EP2563822A1 - Terpolymère quaternisé - Google Patents

Terpolymère quaternisé

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Publication number
EP2563822A1
EP2563822A1 EP11718329A EP11718329A EP2563822A1 EP 2563822 A1 EP2563822 A1 EP 2563822A1 EP 11718329 A EP11718329 A EP 11718329A EP 11718329 A EP11718329 A EP 11718329A EP 2563822 A1 EP2563822 A1 EP 2563822A1
Authority
EP
European Patent Office
Prior art keywords
quaternized
mol
acid
esters
alkyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP11718329A
Other languages
German (de)
English (en)
Inventor
Ivette Garcia Castro
Cornelia RÖGER-GÖPFERT
Wolfgang Grabarse
Klaus MÜHLBACH
Ludwig Völkel
Harald BÖHNKE
Christian Tock
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
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Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to EP11718329A priority Critical patent/EP2563822A1/fr
Publication of EP2563822A1 publication Critical patent/EP2563822A1/fr
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/44—Preparation of metal salts or ammonium salts
    • 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
    • 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
    • C10L1/221—Organic compounds containing nitrogen compounds of uncertain formula; reaction products where mixtures of compounds are obtained
    • 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
    • C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
    • C10L1/2366—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing amine groups
    • 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
    • C10L10/08—Use of additives to fuels or fires for particular purposes for improving lubricity; for reducing wear
    • 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
    • C10L1/16—Hydrocarbons
    • C10L1/1625—Hydrocarbons macromolecular compounds
    • C10L1/1633—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds
    • C10L1/1641—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds from compounds containing aliphatic monomers
    • 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
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/196—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof
    • C10L1/1963—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof mono-carboxylic

Definitions

  • Alkyl esters of acrylic acid or methacrylic acid are examples of acrylic acid or methacrylic acid and
  • the present invention relates to a method for producing such a quaternized terpolymer.
  • the present invention also relates to fuels containing such a quaternized terpolymer. Furthermore, the present invention relates to the use of this quaternized
  • Terpolymer as a fuel additive for reducing or preventing deposits in the injection systems of direct-injection diesel engines, in particular in common-rail injection systems, for reducing the fuel consumption of direct-injection diesel engines, in particular diesel engines with common-rail injection systems, and for minimizing the Power loss in direct injection diesel engines, especially in diesel engines with common rail injection systems.
  • direct-injection diesel engines the fuel is injected through a 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 diesel fuel is pumped by a pump with pressures up to 2000 bar into a high-pressure line, the common rail (literally "common line").
  • 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 however, only one injection is possible.
  • Injection in the common rail is essentially subdivided into three groups: (1) pre-injection, which substantially achieves softer combustion, so that hard combustion noise ("nailing") is reduced and engine running appears quiet; (2.) main injection, which is responsible in particular for a good torque curve; and (3.) post-injection, which in particular ensures a low NO x value.
  • pre-injection which substantially achieves softer combustion, so that hard combustion noise ("nailing") is reduced and engine running appears quiet
  • main injection which is responsible in particular for a good torque curve
  • post-injection which in particular ensures a low NO x 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
  • deposits may form at the injector ports which adversely affect the fuel injection behavior and thereby adversely affect the performance of the engine, i. In particular, reduce the power, but in part also deteriorate the combustion.
  • the formation of deposits is further enhanced by structural developments of the injectors, in particular by the change in the geometry of the nozzles (narrower, conical openings with rounded outlet). For a permanently optimal functioning of engine and injectors such deposits must be prevented or reduced in the nozzle openings by suitable fuel additives.
  • the object of the present invention was therefore to provide fuel additives which remedy the above-described deficiencies, ie in particular deposits in the injection systems, especially in the injectors, of direct-injection diesel engines. prevent or reduce diesel engines, reduce the fuel consumption of direct injection diesel engines and minimize power losses in such engines.
  • C 8 - to C 2 oo-alkyl or -Alkenylbernsteinklaimide as detergent additives for fuels, such as middle distillate fuels and gasolines known.
  • fuels such as middle distillate fuels and gasolines
  • WO 02/092645 (1) describes polyalkenylsuccinimides such as polyisobutenylsuccinimides as additives to fuels such as diesel fuel, heating oil or gasoline or to lubricants which - obviously due to their production - contain up to 30% by weight of the corresponding polyalkenylsuccinic acid amides or Semi-amides may contain.
  • These polyalkenyl succinimides are said to counteract engine deposits and deposits on the injectors.
  • detergent additives reduce the amount of particulates in the exhaust emissions of direct-injection diesel engines, such as diesel engines with common-rail injection systems.
  • Detergent additives include, among others, succinic anhydride-derived moieties containing hydroxyl and / or amino and / or amido and / or imido groups, such as the corresponding derivatives of polyisobutenyl succinic anhydride, especially aliphatic polyamines.
  • the groups 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 diamines or polyamines which, in addition to the amide function, also have free amino 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.
  • EP 1 887 074 A1 (3) describes a process for removing or reducing injector deposits in diesel engines using reaction products between a hydrocarbyl-substituted succinic acid or its anhydride, for example polyisobutenyl succinic anhydride, and hydrazine.
  • reaction products are also called Halbhydrazid structures.
  • European Unexamined Application 09166729.5 discloses low molecular weight or polymeric organic compounds having at least one equivalent of a basic nitrogen function and at least one equivalent of a free carboxyl group capable of forming a betaine structure as fuel additives for prevention or reduction deposits in injectors of direct injection diesel engines and to minimize the power loss in such engines.
  • a betaine structure can be present, for example, in a hemiamide of a succinic anhydride and N- (1-aminopropylimidazole).
  • WO 2006/135881 describes the condensation of hydrocarbyl-substituted acylating agents obtainable by ene reaction of olefins with maleic anhydride with amines having an additional tertiary amino group and subsequent quaternization of the tertiary amino group to give quaternary ammonium salts
  • Fuel additives are suitable for cleaning and keeping clean intake systems of internal combustion engines.
  • the quaternized terpolymer of the invention is a terpolymer
  • the subject of the present application is also a process for the preparation of a quaternized terpolymer, which is characterized in that a terpolymer of the components
  • Alkyl esters of acrylic acid or methacrylic acid are examples of acrylic acid or methacrylic acid and
  • (C) 0.1 to 15 mol% of at least one ethylenically unsaturated monomer containing at least one quaternizable tertiary nitrogen atom, all monomer components together giving 100 mol%, produced by polymerization and then the at least one tertiary nitrogen atom in the component (C ) is partially or fully quaternized with at least one quaternizing agent.
  • C2 to Ci4 alkenyl esters of one or more aliphatic Cr to C2i monocarboxylic acids for the embodiment (i) of component (B) are in particular the vinyl and propenyl esters of aliphatic monocarboxylic acids having 2 to 18 carbon atoms, their hydrocarbon radical can be linear or branched. Preferred among these are the vinyl esters. Independently of the alkenyl radical, monocarboxylic acids which are particularly preferred for this purpose are those having 2 to 16, in particular 2 to 10, carbon atoms. Preferred among the carboxylic acids having a branched hydrocarbon group are those whose branch is in the a position to the carboxyl group, the ⁇ -carbon atom being particularly preferably tertiary, i. H.
  • the carboxylic acid is a so-called neocarboxylic acid.
  • the hydrocarbon radical of the carboxylic acid is linear.
  • suitable carboxylic alkenyl esters (i) are 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.
  • esters of acrylic acid or methacrylic acid for the embodiment (ii) of component (B) are in particular the esters of acrylic and methacrylic acid with Cr to Ci2-alkanols, especially Cr to C4-alkanols, especially with Me- ethanol, ethanol, propanol, isopropanol, n-butanol, sec-butanol, isobutanol, tert-butanol, pentanol, hexanol, heptanol, octanol, 2-ethylhexanol, nonanol and decanol.
  • Cr to Ci2-alkanols especially Cr to C4-alkanols, especially with Me- ethanol, ethanol, propanol, isopropanol, n-butanol, sec-butanol, isobutanol, tert-butanol, pentanol, hexanol, hept
  • the quaternized terpolymer according to the invention can also contain two or more monomer species (i) and / or (ii) of component (B), ie two or more different carboxylic acid alkenyl esters (i) or two or more different acrylic or methacrylic acid esters (ii) or at least one carboxylic acid alkenyl ester (i) and at least one acrylic or methacrylic acid ester (ii) contain copolymerized form, these differing in the alkenyl function and / or in the carboxylic acid group and / or in the alcohol radical.
  • component (B) vinyl acetate is particularly preferred.
  • Suitable ethylenically unsaturated monomers (C) which contain at least one quaternizable nitrogen atom are in particular carboxyl derivatives, for example carboxylic acid esters, carboxylic acid amides or carboximides, of ethylenically unsaturated mono- or dicarboxylic acids, for example of acrylic or methacrylic acid or maleic acid, in the side chain the carbonyl-remote side of the carboxyl derivative function have at least one quaternizable tertiary nitrogen atom.
  • carboxyl derivatives for example carboxylic acid esters, carboxylic acid amides or carboximides, of ethylenically unsaturated mono- or dicarboxylic acids, for example of acrylic or methacrylic acid or maleic acid, in the side chain the carbonyl-remote side of the carboxyl derivative function have at least one quaternizable tertiary nitrogen atom.
  • variable R 1 is hydrogen (for an acrylic acid derivative) or methyl (for a methacrylic acid derivative)
  • the variable X is O, NH or NR 4 and the variables R 2 , R 3 and R 4 are independently d - Denote C2o-alkyl groups
  • the variable n is a number from 1 to 12, in particular from 2 to 6, especially for the number 2 or 3, stands.
  • Typical examples of compounds of the general formula (I) are 2- (N, N-dimethylamino) ethyl acrylate, 2- (N, N-dimethylamino) ethyl methacrylate, N- [2- (N ', N'-dimethylamino ) ethyl] acrylamide, N- [2- (N ', N'-dimethylamino) ethyl] methacrylamide, 3- (N, N-dimethylamino) propyl acrylate, 3- (N, N-dimethylamino) propyl methacrylate, N- [3- (N ', N'-dimethylamino) propyl] acrylamide, N- [3- (N', N'-dimethylamino) propyl] methacrylic acid amide, 2- (N, N-diethylamino) ethyl methacrylate, N- [2 (N, N-diethyla
  • Also suitable as monomers (C) are saturated, partially unsaturated or unsaturated five-membered or six-membered heterocycles which carry an alkenyl substituent, in particular a vinyl group, an acrylate group or a methacrylate group and have at least one quaternizable tertiary nitrogen atom in the ring.
  • the acrylate or methacrylate group is expediently via a hydroxyalkylene side chain, in particular a (jo-hydroxy-Ci-C4-alkylene side chain, at the heterocycle produced by ester formation with acrylic acid or methacrylic acid.
  • a hydroxyl group attached directly to the heterocycle ie attached without an alkylene bridge, is sufficient to link with the acrylic acid or methacrylic acid.
  • Examples of such an alkenyl substituent-bearing saturated, partially unsaturated or unsaturated five-membered or six-membered ring heterocycles are N-vinylimidazole, N-vinylbenzimidazole, N-vinylpyrazole, N-vinyl-3-imidazoline, N- (C 1 -C 20 -alkyl) N'-vinylpiperazines such as N-methyl-N'-vinylpiperazine, 2-, 3- or 4-vinylpyridine and the esters of acrylic acid or methacrylic acid with N- ( ⁇ -hydroxyethyl) imidazole, N- ( ⁇ -hydroxyethyl) benzimidazole , N- ( ⁇ -hydroxyethyl) pyrazole, N- ( ⁇ -hydroxyethyl) -3-imidazoline, N- (C 1 to C 20 alkyl) -N '- ( ⁇ -hydroxyethyl) piperazines, such as N-methyl-
  • Examples of suitable C 1 - to C 20 -alkyl groups which may occur as substituents in the monomers (C) are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl , n-pentyl, sec-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, iso-nonyl, 2-propylheptyl, n-decyl, n-dodecyl , n-tridecyl, isotridecyl, n-tetradecyl, n-hexydecyl, n-octadecyl and eicosyl. Of these, methyl, ethyl, n
  • the quaternized terpolymer according to the invention contains as component (Cq) at least one partially or completely quaternized ethylenically unsaturated monomer from the group 2- (N, N-dialkylamino) ethyl acrylates, 2- (N, N-dialkylamino) ethyl methacrylates , N- [3- (N ', N'-dialkylamino) propyl] acrylamides, N- [3- (N', N'-dialkylamino) propyl] methacrylamides, N-alkyl-N'-vinylpiperazines, N Vinylimidazole, vinylpyridines and the esters of acrylic acid or methacrylic acid with N- ( ⁇ -hydroxyethyl) imidazole, N-alkyl-N '- ( ⁇ -hydroxyethyl) piperazines, ( ⁇ -hydroxyethyl) pyridines and hydroxypyridines.
  • component (Cq) at
  • alkyl substituents methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl, especially methyl.
  • Suitable quaternizing agents are in principle all compounds suitable in principle as such.
  • the quaternization of the at least one quaternizable tertiary nitrogen atom in the monomers (C) is carried out with at least one quaternizing agent selected from epoxides, dialkyl sulfates, dialkyl sulfites, alkyl halides, arylalkyl halides, alkylcarboxylic esters and dialkylcarbonates.
  • Suitable epoxides are, for example, C 2 - to C 12 -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-pentenoxide and aromatic-substituted ethylene oxides such as styrene oxide or 4-methyl styrene oxide.
  • C 2 - to C 12 -alkylene oxides such as ethylene oxide, propylene oxide, 1,2-
  • epoxides are preferably used in combination with protic acids, in particular with d- to Ci2 monocarboxylic acids such as formic acid, acetic acid or propionic acid or C 2 to C 2 dicarboxylic acids such as oxalic acid or adipic acid;
  • d- to Ci2 monocarboxylic acids such as formic acid, acetic acid or propionic acid or C 2 to C 2 dicarboxylic acids such as oxalic acid or adipic acid
  • sulfonic acids such as benzenesulfonic acid or toluenesulfonic acid or aqueous mineral acids such as sulfuric acid or hydrochloric acid are also suitable.
  • Suitable dialkyl sulfates are preferably di- (C 1 -C 20 -alkyl) sulfates, in particular di (C 1 -C 4 -alkyl) sulfates, such as dimethyl sulfate or diethyl sulfate.
  • the by-products formed such as monoalkyl sulfates and sulfates, can be removed by treatment with anion exchangers.
  • Suitable alkyl halides are preferably C 1 -C 20 -alkyl fluorides, chlorides, bromides or iodides, in particular C 1 -C 4 -alkyl fluorides, chlorides, bromides or iodides, such as methyl chloride, methyl bromide, methyl iodide, ethyl chloride, ethyl bromide or ethyl iodide.
  • the resulting by-products such as halide anions can be removed by treatment with anion exchangers.
  • Suitable benzyl halides are, for example, benzyl chloride, benzyl bromide or benzyl iodide; the benzene nucleus of the benzyl radical may in principle still carry one or more substituents such as C 1 -C 4 -alkyl groups. After quaternization, the resulting by-products can be removed by treatment with anion exchangers.
  • Mono- or di- (C 1 -C 20 -alkyl) mono- or -dicarboxylic acid esters in particular mono- or di- (C 1 -C 4 -alkyl) -mono- or -dicarboxylic acid esters are preferably suitable as alkylcarboxylic esters, the basic mono- or di- or Dicarboxylic acid has 1 to 12 or 2 to 12 carbon atoms, for example methyl formate or dimethyl oxalate.
  • Suitable alkyl carbonates are preferably di- (C 1 -C 20 -alkyl) carbonates, in particular di (C 1 -C 4 -alkyl) carbonates, such as dimethyl carbonate or diethyl carbonate.
  • this is done using a high-pressure polymerization process, as described for example in EP-A 007 590, in DE-A 31 41 507 and in the documents cited therein, and operates at pressures of 50 to 5000 bar, in particular 1000 to 2500 bar, especially 500 to 2000 bar, typically 1600 to 1800 bar, and at temperatures of 50 to 450 ° C, in particular 100 to 350 ° C, especially 150 to 250 ° C, typically 210 to 230 ° C.
  • a polymerization apparatus for this purpose in particular a continuously operated tubular reactor is suitable.
  • the polymerization is initiated by radically decomposing initiators, for this purpose, air or oxygen, if appropriate in the presence of additional metered organic peroxides and / or
  • Hydroperoxides examples include diisopropylbenzene hydroperoxide, cumene hydroperoxide, methyl isobutyl ketone peroxide, di-tert-butyl peroxide and tert-butyl perisononate.
  • suitable regulators such as aliphatic aldehydes can be used in the polymerization.
  • the quaternization subsequent to the polymerization of the monomers (A), (B) and (C) is likewise carried out by known and customary working techniques. This is typically carried out at temperatures in the range of 15 to 150 ° C, in particular from 20 to 1 10 ° C, and at atmospheric pressure.
  • the quaternization reaction can be carried out in an inert organic solvent such as toluene or xylene.
  • 0.1 to 1.5 equivalents, in particular 0.5 to 1.25 equivalents, of quaternizing agent are employed per equivalent of quaternizable tertiary nitrogen atom, the quaternizing agent being a single chemical compound or a mixture of different ones suitable for quaternization may be chemical compounds.
  • the quaternized terpolymer according to the invention preferably has a number-average molecular weight (M n ) in the range from 1000 to 20,000, in particular from 1250 to 15,000, in particular from 1,500 to 10,000 (in each case determined by gel permeation chromatography).
  • M n number-average molecular weight
  • the quaternized terpolymer according to the invention is outstandingly suitable as a fuel additive and, in principle, can be used in any fuel. It has a number of beneficial effects on the operation of internal combustion engines with fuels.
  • the quaternized terpolymer of the invention is preferably used in gasoline fuels, but in particular in middle distillate 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 terpolymer 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, each based on the total amount of fuel.
  • the fuel additized with the quaternized terpolymer according to the invention is usually a gasoline fuel or, in particular, a middle distillate fuel, especially a diesel fuel.
  • the fuel may contain other common additives to improve efficacy and reduce wear. These include, in particular, conventional detergent additives, carrier oils, lubricity additives, cetane number improvers, conductivity improvers, anti-corrosion additives, antifoams and dehazers.
  • the hydrophobic hydrocarbon residue in the above detergent additives which provides sufficient solubility in the fuel, has a number average molecular weight (M n ) of from 85 to 20,000, preferably from 13 to 10,000, more preferably from 300 to 5,000, more preferably from 300 to 3000, more preferably from 500 to 2500 and in particular from 700 to 2500, especially from 800 to 1500.
  • M n number average molecular weight
  • a typical hydrophobic hydrocarbon radical in particular in conjunction with the polar, in particular polypropenyl, polybutenyl and polyisobutenyl radicals having a number average Molecular weight M n of preferably in each case 300 to 5000, particularly preferably 300 to 3000, more preferably 500 to 2500, even more preferably 700 to 2500 and in particular 800 to 1500 into consideration.
  • monoamino (Da) -containing additives are the compounds obtainable from polyisobutene epoxides by reaction with amines and subsequent dehydration and reduction of the amino alcohols, as described in particular in DE-A 196 20 262.
  • Polyoxy-C2 to C4-alkylene (Df) containing additives are preferably polyether or polyetheramines, which by reaction of C2 to C6o-alkanols, C6 to C3o-alkanediols, mono- or D1-C2 to C3o-alkylamines, Cr to C 30 -alkylcyclohexanols or C 1 to C 30 -alkylphenols with 1 to 30 mol of ethylene oxide and / or propylene oxide and / or butylene oxide per hydroxyl group or amino group and, in the case of polyetheramines, by subsequent reductive amination with ammonia, monoamines or Polyamines 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, Isononylphenolbutoxyl- late and Polyisobutenolbutoxylate and propoxylates and the corresponding reaction products with ammonia.
  • Carboxyl 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 meet 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).
  • Before- yakt are the reaction products of alkyl- or alkenyl-substituted succinic acids or derivatives thereof with amines, and particularly preferably 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.
  • a fuel in particular a middle distillate fuel, especially a diesel fuel
  • one or more detergent additives from the group (Dh) ie detergent additives with groups derived from succinic anhydride with hydroxyl and / or amino - No- and / or amido and / or imido groups
  • the problem underlying the present invention is particularly well solved.
  • 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.
  • 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. It is also useful as a "hydrocrack oil” known and obtained in the refining of mineral oil fraction (Vakuumdestillatites with a boiling range of about 360 to 500 ° C, available from high pressure catalytically hydrogenated and isomerized and dewaxed natural mineral oil). Also suitable are mixtures of the abovementioned mineral carrier oils.
  • 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 3 -alkylamines, Cr to C 30 -alkylcyclohexanols or C 1 to C 30 -alkylphenols with 1 to 30 mol of ethylene oxide and / or propylene oxide and / or butylene oxide per hydroxyl group or amino group and, in the case of the polyetheramines, 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.
  • Typical examples are tridecanol or isotridecanol butoxylates, isononylphenol butoxylates and polyisobutenol butoxylates and propoxylates, and the corresponding reaction products with ammonia.
  • carboxylic acid esters of long-chain alkanols are in particular esters of mono-, di- or tricarboxylic acids with long-chain alkanols or polyols, 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.
  • particularly suitable synthetic carrier oils are alcohol-started polyethers having about 5 to 35, preferably about 5 to 30, particularly preferably 10 to 30 and in particular 15 to 30 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.
  • Preferred examples are 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 aliphatic C6-C18-alcohols are hexanol, heptanol, octanol, 2-ethylhexanol, nonyl alcohol, decanol, 3-propylheptanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, octadecanol and their constitutional and Positional isomers.
  • the alcohols can be used both in the form of pure isomers and in the form of technical mixtures.
  • a particularly preferred alcohol is tridecanol.
  • C3 to C6 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.
  • C3 to C4 alkylene oxides ie, propylene oxide such as 1,2-propylene oxide and butylene oxide such as 1,2-butylene oxide, 2,3-butylene oxide and isobutylene oxide.
  • butylene oxide is used.
  • suitable synthetic carrier oils are alkoxylated alkylphenols, as described in DE-A 10 102 913.
  • Preferred carrier oils are synthetic carrier oils, the alcohol-initiated polyethers described above being particularly preferred.
  • the carrier oil or the mixture of different carrier oils is added to the fuel in an amount of preferably 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.
  • the fuel may contain other conventional additives and co-additives in the usual amounts.
  • middle distillate fuels particularly diesel fuels
  • these are mainly friction modifiers, corrosion inhibitors, demulsifiers, dehazers, antifoams, combustion improvers, antioxidants or stabilizers, antistatic agents, metallocenes, metal deactivators, dyes and / or solvents.
  • 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. Particularly suitable for this purpose are the middle distillates of fossil origin, ie conventional mineral diesel fuels, used cold flow improvers ("middle distillate flow improvers", "MDFI"). However, it is also possible to use organic compounds which, when used in conventional diesel fuels, have in part or predominantly the properties of a wax anti-settling additive ("WASA"). Also, they can act partly or predominantly as nucleators. However, it is also possible to use mixtures of MDFI-active and / or WASA-active and / or nucleator-active organic compounds. Typically, the cold flow improver is selected
  • 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 ( ⁇ -olefins) and internally.
  • 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 - to C 40 - ⁇ -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,
  • 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.
  • the carboxylic acids with a branched hydrocarbon radical che preferred, 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 genyl 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.
  • terpolymers of a C2 to C4o- ⁇ -olefin, a C to C2o-alkyl ester of an ethylenically unsaturated monocarboxylic acid having 3 to 15 carbon atoms and a C2 to Ci4 alkenyl ester of a saturated monocarboxylic acid having 2 to 21 carbon atoms are copolymers of the Class (K1) suitable.
  • 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 C4o-based olefins.
  • the copolymers of class (K1) preferably have a number average molecular weight M n of from 1000 to 20,000, particularly preferably from 1000 to 10,000 and in particular from 1000 to 8000.
  • Typical comb polymers of component (K2) are obtained, 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 functional groups. on with an alcohol of at least 10 carbon atoms available.
  • Further 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.
  • Polyoxyalkylenes suitable as a component of class (K3) are, for example, polyalkylene esters, polyoxyalkylene ethers, mixed polyoxyalkylene ester ethers and mixtures thereof. These polyoxyalkylene compounds preferably contain at least one, preferably at least two, linear alkyl groups each having from 10 to 30 carbon atoms and a polyoxyalkylene group having a number average molecular weight of up to 5,000. Such polyoxyalkylene compounds are described, for example, in EP-A 061 895 and in US Pat. No. 4,491,455. Preferred polyoxyalkylene compounds are based on polyethylene glycols and polypropylene glycols having a number average molecular weight of 100 to 5000. Further, polyoxyalkylene mono- and diesters of fatty acids having 10 to 30 carbon atoms such as stearic acid or behenic acid are suitable.
  • Primary amines which are suitable for the preparation of said polar nitrogen compounds are, for example, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tetradecylamine and the higher linear homologs
  • 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 with 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 the class (K4) is preferably an oil-soluble reaction product based on poly (C 2 - to C 20 -carboxylic acids) of the general formula I Ia or Ib which has at least one tertiary amino group
  • variable A is a straight-chain or branched C 2 - to C 6 -alkylene group or the grouping of the formula I II
  • the preferred oil-soluble reaction product of component (K4) in particular that of general formula I Ia or Ib, is an amide, an amide ammonium salt or an ammonium salt in which none, one or more carboxylic acid groups are converted into amide groups.
  • Straight-chain or branched C 2 - to C 6 -alkylene groups of the variable A are, for example, 1, 1-ethylene, 1, 2-propylene, 1, 3-propylene, 1, 2-butylene, 1, 3-butylene, 1, 4-butylene 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.
  • 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.
  • these amines are secondary amines to the oil-soluble reaction products of component (K4) and have the general formula HN (R 8 ) 2 in which the two variables R 8 are each independently straight-chain or branched C 10 - to C 30 -alkyl radicals, in particular C14- to C24-alkyl radicals.
  • R 8 are each independently straight-chain or branched C 10 - to C 30 -alkyl radicals, in particular C14- to C24-alkyl radicals.
  • These longer-chain alkyl radicals are preferably straight-chain or only slightly branched.
  • the abovementioned secondary amines are derived with regard to their longer-chain alkyl radicals from naturally occurring fatty acid or from its derivatives.
  • 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.
  • 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, more 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 corrosion inhibitors are succinic esters, especially with polyols, fatty acid derivatives, for example oleic 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-butyl phenol ethoxylate or tert-pentyl phenol ethoxylate, fatty acids, alkyl phenols, condensation points 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 metal deactivators are e.g. Salicylic acid derivatives such as N, N'-disalicylidene-1, 2-propanediamine.
  • 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.
  • the quaternized terpolymer according to the invention can also be used in mixtures of such middle distillates with biofuel oils (biodiesel).
  • biofuel oils biodiesel
  • such mixtures are also encompassed by the term "middle distillate fuel”.
  • They are commercially available and usually contain the biofuel oils in minor amounts, typically in amounts of 1 to 30 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, in particular 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 include, for example, sunflower methyl ester, palm oil methyl ester (“PME”), soybean oil methyl ester (“SME”) and in particular rapeseed oil methyl ester (“RME”).
  • PME palm oil methyl ester
  • SME soybean oil methyl ester
  • RME rapeseed oil methyl ester
  • the middle distillate fuels or diesel fuels are particularly preferably those with a low sulfur content, that is to say having 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 terpolymer according to the invention is particularly suitable as a fuel additive in fuel compositions, in particular in diesel fuels, to overcome the initially described problems in direct injection diesel engines, especially in those with common rail injection systems.
  • the subject matter of the present invention is therefore also the use of the quaternized terpolymer according to the invention as a fuel additive for reducing the fuel consumption of direct-injection diesel engines, in particular of diesel engines with common-rail injection systems.
  • the subject matter of the present invention is therefore also the use of the quaternized terpolymer according to the invention as fuel additive for minimizing power loss in direct injection diesel engines, in particular diesel engines with common rail injection systems.
  • VAc ethylene-vinyl acetate
  • DMAEMA 2- (di-methylamino) ethyl methacrylate
  • the terpolymer T1 from Example 1a was reacted with styrene oxide in an equimolar ratio to the tertiary nitrogen atom in DMAEMA in the presence of an equimolar amount of acetic acid by initially charging the terpolymer and the styrene oxide under a nitrogen atmosphere and heating to 80 ° C., the acetic acid within 15 minutes was then added dropwise and then stirred for 4 hours at 80 ° C until no more free epoxide could be detected by the Preussmann test.
  • the quaternized terpolymer Tq1 -1 was obtained in a yield of 95% in the form of a brown solid.
  • the power loss was determined on the basis of the official test method CEC F-98-08.
  • the power loss is a direct measure of the formation of deposits in the injectors.
  • a common direct-injection diesel engine with common-rail system was used.
  • the fuel used was a commercial diesel fuel from Garrmann (RF-06-03).
  • To this was added 1 wt ppm zinc in the form of a zinc didodecanoate solution to artificially stimulate the formation of deposits on the injectors.
  • the following table shows the results of relative power loss determinations at 4000 rpm after 12 hours of continuous operation without interruption.
  • the value PL 0 indicates the power loss compared to the power value after 10 minutes and the value PL 1 the power loss compared to the power value after 1 hour:

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Abstract

L'invention concerne un terpolymère quaternisé constitué (A) d'éthylène, (B) d'esters d'alcényle en C2 à C14 d'un ou plusieurs acides monocarboxyliques aliphatiques en C1 à C20 ou d'esters d'alkyle en C1 à C24 de l'acide acrylique ou de l'acide méthacrylique et (Cq) de monomères éthyléniquement insaturés, lesquels contiennent au moins un atome d'azote tertiaire, présent en partie ou entièrement sous une forme quaternisée. Ce terpolymère quaternisé peut être utilisé en tant qu'additif de carburant pour réduire ou prévenir les dépôts, pour réduire la consommation de carburant ainsi que pour réduire à un minimum la perte de puissance dans les moteurs diesel à injection directe, en particulier dans les moteurs diesel comportant des systèmes d'injection à rampe commune.
EP11718329A 2010-04-27 2011-04-26 Terpolymère quaternisé Withdrawn EP2563822A1 (fr)

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EP11718329A EP2563822A1 (fr) 2010-04-27 2011-04-26 Terpolymère quaternisé
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FR2984918B1 (fr) 2011-12-21 2014-08-01 Total Raffinage Marketing Compositions d’additifs ameliorant la resistance au lacquering de carburants de type diesel ou biodiesel de qualite superieure
FR2987052B1 (fr) 2012-02-17 2014-09-12 Total Raffinage Marketing Additifs ameliorant la resistance a l'usure et au lacquering de carburants de type gazole ou biogazole
WO2015113681A1 (fr) * 2014-01-29 2015-08-06 Basf Se Additifs à base d'acide polycarbonique, destinés à des carburants et à des lubrifiants
ES2896694T3 (es) 2016-07-05 2022-02-25 Basf Se Uso de inhibidores de la corrosión para combustibles y lubricantes
EP3559107B1 (fr) 2016-12-21 2023-12-13 Braskem S.A. Compositions d'éthylène-acétate de vinyle modifiées, mélanges de polymères et films fabriqués à partir de ceux-ci
FR3074497B1 (fr) 2017-12-06 2020-09-11 Total Marketing Services Composition d’additifs pour carburant
FR3074498B1 (fr) * 2017-12-06 2020-09-11 Total Marketing Services Composition d’additifs pour carburant
EP4212604A1 (fr) 2022-01-13 2023-07-19 TotalEnergies One Tech Compositions stabilisées comportant des oléfines

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CN102858811B (zh) 2015-01-28
AU2011246506A1 (en) 2012-11-01
CA2795545A1 (fr) 2011-11-03
WO2011134923A1 (fr) 2011-11-03
JP2013529232A (ja) 2013-07-18
CN102858811A (zh) 2013-01-02
BR112012025554A2 (pt) 2016-06-28
KR20130060205A (ko) 2013-06-07

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