant or tends to decrease slightly as the injector nozzles remain debris free.

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  • Lubrication Of Internal Combustion Engines (AREA)

Abstract

La présente invention concerne des polyétheramines quaternaires inédites et leur fabrication. L'invention concerne également l'utilisation de ces liaisons en tant qu'additif de carburant et de lubrifiant. L'invention concerne notamment l'utilisation de ces liaisons d'azote quaternaires en tant qu'additif de carburant pour réduire ou empêcher des dépôts dans les systèmes d'injection de moteurs diesel à injection directe, notamment dans des systèmes d'injection Common Rail, pour réduire la consommation de carburant des moteurs diesel à injection directe, notamment des moteurs diesel avec des systèmes d'injection Common Rail, et pour réduire les pertes de puissance (power loss) dans des moteurs diesel à injection directe, notamment dans des moteurs diesel avec des systèmes d'injection Common Rail. L'invention a également pour objet des paquets d'additifs contenant ces polyétheramines ainsi que les carburants et lubrifiants ainsi ajoutés. De plus, l'invention concerne l'utilisation de ces liaisons d'azote quaternaires en tant qu'additif pour des carburants essence, notamment pour l'amélioration de la propreté de l'admission des moteurs à essence.
PCT/EP2012/071844 2011-11-04 2012-11-05 Polyétheramines quaternaires et leur utilisation en tant qu'additifs dans des carburants et des lubrifiants WO2013064689A1 (fr)

Priority Applications (9)

Application Number Priority Date Filing Date Title
BR112014010671A BR112014010671A2 (pt) 2011-11-04 2012-11-05 composição de combustível ou composição de lubrificante, composto de nitrogênio quaternizado, processo para preparar compostos de nitrogênio quaternizados, uso de um composto de nitrogênio quaternizado, e, concentrado de aditivo
ES12780216T ES2726102T3 (es) 2011-11-04 2012-11-05 Uso de polieteraminas cuaternizadas como aditivo en combustibles y lubricantes
AU2012331073A AU2012331073B2 (en) 2011-11-04 2012-11-05 Quaternized polyetheramines and use thereof as additives in fuels and lubricants
CA2854421A CA2854421C (fr) 2011-11-04 2012-11-05 Polyetheramines quaternaires et leur utilisation en tant qu'additifs dans des carburants et des lubrifiants
CN201280065791.5A CN104024385B (zh) 2011-11-04 2012-11-05 季铵化聚醚胺及其在燃料和润滑剂中作为添加剂的用途
KR1020147015015A KR102033606B1 (ko) 2011-11-04 2012-11-05 4급화된 폴리에테르아민 및 연료 및 윤활제의 첨가제로서 이의 용도
EP12780216.3A EP2773729B1 (fr) 2011-11-04 2012-11-05 Utilisation de polyétheramines quaternaires en tant qu'additifs dans des carburants et des lubrifiants
MX2014005325A MX2014005325A (es) 2011-11-04 2012-11-05 Polieteraminas cuaternizadas y uso de las mismas como aditivos en combustibles y lubricantes.
PL12780216T PL2773729T3 (pl) 2011-11-04 2012-11-05 Zastosowanie czwartorzędowanych polieteroamin jako dodatków do paliw silnikowych i smarów

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EP11187959.9 2011-11-04
EP11187959.9A EP2589647A1 (fr) 2011-11-04 2011-11-04 Polyétheramines quaternisées et leur utilisation en tant qu'additifs dans des carburants et des lubrifiants

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CN (1) CN104024385B (fr)
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BR (1) BR112014010671A2 (fr)
CA (1) CA2854421C (fr)
ES (1) ES2726102T3 (fr)
HU (1) HUE044181T2 (fr)
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PL2773729T3 (pl) 2019-07-31
AU2012331073B2 (en) 2017-11-23
AU2012331073A1 (en) 2014-06-26
EP2773729A1 (fr) 2014-09-10
CN104024385A (zh) 2014-09-03
HUE044181T2 (hu) 2019-10-28
TR201905501T4 (tr) 2019-05-21
KR20140097288A (ko) 2014-08-06
CA2854421C (fr) 2020-12-29
BR112014010671A2 (pt) 2017-05-09
EP2589647A1 (fr) 2013-05-08
KR102033606B1 (ko) 2019-10-17
EP2773729B1 (fr) 2019-02-13
ES2726102T3 (es) 2019-10-01
CN104024385B (zh) 2016-03-09
MX2014005325A (es) 2014-06-05

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