WO2005063942A1 - Concentres d'additifs de carburants et de lubrifiants contenant au moins un derive d'anthrachinone comme matiere de marquage - Google Patents

Concentres d'additifs de carburants et de lubrifiants contenant au moins un derive d'anthrachinone comme matiere de marquage Download PDF

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Publication number
WO2005063942A1
WO2005063942A1 PCT/EP2004/014587 EP2004014587W WO2005063942A1 WO 2005063942 A1 WO2005063942 A1 WO 2005063942A1 EP 2004014587 W EP2004014587 W EP 2004014587W WO 2005063942 A1 WO2005063942 A1 WO 2005063942A1
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alkyl
oxygen atoms
optionally
ether function
substituted
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PCT/EP2004/014587
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German (de)
English (en)
Inventor
Sophia Ebert
Rüdiger Sens
Christos Vamvakaris
Laszlo Somogyi
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Basf Aktiengesellschaft
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Priority to MXPA06006135A priority Critical patent/MXPA06006135A/es
Priority to BRPI0417837-8A priority patent/BRPI0417837A/pt
Priority to EP04804183A priority patent/EP1699907A1/fr
Priority to CA002549647A priority patent/CA2549647A1/fr
Priority to JP2006546049A priority patent/JP2007515532A/ja
Priority to AU2004309053A priority patent/AU2004309053B2/en
Priority to US10/584,201 priority patent/US20070149415A1/en
Publication of WO2005063942A1 publication Critical patent/WO2005063942A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/003—Marking, e.g. coloration by addition of pigments
    • 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
    • C10L1/185—Ethers; Acetals; Ketals; Aldehydes; Ketones
    • C10L1/1857—Aldehydes; Ketones
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • C10L1/223—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, 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
    • C10L1/232—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
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
    • C10M171/007—Coloured or dyes-containing lubricant compositions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/08—Aldehydes; Ketones
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/068—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings having amino groups bound to polycyclic aromatic ring systems, i.e. systems with three or more condensed rings
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/42—Flashing oils or marking oils

Definitions

  • the present invention relates to fuel and lubricant additive concentrates containing at least one anthraquinone derivative as a marker, the use of such concentrates for the additive of mineral oils and mineral oils containing such concentrates.
  • the markers are usually substances which are either extracted from the mineral oil and then converted into colored compounds by derivatization, or substances which show absorption in both the visible and non-visible wavelength regions of the spectrum (for example in the NIR).
  • marking substances which are used per se ie not after prior derivatization, a wide variety of classes of compounds, such as e.g. Phthalocyanines, naphthalocyanines, nickel dithiolene complexes, aminium compounds of aromatic amines, methine dyes and azulenesquaric acid dyes (for example WO 94/02570 A1, WO 96/10620 A1), but also bisazo dyes (for example EP 256460 A1).
  • Anthraquinone derivatives for coloring petrol or mineral oils are described in the publications US 2,611,772, US 2,068,372, EP 1 001 003 A1 and EP 1 323811 A2.
  • the object of the present invention was to provide fuel and lubricant additive concentrates which are distinguished by very good long-term storage resistance, especially with regard to the resistance of the marking substances contained therein to the action of the other components of these concentrates.
  • the packages according to the invention contain in particular as components:
  • anthraquinone derivatives are used as component a), which are selected from the group consisting of the compounds
  • Z ⁇ Z z independently of one another hydrogen, hydroxy, OR, NHR, or NR 2,
  • R independently of one another R or COR
  • X is hydrogen, cyano, nitro, hydroxy, OR, amino, NHR, R or CH (R S ) (R 10 )
  • n, m is 0, 1, 2, 3 or 4, where, for n or m greater than 1, the radicals R and X are the same or different from one another,
  • R 9 , R 1ü independently of one another cyano, COOH or COOR,
  • R 3 is hydrogen, R or NHR
  • R 4 to R 8 are independently hydrogen, R or NHR
  • R C ⁇ -C 20 -alkyl which is optionally interrupted by 1 to 4 oxygen atoms in ether function, C 5 -C 7 -cycloalkyl, optionally with one or more C ⁇ C 2 o-alkyl groups, optionally by 1 to 4 oxygen atoms in oxygen Ether function are interrupted, saturated heterocyclic five- or six-membered radical, optionally with one or more which are optionally interrupted by 1 to 4 oxygen atoms in ether, is substituted, C 6 -C ⁇ o-aryl, optionally with one or more halogen, cyano, nitro, hydroxy, amino, C ⁇ Cao-alkyl, optionally substituted by 1 to 4 Oxygen atoms in ether function is interrupted, -CC 20 alkoxy, CrC 2 o-alkyl amino or C 1 -C 20 -dialkylamino, heteroaryl having 3 to 12 carbon atoms optionally substituted by one or more C t -C 2 o-alkyl optionally interrupted by 1
  • C ⁇ C 2 o-alkyl which is optionally interrupted by 1 to 4 oxygen atoms in ether function, -C-C 2 o-alkoxy, -CC 2 o-alkylamino or -CC 2 o-dialkylamino substituted is.
  • C 1 -C 20 -alkyl which is optionally interrupted by 1 to 4 oxygen atoms in ether function
  • Suitable C 5 -C 7 -cycloalkyl radicals are cyclopentyl, cyclohexyl and cycloheptyl. If appropriate, these cycloalkyls are also substituted by one or more, in particular up to three, C 1 -C 20 -alkyl groups, the latter being optionally interrupted by 1 to 4 oxygen atoms in ether function. Examples of such optionally interrupted by oxygen atoms CC 20 alkyl groups have been previously listed.
  • Saturated heterocyclic five- or six-membered radicals which are optionally substituted by one or more -CC 2 o-alkyl groups, which are optionally interrupted by 1 to 4 oxygen atoms in ether function, derived for example from pyrrolidine, 2- or 3-methylpyrrolidine , 2,4-dimethyl-3-ethylpyrrolidine, pyrazolidine, 2-, 3-, 4- or 5-methylpyrazolidine, imidazolidine, 2-, 3-, 4- or 5-methylimidazolidine, oxazolidine, 2-, 4- or 5 Methyloxazolidine, isoxazolidine, 3-, 4- or 5-methylisoxazolidine, piperidine, 2-, 3-, 4-methyl- or -ethylpiperidine, 2,6-dimethylpiperidine, piperazine, 4- (C 1 -C 4 -alkyl ) piperazine, such as 4-methyl- or 4-ethylpiperazine, morpholine, thiomorpholine or thi
  • R in the groups OR, NHR and NR 2 of the definition of the variables Z 1 and / or Z 2 , in the groups OR and NHR of the definition of the variables X, in the group COOR of the definition of the radicals R 9 and R 10 , in the group NHR of the definition of the variable R 3 and R 4 to R 8 corresponds to a corresponding, optionally substituted saturated heterocyclic five- or six-membered radical, the attachment to the respective heteroatom of the relevant group takes place via a carbon atom of the heterocyclic group. or six membered residue.
  • R alone in the definition of the variables R 1 and R 2 and the definition of the variable R 3 corresponds to a corresponding, optionally substituted saturated heterocyclic five- or six-membered radical.
  • the attachment can take place either via a carbon atom or a heteroatom of the heterocyclic five- or six-membered radical which is suitable for attachment.
  • C 6 -C 10 -Aryle in particular phenyl and naphthyl are mentioned. These are optionally substituted with one or more halogens such as fluorine, chlorine or bromine, cyano, nitro, hydroxy, amino, C 1 -C 20 -alkyl optionally interrupted by 1 to 4 oxygen atoms in ether function, C 1 -C 20 -alkoxy, CIC 20- Alkylamino or CrC 2 crDialkyl- amino substituted.
  • halogens such as fluorine, chlorine or bromine, cyano, nitro, hydroxy, amino, C 1 -C 20 -alkyl optionally interrupted by 1 to 4 oxygen atoms in ether function, C 1 -C 20 -alkoxy, CIC 20- Alkylamino or CrC 2 crDialkyl- amino substituted.
  • C 2 -C 4 -alkyl radicals which are optionally interrupted by 1 to 4 oxygen atoms in ether function, or C 1 -C 2 -alkyl radicals which are substituted in the C 1 -C 2 o-alkylamino or CrQzo-dialkylamino groups have been listed by way of example previously.
  • Heteroaryl having 3 to 12 carbon atoms, optionally substituted with one or more C 20 alkyl which is interrupted tion optionally substituted by 1 to 4 oxygen atoms in Etherfunk-, C ⁇ -alkoxy, CC 2 o-alkylamino or C 2 o-dialkylamino are derived, for example, from pyrrole, furan, thiophene, pyrazole, isoxazole, isothiazole, imidazole, 1H-1,2,3-triazole, 1H-1,2,4-triazole, pyridine, pyrazine, pyridazine, 1H-azepine, 2H-azepine, oxazole, thiazole, 1,2,3-, 1,2,4- or 1,3,4-oxadiazole, 1,2,3-, 1,2,4- or 1,3,4- Thiadiazole and optionally the benzo or dibenzoanell believing rings, such as quinoline, isoquinoline
  • R in the groups OR, NHR and NR 2 of the definition of the variables Z 1 and / or Z 2 , in the groups OR and NHR of the definition of the variables X, in the group COOR of the definition of the radicals R 9 and R 10 , in the group NHR of the definition of the variable R 3 and R 4 to R 8 corresponds to a corresponding, optionally substituted heteroaryl
  • the attachment to the respective heteroatom of the relevant group takes place via a carbon atom of the heteroaryl.
  • R alone in the definition of the variables R 1 and / or R 2 and the definition of the variable R 3 corresponds to a corresponding, optionally substituted heteroaryl.
  • the attachment can take place either via a carbon atom or a heteroatom of the heteroaryl which is suitable for attachment.
  • C ⁇ -Cio-aryl-CrOralkyle which in the aryl radical optionally with one or more halogen, cyano, nitro, hydroxy, amino, CrC 2 o-alkyl, which is optionally interrupted by 1 to 4 oxygen atoms in ether function, C 1 -C 2 O-alkoxy, C 1 -C 20 -alkylamino or C 2 -C 20 -dialkylamino are especially benzyl, phenylethyl, 3-phenylpropyl and 4-phenylbutyl mentioned.
  • C 1 -C 20 -alkyl radicals which are optionally interrupted by from 1 to 4 oxygen atoms in ether function, or C ⁇ -C20 alkyl radicals, which in the C ⁇ C 20 alkoxy, C ⁇ -C 20 alkylamino- or C 2 o Dialkylamino groups are included, have already been listed by way of example.
  • Corresponding -C 2 o-alkyl radicals which are, if appropriate, interrupted by 1 to 4 oxygen atoms in ether function, or -C o alkyl radicals in the CC 20 alkoxy, C ⁇ -C 20 -alkylamino or C ⁇ -C 20 - Dialkylamino groups are included, have already been listed by way of example.
  • Preferred novel fuel and lubricant additive concentrates contain anthraquinone derivatives of the formulas I, II and III, in which
  • Z 1 , Z 2 independently of one another are hydrogen or NHR
  • R 1 , R 2 independently of one another R
  • X is hydrogen, cyano or CH (R 9 ) (R 10 ),
  • n, m is 0, 1, 2, 3 or 4, where, for n or m greater than 1, the radicals R and X are the same or different from one another,
  • R 9 , R 10 independently of one another cyano or COOR
  • R 3 is hydrogen, R or NHR
  • R 4 to R 7 are hydrogen or NHR
  • R C ⁇ -C ⁇ -C5 alkyl which is optionally interrupted by 1 to 4 oxygen atoms in ether function, cyclohexyl which is optionally substituted by one or more C ⁇ -C15 alkyl groups optionally interrupted by 1 to 4 oxygen atoms in ether function substituted, saturated heterocyclic five- or six-membered radical which is optionally substituted by one or more -CC 5 alkyl groups which are optionally interrupted by 1 to 4 oxygen atoms in ether function, C 6 -C 10 -aryl, optionally with one or more C 1 -C 5 -alkyl, which is optionally interrupted by 1 to 4 oxygen atoms in ether function, CrC ⁇ 5 -alkoxy, C r C 15 alkylamino or CrCis-dialkylamino is substituted, heteroaryl having 3 to 5 carbon atoms, optionally with one or more is the erstoffatome optionally substituted by 1 to 4 sow in ether function, C ⁇ -C ⁇ 5 -alk
  • anthraquinone derivatives of the formula I which may be mentioned in particular are the compounds of the formulas Ia to If shown below:
  • the variables R in each case independently of one another and in the formula If the variable RC r C 15 -alkyl, which is optionally interrupted by 1 to 4 oxygen atoms in ether function, and C 6 -C 10 -aryl, which may be with one or more CC 15 -alkyl, which is optionally interrupted by 1 to 4 oxygen atoms in ether function, is substituted.
  • the selection of the variables R is preferably carried out from the group consisting of unsubstituted phenyl, simply in 2-, 3- and 4-position, the double in 2,3-, 2,4- and 3,4-position and the triple in 2,3,4-, 2,3,5-, 2 , 3,6-, 2,4,5-, 2,4,6- and 3,4,5-substituted phenyl, which are substituted with the previously exemplified enumerated, optionally interrupted with oxygen in ether function CC 15 -alkyl radicals.
  • Anthraquinone derivatives of the formula II which may be mentioned in particular are the compounds of the formulas IIa to IIc shown below:
  • the variables R, R 1 and R 2 independently of one another are C 1 -C 15 -alkyl, which is optionally interrupted by 1 to 4 oxygen atoms in ether function, and C 6 -C 10 -aryl which is optionally substituted by one or more a plurality of -CC 15 -alkyl, which is optionally interrupted by 1 to 4 oxygen atoms in ether function, is substituted.
  • X in the formulas IIa to IIc assumes either the meaning of two hydrogen atoms, two cyano groups in the 2,3- or 6,7-position or two identical groups CH (R 9 ) (R 10 ) in 2,3- or 6,7- Position of Anthrachinongerüstes on.
  • the latter two groups CH (R 9 ) (R 10 ) are either two groups CH (COOR) 2 , CH (CN) COOR or CH (CN) 2 , where the radicals R are preferably C 1 -C 15 -alkyl optionally interrupted by 1 to 4 oxygen atoms in ether function, or C 6 -C ⁇ o-aryl, which is optionally substituted by one or more -CC 15 -alkyl which is optionally interrupted by 1 to 4 oxygen atoms in ether function, mean ,
  • the selection of the variables R, R 1 and R 2 is preferably selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl , Isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neo-pentyl, tert-penty
  • the selection of the variables R, R 1 and R 2 is preferably carried out from the group consisting of unsubstituted phenyl which is simply in the 2-, 3- and 4-positions, the double in the 2,3-, 2,4- and 3,4-position and the triple in 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6- and 3,4,5-substituted phenyl, which are substituted with the previously enumerated by way of example, optionally with oxygen ether C ⁇ -C ⁇ interrupted 5 alkyl radicals.
  • anthraquinone derivatives of the formula III to be used according to the invention are, in particular, the compounds of the formulas IIIa to IIId shown below:
  • p is 1, 2, 3 or 4, where p is greater than 1, the radicals are the same,
  • R C ⁇ -C ⁇ -C5 alkyl which is optionally interrupted by 1 to 4 oxygen atoms in ether function
  • cyclohexyl which is optionally substituted by one or more C ⁇ -C ⁇ 5 alkyl groups which are optionally interrupted by 1 to 4 oxygen atoms in ether function substituted, which are optionally interrupted by from 1 to 4 oxygen atoms in ether function
  • substituted saturated heterocyclic five- or six-membered radical which groups are optionally substituted with one or more CrC ⁇ 5 alkyl, C 6 -C ⁇ 0 aryl optionally substituted with one or more C r C ⁇ -C5 alkyl optionally substituted by 1 to 4 oxygen atoms in
  • Ether function is interrupted, C -C 5 alkoxy, CrC ⁇ 5 -alkylamino or C -C 5 -dialkylamino is substituted, heteroaryl having 3 to 5 carbon atoms, optionally with one or more -CC 5 alkyl, optionally substituted by 1 to 4 oxygen atoms in ether function is interrupted, CC 5 -alkoxy, C ds-alkyl-amino or -CC 15 dialkylamino is substituted, phenyl-C 1 -C 4 -alkyl which in the phenyl radical is optionally substituted by one or more C 1 -C 5 - Alkyi which is optionally interrupted by 1 to 4 oxygen atoms in ether function, CrC ⁇ 5 -AI- koxy, -CC 5 alkylamino or CrC ⁇ 5 -Dialkylamino is substituted, or heteroaryl-C -C 4 alkyl having 3 to 5 Carbon atoms in the heteroaryl radical, the latter optional
  • oxygen atoms are interrupted in ether function, C 1 -C 15 -alkoxy, C 1 -C 5 -alkylamino or C 1 -C 5 -dialkylamino is substituted,
  • R in the formulas IIIa to IIId is particularly preferably C ⁇ -C ⁇ -C5 alkyl, which is optionally interrupted by 1 to 4 oxygen atoms in ether function, or C 6 -C 10 aryl which is optionally substituted with one or more C -C ⁇ 5 alkyl, which is optionally interrupted by 1 to 4 oxygen atoms in ether function.
  • R in the formulas IIIa to IIId is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, 2 Methylpentyl, heptyl, hept-3-yl, octyl, 2-ethylhexyl, isooctyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tridecyl, 3,5,5,7-tetramethyl-nonyl, isotridecyl, tetradecyl , Pentadecyl, methoxymethyl, 2-ethylhexoxymethyl, 2-methoxyethyl, 2-ethoxye
  • the carrier oils used are usually viscous, high-boiling and in particular thermostable liquids. They coat the hot metal surfaces, eg. As the intake valves, with a thin film of liquid and prevent or delay thereby the formation and deposition of decomposition products on the metal surfaces.
  • base oils mineral carrier oils
  • synthetic carrier oils based on olefin polymers with M N 400 up to 1800, in particular based on polybutene or polyisobutene (hydrogenated or non-hydrogenated), of polyalphaolefin or poly-internalolefins and synthetic carrier oils based on alkoxylated long-chain alcohols or phenols.
  • Adducts of ethylene oxide, propylene oxide and / or butylene oxide to polybutyl or polyisobutene alcohols to be used according to the invention as carrier oils are described, for example, in document EP 277345 A1, further polyalkene alcohol polyalkoxylates to be used according to the invention in WO 00/50543 A1.
  • Further carrier oils to be used according to the invention also include polyalkene alcohol polyether amines, as listed in WO 00/61708.
  • mixtures of different carrier oils can also be used provided that they are compatible with one another and with the other components of the packages according to the invention.
  • Carburettors and intake systems of internal combustion engines, but also injection systems for fuel metering, are increasingly burdened by impurities caused, for example, by dust particles from the air and unburned hydrocarbon radicals from the combustion chamber.
  • additives are added to the fuel to keep valves and carburettors or injection systems clean.
  • Such detergents are generally used in combination with one or more carrier oils.
  • the carrier oils exert an additional "washing function", often assist and promote the detergents in their cleansing and pure-preserving action and can thus contribute to the reduction of the required amount of detergents.
  • Typical detergents which are used in the packages according to the invention are listed, for example, in the publications WO 00/50543 A1 and WO 00/61708 A1 and comprise: Polyisobuteneamines which are obtainable according to EP 244616 by hydroformylation of highly reactive polyisobutene and subsequent reductive amination with ammonia, monoamines or polyamines, such as dimethyleneaminopropylamine, ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine,
  • Poly (iso) buteneamines which are obtainable by chlorination of polybutenes or polyisobutenes having double bonds predominantly in the b and g positions and subsequent amination with ammonia, monoamines or the abovementioned polyamines,
  • Polyisobuteneamines which are obtainable according to DE-A 19620262 from polyisobutene epoxides by reaction with amines and subsequent dehydration and reduction of the amino alcohols,
  • Hydroxyl-containing polyisobuteneamines which are obtainable according to EP-A 476485 by reacting polyisobutene epoxides with ammonia, monoamines or the abovementioned polyamines,
  • Polyetheramines which by reaction of C 2 - to C 30 alkanols, C 6 - to C 30 - alkanediols, mono- or di-C 2 - to C 30 -alkylamines, C to C 30 -alkylcyclohexanols or C to C 30- Alkylphenolen with 1 to 30 mol of ethylene oxide and / or propylene oxide and / or butylene oxide per hydroxyl or amino group and subsequent reductive amination with ammonia, monoamines or the above-mentioned polyamines are available, and "Polyisobutene Mannich bases", which are obtainable according to EP-A 831 141 by reacting polyisobutene-substituted phenols with aldehydes and monoamines or the abovementioned polyamines.
  • detergents and / or valve seat wear-inhibiting additives to be used according to the invention are listed, for example, in WO 00/47698 A1 and comprise compounds which have at least one hydrophobic hydrocarbon radical with a number average molecular weight (M N ) of 85 to 20,000 and at least one polar group and which are selected from:
  • polyoxy-C 2 - to C 4 -alkylene groups terminated by hydroxyl groups, mono- or polyamino groups, at least one nitrogen atom having basic properties, or terminated by carbamate groups,
  • Such additives based on highly reactive polyisobutene which can be prepared from the polyisobutene, which may contain up to 20 wt .-% of n-butene units by hydroformylation and reductive amination with ammonia, monoamines or polyamines such Dimethylaminopropylamin, ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine , are known in particular from document EP 244616 A2.
  • the preparation route is afforded by chlorination and subsequent amination or by oxidation of the double bond with air or ozone to carbonyl - or carboxyl compound and subsequent amination under reductive (hydrogenating) conditions.
  • amination the same amines as described above can be used for the reductive amination of the hydroformylated highly reactive polyisobutene.
  • Corresponding additives based on polypropene are described in particular in the document WO 94/24231 A1.
  • monoamino groups (i) 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 the document DE 19620262 A1.
  • Carboxyl groups or their alkali metal or alkaline earth metal salts (iv) containing additives are preferably copolymers of C 2 -C 40 olefins with maleic anhydride having a total molecular weight of 500 to 20,000, their carboxyl groups wholly or partly to the alkali metal or alkaline earth metal salts and a remaining Rest of the carboxyl groups are reacted with alcohols or amines.
  • Such additives are known in particular from document EP 307815 A1.
  • Such additives are mainly used to prevent valve seat wear and, as described in document WO 87/01126 A1, may advantageously be used in combination with conventional detergents, such as poly (iso) butenamines or polyetheramines.
  • Sulfonic acid groups or their alkali metal or alkaline earth metal salts (v) containing additives are preferably alkali metal or alkaline earth metal salts of a Sulfobern- steinklaklalesters, as described in particular in EP 639632 A1.
  • Such additives serve primarily to prevent valve seat wear and can be used to advantage in combination with conventional detergents such as poly (iso) buteneamines or polyetheramines.
  • Polyoxy-C 2 - to C -alkylene additives are preferably polyethers or polyetheramines which are obtainable by reaction of C 2 - to C 60 alkanols, C 6 - to C 3 o-alkanediols, mono- or di-C 2 C 30 -alkylamines, -CC 3 o-Alkylcyclohexa- nolen or C -C 30 alkylphenols with 1 to 30 moles 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 310 875 A1, EP 356725 A1, EP 700985 A1 and US Pat. No. 4,877,416.
  • polyethers such products also meet carrier oil properties. Typical examples thereof are tridecanol or isotridecanol butoxylates, isononylphenol butoxylates and also polyisobutenol butoxylates and propoxylates and the corresponding reaction products with ammonia.
  • Carboxyl ester groups (vii) containing additives are preferably esters of mono-, di- or tricarboxylic acids with long-chain alkanols or polyols, in particular those having a minimum viscosity of 2 mm / s at 100 ° C, as described in particular in DE 38 38 918 A1 are.
  • 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.
  • Typical representatives of the 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.
  • Mannich reaction of phenolic hydroxyl groups with aldehydes and mono- or polyamines generated groupings (ix) containing 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 document EP 831 141 A1.
  • Dispersants as component c) are, for example, imides, amides, esters and ammonium and alkali metal salts of polyisobutene succinic anhydrides. These compounds find particular use in lubricating oils, but sometimes also as detergents in fuel compositions.
  • organic solvents for example alcohols, such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, pentanol, isopentanol, neopentanol or hexanol
  • glycols such as 1,2-ethylene glycol, 1,2- or 1, 3-propylene glycol, 1,2-, 2,3- or 1, 4-butylene glycol, di- or triethylene glycol or di- or tripropylene glycol
  • ethers such as methyl tert-butyl ether, 1, 2-ethylene glycol mono- or dimethyl ether, 1, 2-ethylene glycol mono- or diethyl ether, 3-methoxypropanol, 3-isopropoxypropanol, tetrahydrofuran or dioxane
  • ketones such as acetone, methyl ethyl ketone or diacetone alcohol
  • esters such as methyl
  • Corrosion inhibitors for example based on film-forming ammonium salts of organic carboxylic acids or of heterocyclic aromatics in non-ferrous metal corrosion protection,
  • Antioxidants or stabilizers for example based on amines such as p-phenylendiamin, dicyclohexylamine or derivatives thereof or of phenols such as 2,4-di-tert-butylphenol or 3,5-di-tert-butyl-4-hydroxyphenylpropionklare, demulsifiers .
  • Metallocenes such as ferrocene or methylcyclopentadienyl manganese tricarbonyl,
  • Lubricity additives such as certain fatty acids, alkenylsuccinic acid esters, bis (hydroxyalkyl) fatty amines, hydroxyacetamides or castor oil,
  • the concentration of component a), i. the at least one anthraquinone derivative in the packages according to the invention is usually selected at a level such that after addition of the package to the mineral oil the desired concentration of marker substance (s) is contained therein.
  • Typical concentrations of the marking substances in the mineral oil are approximately in the range of 0.01 to a few 10 ppm by weight.
  • Component b i. the at least one carrier oil is usually present in the packagings of the invention in a concentration of from 1 to 50, in particular from 5 to 30,% by weight, and
  • Component c) ie the at least one detergent and / or the at least one dispersant, usually in a concentration of 25 to 90 wt .-%, in particular 30 to 80 wt .-%, in each case based on the total amount of components a) to c) and optionally d), wherein the sum of the individual concentrations of components a) to c) and optionally d) is added to 100 wt .-%.
  • corrosion inhibitors for lowering the pH of the fuel are contained in the packages according to the invention, their total concentration usually amounts to not more than 10% by weight %, based on the total amount of the package (ie, the total amount of components a) to c) and d)), wherein the concentration of the corrosion inhibitors and demulsifiers usually in the range of about 0.01 to 0.5 wt. -% of the total amount of the package.
  • organic solvents are present in the packages according to the invention, their total concentration usually amounts to not more than 20% by weight, based on the total amount of the package.
  • these solvents are obtained from solutions of the markers and / or dyes which are added to the packages with a view to a more precise meterability instead of the pure markers and / or dyes.
  • component d further markers other than anthraquinone derivatives are contained in the packages according to the invention, their concentration is again measured at the content which they should have after addition of the packages in the mineral oil. The same applies to component a).
  • dyes are present in the packages according to the invention as component d), their concentration is usually about between 0.1 to 5 wt .-%, based on the total amount of the package.
  • test mixture used of a fuel and lubricant additive concentrate with the components contained therein and their respective proportions is listed below in Table 1:
  • 1 to 3 ml of the filtrate was made up to 10 ml with detergent or carrier oil (corresponding to a concentration of each compound of 0.01 to 0.08%) and measured in 1mm cuvettes against the corresponding non-additized reference.
  • the samples were filled in 10 ml ampoules, sealed airtight and stored at 50 ° C in a water bath.
  • the comparison compound showed a significantly faster decrease in the normalized extinction as a function of time
  • solutions with a content of 1 wt .-% of the compounds 10 to 12 in the detergent or the Kraft and lubricant additive concentrate forth and determined the normalized extinction depending on the storage time both at room temperature and at 40 ° C. Scaling was carried out to the extinction value at the start of storage (i.e., immediately after preparation of the appropriate solution). The results are listed below.
  • Kraft and lubricant additive concentrate at room temperature after storage times of 7 and 14 days, no change in the normalized extinction could be detected.
  • Kraft and lubricant additive concentrate at room temperature after storage times of 21 and 28 days, no change in the normalized extinction could be detected.

Abstract

L'invention concerne des concentrés d'additifs de carburants et de lubrifiants contenant au moins un dérivé d'anthrachinone comme matière de marquage. L'invention concerne également l'utilisation de tels concentrés pour l'addition d'huiles minérales ainsi que des huiles minérales contenant de tels concentrés.
PCT/EP2004/014587 2003-12-23 2004-12-22 Concentres d'additifs de carburants et de lubrifiants contenant au moins un derive d'anthrachinone comme matiere de marquage WO2005063942A1 (fr)

Priority Applications (7)

Application Number Priority Date Filing Date Title
MXPA06006135A MXPA06006135A (es) 2003-12-23 2004-12-22 Concentrados de aditivos para carburantes y lubricantes, que contienen por lo menos un derivado de antraquinona como sustancia marcadora.
BRPI0417837-8A BRPI0417837A (pt) 2003-12-23 2004-12-22 concentrado de aditivo para combustìvel e lubrificante, uso do concentrado, e, óleo mineral
EP04804183A EP1699907A1 (fr) 2003-12-23 2004-12-22 Concentres d'additifs de carburants et de lubrifiants contenant au moins un derive d'anthrachinone comme matiere de marquage
CA002549647A CA2549647A1 (fr) 2003-12-23 2004-12-22 Concentres d'additifs pour carburants et lubrifiants renfermant au moins un derive d'anthraquinone comme marqueur
JP2006546049A JP2007515532A (ja) 2003-12-23 2004-12-22 標識物質として少なくとも１のアントラキノン誘導体を含有する燃料および潤滑剤添加剤の濃縮物
AU2004309053A AU2004309053B2 (en) 2003-12-23 2004-12-22 Power and lubricant additive concentrates containing at least one anthrachinone derivative as a marking substance
US10/584,201 US20070149415A1 (en) 2003-12-23 2004-12-22 Power and lubricant additive concentrates containing at least one anthrachinone derivative as a marking substance

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10361504.0 2003-12-23
DE10361504A DE10361504A1 (de) 2003-12-23 2003-12-23 Kraft- und Schmierstoffadditiv-Konzentrate, enthaltend mindestens ein Anthrachinon-derivat als Markierungsstoff

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WO2005063942A1 true WO2005063942A1 (fr) 2005-07-14

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EP (1) EP1699907A1 (fr)
JP (1) JP2007515532A (fr)
KR (1) KR20060126710A (fr)
CN (1) CN1898365A (fr)
AR (1) AR048665A1 (fr)
AU (1) AU2004309053B2 (fr)
BR (1) BRPI0417837A (fr)
CA (1) CA2549647A1 (fr)
DE (1) DE10361504A1 (fr)
MX (1) MXPA06006135A (fr)
MY (1) MY143699A (fr)
PE (1) PE20051059A1 (fr)
TW (1) TW200535234A (fr)
WO (1) WO2005063942A1 (fr)
ZA (1) ZA200606004B (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101538495B (zh) * 2009-02-02 2012-04-25 王嘉兴 一种用松重油制备的高温工业燃料技术
WO2020239942A1 (fr) * 2019-05-31 2020-12-03 Katholieke Universiteit Leuven Molécules organiques à activité redox multi-électrons pour batteries à flux redox non aqueux à haute densité d'énergie
WO2022026225A1 (fr) * 2020-07-29 2022-02-03 Dow Global Technologies Llc Anthraquinone aromatique soluble dans des hydrocarbures
ES2957535A1 (es) * 2022-06-08 2024-01-22 Kemegal Quim S L Aditivo para combustibles para motores de combustion interna

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008074709A1 (fr) * 2006-12-20 2008-06-26 Basf Se Dérivés d'anthraquinone en tant que marqueurs pour liquides
US8664442B2 (en) * 2008-09-09 2014-03-04 Chemtura Corporation Anti-oxidants
WO2011032857A2 (fr) 2009-09-15 2011-03-24 Basf Se Utilisation de dérivés de composés aromatiques en tant que marqueurs pour des liquides
FR2971254B1 (fr) 2011-02-08 2014-05-30 Total Raffinage Marketing Compositions liquides pour marquer les carburants et combustibles hydrocarbones liquides, carburants et combustibles les contenant et procede de detection des marqueurs

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US3164449A (en) * 1961-03-01 1965-01-05 Du Pont Anthraquinone dyes for gasoline
US3476500A (en) * 1965-08-09 1969-11-04 Allied Chem Concentrated colorants
US3597254A (en) * 1967-10-03 1971-08-03 Basf Ag Blue dye mixtures
DE2238174A1 (de) * 1972-08-03 1974-02-21 Basf Ag Konzentrierte loesungen eines mittels zur kennzeichnung von mineraloel
US4303407A (en) * 1979-05-23 1981-12-01 Aziende Colori Nazionali Affini Acna S.P.A. Concentrated coloring solutions of a blue tinge based on mixture of 1.4-dialkyl-anthraquinones for the coloring of petroliferous products
EP0095975A1 (fr) * 1982-05-27 1983-12-07 PIGMENTI ITALIA S.p.A. Solutions concentrées de colorants de 1,4-dialkyl-arylamino-anthraquinone pour la coloration de produits pétroliers
EP0201368A1 (fr) * 1985-04-12 1986-11-12 BASF Italia SpA Composition de marquage et de dénaturation, particulièrement adaptée au marquage et à la dénaturation de carburants diesel et similaires
FR2694564A1 (fr) * 1992-08-07 1994-02-11 Sepia Chim Sa Procédé de préparation de solutions concentrées de colorants de type 1,4-dialkylamino-anthraquinone, les solutions obtenues par ce procédé et leur emploi pour la coloration de produits pétroliers.
EP1001003A1 (fr) * 1998-11-09 2000-05-17 Morton International, Inc. Methode de marquage invisible de produits pétroliers au moyen de colorants visibles
EP1323811A2 (fr) * 2001-12-20 2003-07-02 Rohm And Haas Company Procédé de marquage des hydrocarbures avec des anthraquinones

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US2068372A (en) * 1936-03-25 1937-01-19 Du Pont Preparation of aralkylamino-anthraquinone compounds
US2611772A (en) * 1950-12-30 1952-09-23 Eastman Kodak Co Preparation of 1, 4, 5, 8-tetraamino-anthraquinone compounds
DE19908262A1 (de) * 1999-02-25 2000-08-31 Basf Ag Polyalkenalkohol-Polyalkoxylate und deren Verwendung in Kraft- und Schmierstoffen
DE19916512A1 (de) * 1999-04-13 2000-10-19 Basf Ag Polyalkenalkohol-Polyetheramine und deren Verwendung in Kraft- und Schmierstoffen
JP4201965B2 (ja) * 2000-08-10 2008-12-24 三菱樹脂株式会社 耐熱性樹脂組成物及びこれよりなる耐熱性フィルムまたはシート並びにこれを基材とする積層板

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3164449A (en) * 1961-03-01 1965-01-05 Du Pont Anthraquinone dyes for gasoline
US3476500A (en) * 1965-08-09 1969-11-04 Allied Chem Concentrated colorants
US3597254A (en) * 1967-10-03 1971-08-03 Basf Ag Blue dye mixtures
DE2238174A1 (de) * 1972-08-03 1974-02-21 Basf Ag Konzentrierte loesungen eines mittels zur kennzeichnung von mineraloel
US4303407A (en) * 1979-05-23 1981-12-01 Aziende Colori Nazionali Affini Acna S.P.A. Concentrated coloring solutions of a blue tinge based on mixture of 1.4-dialkyl-anthraquinones for the coloring of petroliferous products
EP0095975A1 (fr) * 1982-05-27 1983-12-07 PIGMENTI ITALIA S.p.A. Solutions concentrées de colorants de 1,4-dialkyl-arylamino-anthraquinone pour la coloration de produits pétroliers
EP0201368A1 (fr) * 1985-04-12 1986-11-12 BASF Italia SpA Composition de marquage et de dénaturation, particulièrement adaptée au marquage et à la dénaturation de carburants diesel et similaires
FR2694564A1 (fr) * 1992-08-07 1994-02-11 Sepia Chim Sa Procédé de préparation de solutions concentrées de colorants de type 1,4-dialkylamino-anthraquinone, les solutions obtenues par ce procédé et leur emploi pour la coloration de produits pétroliers.
EP1001003A1 (fr) * 1998-11-09 2000-05-17 Morton International, Inc. Methode de marquage invisible de produits pétroliers au moyen de colorants visibles
EP1323811A2 (fr) * 2001-12-20 2003-07-02 Rohm And Haas Company Procédé de marquage des hydrocarbures avec des anthraquinones

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101538495B (zh) * 2009-02-02 2012-04-25 王嘉兴 一种用松重油制备的高温工业燃料技术
WO2020239942A1 (fr) * 2019-05-31 2020-12-03 Katholieke Universiteit Leuven Molécules organiques à activité redox multi-électrons pour batteries à flux redox non aqueux à haute densité d'énergie
WO2022026225A1 (fr) * 2020-07-29 2022-02-03 Dow Global Technologies Llc Anthraquinone aromatique soluble dans des hydrocarbures
ES2957535A1 (es) * 2022-06-08 2024-01-22 Kemegal Quim S L Aditivo para combustibles para motores de combustion interna

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PE20051059A1 (es) 2006-01-20
AU2004309053B2 (en) 2010-06-10
CN1898365A (zh) 2007-01-17
ZA200606004B (en) 2007-12-27
US20070149415A1 (en) 2007-06-28
TW200535234A (en) 2005-11-01
AR048665A1 (es) 2006-05-17
KR20060126710A (ko) 2006-12-08
MXPA06006135A (es) 2006-08-11
MY143699A (en) 2011-06-30
CA2549647A1 (fr) 2005-07-14
EP1699907A1 (fr) 2006-09-13
DE10361504A1 (de) 2005-07-28
AU2004309053A1 (en) 2005-07-14
BRPI0417837A (pt) 2007-04-10
JP2007515532A (ja) 2007-06-14

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