EP2726580B2 - Composés d'azote quaternisés et leur utilisation en tant qu'additifs dans des carburants et des lubrifiants - Google Patents

Composés d'azote quaternisés et leur utilisation en tant qu'additifs dans des carburants et des lubrifiants

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Publication number
EP2726580B2
EP2726580B2 EP12737233.2A EP12737233A EP2726580B2 EP 2726580 B2 EP2726580 B2 EP 2726580B2 EP 12737233 A EP12737233 A EP 12737233A EP 2726580 B2 EP2726580 B2 EP 2726580B2
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European Patent Office
Prior art keywords
oder
quaternizable
amino group
primary
acid
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EP12737233.2A
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German (de)
English (en)
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EP2726580B1 (fr
EP2726580B9 (fr
EP2726580A1 (fr
Inventor
Cornelia RÖGER-GÖPFERT
Harald BÖHNKE
Wolfgang Grabarse
Hannah Maria KÖNIG
Markus Hansch
Ludwig Völkel
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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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)
    • C10L1/2387—Polyoxyalkyleneamines (poly)oxyalkylene amines and derivatives thereof (substituted by a macromolecular group containing 30C)
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular compounds
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
    • C10L1/2225—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates hydroxy containing
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • C10L1/223—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond having at least one amino group bound to an aromatic carbon atom
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • C10L1/224—Amides; Imides carboxylic acid amides, imides
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/232—Organic compounds containing nitrogen containing nitrogen in a heterocyclic ring
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/14—Use of additives to fuels or fires for particular purposes for improving low temperature properties
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/18—Use of additives to fuels or fires for particular purposes use of detergents or dispersants for purposes not provided for in groups C10L10/02 - C10L10/16

Definitions

  • direct-injection diesel engines the fuel is injected through a multi-hole injection nozzle directly into the combustion chamber and finely dispersed (atomized), rather than being introduced into a pre-chamber or swirl chamber as in a conventional (chamber) diesel engine.
  • the advantage of direct-injection diesel engines is their high power for a diesel engine while maintaining low fuel consumption. These engines also achieve very high torque even at low engine speeds.
  • the common-rail injection system can positively influence the engine's pollutant emissions, such as nitrogen oxide (NO x ), carbon monoxide (CO), and especially particulate matter (soot). This allows, for example, engines equipped with common-rail injection systems to theoretically meet the Euro 4 standard without the need for an additional particulate filter.
  • pollutant emissions such as nitrogen oxide (NO x ), carbon monoxide (CO), and especially particulate matter (soot).
  • Polyisobutenes which have uniform polymer backbones are particularly preferred. Uniform polymer backbones are particularly those polyisobutenes which are composed of at least 85 wt. %, preferably at least 90 wt. % and particularly preferably at least 95 wt. % of isobutene units. Such highly reactive polyisobutenes preferably have a number-average molecular weight in the abovementioned range. In addition, the highly reactive polyisobutenes can have a polydispersity in the range from 1.05 to 7, in particular from about 1.1 to 2.5, such as, for example, less than 1.9 or less than 1.5. Polydispersity is the quotient of the weight-average molecular weight Mw divided by the number-average molecular weight Mn.
  • PIBSA is produced in a known manner by reacting PIB with maleic anhydride (MA), which essentially produces a mixture of PIBSA and bismaleic PIBSA (BM PIBSA, see Scheme 1 below), which is generally not separated but used as such in subsequent reactions.
  • MA maleic anhydride
  • BM PIBSA bismaleic PIBSA
  • the ratio of the two components to each other can be expressed as the "degree of bismaleic acid” (BMG).
  • BMG degree of bismaleic acid
  • Short-chain hydrocarbyl or “low molecular weight hydrocarbyl” particularly represents straight-chain or branched alkyl or alkenyl, optionally interrupted by one or more, for example, 2, 3, or 4, heteroatom groups, such as -O- or -NH-, or optionally mono- or polysubstituted, for example, 2, 3, or 4-fold.
  • Alkyl or “lower alkyl” stands in particular for saturated, straight-chain or branched hydrocarbon radicals having 1 to 4, 1 to 6, 1 to 8, or 1 to 10 or 1 to 20 carbon atoms, such as: B. Methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methyl-propyl, 2-methylpropyl, 1,1-dimethylethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-di-methylpropyl, 1-ethylpropyl, n-hexyl, 1,1-Dimethylpropyl, 1,2-Dimethylpropyl, 1-Methylpentyl, 2-Methylpentyl, 3-Methylpentyl, 4-Methylpentyl, 1,1-Dimethylbutyl, 1,2-Dimethylbutyl, 1,3-Dimethylbutyl
  • C 2 -C 6 alkenyl such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-Pentenyl, 2-Pentenyl, 3-Pentenyl, 4-Pentenyl, 1-Methyl-1-butenyl, 2-Methyl-1-butenyl, 3-Methyl-1-butenyl, 1-Methyl-2-butenyl, 2-Methyl-2-butenyl, 3-Methyl-2-butenyl, 1-Methyl-3-butenyl, 2-methyl-3-butenyl, 3-Methyl-3-butenyl, 1,1-Dimethyl-2-propenyl, 1,2-Dimethyl-1-propenyl, 1,2-D
  • Alkylene stands for straight-chain or singly or multiply branched hydrocarbon bridging groups having 1 to 10 carbon atoms, such as C 1 -C 7 alkylene groups selected from -CH 2 -, -(CH 2 ) 2 -, -(CH 2 ) 3 -, -CH 2 -CH(CH 3 )-, -CH(CH 3 )-CH 2 -, -(CH 2 ) 4 -, - (CH 2 ) 2 -CH(CH 3 )-, -CH 2 -CH(CH 3 )-CH 2 -, (CH 2 ) 4 -, -(CH 2 ) 5 -, -(CH 2 ) 6 , -(CH 2 ) 7 -, -CH(CH 3 )-CH 2 -CH 2 -CH(CH 3 )- or - CH(CH 3 )-CH 2 -CH 2 -CH(CH 3 )- or C 1 -C 4 -
  • the polycarboxylic acid compounds used are aliphatic di- or polyvalent (such as tri- or tetra-valent), in particular di-, tri- or tetracarboxylic acids, and analogues thereof, such as anhydrides or lower alkyl esters (partially or fully esterified), and optionally substituted by one or more (such as 2 or 3), in particular a long-chain alkyl radical and/or a high molecular weight hydrocarbyl radical, in particular a polyalkylene radical.
  • di- or polyvalent such as tri- or tetra-valent
  • di-, tri- or tetracarboxylic acids and analogues thereof, such as anhydrides or lower alkyl esters (partially or fully esterified), and optionally substituted by one or more (such as 2 or 3), in particular a long-chain alkyl radical and/or a high molecular weight hydrocarbyl radical, in particular a polyalkylene radical.
  • the hydrophobic "long-chain” or “high molecular weight” hydrocarbyl radical which ensures sufficient solubility of the quaternized product in the fuel, has a number average molecular weight (M n ) of 85 to 20,000, such as 113 to 10,000, or 200 to 10,000 or 350 to 5,000, such as 350 to 3,000, 500 to 2,500, 700 to 2,500, or 800 to 1,500.
  • Typical hydrophobic hydrocarbyl radicals are polypropenyl, polybutenyl and polyisobutenyl radicals, e.g. with a number average molecular weight M n of 3,500 to 5,000, 350 to 3,000, 500 to 2,500, 700 to 2,500 and 800 to 1,500.
  • Particularly suitable quaternizing agents are the lower alkyl esters of salicylic acid, such as methyl salicylate, ethyl salicylate, n- and i-propyl salicylate, and n-, i- or tert-butyl salicylate.
  • hydroxyalkyl-substituted monoamines include: N-hydroxyalkyl monoamines, N,N-dihydroxyalkyl monoamines, and N,N,N-trihydroxyalkyl monoamines, where the hydroxyalkyl groups are identical or different and are also defined as above.
  • Hydroxyalkyl stands in particular for 2-hydroxyethyl, 3-hydroxypropyl, or 4-hydroxybutyl.
  • the reaction of the hydrocarbyl-substituted polycarboxylic acid compound with the quaternizable nitrogen compound according to the present invention can be carried out under thermally controlled conditions, so that essentially no condensation reaction occurs. In particular, no formation of water of reaction is observed. In particular, such a reaction takes place at a temperature in the range of 10 to 80, in particular 20 to 60 or 30 to 50 °C.
  • the reaction time can range from a few minutes to several hours, for example, from about 1 minute to about 10 hours.
  • the reaction can take place at about 0.1 to 2 atm pressure, but in particular at about atmospheric pressure. For example, an inert gas atmosphere, such as nitrogen, is advantageous.
  • reaction product thus formed can theoretically be further purified or the solvent removed in a non-inventive embodiment. However, this is usually not absolutely necessary, so the reaction product can be transferred to the next synthesis step, quaternization, without further purification.
  • the reaction product or reaction mixture from step a) is mixed with at least one compound of formula 1 or 2 above, particularly in the required stoichiometric amounts to achieve the desired quaternization.
  • the quaternizing agent is added in excess per equivalent of quaternizable tertiary nitrogen atom, such as 1.25 to 2.0 equivalents of quaternizing agent per equivalent of quaternizable tertiary nitrogen atom.
  • the reaction typically takes place at temperatures in the range of 50 to 180°C, such as 90 to 160°C or 100 to 140°C.
  • the reaction time can range from a few minutes to several hours, such as about 10 minutes to about 24 hours.
  • the reaction can take place at pressures of about 0.1 to 20 bar, such as 1 to 10 or 1.5 to 3 bar, but in particular at approximately atmospheric pressure.
  • the reactants can be placed in a suitable inert organic aliphatic or aromatic solvent, or a mixture thereof, for quaternization, or a sufficient amount of solvent from reaction step a) is still present.
  • Typical examples are solvents from the Solvesso series, toluene, or xylene. However, quaternization can also be carried out in the absence of a solvent.
  • the addition of catalytically effective amounts of an acid may be advantageous.
  • Aliphatic monocarboxylic acids such as C 1 -C 18 monocarboxylic acids, such as lauric acid, isononanoic acid, or neodecanoic acid, are preferred.
  • the quaternization can also be carried out in the presence of a Lewis acid. However, the quaternization can also be carried out in the absence of any acid.
  • the resulting reaction product can theoretically be further purified in a non-inventive embodiment, or the solvent can be removed.
  • solvents such as Solvesso series solvents, 2-ethylhexanol, or essentially aliphatic solvents can also be added after the reaction.
  • this is usually not absolutely necessary, so the reaction product can be used as an additive without further purification, optionally after blending with other additive components (see below).
  • these are primarily common detergent additives, carrier oils, cold flow improvers, lubricity improvers, corrosion inhibitors, demulsifiers, dehazers, antifoams, cetane number improvers, combustion improvers, antioxidants or stabilizers, antistatic agents, metallocenes, metal deactivators, dyes and/or solvents.
  • hydrophobic hydrocarbon radical in particular in combination with the polar, in particular polypropenyl, polybutenyl and polyisobutenyl radicals with a number-average molecular weight M n of preferably in each case 300 to 5,000, particularly preferably 300 to 3,000, more preferably 500 to 2,500, more preferably 700 to 2,500 and especially 800 to 1,500.
  • Such additives based on highly reactive polyisobutene which can be prepared from the polyisobutene, which can contain up to 20 wt.
  • Additives containing carboxyl groups or their alkali metal or alkaline earth metal salts (Dd) are preferably copolymers of C 2 - to C 40 -olefins with maleic anhydride having a total molecular weight of 500 to 20,000, whose carboxyl groups are wholly or partly converted to the alkali metal or alkaline earth metal salts and a remaining residue of the carboxyl groups is converted with alcohols or amines.
  • Such additives are particularly suitable for EP-A 307 815
  • Such additives are mainly used to prevent valve seat wear and can, as described in WO-A 87/01126 described, can be used advantageously in combination with conventional fuel detergents such as poly(iso)butenamines or polyetheramines.
  • Additives containing carboxylic acid ester groups (Dg) are preferably esters of mono-, di- or tricarboxylic acids with long-chain alkanols or polyols, in particular those with a minimum viscosity of 2 mm 2 /s at 100 °C, as used in particular in the DE-A 38 38 918 are described.
  • Aliphatic or aromatic acids can be used as mono-, di-, or tricarboxylic acids; long-chain ester alcohols or polyols, for example, with 6 to 24 carbon atoms, are particularly suitable.
  • the groups with hydroxyl and/or amino and/or amido and/or imido groups are, for example, carboxylic acid groups, acid amides of monoamines, acid amides of di- or polyamines which, in addition to the amide function, also 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, also have free amine groups, or diimides which are formed by the reaction of di- or polyamines with two succinic acid derivatives.
  • Additives containing groups (Di) produced by Mannich reactions of substituted phenols with aldehydes and mono- or polyamines are preferably reaction products of polyisobutene-substituted phenols with formaldehyde and mono- or polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, or dimethylaminopropylamine.
  • Such "polyisobutene Mannich bases” are particularly useful in EP-A 831 141 described.
  • Carrier oils used can be mineral or synthetic.
  • suitable mineral carrier oils include fractions obtained during petroleum processing, such as brightstock or base oils with viscosities such as SN 500 to 2000, as well as aromatic hydrocarbons, paraffinic hydrocarbons, and alkoxyalkanols.
  • hydrocrack oil obtained during mineral oil refining (vacuum distillate cut with a boiling range of approximately 360 to 500 °C, obtainable from natural mineral oil catalytically hydrogenated, isomerized, and dewaxed under high pressure). Blends of the above-mentioned mineral carrier oils are also suitable.
  • suitable polyethers or polyetheramines are preferably compounds containing polyoxy-C 2 - to C 4 -alkylene groups, which are obtainable by reacting C 2 - to C 60 -alkanols, C 6 - to C 30 -alkanediols, mono- or di-C 2 - to C 30 -alkylamines, C 1 - to C 30 -alkylcyclohexanols or C 1 - to C 30 -alkylphenols with 1 to 30 mol of ethylene oxide and/or propylene oxide and/or butylene oxide per hydroxyl group or amino group and, in the case of polyetheramines, by subsequent reductive amination with ammonia, monoamines or polyamines.
  • carboxylic acid esters of long-chain alkanols are in particular esters of mono-, di- or tricarboxylic acids with long-chain alkanols or polyols, as they are used in particular in DE-A 38 38 918 are described.
  • Aliphatic or aromatic acids can be used as mono-, di-, or tricarboxylic acids; long-chain representatives with, for example, 6 to 24 carbon atoms are particularly suitable as ester alcohols or polyols.
  • esters are adipates, phthalates, isophthalates, terephthalates, and trimellitates of isooctanol, isononanol, isodecanol, and isotridecanol, e.g., di-(n- or isotridecyl) phthalate.
  • particularly suitable synthetic carrier oils are alcohol-initiated polyethers having about 5 to 35, preferably about 5 to 30, particularly preferably 10 to 30, and in particular 15 to 30 C 3 - to C 6 -alkylene oxide units, e.g. propylene oxide, n-butylene oxide, and isobutylene oxide units, or mixtures thereof, per alcohol molecule.
  • suitable starter alcohols are long-chain alkanols or 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.
  • Particular examples include tridecanol and nonylphenol.
  • the carrier oil or the mixture of different carrier oils is added to the fuel in an amount of preferably 1 to 1000 ppm by weight, particularly preferably 10 to 500 ppm by weight and in particular 20 to 100 ppm by weight.
  • Suitable cold flow improvers are, in principle, any organic compound capable of improving the flow behavior of middle distillate fuels or diesel fuels in cold conditions. They must ideally exhibit sufficient oil solubility.
  • Cold flow improvers (“middle distillate flow improvers” (“MDFI") commonly used in middle distillates of fossil origin, i.e., in conventional mineral diesel fuels, are particularly suitable for this purpose.
  • MDFI middle distillate flow improvers
  • WASA wax anti-settling additive
  • mixtures of organic compounds effective as MDFIs and/or WASAs and/or nucleators can also be used.
  • Suitable C2 to C40 olefin monomers for the copolymers of class (K1) are, for example, those having 2 to 20, in particular 2 to 10, carbon atoms, and having 1 to 3, preferably 1 or 2, in particular one, carbon-carbon double bond. In the latter case, the carbon-carbon double bond can be arranged either terminally ( ⁇ -olefins) or internally.
  • ⁇ -olefins are preferred, particularly preferably ⁇ -olefins having 2 to 6 carbon atoms, for example propene, 1-butene, 1-pentene, 1-hexene, and especially ethylene.
  • the at least one further ethylenically unsaturated monomer is preferably selected from carboxylic acid alkenyl esters, (meth)acrylic acid esters and other olefins.
  • additional olefins are incorporated into the polymer, they are preferably higher molecular weight olefins than the above-mentioned C 2 - to C 40 -olefin base monomer.
  • C 10 - to C 40 - ⁇ -olefins are particularly suitable as additional olefins.
  • additional olefins are only incorporated into the polymer if monomers with carboxylic acid ester functions are also used.
  • Typical comb polymers of component (K2) are obtainable, for example, by copolymerizing maleic anhydride or fumaric acid with another ethylenically unsaturated monomer, for example with an ⁇ -olefin or an unsaturated ester such as vinyl acetate, and subsequent esterification of the anhydride or acid function with an alcohol having at least 10 carbon atoms.
  • Other suitable comb polymers are copolymers of ⁇ -olefins and esterified comonomers, for example esterified copolymers of styrene and maleic anhydride or esterified copolymers of styrene and fumaric acid.
  • Suitable comb polymers can also be polyfumarates or polymaleates.
  • Comb polymers suitable as components of class (K2) are, for example, those which are in the WO 2004/035715 and in " Comb-Like Polymers. Structure and Properties", N.A. Platé and V.P. Shibaev, J. Poly. Sci. Macromolecular Revs. 8, pages 117 to 253 (1974) )". Mixtures of comb polymers are also suitable.
  • Amine mixtures are also suitable for this purpose, particularly industrially accessible amine mixtures such as fatty amines or hydrogenated tall amines, as described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 6th edition, in the chapter "Amines, Aliphatic.”
  • Acids suitable for the reaction include cyclohexane-1,2-dicarboxylic acid, cyclohexene-1,2-dicarboxylic acid, cyclopentane-1,2-dicarboxylic acid, naphthalenedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, and succinic acids substituted with long-chain hydrocarbon radicals.
  • the component of class (K4) is an oil-soluble reaction product of poly(C 2 - to C 20 -carboxylic acids) containing at least one tertiary amino group with primary or secondary amines.
  • the poly(C 2 - to C 20 -carboxylic acids) containing at least one tertiary amino group on which this reaction product is based preferably contain at least 3 carboxyl groups, in particular 3 to 12, especially 3 to 5 carboxyl groups.
  • the carboxylic acid units in the polycarboxylic acids preferably have 2 to 10 carbon atoms, in particular These are acetic acid units.
  • the carboxylic acid units are linked in a suitable manner to form polycarboxylic acids, usually via one or more carbon and/or nitrogen atoms. They are preferably attached to tertiary nitrogen atoms, which, in the case of multiple nitrogen atoms, are linked via hydrocarbon chains.
  • the preferred oil-soluble reaction product of component (K4) in particular that of the general formula IIa or IIb, is an amide, an amide ammonium salt or an ammonium salt in which no, one or more carboxylic acid groups are converted into amide groups.
  • variable A Examples of straight-chain or branched C2- to C6 -alkylene groups of variable A are 1,1-ethylene, 1,2-propylene, 1,3-propylene, 1,2-butylene, 1,3-butylene, 1,4-butylene, 2-methyl-1,3-propylene, 1,5-pentylene, 2-methyl-1,4-butylene, 2,2-dimethyl-1,3-propylene, 1,6-hexylene (hexamethylene), and especially 1,2-ethylene.
  • the variable A preferably comprises 2 to 4, in particular 2 or 3, carbon atoms.
  • C1 to C19 alkylene groups of the variable B are, for example, 1,2-ethylene, 1,3-propylene, 1,4-butylene, hexamethylene, octamethylene, decamethylene, dodecamethylene, tetradecamethylene, hexadecamethylene, octadecamethylene, nonadecamethylene, and especially methylene.
  • the variable B preferably comprises 1 to 10, in particular 1 to 4, carbon atoms.
  • the amines underlying the oil-soluble reaction products of component (K4) are usually secondary amines and have the general formula HN(R 8 ) 2 , in which the two variables R 8 independently of one another each denote straight-chain or branched C 10 - to C 30 -alkyl radicals, in particular C 14 - to C 24 -alkyl radicals. These longer-chain alkyl radicals are preferably straight-chain or only slightly branched.
  • the said secondary amines are derived, with regard to their longer-chain alkyl radicals, from naturally occurring fatty acids or their derivatives.
  • the two radicals R 8 are preferably identical.
  • component of class (K4) are cyclic compounds with tertiary amino groups or condensates of long-chain primary or secondary amines with carboxylic acid-containing polymers, as described in the WO 93/18115 are described.
  • Sulfocarboxylic acids, sulfonic acids or their derivatives suitable as cold flow improvers for the component of class (K5) are, for example, the oil-soluble carboxamides and carboxylic acid esters of ortho-sulfobenzoic acid, in which the sulfonic acid function is present as a sulfonate with alkyl-substituted ammonium cations, as described in EP-A 261 957 be described.
  • the cold flow improver or the mixture of various cold flow improvers is added to the middle distillate fuel or diesel fuel in a total amount of preferably 10 to 5000 ppm by weight, particularly preferably 20 to 2000 ppm by weight, more preferably 50 to 1000 ppm by weight and in particular 100 to 700 ppm by weight, e.g. 200 to 500 ppm by weight.
  • Suitable lubricity improvers or friction modifiers are usually based on fatty acids or fatty acid esters. Typical examples are tall oil fatty acids, as used in WO 98/004656 described, and glycerol monooleate.
  • the US 6 743 266 B2 The reaction products described above from natural or synthetic oils, for example triglycerides, and alkanolamines are suitable as lubricity improvers.
  • Suitable corrosion inhibitors include succinic acid esters, especially with polyols, fatty acid derivatives, e.g. oleic acid esters, oligomerized fatty acids, substituted ethanolamines and products sold under the trade name RC 4801 (Rhein Chemie Mannheim, Germany) or HiTEC 536 (Ethyl Corporation).
  • Suitable demulsifiers include, for example, the alkali or alkaline earth salts of alkyl-substituted phenol and naphthalene sulfonates and the alkali or alkaline earth salts of fatty acids, as well as neutral compounds such as alcohol alkoxylates, e.g. alcohol ethoxylates, phenol alkoxylates, e.g. tert-butylphenol ethoxylate or tert-pentylphenol ethoxylate, fatty acids, alkylphenols, condensation products of ethylene oxide (EO) and propylene oxide (PO), e.g. also in the form of EO/PO block copolymers, polyethyleneimines or polysiloxanes.
  • EO ethylene oxide
  • PO propylene oxide
  • Suitable dehazers include alkoxylated phenol-formaldehyde condensates, such as the products available under the trade name NALCO 7D07 (Nalco) and TOLAD 2683 (Petrolite).
  • Suitable antifoam agents are, for example, polyether-modified polysiloxanes, such as the products available under the trade names TEGOPREN 5851 (Goldschmidt), Q 25907 (Dow Corning) and RHODOSIL (Rhone Poulenc).
  • Suitable cetane number improvers include aliphatic nitrates such as 2-ethylhexyl nitrate and cyclohexyl nitrate as well as peroxides such as di-tert-butyl peroxide.
  • Suitable metal deactivators include salicylic acid derivatives such as N,N'-disalicylidene-1,2-propanediamine.
  • the additive described here is ideally suited as a fuel additive and can, in principle, be used in any fuel. It exhibits a wide range of beneficial effects when operating internal combustion engines with fuels.
  • the quaternized additive described here is preferably used in middle distillate fuels, especially diesel fuels.
  • the present invention therefore also provides fuels, in particular middle distillate fuels, with an effective content of the quaternized additive described here as an additive for achieving advantageous effects in the operation of internal combustion engines, for example diesel engines, in particular direct-injection diesel engines, especially diesel engines with common-rail injection systems.
  • This effective content (dosage rate) is generally from 10 to 5000 ppm by weight, preferably from 20 to 1500 ppm by weight, in particular from 25 to 1000 ppm by weight, especially from 30 to 750 ppm by weight, in each case based on the total amount of fuel.
  • Middle distillate fuels such as diesel fuels or heating oils are preferably petroleum raffinates, which typically have a boiling range of 100 to 400°C. These are usually distillates with a 95% boiling point of up to 360°C or even higher. However, they can also be so-called “ultra-low sulfur diesel” or "city diesel,” characterized by a 95% boiling point of, for example, a maximum of 345°C and a maximum sulfur content of 0.005 wt.%, or by a 95% boiling point of, for example, 285°C and a maximum sulfur content of 0.001 wt.%.
  • mineral middle distillate fuels or diesel fuels obtainable through refining
  • those obtainable through coal gasification or gas liquefaction [gas to liquid (GTL) fuels] or biomass liquefaction [biomass to liquid (BTL) fuels] are also suitable.
  • Mixtures of the above-mentioned middle distillate fuels or diesel fuels with renewable fuels such as biodiesel or bioethanol are also suitable.
  • Biofuel oils are generally based on fatty acid esters, preferably essentially on alkyl esters of fatty acids derived from vegetable and/or animal oils and/or fats.
  • Alkyl esters are usually understood to be lower alkyl esters, in particular C 1 - to C 4 -alkyl esters, which are obtainable by transesterification of the glycerides, in particular triglycerides, found in vegetable and/or animal oils and/or fats using lower alcohols, for example ethanol or especially methanol (“FAME").
  • test methods described herein are not limited to the specific exemplary embodiments but are part of the general disclosure of the description and are generally applicable within the scope of the present invention.
  • Power loss is a direct measure of deposit formation in the injectors.
  • the final power (P end , KC) is determined in the 12th cycle in stage 12 (see table above).
  • the operating point is 4000 rpm at full load.
  • P end , KC [kW] is calculated from the measured torque.
  • the reaction mixture is heated to 150°C over a period of 80 minutes, and the reaction mixture is then held at this temperature for 3 hours, during which the resulting water of reaction is distilled off.
  • the PIBSA-DMAPA succinimide is obtained as a solution in Pilot 900 oil (TBN 0.62 mmol/g).
  • the reaction mixture is heated to 150°C over a period of 80 minutes, and the reaction mixture is then held at this temperature for 3 hours, during which the resulting water of reaction is distilled off.
  • the PIBSA-DMAPA succinimide is obtained as a solution in Pilot 900 oil (TBN 0.62 mmol/g).
  • a portion of the resulting PIBSA-DMAPA succinimide solution in Pilot 900 oil, Petrochem Carless Ltd. (130 g), dimethyl carbonate (20 g), and methanol (17.4 g) are filled into an autoclave, inertized with nitrogen, and a pre-pressure of 1.3 bar is set.
  • the reaction mixture is then stirred under autogenous pressure, first for 1 h at 90°C, then for 24 h at 140°C. After cooling to room temperature, the autoclave is depressurized, and the contents are washed with a little Toluene is used as a solvent and is completely rinsed out.
  • Power loss is a direct measure of deposit formation in the injectors.
  • a conventional direct-injection diesel engine with a common-rail system was used.

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Claims (8)

  1. Composition de carburant, contenant, dans une quantité principale d'un carburant usuel, une proportion d'au moins un produit de réaction comprenant un composé azoté quaternisé, le produit de réaction pouvant être obtenu par
    a1) transformation d'un composé d'acide polycarboxylique substitué par hydrocarbyle avec un composé, comprenant au moins un groupe oxygéné ou azoté réactif, en particulier par addition ou par condensation, avec l'acide polycarboxylique et contenant au moins un groupe amino quaternisable, un composé d'acide polycarboxylique quaternisable, substitué par hydrocarbyle étant obtenu, et
    a2) sa transformation consécutive avec un agent de quaternisation, qui transforme ledit au moins un groupe amino quaternisable en un groupe d'ammonium quaternaire, l'agent de quaternisation étant l'ester alkylique d'un acide monocarboxylique ou polycarboxylique, en particulier d'un acide monocarboxylique ou d'un acide dicarboxylique, cycloaromatique ou cycloaliphatique, ou d'un acide polycarboxylique aliphatique ; ou
    b) transformation d'un composé d'acide polycarboxylique quaternisable, substitué par hydrocarbyle, contenant au moins un groupe amino quaternisable avec un agent de quaternisation, qui transforme ledit au moins un groupe amino quaternisable en un groupe d'ammonium quaternaire, l'agent de quaternisation étant l'ester alkylique d'un acide monocarboxylique ou polycarboxylique, en particulier d'un acide monocarboxylique ou d'un acide dicarboxylique, cycloaromatique ou cycloaliphatique, ou d'un acide polycarboxylique aliphatique ;
    1,25 à environ 2,0 équivalents d'agent de quaternisation étant utilisés par équivalent d'atome d'azote tertiaire quaternisable.
  2. Composition de carburant selon la revendication précédente, l'agent de quaternisation étant un composé de formule générale 1

            R1OC(O)R2     (1)

    dans laquelle
    R1 représente un radical alkyle inférieur et
    R2 représente un radical aryle ou cycloalkyle à un noyau, le cas échéant substitué, le substituant étant choisi parmi OH, NH2, NO2, C(O)OR3, et R1OC(O)-, R1 présentant les significations indiquées ci-dessus et R3 représentant H ou R1.
  3. Composition de carburant selon l'une quelconque des revendications précédentes, l'agent de quaternisation étant un composé de formule générale 2

            R1OC(O)-A-C(O)OR1a,     (2)

    dans laquelle
    R1 et R1a représentent, indépendamment l'un de l'autre, un radical alkyle inférieur et
    A représente hydrocarbylène.
  4. Composition de carburant selon l'une quelconque des revendications précédentes, le composé azoté quaternisé présentant un poids moléculaire numérique moyen dans la plage de 500 à 5000, de 800 à 3000 ou de 900 à 1500.
  5. Composition de carburant selon l'une quelconque des revendications précédentes, l'agent de quaternisation étant choisi parmi les salicylates d'alkyle, les phtalates de dialkyle et les oxalates de dialkyle.
  6. Composition de carburant selon la revendication 1, le composé réactif, en particulier par addition ou par condensation, avec l'acide polycarboxylique, contenant un groupe oxygéné ou azoté ainsi qu'au moins un groupe amino quaternisable étant choisi parmi
    a) les monoamines ou les polyamines substituées par hydroxyalkyle présentant au moins un groupe amino primaire, secondaire ou tertiaire quaternisable
    b) les polyamines linéaires ou ramifiées, cycliques, hétérocycliques, aromatiques ou non aromatiques, présentant au moins un groupe amino primaire ou secondaire et présentant au moins un groupe amino primaire, secondaire ou tertiaire quaternisable ;
    c) les pipérazines.
  7. Composition de carburant selon la revendication 6, le composé réactif, en particulier par addition ou par condensation, avec l'acide polycarboxylique, contenant un groupe oxygéné ou azoté ainsi qu'au moins un groupe amino quaternisable étant choisi parmi
    a) les monoamines primaires, secondaires ou tertiaires, substituées par hydroxyalkyle et les diamines primaires, secondaires ou tertiaires, substituées par hydroxyalkyle,
    b) les diamines aliphatiques linéaires ou ramifiées présentant deux groupes amino primaire ; les diamines ou les polyamines présentant au moins un groupe amino primaire et au moins un groupe amino secondaire ; les diamines ou les polyamines présentant au moins un groupe amino primaire et au moins un groupe amino tertiaire ; les diamines aromatiques carbocycliques présentant deux groupes amino primaire ; les polyamines hétérocycliques aromatiques présentant deux groupes amino primaire ; les hétérocycles aromatiques ou non aromatiques présentant un groupe amino primaire et un groupe amino tertiaire.
  8. Composition de carburant selon l'une quelconque des revendications précédentes, choisie parmi les carburants diesel, les carburants biodiesel, les essences et les essences contenant de l'alcanol.
EP12737233.2A 2011-06-28 2012-06-28 Composés d'azote quaternisés et leur utilisation en tant qu'additifs dans des carburants et des lubrifiants Active EP2726580B9 (fr)

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PCT/EP2012/062553 WO2013000997A1 (fr) 2011-06-28 2012-06-28 Composés azotés quaternisés et utilisation desdits composés comme additifs pour carburants ou pour lubrifiants
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CN103764806B (zh) 2016-08-17
AU2012277805C1 (en) 2020-09-03
KR102070364B1 (ko) 2020-01-29
HUE030070T2 (en) 2017-04-28
WO2013000997A1 (fr) 2013-01-03
AU2016273853B2 (en) 2018-12-20
PL2726580T5 (pl) 2025-11-03
EP2540808A1 (fr) 2013-01-02
EP2726580B1 (fr) 2016-04-27
MX2014000038A (es) 2014-02-17
CN103764806A (zh) 2014-04-30
AU2019201700B2 (en) 2020-05-21
BR112013033798A2 (pt) 2017-02-14
ES2579852T5 (en) 2025-12-02
CA2840524A1 (fr) 2013-01-03
EP2726580B9 (fr) 2025-09-10
AU2012277805B2 (en) 2016-09-15
ES2579852T3 (es) 2016-08-17
KR20140051253A (ko) 2014-04-30
PL2726580T3 (pl) 2016-12-30
AU2012277805A1 (en) 2014-02-20
EP2726580A1 (fr) 2014-05-07
AU2016273853A1 (en) 2017-01-05
CA2840524C (fr) 2020-09-08
AU2019201700A1 (en) 2019-04-04

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