EP2646530B1 - Utilisation du produit de réaction d'un acide dicarboxylique substitué par un hydrocarbyle et d'un composé de l'azote pour la réduction de la consommation de carburant. - Google Patents

Utilisation du produit de réaction d'un acide dicarboxylique substitué par un hydrocarbyle et d'un composé de l'azote pour la réduction de la consommation de carburant. Download PDF

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Publication number
EP2646530B1
EP2646530B1 EP11796948.5A EP11796948A EP2646530B1 EP 2646530 B1 EP2646530 B1 EP 2646530B1 EP 11796948 A EP11796948 A EP 11796948A EP 2646530 B1 EP2646530 B1 EP 2646530B1
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Prior art keywords
fuel
groups
additive
hydrocarbyl
reaction product
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German (de)
English (en)
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EP2646530A2 (fr
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Ludwig Völkel
Marc Walter
Harald BÖHNKE
Hannah Maria KÖNIG
Markus Hansch
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BASF SE
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BASF SE
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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
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/226—Organic compounds containing nitrogen containing at least one nitrogen-to-nitrogen bond, e.g. azo compounds, azides, hydrazines
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    • C10L1/00—Liquid carbonaceous fuels
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    • C10L1/14—Organic compounds
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    • C10L1/221—Organic compounds containing nitrogen compounds of uncertain formula; reaction products where mixtures of compounds are obtained
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    • C10L1/228—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen double bond, e.g. guanidines, hydrazones, semicarbazones, imines; containing at least one carbon-to-nitrogen triple bond, e.g. nitriles
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    • C10L1/234—Macromolecular compounds
    • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
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    • C10L10/04—Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
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    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/08—Use of additives to fuels or fires for particular purposes for improving lubricity; for reducing wear
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    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/16—Hydrocarbons
    • C10L1/1616—Hydrocarbons fractions, e.g. lubricants, solvents, naphta, bitumen, tars, terpentine
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
    • C10L1/1822—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms
    • C10L1/1824—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms mono-hydroxy
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10L1/00—Liquid carbonaceous fuels
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    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
    • C10L1/1985—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid polyethers, e.g. di- polygylcols and derivatives; ethers - esters
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    • C10L1/234—Macromolecular compounds
    • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/2381—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds polyamides; polyamide-esters; polyurethane, polyureas
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    • C10L2200/00—Components of fuel compositions
    • C10L2200/02—Inorganic or organic compounds containing atoms other than C, H or O, e.g. organic compounds containing heteroatoms or metal organic complexes
    • C10L2200/0259—Nitrogen containing compounds
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    • C10L2230/00—Function and purpose of a components of a fuel or the composition as a whole
    • C10L2230/22—Function and purpose of a components of a fuel or the composition as a whole for improving fuel economy or fuel efficiency
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    • C10L2270/00—Specifically adapted fuels
    • C10L2270/02—Specifically adapted fuels for internal combustion engines
    • C10L2270/023—Specifically adapted fuels for internal combustion engines for gasoline engines

Definitions

  • the present invention relates to the use as described in claim 1, of the reaction product of (a) a hydrocarbyl-substituted dicarboxylic acid whose hydrocarbyl radical has 8 to 250 carbon atoms or its anhydride and (b) a nitrogen compound of the general formula I or a salt of the nitrogen compound I, where R 1 and R 2, independently of one another, denote hydrogen or a C 1 - to C 20 -hydrocarbyl radical, as an additive in a fuel to reduce fuel consumption when operating a spark-ignited internal combustion engine with this fuel or as an additive in a gasoline to reduce fuel consumption when operating a self-igniting internal combustion engine with this fuel.
  • the present invention relates to a fuel composition as described in claim 4, which contains a gasoline fuel, said reaction product and at least one detergent additive.
  • the present invention relates to an additive concentrate, as described in claim 8, which contains said reaction product and at least one detergent additive with a fuel effect.
  • lubricity improvers for gasoline fuels are usually condensation products of naturally occurring carboxylic acids such as fatty acids with polyols such as glycerol or with alkanolamines, eg. B. glycerol monooleate.
  • a disadvantage of the aforementioned lubricity improvers of the prior art is the poor miscibility with other typically used fuel additives, in particular with detergent additives such as polyisobuteneamines and / or carrier oils such as polyalkylene oxides.
  • An important requirement for practice is that the provided component mixtures or additive concentrates are easily pumpable even at lower temperatures, in particular in winter outside temperatures of, for example, down to -20 ° C and remain stable over a longer period stable homogeneous, ie it may not be Phase separation and / or precipitation occur.
  • the component mixtures or additive concentrates are accompanied by relatively large amounts of mixtures of paraffinic or aromatic hydrocarbons with alcohols such as tert-butanol or 2-ethylhexanol as solubilizers.
  • alcohols such as tert-butanol or 2-ethylhexanol
  • the cited prior art lubricity improvers often have the tendency to form emulsions with water in the component blends or additive concentrates or in the fuel itself, so that infiltrated water is difficult, or at least very slowly, to be separated again via phase deposition.
  • reaction products can be used as additives to skimmers or fuels.
  • the object of the present invention was to provide fuel additives which, on the one hand, bring about effective fuel savings when operating a spark-ignited internal combustion engine and, on the other hand, the described deficiencies of the prior art, that is, in particular the poor miscibility with other fuel additives and no tendency to emulsify with water. In addition, they should not worsen the high level of intake valve cleanliness achieved by modern fuel additives.
  • reaction product of (a) a hydrocarbyl-substituted dicarboxylic acid or derem anhydride and (b) a nitrogen compound of general formula I was found. It is to be assumed that the fuel saving due to said reaction product is largely due to its effect as an additive which reduces the internal friction in the internal combustion engines, in particular in gasoline engines.
  • the said reaction product thus functions essentially as a lubricity improver in the context of the present invention.
  • Reaction products of a hydrocarbyl-substituted dicarboxylic acid or anhydride and an aminoguanidine or salt thereof are disclosed in US Pat US 2009/0282731 A1 and US 2010/0037514 A1 as additives for improving the performance of diesel engines and for cleaning injectors in diesel engines.
  • Under externally ignited internal combustion engines are preferably gasoline engines, which are usually ignited with spark plugs to understand.
  • gasoline engines In addition to the usual four- and two-stroke gasoline engines include spark-ignition internal combustion engines but also other types of engines, such as the Wankel engine. These are usually engines with commercial gasoline grades, especially gasoline grades according to EN 228, gasoline-alcohol blends such as flex fuel with 75 to 85 vol .-% ethanol, liquid pressure gas (“LPG”) or compressed natural gas (“CNG”, "natural gas”) as fuel.
  • LPG liquid pressure gas
  • CNG compressed natural gas
  • the nitrogen compounds of the general formula I for the reaction component (a) are guanidine, substituted guanidines or salts thereof.
  • Possible hydrocarbyl radicals in these compounds contain 1 to 20, in particular 1 to 12, especially 1 to 8 carbon atoms.
  • a hydrocarbyl radical is to be understood here as meaning a hydrocarbon radical of any structure, but containing minor amounts of heteroatoms such as oxygen and / or nitrogen atoms and / or halogen atoms and / or functional groups such as hydroxyl groups, carboxyl groups, carboxylic acid ester groups, cyano groups, nitro groups and / or sulfo groups can carry as long as the dominant hydrocarbon character of the rest is not distorted by this.
  • the said hydrocarbyl radical may be saturated or unsaturated in nature; it can be linear or branched; it may contain aromatic and / or heterocyclic substructures.
  • the nitrogen compound I may have two such hydrocarbyl radicals for R 1 and R 2 or only one such hydrocarbyl radical for R 1 or R 2 , in the latter case the other substituent then being hydrogen.
  • both substituents R 1 and R 2 preferably denote hydrogen, ie unsubstituted aminoguanidine is present.
  • Possible hydrocarbyl radicals for R 1 and / or R 2 are preferably linear or branched alkyl or alkenyl radicals, in particular those having 1 to 8, preferably 1 to 4, carbon atoms, such as methyl, ethyl, vinyl, n-propyl, isopropyl, 1-propenyl, 2-propenyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, 2-ethylhexyl, neo-octyl, nonyl, neononyl, isononyl, decyl, neodecyl, 2-propylheptyl, Undecyl, neoundecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, pent
  • hydrocarbyl radicals for R 1 and / or R 2 may also denote cycloalkyl radicals, for example cyclopentyl, cyclohexyl, 2-, 3- the 4-methylcyclohexyl or cycloheptyl.
  • hydrocarbyl radicals for R 1 and / or R 2 may also denote aryl, alkaryl or arylalkyl radicals, for example phenyl, naphthyl, benzyl, 2-phenylethyl, 3-phenylpropyl, 4-phenylbutyl, tolyl or o-, m- or p -xylyl.
  • nitrogen compounds I are used in the form of one of their salts, this is in particular a halide such as chloride or bromide, carbonate, hydrogen carbonate (bicarbonate), nitrate or orthophosphate.
  • a halide such as chloride or bromide
  • carbonate hydrogen carbonate (bicarbonate)
  • hydrogen carbonate nitrate or orthophosphate.
  • bicarbonate bicarbonate
  • the nitrogen compound of component (b) is unsubstituted aminoguanidine bicarbonate.
  • the hydrocarbyl-substituted dicarboxylic acid or its anhydride of component (a) typically has a saturated C 2 to C 10 dicarboxylic acid or its anhydride as a backbone.
  • the dicarboxylic acid or its anhydride may carry a plurality, for example two or three, hydrocarbyl substituents, but only one hydrocarbyl substituent is preferred.
  • the anhydride is usually in cyclic form when anhydride formation is intramolecular. However, open-chain anhydrides formed by intermolecular anhydride formation are also suitable.
  • dicarboxylic acids examples include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid.
  • Aromatic dicarboxylic acids such as phthalic acid or terephthalic acid are also suitable.
  • the hydrocarbyl-substituted dicarboxylic acid used as the reaction component (a) is based on succinic acid or its anhydride.
  • succinic acid or its anhydride is the corresponding Succinanhydrid of formula II in which R 3 denotes a hydrocarbyl radical having 8 to 250 carbon atoms, suitable.
  • a hydrocarbyl radical is to be understood to mean a hydrocarbon radical of any structure which, however, contains in a minor amount heteroatoms such as oxygen and / or nitrogen atoms and / or halogen atoms and / or functional groups such as hydroxyl groups, carboxyl groups, carboxylic acid ester groups, cyano groups, nitro groups and / or Can carry sulfo groups, as long as the dominating hydrocarbon character of the rest is not distorted by this.
  • This hydrocarbyl radical is typically an alkyl, alkenyl, cycloalkyl, aryl, heteroaryl, aralkyl or alkylaryl radical.
  • it may be based on an olefin polymer, for example on a polyethylene, polypropylene or polyisobutylene.
  • the hydrocarbyl radical in component (a) or the radical R 3 is a linear or branched C 8 - to C 40 -alkyl or -alkenyl radical or a polyisobutenyl radical having 24 to 250 carbon atoms.
  • Linear or branched C 8 to C 40 alkenyl groups and polyisobutenyl groups are usually generated by a thermal ene reaction between the unsubstituted dicarboxylic acid or anhydride and a long-chain ⁇ -olefin to give an olefinic double bond in the ⁇ , ⁇ position of the hydrocarbyl side chain ,
  • the reactants are usually heated to temperatures of 150 to 250 ° C.
  • Alkenyl radicals can then be hydrogenated to the corresponding saturated alkyl radicals.
  • C 8 - to C 40 -alkenyl radicals are, for example, 1-nonenyl, 1-decenyl, 1-undecenyl, 1-dodecenyl, 1-tridecenyl, 1-tetradecenyl, 1-pentadecenyl, 1-hexadecenyl, 1-octadecenyl, 1-eicosenyl and the corresponding alkenyl radicals from oligoisobutenes such as di-, tri-, tetra- or pentaisobutene or from technical ⁇ -olefin mixtures such as C 20 -C 24 - ⁇ -olefin into consideration.
  • a polyisobutenyl radical in the presence of a polyisobutenyl radical, this preferably comprises 24 to 250, in particular 28 to 180, especially 36 to 80 carbon atoms or thus has a number average molecular weight M n of preferably 330 to 3500, in particular 390 to 2500, especially 500 to 1100.
  • Such polyisobutenyl radicals are normally prepared from highly reactive polyisobutenes, ie from polyisobutenes with a high proportion, usually at least 60%, in particular at least 70%, especially at least 80%, of terminal vinylidene double bonds.
  • polyisobutenyl succinimides generally have a degree of succinylation, i. a molar ratio of succinic anhydride moiety to polyisobutene moieties, from 0.8 to 2.0, especially from 1.0 to 1.3.
  • PIBSA polyisobutenyl succinimides
  • the resulting reaction product of (a) the hydrocarbyl-substituted dicarboxylic acid or anhydride and (b) the nitrogen compound I is often a mixture of several compounds of different structure.
  • reaction product according to the invention of (a) the hydrocarbyl-substituted dicarboxylic acid or anhydride and (b) the nitrogen compound I are outstandingly suitable as a fuel additive, which is an effective fuel economy in the Operating a spark-ignited internal combustion engine, in particular a gasoline engine, causes and is well miscible with other fuel additives and has no significant tendency to form emulsions with water.
  • the advantageous properties mentioned are particularly evident in the use in gasoline fuels in the co-use of detergent-additive fuel additives.
  • the subject of the present invention is also a fuel composition
  • a fuel composition comprising a gasoline in a larger amount and in a smaller amount at least one inventive reaction product of (a) a hydrocarbyl-substituted dicarboxylic acid and (b) a nitrogen compound of general formula I and at least one of said reaction product contains various fuel additive with detergent effect.
  • the amount of this at least one reaction product according to the invention in the gasoline is usually from 10 to 5000 ppm by weight, more preferably from 20 to 2000 ppm by weight, more preferably from 30 to 1000 ppm by weight and in particular from 40 to 500% by weight. ppm, eg from 50 to 300 ppm by weight.
  • 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.
  • petrol fuel compositions of the specification are also according to WO 00/47698 Possible fields of use for the present invention.
  • gasoline fuels also alcoholic gasoline fuels, especially ethanol-containing gasoline fuels, as described for example in the WO 2004/090079 are described, for. B.
  • the reaction product according to the invention of (a) the hydrocarbyl-substituted dicarboxylic acid or anhydride and (b) the nitrogen compound I can be added either to the respective base fuel alone or in the form of fuel additive packages.
  • Such packages are fuel additive concentrates and usually contain in addition to solvents in addition to the at least one different from the reaction product according to the invention detergent additive still a number of other components as co-additives, in particular these are carrier oils, corrosion inhibitors, demulsifiers, dehazers, anti-foaming agents, combustion improvers, antioxidants or Stabilizers, antistatic agents, metallocenes, metal deactivators, solubilizers, markers and / or dyes.
  • Detergents or detergent additives hereinafter referred to as component (D), are commonly referred to as fuel deposit inhibitors.
  • component (D) is commonly referred to as fuel deposit inhibitors.
  • the detergent additives are amphiphilic substances having at least one hydrophobic hydrocarbon radical having a number average molecular weight (M n ) of 85 to 20,000, especially from 300 to 5000, especially from 500 to 2500, and at least one polar grouping.
  • the hydrophobic hydrocarbon radical in the above detergent additives which provides sufficient solubility in the fuel composition, has a number average molecular weight (M n ) of from 85 to 20,000, especially from 300 to 5,000, especially from 500 to 2,500.
  • M n number average molecular weight
  • 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 they are in particular DE-A-196 20 262 are described.
  • Additives carboxyl groups or their alkali metal or alkaline earth metal salts (Dd) are preferably copolymers of C2-C40 olefins with maleic anhydride having a total molar mass of 500 to 20,000, the carboxyl groups completely or partially to the alkali metal or alkaline earth metal salts and a remaining residue the carboxyl groups are reacted with alcohols or amines.
  • Such additives are in particular from the EP-A-307,815 known.
  • Such additives are primarily for preventing valve seat wear and can, as in the WO-A-87/01126 described, be used with advantage in combination with conventional fuel detergents such as poly (iso) -butene amines 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 Sulfobernsteinklaklalesters, as described in particular in EP-A-639 632 is described.
  • Such additives are primarily for preventing valve seat wear and can be used to advantage in combination with conventional fuel detergents such as poly (iso) buteneamines or polyetheramines.
  • Polyoxy-C 2 -C 4 -alkylene (Df) containing additives are preferably polyether or polyetheramines, which by reacting C 2 -C 60 alkanols, C 6 -C 30 alkanediols, mono- or di-C 2 -C 30 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 used in particular EP-A-310 875 .
  • polyethers such products also meet carrier oil properties. Typical examples of these are tridecanol or Isotridecanolbutoxylate, Isononylphenolbutoxylate 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 in particular 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.
  • derivatives with aliphatic polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine.
  • 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, still have free amine groups, succinic acid derivatives with a Acid and an amide, Carbon Textreimide with monoamines, Carbonklareimide with di- or polyamines, which still have free amine groups in addition to the imide function, or diimides, which are formed by the reaction of di- or polyamines with two succinic acid derivatives.
  • Such fuel additives are particularly in U.S. Patent 4,849,572 described.
  • the detergent additives from the group (Dh) are preferably the reaction products of alkyl- or alkenyl-substituted succinic anhydrides, in particular of polyisobutenylsuccinic anhydrides ("PIBSA"), with amines and / or alcohols. These are thus derived from alkyl, alkenyl or polyisobutenyl succinic anhydride derivatives with amino and / or amido and / or imido and / or hydroxyl groups. It goes without saying that these reaction products are obtainable not only when substituted succinic anhydride is used, but also when substituted succinic acid or suitable acid derivatives such as succinic acid halides or esters are used.
  • PIBSA polyisobutenylsuccinic anhydrides
  • the additized fuel comprises at least one detergent based on a polyisobutenyl-substituted succinimide.
  • a polyisobutenyl-substituted succinimide is the imides with aliphatic polyamines.
  • Particularly preferred polyamines are ethylenediamine, diethylenetriamine, triethylenetetramine, pentaethylenehexamine and especially tetraethylenepentamine.
  • the polyisobutenyl radical has a number average molecular weight M n of preferably 500 to 5000, particularly preferably 500 to 2000 and in particular about 1000.
  • 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 particularly in the EP-A-831 141 described.
  • the fuel composition of the present invention contains the at least one detergent-type fuel additive other than the reaction product of the present invention, which is normally selected from the above groups (Da) to (Di) in an amount of usually 10 to 5000 ppm by weight, more preferably from 20 to 2000 ppm by weight, more preferably from 30 to 1000 ppm by weight, and especially from 40 to 500 ppm by weight, e.g. B. from 50 to 250 ppm by weight.
  • said detergent additives (D) are used in combination with at least one carrier oil.
  • the fuel composition according to the invention contains at least one carrier oil in a smaller amount as a further fuel additive.
  • Suitable mineral carrier oils are fractions obtained in petroleum processing, such as bright stock or base oils with viscosities such as from class SN 500-2000; 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 selected from: polyolefins (polyalphaolefins or polyinteralalefins), (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 polyoxy-C 2 -C 4 -alkylene group-containing compounds which are obtained by reacting C 2 -C 60 -alkanols, C 6 -C 30 -alkanediols, mono- or di-C 2 -C 30 alkylamines, C 1 -C 30 -alkyl-cyclohexanols 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.
  • EP-A310 875 Such products are used in particular EP-A310 875 .
  • EP-A356 725 EP-A 700 985 and US-A 4,877,416 described.
  • polyetheramines poly-C 2 -C 6 alkylene oxide amines or functional derivatives thereof can be used. Typical examples of 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 are described in particular in US Pat DE-A 38 38 918 are described.
  • mono-, di- or tricarboxylic acids Aliphatic or aromatic acids can be used as ester alcohols or polyols are especially long-chain representatives with, for example, 6 to 24 carbon atoms.
  • Typical representatives of the esters are adipates, phthalates, isophthalates, terephthalates and trimellitates of isooctanol, isononanol, isodecanol and Isotridecanols, such as.
  • suitable synthetic carrier oils are alcohol-started polyethers with about 5 to 35, such as. B. about 5 to 30, C 3 -C 6 alkylene oxide, such as. B. selected from propylene oxide, n-butylene oxide and i-butylene oxide units, or mixtures thereof.
  • 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 ⁇ -C 18 -alkyl radical.
  • Preferred examples are tridecanol and nonylphenol.
  • Preferred carrier oils are synthetic carrier oils, with polyethers being particularly preferred.
  • a carrier oil is used, it is added to the additive fuel according to the invention 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 composition according to the invention contains at least one corrosion inhibitor as at least one detergent-active fuel additive and optionally the at least one carrier oil in a smaller amount as a further fuel additive.
  • Suitable corrosion inhibitors as such coadditives are succinic esters, especially with polyols, fatty acid derivatives, e.g. Oleic acid esters, oligomerized fatty acids and substituted ethanolamines.
  • Demulsifiers suitable as further coadditives are, for example, the alkali and alkaline earth metal salts of alkyl-substituted phenol and naphthalene sulfonates and the alkali and alkaline earth metal salts of fatty acid, furthermore alcohol alkoxylates, for example alcohol ethoxylates, phenol alkoxylates, for example tert-butylphenol ethoxylates or tert-pentylphenol ethoxylates, Fatty acid, alkylphenols, condensation products of ethylene oxide and propylene oxide, for example ethylene oxide-propylene oxide block copolymers, polyethyleneimines and polysiloxanes.
  • the alkali and alkaline earth metal salts of alkyl-substituted phenol and naphthalene sulfonates and the alkali and alkaline earth metal salts of fatty acid, furthermore alcohol alkoxylates, for example alcohol eth
  • Dehazers suitable as further coadditives are, for example, alkoxylated phenol-formaldehyde condensates.
  • Antifoams which are suitable as further coadditives are, for example, polyether-modified polysiloxanes.
  • suitable antioxidants are, for example, substituted phenols, e.g. 2,6-di-tert-butylphenol and 2,6-di-tert-butyl-3-methylphenol, as well as phenylenediamines, e.g. N, N'-di-sec-butyl-p-phenylenediamine.
  • Metal deactivators suitable as further co-additives include, for example, salicylic acid derivatives, e.g. N, N'-disalicylidene-1,2-propanediamine.
  • Suitable solvents are, in particular also for fuel additive packages, for example non-polar organic solvents, in particular aromatic and aliphatic hydrocarbons, e.g. Toluene, xylenes, "wide spirit" and the technical solvent mixtures of the names Shellsol® (manufacturer: Royal Dutch / Shell Group), Exxol® (manufacturer: ExxonMobil) and Solvent Naphtha.
  • non-polar organic solvents especially aromatic and aliphatic hydrocarbons, e.g. Toluene, xylenes, "wide spirit" and the technical solvent mixtures of the names Shellsol® (manufacturer: Royal Dutch / Shell Group), Exxol® (manufacturer: ExxonMobil) and Solvent Naphtha.
  • polar organic solvents especially alcohols such as tert-butanol, isoamyl alcohol, 2-ethylhexanol and 2-propylheptanol into consideration
  • the present invention also provides an additive concentrate which comprises at least one reaction product according to the invention of (a) a hydrocarbyl-substituted dicarboxylic acid or anhydride and (b) a nitrogen compound of the general formula I and at least one detergent-type fuel additive which is different from said reaction product.
  • the additive concentrate of the invention may contain the other above-mentioned co-additives.
  • the reaction product according to the invention is preferably present in the additive concentrate according to the invention in an amount of from 1 to 99% by weight, more preferably from 15 to 95% by weight and in particular from 30 to 90% by weight, based in each case on the total weight of the concentrate ,
  • the at least one detergent additive other than said reaction product is preferably present in the additive concentrate of the invention in an amount of from 1 to 99% by weight, especially preferably from 5 to 85 wt .-% and in particular from 10 to 70 wt .-%, each based on the total weight of the concentrate, before.
  • reaction product of a polyisobutenyl succinic anhydride, produced by thermal ene reaction (200 ° C) of maleic anhydride with a polyisobutene of number average molecular weight M n of 1000 and a content of terminal vinylidene double bonds of 85%, and aminoguanidine bicarbonate was in analogy to Example 1 of US 2009/0282731 A1 Solvesso TM 150 (manufacturer: ExxonMobil) was used as the diluent.
  • the components mentioned could be easily mixed together to form a clear liquid whose consistency remained stable for several days.
  • RP2 a conventional lubricity improver of the prior art
  • a typical commercially available Eurosuper base fuel according to EN 228 was added as a gasoline each with the additive concentrate AK1 (according to the invention) and AK2 (for comparison) in such an amount that the dosage of lubricity enhancer RP1 (according to the invention) and RP2 (for comparison) each 390 wt . ppm.
  • ASTM D 1094 phase separation test ASTM D 1094
  • water was added to the systems and the phase separation behavior was evaluated. After 5 minutes, AK1 gave two clear and sharply separated phases (phase separation according to ASTM D 1094: 1), whereas after 5 minutes with AK 2 an emulsion resulted in the water phase and a cloudy fuel phase (phase separation according to ASTM D 1094: 4).
  • a gasoline produced by the addition of AK1 at the rate of dosing based on a U.S. commercial baseline fuel used in Example 2 was used to determine fuel economy in a fleet test with three different automobiles according to U.S. Pat. Environmental Protection Agency Test Protocol, C.F.R. Title 40, Part 600, Subpart B, used.
  • the fuel consumption was first determined with unaddit Arthurm fuel and then with the same fuel, but now containing the additive concentrate AK1 in the dosage indicated in Example 2. On average for all cars used this resulted in an average fuel saving of 1.3%
  • IVD Intake valve cleanliness

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Claims (8)

  1. Utilisation du produit de réaction de (a) un acide dicarboxylique substitué par hydrocarbyle, dont le radical hydrocarbyle est un radical alkyle ou alcényle en C8-C40 linéaire ou ramifié ou un radical polyisobutényle ayant de 24 à 250 atomes de carbone, ou son anhydride, et (b) un composé azoté de formule générale I
    Figure imgb0007
    ou un sel du composé azoté I, R1 et R2 représentant indépendamment l'un de l'autre un atome d'hydrogène ou un radical hydrocarbyle en C1-C20,
    conjointement avec un additif pour carburant à action détergente, pour ce qui est duquel il s'agit d'au moins une substance amphiphile qui comporte au moins un radical hydrocarboné hydrophobe ayant une masse moléculaire moyenne en nombre (Mn) de 85 à 20 000 et au moins un groupement polaire,
    en tant qu'additif dans un carburant pour la réduction de la consommation de carburant lors du fonctionnement d'un moteur à combustion interne, à allumage commandé, avec ce carburant ou en tant qu'additif dans un carburant pour moteur à explosion, pour la réduction de la consommation de carburant lors du fonctionnement d'un moteur à combustion interne, à auto-allumage, avec ce carburant.
  2. Utilisation selon la revendication 1, dans laquelle l'acide dicarboxylique substitué par hydrocarbyle du composant (a) est à base d'acide succinique ou de son anhydride.
  3. Utilisation selon les revendications 1 et 2, dans laquelle le composé azoté du composant (b) est l'hydrogénocarbonate d'aminoguanidine non substitué.
  4. Composition de carburant, contenant en une plus grande quantité un carburant pour moteur à explosion et en une quantité moindre au moins un produit de réaction, tel que défini dans les revendications 1 à 3, de (a) un acide dicarboxylique substitué par hydrocarbyle et (b) un composé azoté de formule générale I ainsi qu'au moins un additif pour carburant à action détergente, différent dudit produit de réaction, pour ce qui est duquel il s'agit d'au moins une substance amphiphile qui comporte au moins un radical hydrocarboné hydrophobe ayant une masse moléculaire moyenne en nombre (Mn) de 85 à 20 000 et au moins un groupement polaire.
  5. Composition de carburant selon la revendication 4, contenant en tant qu'additif pour carburant à action détergente, différent dudit produit de réaction, au moins un représentant choisi parmi :
    (Da) des groupes mono- ou polyamino ayant jusqu'à 6 atomes d'azote, dans lesquels au moins un atome d'azote a des propriétés basiques ;
    (Db) des groupes nitro, éventuellement en association avec des groupes hydroxy ;
    (Dc) des groupes hydroxy en association avec des groupes mono- ou polyamino, dans lesquels au moins un atome d'azote a des propriétés basiques ;
    (Dd) des groupes carboxy ou leurs sels de métaux alcalins ou alcalino-terreux ;
    (De) des groupes sulfo ou leurs sels de métaux alcalins ou alcalino-terreux ;
    (Df) des groupements polyoxyalkylène(C2-C4) qui sont terminés par des groupes hydroxy, des groupes mono- ou polyamino, dans lesquels au moins un atome d'azote a des propriétés basiques, ou par des groupes carbamate ;
    (Dg) des groupes ester d'acide carboxylique ;
    (Dh) des groupements dérivés d'anhydride succinique, à groupes hydroxy et/ou amino et/ou amido et/ou imido ; et/ou
    (Di) des groupements produits par réaction de Mannich de phénols, substitués, avec des aldéhydes et des mono- ou polyamines.
  6. Composition de carburant selon la revendication 4 ou 5, contenant en outre en une moindre quantité, en tant qu'autre additif, au moins une huile de support.
  7. Composition de carburant selon les revendications 4 à 6, contenant en outre en une moindre quantité, en tant qu'autre additif, au moins un agent anticorrosion.
  8. Concentré d'additif pour carburant, contenant au moins un produit de réaction, tel que défini dans les revendications 1 à 3, de (a) un acide dicarboxylique substitué par hydrocarbyle, ou son anhydride, et (b) un composé azoté de formule générale I ainsi qu'au moins un additif pour carburant à action détergente, différent dudit produit de réaction, pour ce qui est duquel il s'agit d'au moins une substance amphiphile qui comporte au moins un radical hydrocarboné hydrophobe ayant une masse moléculaire moyenne en nombre (Mn) de 85 à 20 000 et au moins un groupement polaire.
EP11796948.5A 2010-12-02 2011-12-01 Utilisation du produit de réaction d'un acide dicarboxylique substitué par un hydrocarbyle et d'un composé de l'azote pour la réduction de la consommation de carburant. Not-in-force EP2646530B1 (fr)

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PL11796948T PL2646530T3 (pl) 2010-12-02 2011-12-01 ZASTOSOWANIE PRODUKTU REAKCJl PODSTAWIONEGO HYDROKARBYLEM KWASU DIKARBOKSYLOWEGO I ZWIĄZKU AZOTU DO ZMNIEJSZENIA ZUŻYCIA PALIWA SILNIKOWEGO

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PCT/EP2011/071470 WO2012072723A2 (fr) 2010-12-02 2011-12-01 Utilisation du produit réactionnel d'un acide dicarbonique à substitution hydrocarbyle et d'un composé azote pour réduire la consommation de carburant
EP11796948.5A EP2646530B1 (fr) 2010-12-02 2011-12-01 Utilisation du produit de réaction d'un acide dicarboxylique substitué par un hydrocarbyle et d'un composé de l'azote pour la réduction de la consommation de carburant.

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WO2012072723A2 (fr) 2012-06-07
PL2646530T3 (pl) 2017-08-31
CA2818837C (fr) 2018-12-18
AU2011334961B2 (en) 2017-02-23
CA2818837A1 (fr) 2012-06-07
MX2013006022A (es) 2013-07-15
EP2646530A2 (fr) 2013-10-09
KR20130126648A (ko) 2013-11-20
BR112013012874A2 (pt) 2016-09-06
ZA201304841B (en) 2014-09-25
KR101970939B1 (ko) 2019-04-22
JP2014501813A (ja) 2014-01-23
MY166033A (en) 2018-05-21
SG10201509787PA (en) 2015-12-30
CN103228769A (zh) 2013-07-31
CN103228769B (zh) 2016-04-13
BR112013012874B1 (pt) 2019-09-03
AU2011334961A1 (en) 2013-06-13
SG190391A1 (en) 2013-06-28
WO2012072723A3 (fr) 2012-07-26

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