WO2005063942A1 - Power and lubricant additive concentrates containing at least one anthrachinone derivative as a marking substance - Google Patents

Power and lubricant additive concentrates containing at least one anthrachinone derivative as a marking substance 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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Prior art keywords
alkyl
oxygen atoms
optionally
ether function
substituted
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PCT/EP2004/014587
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German (de)
French (fr)
Inventor
Sophia Ebert
Rüdiger Sens
Christos Vamvakaris
Laszlo Somogyi
Original Assignee
Basf Aktiengesellschaft
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Publication date
Application filed by Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Priority to AU2004309053A priority Critical patent/AU2004309053B2/en
Priority to JP2006546049A priority patent/JP2007515532A/en
Priority to US10/584,201 priority patent/US20070149415A1/en
Priority to CA002549647A priority patent/CA2549647A1/en
Priority to MXPA06006135A priority patent/MXPA06006135A/en
Priority to EP04804183A priority patent/EP1699907A1/en
Priority to BRPI0417837-8A priority patent/BRPI0417837A/en
Publication of WO2005063942A1 publication Critical patent/WO2005063942A1/en

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Classifications

    • 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.

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Abstract

The invention relates to power and lubricant additive concentrates which contain at least one anthrachinone derivative as a marking substance, to the use of said types of concentrates for adding mineral oils in addition to mineral oils which contain said concentrates.

Description

Kraft- und Schmierstoffadditiv-Konzentrate, enthaltend mindestens ein Anthrachinon- derivat als Markierungsstoff Kraft and lubricant additive concentrates containing at least one anthraquinone derivative as a marker
Beschreibungdescription
Die vorliegende Erfindung betrifft Kraft- und Schmierstoffadditiv-Konzentrate, welche mindestens ein Anthrachinonderivat als Markierungsstoff enthalten, die Verwendung solcher Konzentrate zur Additivierung von Mineralölen sowie Mineralöle, welche solche Konzentrate enthalten.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.
Zur Mineralöladditivierung kommen meist Additiv-Konzentrate (im Folgenden, dem einschlägigen Sprachgebrauch folgend auch "Packages" genannt) zur Anwendung, welche neben einem Trägeröl und einem Gemisch verschiedener Kraftstoffadditive in der Regel auch Farbstoffe sowie, zur unsichtbaren fiskalischen oder herstellerspezifi- sehen Markierung, zusätzlich noch Markierungsstoffe enthalten. Diese Packages ermöglichen es, dass sich verschiedene Mineralölvertriebsfirmen aus einem "Pool" von unadditiviertem Mineralöl versorgen können und erst mit Hilfe ihrer individuellen Packages dem Mineralöl, z.B. während der Abfüllung in entsprechende Transportbehälter, die firmenspezifische Additivierung, Farbigkeit sowie Markierung verleihen.For Mineralöladditivierung usually additive concentrates (hereinafter, the pertinent language usage also called "packages") are used, which in addition to a carrier oil and a mixture of different fuel additives usually dyes and, for invisible fiscal or manufacturer-specific mark, in addition still contain markers. These packages enable various mineral oil distribution companies to supply themselves from a "pool" of unadditized mineral oil and only with the aid of their individual packages to supply the mineral oil, e.g. during filling into appropriate transport containers, which give company-specific additives, colouration and marking.
Bei den Markierungsstoffen handelt es sich meist um Substanzen, welche entweder aus dem Mineralöl extrahiert und anschließend durch Derivatisierung in farbige Verbindungen überführt werden, oder um Stoffe, welche sowohl im sichtbaren wie auch im nicht sichtbaren Wellenlängenbereich des Spektrums Absorption zeigen (z.B. im NIR). Als Markierungsstoffe, welche per se, also nicht erst nach vorheriger Derivatisierung, Verwendung finden, wurden verschiedenste Verbindungsklassen, wie z.B. Phthalocya- nine, Naphthalocyanine, Nickel-Dithiolen-Komplexe, Aminiumverbindungen von aromatischen Aminen, Methinfarbstoffe und Azulenquadratsäurefarbstoffe (z.B. WO 94/02570 A1, WO 96/10620 A1), aber auch Bisazofarbstoffe (z.B. EP 256460 A1) vorgeschlagen. Anthrachinonderivate zur Einfärbung von Benzin bzw. Mineralölen sind in den Schriften US 2,611,772, US 2,068,372, EP 1 001 003 A1 und EP 1 323811 A2 beschrieben.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). As 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.
In der Praxis zeigt sich, dass viele der gängigen Markierungsstoffe zwar unter den ver- dünnten Verhältnissen im Mineralöl stabil sind, nicht jedoch unter den konzentrierten Bedingungen in den Packages; durch die Einwirkung der Package-Komponenten verändert sich die Charakteristik (z.B. Extinktion) der Markierungsstoffe innerhalb kürzester Zeit.In practice it can be seen that while many of the common tracers are stable under the diluted conditions in mineral oil, they are not stable under the concentrated conditions in the packages; the action of the package components changes the characteristics (e.g., absorbance) of the tags within a very short time.
Die Aufgabe der vorliegenden Erfindung bestand nun darin, Kraft- und Schmierstoffadditiv-Konzentrate zur Verfügung zu stellen, welche sich durch sehr gute Langzeitlager- beständigkeit auszeichnen, gerade auch im Hinblick auf die Beständigkeit der darin enthaltenen Markierungsstoffe gegen die Einwirkung der übrigen Komponenten dieser Konzentrate.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.
Demgemäß wurden die eingangs erwähnten Kraft- und Schmierstoffadditiv-Konzentrate (Packages) gefunden, welche mindestens ein Anthrachinonderivat als Markierungsstoff enthalten.Accordingly, the above-mentioned fuel and lubricant additive concentrates (packages) were found which contain at least one Anthrachinonderivat as a marker.
Die erfindungsgemäßen Packages enthalten insbesondere als Komponenten:The packages according to the invention contain in particular as components:
a) mindestens einen Anthrachinonderivat, b) mindestens ein Trägeröl, c) mindestens ein Additiv ausgewählt aus der Gruppe bestehend aus Detergenzien, Dispergatoren und ventilsitzverschleißhemmenden Additiven, d) sowie gegebenenfalls weitere Additive und Hilfsmittel.a) at least one anthraquinone derivative, b) at least one carrier oil, c) at least one additive selected from the group consisting of detergents, dispersants and valve seat wear-inhibiting additives, d) and optionally further additives and auxiliaries.
Als Komponente a) finden insbesondere Anthrachinonderivate Verwendung, welche ausgewählt sind aus der Gruppe bestehend aus den VerbindungenIn particular anthraquinone derivatives are used as component a), which are selected from the group consisting of the compounds
der Formel Ithe formula I
Figure imgf000003_0001
der Formel II
Figure imgf000003_0001
of formula II
Figure imgf000003_0002
und der Formel III
Figure imgf000003_0002
and the formula III
Figure imgf000004_0001
Figure imgf000004_0001
worin bedeutenin which mean
Z\ Zz unabhängig voneinander Wasserstoff, Hydroxy, OR, NHR oder NR2,Z \ Z z independently of one another hydrogen, hydroxy, OR, NHR, or NR 2,
R , R unabhängig voneinander R oder COR,R, R independently of one another R or COR,
X Wasserstoff, Cyano, Nitro, Hydroxy, OR, Amino, NHR, R oder CH(RS)(R10)X is hydrogen, cyano, nitro, hydroxy, OR, amino, NHR, R or CH (R S ) (R 10 )
n, m 0, 1, 2, 3 oder 4, wobei für n bzw. m größer als 1 die Reste R bzw. X gleich oder voneinander verschieden sind,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,
R9, R1ü unabhängig voneinander Cyano, COOH oder COOR,R 9 , R 1ü independently of one another cyano, COOH or COOR,
R3 Wasserstoff, R oder NHR,R 3 is hydrogen, R or NHR,
R4 bis R8 unabhängig voneinander Wasserstoff, R oder NHRR 4 to R 8 are independently hydrogen, R or NHR
undand
R Cι-C20-Alkyl, das gegebenenfalls durch 1 bis 4 Sauerstoffatome in Etherfunktion unterbrochen ist, C5-C7-Cycloalkyl, das gegebenenfalls mit einer oder mehreren CτC2o-Alkylgruppen, die gegebenenfalls durch 1 bis 4 Sau- erstoffatome in Etherfunktion unterbrochen sind, substituiert ist, gesättigter heterocyclischer fünf- oder sechsgliedriger Rest, der gegebenenfalls mit einer oder mehreren
Figure imgf000004_0002
die gegebenenfalls durch 1 bis 4 Sauerstoffatome in Etherfunktion unterbrochen sind, substituiert ist, C6-Cιo- Aryl, das gegebenenfalls mit einem oder mehreren Halogen, Cyano, Nitro, Hydroxy, Amino, C^Cao-Alkyl, das gegebenenfalls durch 1 bis 4 Sauerstoffatome in Etherfunktion unterbrochen ist, Cι-C20-Alkoxy, CrC2o-Alkyl- amino oder CrC20-Dialkylamino substituiert ist, Heteroaryl mit 3 bis 12 Kohlenstoffatomen, das gegebenenfalls mit einem oder mehreren Ct-C2o-Alkyl, das gegebenenfalls durch 1 bis 4 Sauerstoffatome in Etherfunktion unterbrochen ist, CrC20-Alkoxy, CrC20-Alkylamino oder Cι-C20-Dialkylamino substituiert ist, Ce-C^-Aryl-d-C^alkyl, das im Arylrest gegebenenfalls mit einem oder mehreren Halogen, Cyano, Nitro, Hydroxy, Amino, CrC20-Alkyl, das gegebenenfalls durch 1 bis 4 Sauerstoffatome in Etherfunktion unterbrochen ist, CrC20-Alkoxy, Cι-C20-Alkylamino oder Cι-C2o-Dialkylamino substituiert ist, oder Heteroaryl-CrC4-alkyl mit 3 bis 12 Kohlenstoffatomen im Heteroarylrest, wobei letzterer gegebenenfalls mit einem oder mehrerenR Cι-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 CτC 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
Figure imgf000004_0002
which are optionally interrupted by 1 to 4 oxygen atoms in ether, is substituted, C 6 -Cιo-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 to 4 oxygen atoms in ether function, C 1 -C 20 -alkoxy, Ccr 20 -Alkylamino or -CC 20 dialkylamino, Ce-C ^ -aryl-dC ^ alkyl, in the aryl radical optionally with one or more halogen, cyano, nitro, hydroxy, amino, C 1 -C 20 -alkyl, which is optionally substituted by 1 interrupted to 4 oxygen atoms in ether, CrC 20 alkoxy, -CC 20 alkylamino or -CC 2 o-dialkylamino is substituted, or heteroaryl-CrC 4 -alkyl having 3 to 12 carbon atoms in the heteroaryl radical, the latter optionally with a or more
CτC2o-Alkyl, das gegebenenfalls durch 1 bis 4 Sauerstoffatome in Etherfunktion unterbrochen ist, Cι-C2o-Alkoxy, Cι-C2o-Alkylamino oder Cι-C2o-Di- alkylamino substituiert ist.CτC 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.
Als Cι-C20-Alkyl, das gegebenenfalls durch 1 bis 4 Sauerstoffatome in Etherfunktion unterbrochen ist, sind zu nennen z.B. 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, Unde- cyl, Dodecyl, Tridecyl, 3,5,5,7-Tetramethylnonyl, Isotridecyl (die obigen Bezeichnungen Isooctyl, Isononyl, Isodecyl und Isotridecyl sind Trivialbezeichnungen und stammen von den nach der Oxosynthese erhaltenen Alkoholen - vgl. dazu Ulimanns Encyklopä- die der technischen Chemie, 4. Auflage, Band 7, Seiten 215 bis 217, sowie Band 11, Seiten 435 und 436), Tetradecyl, Pentadecyl, Hexadecyl, Heptadecyl, Octadecyl, No- nadecyl, Eicosyl, Methoxymethyl, 2-Ethylhexoxym ethyl, 2-Methoxyethyl, 2-Ethoxyethyl, 2-Propoxyethyl, 2-lsopropoxyethyl, 2-Butoxyethyl, 2- oder 3-Methoxypropyl, 2- oder 3- Ethoxypropyl, 2- oder 3-Propoxypropyl, 2- oder 3-Butoxypropyl, 2- oder 4-Methoxy- butyl, 2- oder 4-Ethoxy butyl, 2- oder 4-Propoxybutyl, 2- oder 4-Butoxybutyl, 3,6-Di- oxaheptyl, 3,6-Dioxaoctyl, 4,8-Dioxanonyl, 3,7-Dioxaoctyl, 3,7-Dioxanonyl, 4,7-Di- oxaoctyl, 4,7-Dioxanonyl, 4,8-Dioxadecyl, 3,6,8-Trioxadecyl, 3,6,9-Trioxaundecyl, 3,6,9, 12-Tetraoxatridecyl oder 3,6,9, 12-Tetraoxatetradecyl.As C 1 -C 20 -alkyl, which is optionally interrupted by 1 to 4 oxygen atoms in ether function, there may be mentioned, for example, 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- Tetramethylnonyl, isotridecyl (the above names isooctyl, isononyl, isodecyl and isotridecyl are Trivialbezeichnungen and derived from the obtained by the oxo process alcohols - see Ulimanns Encyklopä- the technical chemistry, 4th Edition, Volume 7, pages 215 to 217, and Vol. 11, pages 435 and 436), tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, noonadecyl, eicosyl, methoxymethyl, 2-ethylhexoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-isopropoxyethyl, 2- Butoxyethyl, 2- or 3-methoxypropyl, 2- or 3-ethoxypropyl, 2- or 3-propoxypropyl, 2- or 3-butoxy propyl, 2- or 4-methoxybutyl, 2- or 4-ethoxybutyl, 2- or 4-propoxybutyl, 2- or 4-butoxybutyl, 3,6-dioxaheptyl, 3,6-dioxaoctyl, 4.8 Dioxanonyl, 3,7-dioxaoctyl, 3,7-dioxanonyl, 4,7-dioxaoctyl, 4,7-dioxanonyl, 4,8-dioxadecyl, 3,6,8-trioxadecyl, 3,6,9-trioxaundecyl , 3,6,9,12-tetraoxatridecyl or 3,6,9,12-tetraoxatetradecyl.
Als C5-C7-Cycloalkylreste kommen in Frage Cyclopentyl, Cyclohexyl und Cycloheptyl. Diese Cycloalkyle sind gegebenenfalls noch mit einem oder mehreren, insbesondere bis zu drei CrC20-Alkylgruppen substituiert, wobei letztere gegebenenfalls noch durch 1 bis 4 Sauerstoffatome in Etherfunktion unterbrochen sind. Beispiele solcher gegebenenfalls noch durch Sauerstoffatome unterbrochene C C20-Alkylgruppen wurden bereits zuvor aufgeführt. Gesättigte heterocyclische fünf- oder sechsgliedrige Reste, die gegebenenfalls mit einer oder mehreren Cι-C2o-Alkylgruppen, die gegebenenfalls durch 1 bis 4 Sauerstoffatome in Etherfunktion unterbrochen sind, substituiert sind, leiten sich beispielsweise ab von Pyrrolidin, 2- oder 3-Methylpyrrolidin, 2,4-Dimethyl-3-ethylpyrrolidin, Pyrazolidin, 2-, 3-, 4- oder 5-Methylpyrazolidin, Imidazolidin, 2-, 3-, 4- oder 5-Methylimidazolidin, Oxazolidin, 2-, 4- oder 5-Methyloxazolidin, Isoxazolidin, 3-, 4- oder 5-Methylisoxa- zolidin, Piperidin, 2-, 3-, 4-Methyl- oder -Ethylpiperidin, 2,6-Dimethylpiperidin, Pipera- zin, 4-(CrC4-Alkyl)piperazin, wie 4-Methyl- oder 4-Ethylpiperazin, Morpholin, Thio- morpholin oder Thiomorpholin-S,S-dioxid ab.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 thiomorpholine-S, S-dioxide.
Sofern R in den Gruppen OR, NHR und NR2der Definition der Variablen Z1 und/oder Z2, in den Gruppen OR und NHR der Definition der Variablen X, in der Gruppe COOR der Definition der Reste R9 und R10, in der Gruppe NHR der Definition der Variablen R3 sowie R4 bis R8 einem entsprechenden, gegebenenfalls substituierten gesättigten hete- rocyclischen fünf- oder sechsgliedrigen Rest entspricht, erfolgt die Anbindung an das jeweilige Heteratom der betreffenden Gruppe über ein Kohlenstoffatom des heterocyc- lischen fünf- oder sechsgliedrigen Restes. Dasselbe gilt, sofern R für sich alleine in der Definition der Variablen R1 und R2 und der Definition der Variablen R3 einem entsprechenden, gegebenenfalls substituierten gesättigten heterocyclischen fünf- oder sechs- gliedrigen Rest entspricht. In den übrigen Fällen kann die Anbindung entweder über ein Kohlenstoffatom oder ein zur Anbindung geeignetes Heteroatom des heterocyclischen fünf- oder sechsgliedrigen Restes erfolgen.If 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. The same applies if 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. In the remaining cases, 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.
Als C6-C10-Aryle sind insbesondere Phenyl und Naphthyl zu nennen. Diese sind gege- benenfalls mit einem oder mehreren Halogen, wie etwa Fluor, Chlor oder Brom, Cyano, Nitro, Hydroxy, Amino, CrC20-Alkyl, das gegebenenfalls durch 1 bis 4 Sauerstoffatome in Etherfunktion unterbrochen ist, CrC20-Alkoxy, CrC20-Alkylamino oder CrC2crDialkyl- amino substituiert. Entsprechende C C20-Alkylreste, welche gegebenenfalls durch 1 bis 4 Sauerstoffatome in Etherfunktion unterbrochen sind, bzw. Cι-C2o-Alkylreste, welche in den
Figure imgf000006_0001
Cι-C2o-Alkylamino- oder CrQzo-Dialkylaminogruppen enthalten sind, wurden exemplarisch bereits zuvor aufgeführt.As 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. Corresponding 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
Figure imgf000006_0001
C 1 -C 2 o-alkylamino or CrQzo-dialkylamino groups have been listed by way of example previously.
Heteroarylreste mit 3 bis 12 Kohlenstoffatomen, die gegebenenfalls mit einem oder mehreren C C20-Alkyl, das gegebenenfalls durch 1 bis 4 Sauerstoffatome in Etherfunk- tion unterbrochen ist, C^o-Alkoxy, C C2o-Alkylamino oder C C2o-Dialkylamino substituiert sind, leiten sich z.B. von Pyrrol, Furan, Thiophen, Pyrazol, Isoxazol, Isothiazol, Imidazol, 1H-1,2,3-Triazol, 1H-1,2,4-Triazol, Pyridin, Pyrazin, Pyridazin, 1H-Azepin, 2H-Azepin, Oxazol, Thiazol, 1,2,3-, 1,2,4- oder 1 ,3,4-Oxadiazol, 1,2,3-, 1,2,4- oder 1,3,4-Thiadiazol sowie gegebenenfalls den benzo- oder dibenzoanellierten Ringen, wie z.B. Chinolin, Isochinolin, Indol, Benzo[b]furan (Cumaron), Benzo[b]thiophen (Thio- naphthen), Carbazol, Dibenzofuran, Dibenzothiophen, 1H-lndazol, Indoxazol, Ben- zo[d]isothiazol, Anthranil, Benzimidazol, Benzoxazol, Benzothiazol, Cinnolin, Phthala- zin, Chinazolin, Chinoxalin oder Phenazin ab. C C2o-Alkylsubstituenten, die gegebenenfalls durch 1 bis 4 Sauerstoffatome in Etherfunktion unterbrochen sind, wurden be- reits zuvor exemplarisch genannt.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 dibenzoanellierten rings, such as quinoline, isoquinoline, indole, benzo [b] furan (coumarone), benzo [b] thiophene (thio) naphthen), carbazole, dibenzofuran, dibenzothiophene, 1H-indazole, indoxazole, benzo [d] isothiazole, anthranil, benzimidazole, benzoxazole, benzothiazole, cinnoline, phthalazine, quinazoline, quinoxaline or phenazine. CC 2 o-alkyl substituents, which are optionally interrupted by 1 to 4 oxygen atoms in ether function, have already been mentioned by way of example.
Sofern R in den Gruppen OR, NHR und NR2der Definition der Variablen Z1 und/oder Z2, in den Gruppen OR und NHR der Definition der Variablen X, in der Gruppe COOR der Definition der Reste R9 und R10, in der Gruppe NHR der Definition der Variablen R3 sowie R4 bis R8 einem entsprechenden, gegebenenfalls substituierten Heteroaryl entspricht, erfolgt die Anbindung an das jeweilige Heteratom der betreffenden Gruppe über ein Kohlenstoffatom des Heteroaryls. Dasselbe gilt sofern R für sich alleine in der Definition der Variablen R1 und/oder R2 und der Definition der Variablen R3 einem entsprechenden, gegebenenfalls substituierten Heteroaryl entspricht. In den übrigen Fäl- len kann die Anbindung entweder über ein Kohlenstoffatom oder ein zur Anbindung geeignetes Heteroatom des Heteroaryls erfolgen.If 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. The same applies if 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. In the remaining cases, the attachment can take place either via a carbon atom or a heteroatom of the heteroaryl which is suitable for attachment.
Als Cβ-Cio-Aryl-CrOralkyle, welche im Arylrest gegebenenfalls mit einem oder mehreren Halogen, Cyano, Nitro, Hydroxy, Amino, CrC2o-Alkyl, das gegebenenfalls durch 1 bis 4 Sauerstoffatome in Etherfunktion unterbrochen ist, C1-C2o-Alkoxy, CrC20-Alkyl- amino oder C C2o-Dialkylamino substituiert sind, sind insbesondere Benzyl, Phenyl- ethyl, 3-Phenylpropyl und 4-Phenylbutyl zu nennen. Entsprechende C1-C20-Alkylreste, welche gegebenenfalls durch 1 bis 4 Sauerstoffatome in Etherfunktion unterbrochen sind, bzw. Cι-C20-Alkylreste, welche in den CτC20-Alkoxy-, Cι-C20-Alkylamino- oder C C2o-Dialkylaminogruppen enthalten sind, wurden exemplarisch bereits zuvor aufgeführt.As Cβ-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. Corresponding C 1 -C 20 -alkyl radicals which are optionally interrupted by from 1 to 4 oxygen atoms in ether function, or Cι-C20 alkyl radicals, which in the CτC 20 alkoxy, Cι-C 20 alkylamino- or C 2 o Dialkylamino groups are included, have already been listed by way of example.
Heteroaryl-C C4-alkyle mit 3 bis 12 Kohlenstoffatomen im Heteroarylrest, wobei letzterer gegebenenfalls mit einem oder mehreren Cι-C2o-Alkyl, das gegebenenfalls durch 1 bis 4 Sauerstoffatome in Etherfunktion unterbrochen ist, Cι-C20-Alkoxy, Cι-C20-Alkyl- amino oder Cι-C20-Dialkylamino substituiert ist, leiten sich beispielsweise von den be- riets weiter oben genannten Heteroarylresten ab, welche an die C C -Alkylreste entweder über ein Kohlenstoffatom oder ein zur Anbindung geeignetes Heteroatom des Heteroaryls angebunden sind. Entsprechende CrC2o-Alkylreste, welche gegebenen- falls durch 1 bis 4 Sauerstoffatome in Etherfunktion unterbrochen sind, bzw. CrC o- Alkylreste, welche in den C C20-Alkoxy-, Cι-C20-Alkylamino- oder Cι-C20-Dialkylamino- gruppen enthalten sind, wurden exemplarisch bereits zuvor aufgeführt. Bevorzugte erfindungsgemäße Kraft- und Schmierstoffadditiv-Konzentrate enthalten Anthrachinonderivate der Formeln I, II und III, worin bedeutenHeteroaryl-C C 4 -alkyls having 3 to 12 carbon atoms in the heteroaryl, the latter optionally with one or more -CC 2 o-alkyl, which is optionally interrupted by 1 to 4 oxygen atoms in ether function, -C-C 20 alkoxy, -C -C 20 alkyl amino or Cι-C 20 dialkylamino radicals, derived for example from the loading Riets above mentioned heteroaryl groups from which bound to the CC alkyl either via a carbon atom or a heteroatom suitable for binding the heteroaryl are. 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, Cι-C 20 -alkylamino or Cι-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
Z1, Z2 unabhängig voneinander Wasserstoff oder NHR,Z 1 , Z 2 independently of one another are hydrogen or NHR,
R1, R2 unabhängig voneinander R,R 1 , R 2 independently of one another R,
X Wasserstoff, Cyano oder CH(R9)(R10),X is hydrogen, cyano or CH (R 9 ) (R 10 ),
n, m 0, 1 , 2, 3 oder 4, wobei für n bzw. m größer als 1 die Reste R bzw. X gleich oder voneinander verschieden sind,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,
R9, R10 unabhängig voneinander Cyano oder COOR,R 9 , R 10 independently of one another cyano or COOR,
R3 Wasserstoff, R oder NHR,R 3 is hydrogen, R or NHR,
R4 bis R7 Wasserstoff oder NHR,R 4 to R 7 are hydrogen or NHR,
R8 NHRR 8 NHR
undand
R Cι-Cι5-Alkyl, das gegebenenfalls durch 1 bis 4 Sauerstoffatome in Etherfunktion unterbrochen ist, Cyclohexyl, das gegebenenfalls mit einer oder mehreren Cι-C15-Alkylgruppen, die gegebenenfalls durch 1 bis 4 Sauerstoffatome in Etherfunktion unterbrochen sind, substituiert ist, gesättigter heterocyclischer fünf- oder sechsgliedriger Rest, der gegebenenfalls mit einer oder mehreren Cι-Cι5-Alkylgruppen, die gegebenenfalls durch 1 bis 4 Sauerstoffatome in Etherfunktion unterbrochen sind, substituiert ist, C6-C10-Aryl, das gegebenenfalls mit einem oder mehreren Cι-Cι5-Alkyl, das gegebenenfalls durch 1 bis 4 Sauerstoffatome in Etherfunktion unterbrochen ist, CrCι5-Alkoxy, CrC15-Alkylamino oder CrCis-Dialkylamino substituiert ist, Heteroaryl mit 3 bis 5 Kohlenstoffatomen, das gegebenenfalls mit einem oder mehreren
Figure imgf000008_0001
das gegebenenfalls durch 1 bis 4 Sau- erstoffatome in Etherfunktion unterbrochen ist, Cι-Cι5-Alkoxy, Cι-C15-Alkyl- amino oder Cι-C15-Dialkylamino substituiert ist, Phenyl-CrC4-alkyl, das im Phenylrest gegebenenfalls mit einem oder mehreren Cι-C 5-Alkyl, das gegebenenfalls durch 1 bis 4 Sauerstoffatome in Etherfunktion unterbrochen ist, C C^-Alkoxy, C C15-Alkylamino oder C-i-Cis-Dialkylamino substituiert ist, oder Heteroaryl-C C4-alkyl mit 3 bis 5 Kohlenstoffatomen im Heteroa- rylrest, wobei letzterer gegebenenfalls mit einem oder mehreren Cι-C15-Al- kyl, das gegebenenfalls durch 1 bis 4 Sauerstoffatome in Etherfunktion unterbrochen ist, Cι-Ci5-Alkoxy, CrC15-Alkylamino oder C Cι5-Dialkylamino substituiert ist,R Cι-Cι-C5 alkyl, which is optionally interrupted by 1 to 4 oxygen atoms in ether function, cyclohexyl which is optionally substituted by one or more Cι-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, CrCι 5 -alkoxy, C r C 15 alkylamino or CrCis-dialkylamino is substituted, heteroaryl having 3 to 5 carbon atoms, optionally with one or more
Figure imgf000008_0001
is the erstoffatome optionally substituted by 1 to 4 sow in ether function, Cι-Cι 5 -alkoxy, C 15 alkyl amino or Cι-C 15 dialkylamino substituted, phenyl-CrC 4 -alkyl which is optionally substituted in the phenyl radical with one or more -CC 5 -alkyl, which is optionally interrupted by 1 to 4 oxygen atoms in ether function, CC ^ alkoxy, CC 15 -alkylamino or Ci-cis-dialkylamino is substituted, or heteroaryl-C C 4 -alkyl with 3 to 5 carbon atoms in the hetero Rylrest, the latter being optionally substituted by one or more -CC 15 -alkyl which is optionally interrupted by 1 to 4 oxygen atoms in ether function, C 1 -C 5 -alkoxy, C 1 -C 15 -alkylamino or C 5 -C 5 -dialkylamino,
wobei die bevorzugten Reste R bereits in der zuvor gegebenenen exemplarischen Aufzählung mit aufgeführt wurden.wherein the preferred radicals R have already been listed in the exemplary list given above.
Als Anthrachinonderivate der Formel I sind insbesondere die nachfolgend gezeigten Verbindungen der Formeln la bis If zu nennen:The anthraquinone derivatives of the formula I which may be mentioned in particular are the compounds of the formulas Ia to If shown below:
Figure imgf000009_0001
Figure imgf000009_0001
Hierbei bedeuten in den Formeln la bis le die Variablen R jeweils unabhängig voneinander und in Formel If die Variable R CrC15-Alkyl, das gegebenenfalls durch 1 bis 4 Sauerstoffatome in Etherfunktion unterbrochen ist, und C6-C10-Aryl, das gegebenenfalls mit einem oder mehreren C C15-Alkyl, das gegebenenfalls durch 1 bis 4 Sauerstoffatome in Etherfunktion unterbrochen ist, substituiert ist.Here, in the formulas la to le, 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.
In der Bedeutung eines Cι-C15-Alkyl, das gegebenenfalls durch 1 bis 4 Sauerstoffatome in Etherfunktion unterbrochen ist, erfolgt die Auswahl der Variablen R vorzugswei- se aus der Gruppe bestehend aus 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, Do- decyl, Tridecyl, 3,5,5,7-Tetramethyl-nonyl, Isotridecyl, Tetradecyl, Pentadecyl, Metho- xymethyl, 2-Ethylhexoxymethyl, 2-Methoxyethyl, 2-Ethoxyethyl, 2-Propoxyethyl, 2-lso- propoxyethyl, 2-Butoxyethyl, 2- und 3-Methoxypropyl, 2- und 3-Ethoxypropyl, 2- und 3- Propoxypropyl, 2- und 3-Butoxypropyl, 2- und 4-Methoxybutyl, 2- und 4-Ethoxybutyl, 2- und 4-Propoxybutyl, 2- und 4-Butoxybutyl, 3,6-Dioxaheptyl, 3,6-DioxaoctyI, 4,8-Dio- xanonyl, 3,7-Dioxaoctyl, 3,7-Dioxanonyl, 4,7-Dioxaoctyl, 4,7-Dioxanonyl, 4,8-Dio- xadecyl, 3,6,8-Trioxadecyl, 3,6,9-Trioxaundecyl, 3,6,9, 12-Tetraoxatridecyl und 3,6,9, 12-Tetraoxatetradecyl.In the meaning of a Cι-C 15 -alkyl which is optionally interrupted by 1 to 4 oxygen atoms in ether function, the selection of the variables R vorzugswei- se 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, Do - decyl, tridecyl, 3,5,5,7-tetramethyl-nonyl, isotridecyl, tetradecyl, pentadecyl, methoxymethyl, 2-ethylhexoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-isopropoxyethyl, 2 Butoxyethyl, 2- and 3-methoxypropyl, 2- and 3-ethoxypropyl, 2- and 3-propoxypropyl, 2- and 3-butoxypropyl, 2- and 4-methoxybutyl, 2- and 4-ethoxybutyl, 2- and 4- Propoxybutyl, 2- and 4-butoxybutyl, 3,6-dioxaheptyl, 3,6-dioxaoctyl, 4,8-dioxanonyl, 3,7-dioxaoctyl, 3,7-dioxanonyl, 4,7-dioxaoctyl, 4,7 Dioxanonyl, 4,8-dio xadecyl, 3,6,8-trioxadecyl, 3,6,9-trioxaundecyl, 3,6,9, 12-tetraoxatridecyl and 3,6,9,12-tetraoxatetradecyl.
In der Bedeutung eines C6-C10-Aryl, das gegebenenfalls mit einem oder mehreren CrC15-Alkyl, das gegebenenfalls durch 1 bis 4 Sauerstoffatome in Etherfunktion unterbrochen ist, erfolgt die Auswahl der Variablen R vorzugsweise aus der Gruppe bestehend aus unsubstituiertem Phenyl, den einfach in 2-, 3- und 4-Stellung, den zweifach in 2,3-, 2,4- und 3,4-Stellung und den dreifach in 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6- und 3,4,5-Stellung substituierten Phenylresten, welche substituiert sind mit den zuvor exemplarisch aufgezählten, gegebenenfalls mit Sauerstoff in Etherfunktion unterbrochenen C C15-Alkylresten.In the meaning of a C 6 -C 10 -aryl which is optionally interrupted by one or more C 1 -C 15 -alkyl which is optionally interrupted by 1 to 4 oxygen atoms in ether function, 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.
Vorzugsweise sind die jeweiligen Reste R in den Verbindungen der Formeln la bis le gleich.The respective radicals R in the compounds of the formulas Ia to Ie are preferably identical.
Als Anthrachinonderivate der Formel II sind insbesondere die nachfolgend gezeigten Verbindungen der Formeln lla bis llc zu nennen:Anthraquinone derivatives of the formula II which may be mentioned in particular are the compounds of the formulas IIa to IIc shown below:
Figure imgf000010_0001
Figure imgf000010_0001
(lla) (llb) (llc)(IIa) (IIb) (IIc)
Hierbei bedeuten in den Formeln lla bis llc die Variablen R, R1 und R2 unabhängig voneinander CrC15-Alkyl, das gegebenenfalls durch 1 bis 4 Sauerstoffatome in Etherfunktion unterbrochen ist, und C6-C10-Aryl, das gegebenenfalls mit einem oder mehreren Cι-C15-Alkyl, das gegebenenfalls durch 1 bis 4 Sauerstoffatome in Etherfunktion unterbrochen ist, substituiert ist.Here, in the formulas IIa to llc, 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 nimmt in den Formeln lla bis llc entweder die Bedeutung von zwei Wasserstoffatomen, zwei Cyanogruppen in 2,3- oder 6,7-Stellung oder zwei gleichen Gruppen CH(R9)(R10) in 2,3- oder6,7-Stellung des Anthrachinongerüstes an. Bei den letzteren beiden Gruppen CH(R9)(R10) handelt es sich entweder um zwei Gruppen CH(COOR)2, CH(CN)COOR oder CH(CN)2 , wobei die Reste R vorzugsweise Cι-C15-Alkyl, das gegebenenfalls durch 1 bis 4 Sauerstoffatome in Etherfunktion unterbrochen ist, oder C6-Cιo-Aryl, das gegebenenfalls mit einem oder mehreren Cι-C15-Alkyl, das gegebenenfalls durch 1 bis 4 Sauerstoffatome in Etherfunktion unterbrochen ist, substituiert ist, bedeuten. In der Bedeutung eines Cι-Cι5-Alkyl, das gegebenenfalls durch 1 bis 4 Sauerstoffatome in Etherfunktion unterbrochen ist, erfolgt die Auswahl der Variablen R, R1 und R2 vorzugsweise aus der Gruppe bestehend aus Methyl, Ethyl, Propyl, Isopropyl, Butyl, Isobutyl, sec-Butyl, tert-Butyl, Pentyl, Isopentyl, Neopentyl, tert-Pentyl, Hexyl, 2-Methyl- pentyl, Heptyl, Hept-3-yl, Octyl, 2-Ethylhexyl, Isooctyl, Nonyl, Isononyl, Decyl, Isodecyl, Undecyl, Dodecyl, Tridecyl, 3,5,5,7-Tetramethyl-nonyl, Isotridecyl, Tetradecyl, Penta- decyl, Methoxymethyl, 2-Ethylhexoxymethyl, 2-Methoxyethyl, 2-Ethoxyethyl, 2-Pro- poxyethyl, 2-lsopropoxyethyl, 2-Butoxyethyl, 2- und 3-Methoxypropyl, 2- und 3-Ethoxy- propyl, 2- und 3-Propoxypropyl, 2- und 3-Butoxypropyl, 2- und 4-Methoxybutyl, 2- und 4-Ethoxybutyl, 2- und 4-Propoxybutyl, 2- und 4-Butoxy butyl, 3,6-Dioxaheptyl, 3,6-Dio- xaoctyl, 4,8-Dioxanonyl, 3,7-Dioxaoctyl, 3,7-Dioxanonyl, 4,7-Dioxaoctyl, 4,7-Dioxa- nonyl, 4,8-Dioxadecyl, 3,6,8-Trioxadecyl, 3,6,9-Trioxaundecyl, 3,6,9, 12-Tetraoxatri- decyl und 3,6,9, 12-Tetraoxatetradecyl.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 -Cιo-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 , In the meaning of a -CC 5 alkyl, which is optionally interrupted by 1 to 4 oxygen atoms in ether function, 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-pentyl, hexyl, 2-methylpentyl, heptyl, hept-3-yl, octyl, 2-ethylhexyl, isooctyl, nonyl, isononyl, decyl , Isodecyl, undecyl, dodecyl, tridecyl, 3,5,5,7-tetramethylnonyl, isotridecyl, tetradecyl, penta-decyl, methoxymethyl, 2-ethylhexoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2 1-isopropoxyethyl, 2-butoxyethyl, 2- and 3-methoxypropyl, 2- and 3-ethoxypropyl, 2- and 3-propoxypropyl, 2- and 3-butoxypropyl, 2- and 4-methoxybutyl, 2- and 4-ethoxybutyl , 2- and 4-propoxybutyl, 2- and 4-butoxy-butyl, 3,6-dioxaheptyl, 3,6-dioxaoctyl, 4,8-dioxanonyl, 3,7-dioxaoctyl, 3,7-dioxanonyl, 4, 7-dioxaoctyl, 4,7-dioxanonyl, 4,8-dioxadecyl, 3,6,8-trioxadecyl, 3,6,9- Trioxaundecyl, 3,6,9,12-tetraoxatri- decyl and 3,6,9,12-tetraoxatetradecyl.
In der Bedeutung eines C6-Cι0-Aryl, das gegebenenfalls mit einem oder mehreren C^ C s-Alkyl, das gegebenenfalls durch 1 bis 4 Sauerstoffatome in Etherfunktion unterbrochen ist, erfolgt die Auswahl der Variablen R, R1 und R2 vorzugsweise aus der Gruppe bestehend aus unsubstituiertem Phenyl, den einfach in 2-, 3- und 4-Stellung, den zweifach in 2,3-, 2,4- und 3,4-Stellung und den dreifach in 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6- und 3,4,5-Stellung substituierten Phenylresten, welche substituiert sind mit den zuvor exemplarisch aufgezählten, gegebenenfalls mit Sauerstoff in Etherfunktion unterbrochenen Cι-Cι5-Alkylresten.In the meaning of a C 6 -C 0 -aryl which is optionally interrupted by one or more C 1 -C 5 -alkyl which is optionally interrupted by 1 to 4 oxygen atoms in ether function, 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 Cι-Cι interrupted 5 alkyl radicals.
Besonders bevorzugt sind Verbindungen der Formeln lla, Mb und llc, in welchen beide Variablen R, R1 und R2 bzw. R, R1 und R2 bzw. R1 und R2 untereinander gleich sind, d.h. als entsprechende Verbindungen sind zu nennen:Particular preference is given to compounds of the formulas IIa, Mb and IIc in which both variables R, R 1 and R 2 or R, R 1 and R 2 or R 1 and R 2 are identical to one another, ie suitable compounds :
Figure imgf000011_0001
und
Figure imgf000012_0001
Figure imgf000011_0001
and
Figure imgf000012_0001
sowie die entsprechenden mit Cyanogruppen oder Gruppen CH(R9)(R10) in 6,7- Stellung substituierten Verbindungen, wobei die Variablen R den zuvor aufgeführten Auswahlen entsprechen.and the corresponding compounds substituted with cyano groups or groups CH (R 9 ) (R 10 ) in the 6,7-position, wherein the variables R correspond to the choices listed above.
Als erfindungsgemäß zu verwendende Anthrachinonderivate der Formel III sind insbe- sondere die nachfolgend gezeigten Verbindungen der Formeln lila bis llld zu nennen:The 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:
Figure imgf000012_0002
worin bedeuten
Figure imgf000012_0002
in which mean
R3 R oder NHR,R 3 R or NHR,
R8 NHRR 8 NHR
W Reste R4 bis R7 in der Bedeutung Wasserstoff oder NHR,W radicals R 4 to R 7 in the meaning of hydrogen or NHR,
p 1 , 2, 3 oder 4, wobei für p größer als 1 die Reste gleich sind,p is 1, 2, 3 or 4, where p is greater than 1, the radicals are the same,
undand
R Cι-Cι5-Alkyl, das gegebenenfalls durch 1 bis 4 Sauerstoffatome in Etherfunktion unterbrochen ist, Cyclohexyl, das gegebenenfalls mit einer oder mehreren Cι-Cι5-Alkylgruppen, die gegebenenfalls durch 1 bis 4 Sauerstoffatome in Etherfunktion unterbrochen sind, substituiert ist, gesättigter heterocyclischer fünf- oder sechsgliedriger Rest, der gegebenenfalls mit einer oder mehreren CrCι5-Alkyl- gruppen, die gegebenenfalls durch 1 bis 4 Sauerstoffatome in Etherfunktion unterbrochen sind, substituiert ist, C6-Cι0-Aryl, das gegebenenfalls mit einem oder mehreren CrCι5-Alkyl, das gegebenenfalls durch 1 bis 4 Sauerstoffatome inR Cι-Cι-C5 alkyl, which is optionally interrupted by 1 to 4 oxygen atoms in ether function, cyclohexyl which is optionally substituted by one or more Cι-Cι 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 CrCι 5 alkyl, C 6 -Cι 0 aryl optionally substituted with one or more C r Cι-C5 alkyl optionally substituted by 1 to 4 oxygen atoms in
Etherfunktion unterbrochen ist, C Cι5-Alkoxy, CrCι5-Alkylamino oder C -Ci5-Di- alkylamino substituiert ist, Heteroaryl mit 3 bis 5 Kohlenstoffatomen, das gegebenenfalls mit einem oder mehreren Cι-Cι5-Alkyl, das gegebenenfalls durch 1 bis 4 Sauerstoffatome in Etherfunktion unterbrochen ist, C C 5-Alkoxy, C ds-Alkyl- amino oder Cι-C15-Dialkylamino substituiert ist, Phenyl-CrC4-alkyl, das im Phe- nylrest gegebenenfalls mit einem oder mehreren Cι-Cι5-Alkyi, das gegebenenfalls durch 1 bis 4 Sauerstoffatome in Etherfunktion unterbrochen ist, CrCι5-AI- koxy, Cι-C 5-Alkylamino oder CrCι5-Dialkylamino substituiert ist, oder Heteroa- ryl-C -C4-alkyl mit 3 bis 5 Kohlenstoffatomen im Heteroarylrest, wobei letzterer gegebenenfalls mit einem oder mehreren CrC 5-Alkyl, das gegebenenfalls durchEther function is interrupted, C -C 5 alkoxy, CrCι 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, CrCι 5 -AI- koxy, -CC 5 alkylamino or CrCι 5 -Dialkylamino is substituted, or heteroaryl-C -C 4 alkyl having 3 to 5 Carbon atoms in the heteroaryl radical, the latter optionally with one or more C r C 5 alkyl, optionally substituted by
1 bis 4 Sauerstoffatome in Etherfunktion unterbrochen ist, Cι-C15-Alkoxy, Cι-Ci5-Alkylamino oder Cι-Cι5-Dialkylamino substituiert ist,1 to 4 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,
wobei die bevorzugten Reste R bereits in der zuvor beschriebenen allgemeinen Defini- tion der Reste R exemplarisch mit aufgeführt wurden.the preferred radicals R have already been listed by way of example in the general definition of the radicals R described above.
R in den Formeln lila bis llld bedeutet besonders bevorzugt Cι-Cι5-Alkyl, das gegebenenfalls durch 1 bis 4 Sauerstoffatome in Etherfunktion unterbrochen ist, oder C6-C10-Aryl, das gegebenenfalls mit einem oder mehreren C -Cι5-Alkyl, das gegebe- nenfalls durch 1 bis 4 Sauerstoffatome in Etherfunktion unterbrochen ist. Insbesondere ist R in den Formeln lila bis llld ausgewählt aus der Gruppe bestehend aus Methyl, Ethyl, Propyl, Isopropyl, Butyl, Isobutyl, sec-Butyl, tert-Butyl, Pentyl, Iso- pentyl, Neopentyl, tert-Pentyl, Hexyl, 2-Methylpentyl, Heptyl, Hept-3-yl, Octyl, 2-Ethyl- hexyl, Isooctyl, Nonyl, Isononyl, Decyl, Isodecyl, Undecyl, Dodecyl, Tridecyl, 3,5,5,7-Tetramethyl-nonyl, Isotridecyl, Tetradecyl, Pentadecyl, Methoxymethyl, 2-Ethyl- hexoxymethyl, 2-Methoxyethyl, 2-Ethoxyethyl, 2-Propoxyethyl, 2-lsopropoxyethyl, 2-Butoxyethyl, 2- und 3-Methoxypropyl, 2- und 3-Ethoxypropyl, 2- und 3-Propoxy- propyl, 2- und 3-Butoxypropyl, 2- und 4-Methoxybutyl, 2- und 4-Ethoxybutyl, 2- und 4- Propoxybutyl, 2- und 4-Butoxybutyl, 3,6-Dioxaheptyl, 3,6-Dioxaoctyl, 4,8-Dioxanonyl, 3,7-Dioxaoctyl, 3,7-Dioxanonyl, 4,7-Dioxaoctyl, 4,7-Dioxanonyl, 4,8-Dioxadecyl, 3,6,8- Trioxadecyl, 3,6,9-Trioxaundecyl, 3,6,9,12-Tetraoxatridecyl, 3,6,9, 12-Tetraoxatetra- decyl, unsubstituiertem Phenyl, den einfach in 2-, 3- und 4-Stellung substituierten, den zweifach in 2,3-, 2,4- und 3,4-Stellung substituierten und den dreifach in 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6- und 3,4,5-Stellung substituierten Phenylresten, welche substituiert sind mit den zuvor exemplarisch aufgezählten, gegebenenfalls mit Sauerstoff in Etherfunktion unterbrochenen C -Cι5-Alkylresten, ausgewählt aus der Gruppe bestehend aus Methyl, Ethyl, Propyl, Isopropyl, Butyl, Isobutyl, sec-Butyl, tert-Butyl, Pentyl, Iso- pentyl, Neopentyl, tert-Pentyl, Hexyl, 2-Methylpentyl, Heptyl, Hept-3-yl, Octyl, 2-Ethyl- hexyl, Isooctyl, Nonyl, Isononyl, Decyl, Isodecyl, Undecyl, Dodecyl, Tridecyl, 3,5,5,7-Tetramethyl-nonyl, Isotridecyl, Tetradecyl, Pentadecyl, Methoxymethyl, 2-Ethyl- hexoxymethyl, 2-Methoxyethyl, 2-Ethoxyethyl, 2-Propoxyethyl, 2-lsopropoxyethyl, 2-Butoxyethyl, 2- und 3-Methoxypropyl, 2- und 3-Ethoxypropyl, 2- und 3-Propoxy- propyl, 2- und 3-Butoxypropyl, 2- und 4-Methoxybutyl, 2- und 4-Ethoxybutyl, 2- und 4-Propoxybutyl, 2- und 4-Butoxybutyl, 3,6-Dioxaheptyl, 3,6-Dioxaoctyl, 4,8-Di- oxanonyl, 3,7-Dioxaoctyl, 3,7-Dioxanonyl, 4,7-Dioxaoctyl, 4,7-Dioxanonyl, 4,8-Di- oxadecyl, 3,6,8-Trioxadecyl, 3,6,9-Trioxaundecyl, 3,6,9, 12-Tetraoxatridecyl und 3,6,9,12-Tetraoxatetradecyl.R in the formulas IIIa to IIId is particularly preferably Cι-Cι-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 -Cι 5 alkyl, which is optionally interrupted by 1 to 4 oxygen atoms in ether function. In particular, 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-ethoxyethyl, 2-propoxyethyl, 2-isopropoxyethyl, 2-butoxyethyl, 2- and 3-methoxypropyl, 2- and 3-ethoxypropyl, 2- and 3- Propoxypropyl, 2- and 3-butoxypropyl, 2- and 4-methoxybutyl, 2- and 4-ethoxybutyl, 2- and 4-propoxybutyl, 2- and 4-butoxybutyl, 3,6-dioxaheptyl, 3,6-dioxaoctyl , 4,8-dioxanonyl, 3,7-dioxaoctyl, 3,7-dioxanonyl, 4,7-dioxaoctyl, 4,7-dioxanonyl, 4,8-dioxadecyl, 3,6,8-trioxadecyl, 3,6,9 Trioxaundecyl, 3,6,9,12-tetraoxatridecyl, 3,6,9,12-tetraoxatetra-decyl, unsubstituted phenyl, which is readily substituted in 2-, 3- and 4-Ste substituted, doubly substituted in the 2,3-, 2,4- and 3,4-position and the threefold 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 C -C 5 alkyl radicals selected from the group consisting of methyl , Ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neo-pentyl, tert-pentyl, hexyl, 2-methylpentyl, heptyl, hept-3-yl, octyl, 2-ethyl - hexyl, isooctyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tridecyl, 3,5,5,7-tetramethyl-nonyl, isotridecyl, tetradecyl, pentadecyl, methoxymethyl, 2-ethyl-hexoxymethyl, 2-methoxyethyl, 2 Ethoxyethyl, 2-propoxyethyl, 2-isopropoxyethyl, 2-butoxyethyl, 2- and 3-methoxypropyl, 2- and 3-ethoxypropyl, 2- and 3-propoxy-propyl, 2- and 3-butoxypropyl, 2- and 4- Methoxybutyl, 2- and 4-ethoxybutyl, 2- and 4-propoxybutyl, 2- and 4-butoxyb ethyl, 3,6-dioxaheptyl, 3,6-dioxaoctyl, 4,8-dioxanonyl, 3,7-dioxaoctyl, 3,7-dioxanonyl, 4,7-dioxaoctyl, 4,7-dioxanonyl, 4,8- Dioxadecyl, 3,6,8-trioxadecyl, 3,6,9-trioxaundecyl, 3,6,9, 12-tetraoxatridecyl and 3,6,9,12-tetraoxatetradecyl.
Als Trägeröle werden üblicherweise viskose, hochsiedende und insbesondere thermo- stabile Flüssigkeiten verwendet. Sie überziehen die heißen Metalloberflächen, z. B. die Einlaßventile, mit einem dünnen Flüssigkeitsfilm und verhindern oder verzögern dadurch die Bildung und Ablagerung von Zersetzungsprodukten an den Metalloberflächen.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.
Als Komponente b) der erfindungsgemäßen Kraft- und Schmierstoffadditiv-Konzentrate in Frage kommende Trägeröle sind beispielsweise mineralische Trägeröle (Grundöle), insbesondere solche der Viskositätsklasse "Solvent Neutral (SN) 500 bis 2000", synthetische Trägeröle auf Basis von Olefinpolymerisaten mit MN = 400 bis 1800, vor allem auf Polybuten- oder Polyisobuten-Basis (hydriert oder nicht hydriert), von Polyalphaole- finen oder Polyinternalolefinen sowie synthetische Trägeröle auf Basis alkoxylierter langkettiger Alkohole oder Phenole. Erfindungsgemäß als Trägeröle zu verwendende Addukte von Ethylenoxid, Propylenoxid und/oder Butylenoxid an Polybutyl- oder Polyi- sobutenalkohole sind etwa in der Schrift EP 277345 A1 , weitere erfindungesgemäß zu verwendende Polyalkenalkohol-Polyalkoxylate in der Schrift WO 00/50543 A1 be- schrieben. Als weitere, erfindungsgemäß zu verwendende Trägeröle sind auch Polyal- kenalkohol-Polyetheramine zu nennen, wie sie in der Schrift WO 00/61708 aufgeführt sind.Suitable carrier oils for component (b) of the novel fuel and lubricant additive concentrates are, for example, mineral carrier oils (base oils), in particular those of the viscosity class "Solvent Neutral (SN) 500 to 2000", 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.
Selbstverständlich können auch Mischungen verschiedener Trägeröle zum Einsatz kommen, sofern sie untereinander und mit den übrigen Komponenten der erfindungsgemäßen Packages verträglich sind.Of course, 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.
Vergaser und Einlaßsysteme von Verbrennungsmotoren, aber auch Einspritzsysteme für die Kraftstoffdosierung, werden in zunehmendem Maße durch Verunreinigungen belastet, die beispielsweise durch Staubteilchen aus der Luft und unverbrannte Kohlenwasserstoffreste aus dem Brennraum verursacht werden.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.
Zur Reduzierung oder Vermeidung dieser Verunreinigungen werden dem Kraftstoff Additive ("Detergenzien") zur Reinhaltung von Ventilen und Vergasern bzw. Einspritz- Systemen beigegeben. Derartige Detergenzien gelangen im allgemeinen in Kombination mit einem oder mehreren Trägerölen zur Anwendung. Die Trägeröle üben eine zusätzliche "Waschfunktion" aus, unterstützen und fördern oft die Detergenzien in ihrer reinigenden und reinerhaltenden Wirkung und können so zur Reduzierung der benötigten Menge an Detergenzien beitragen.To reduce or avoid these impurities, additives ("detergents") 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.
Erwähnt sei hier weiter, dass viele der üblicherweise als Trägeröle verwendeten Substanzen zusätzliche Wirkung als Detergenzien und/oder Dispergatoren entfalten, weshalb in einem solchen Fall der Anteil an letzteren reduziert werden kann. Solche Trägeröle mit Detergens-/Dispergatorwirkung sind etwa in der letztgenannten WO-Schrift dargelegt.It should also be mentioned here that many of the substances commonly used as carrier oils have an additional effect as detergents and / or dispersants, so that in such a case the proportion of the latter can be reduced. Such carrier oils with detergent / dispersant effect are set out, for example, in the last-mentioned WO document.
Auch lässt sich die Wirkungsweise von Detergenzien, Dispergatoren und ventilsitzver- schleißhemmenden Additiven oftmals nicht klar voneinander abgrenzen, weshalb diese Verbindungen summarisch unter Komponente c) aufgeführt sind. Übliche Detergen- zien, welche in den erfindungesgemäßen Packages Anwendung finden, sind beispielsweise in den Schriften WO 00/50543 A1 und WO 00/61708 A1 aufgeführt und umfassen: Polyisobutenamine, welche gemäß der EP- 244616 durch Hydroformylierung von hochreaktivem Polyisobuten und anschließende reduktive Aminierung mit Ammoniak, Monoaminen oder Polyaminen wie Dimethylenaminopropylamin, Ethylendiamin, Diethylentriamin, Triethylentetramin oder Tetraethylenpentamin erhältlich sind,In addition, the mode of action of detergents, dispersants and valve seat wear-inhibiting additives is often not clearly distinguishable, which is why these compounds are listed in summary under component c). 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)butenamine, welche durch Chlorierung von Polybutenen oder Polyisobu- tenen mit Doppelbindungen überwiegend in der b- und g-Position und anschlie- ßende Aminierung mit Ammoniak, Monoaminen oder den oben genannten Polyaminen erhältlich sind,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,
Poly(iso)butenamine, welche durch Oxidation von Doppelbindungen in Poly(iso)- butenen mit Luft oder Ozon zu Carbonyl- oder Carboxylverbindungen und an- schließende Aminierung unter reduzierenden (hydrierenden) Bedingungen erhältlich sind,Poly (iso) buteneamines which are obtainable by oxidation of double bonds in poly (iso) butenes with air or ozone to form carbonyl or carboxyl compounds and subsequent amination under reducing (hydrogenating) conditions,
Polyisobutenamine, welche gemäß der DE-A 19620262 aus Polyisobutenepoxi- den durch Umsetzung mit Aminen und nachfolgende Dehydratisierung und Re- duktion der Aminoalkohole erhältlich sind,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,
gegebenenfalls Hydroxylgruppen enthaltende Polyisobutenamine, welche gemäß der WO-A 97/03946 durch Umsetzung von Polyisobutenen mit einem mittleren Polymerisationsgrad P = 5 bis 100 mit Stickoxiden oder Gemischen aus Stickoxi- den und Sauerstoff und anschließende Hydrierung dieser Umsetzungsprodukte erhältlich sind,optionally hydroxyl-containing polyisobuteneamines, which are obtainable according to WO-A 97/03946 by reaction of polyisobutenes having an average degree of polymerization P = 5 to 100 with nitrogen oxides or mixtures of nitrogen oxides and oxygen and subsequent hydrogenation of these reaction products,
Hydroxylgruppen enthaltende Polyisobutenamine, welche gemäß der EP-A 476485 durch Umsetzung von Polyisobutenepoxiden mit Ammoniak, Monoaminen oder den oben genannten Polyaminen erhältlich sind,Hydroxyl-containing polyisobuteneamines, which are obtainable according to EP-A 476485 by reacting polyisobutene epoxides with ammonia, monoamines or the abovementioned polyamines,
Polyetheramine, welche durch Umsetzung von C2- bis C30-Alkanolen, C6- bis C30- Alkandiolen, Mono- oder Di-C2- bis C30-Alkylaminen, C bis C30-Alkylcyclohexa- nolen oder C bis C30-Alkylphenolen mit 1 bis 30 mol Ethylenoxid und/oder Pro- pylenoxid und/oder Butylenoxid pro Hydroxyl- bzw. Aminogruppe und anschließende reduktive Aminierung mit Ammoniak, Monoaminen oder den oben genannten Polyaminen erhältlich sind, sowie "Polyisobuten-Mannichbasen", welche gemäß EP-A 831 141 durch Umsetzung von polyisobutensubstituierten Phenolen mit Aldehyden und Monoaminen oder den oben genannten Polyaminen erhältlich sind.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.
Weitere, erfindungsgemäß zu verwendende Detergenzien und/oder ventilsitzver- schleißhemmende Additive sind beispielsweise in der Schrift WO 00/47698 A1 aufgeführt und umfassen Verbindungen, welche mindestens einen hydrophoben Kohlenwasserstoffrest mit einem zahlengemittelten Molekulargewicht (MN) von 85 bis 20000 und mindestens eine polare Gruppierung aufweisen, und welche ausgewählt sind aus:Further 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:
(i) Mono- oder Polyaminogruppen mit bis zu 6 Stickstoffatomen, wobei mindestens ein Stickstoffatom basische Eigenschaften hat,(i) mono- or polyamino groups having up to 6 nitrogen atoms, at least one nitrogen atom having basic properties,
(ii) Nitrogruppen, ggf. in Kombination mit Hydroxylgruppen,(ii) nitro groups, optionally in combination with hydroxyl groups,
(iii) Hydroxylgruppen in Kombination mit Mono- oder Polyaminogruppen, wobei mindestens ein Stickstoffatom basische Eigenschaften hat,(iii) hydroxyl groups in combination with mono- or polyamino groups, wherein at least one nitrogen atom has basic properties,
(iv) Carboxylgruppen oder deren Alkalimetall- oder Erdalkalimetallsalzen,(iv) carboxyl groups or their alkali metal or alkaline earth metal salts,
(v) Sulfonsäuregruppen oder deren Alkalimetall- oder Erdalkalimetallsalzen,(v) sulphonic acid groups or their alkali metal or alkaline earth metal salts,
(vi) Polyoxy-C2- bis C4-alkylengruppierungen, die durch Hydroxylgruppen, Mono- oder Polyaminogruppen, wobei mindestens ein Stickstoffatom basische Eigenschaften hat, oder durch Carbamatgruppen terminiert sind,(vi) 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,
(vii) Carbonsäureestergruppen,(vii) carboxylic ester groups,
(viii) aus Bernsteinsäureanhydrid abgeleitete Gruppierungen mit Hydroxy- und/oder Amino- und/oder Amido- und/oder Imidogruppen und(viii) succinic anhydride-derived moieties having hydroxy and / or amino and / or amido and / or imido groups and
(ix) durch Mannich-Umsetzung von phenolischen Hydroxylgruppen mit Aldehyden und Mono- oder Polyaminen erzeugte Gruppierungen.(ix) groups generated by Mannich reaction of phenolic hydroxyl groups with aldehydes and mono- or polyamines.
Mono- oder Polyaminogruppen (i) enthaltende Additive sind vorzugsweise Polyalken- mono- oder Polyalkenpolyamine auf Basis von Polypropen oder von hochreaktivem (d.h. mit überwiegend endständigen Doppelbindungen - meist in der ß- und γ-Po- sition) oder konventionellem (d.h. mit überwiegend mittenständigen Doppelbindungen) Polybuten oder Polyisobuten mit MN = 300 bis 5000. Derartige Additive auf Basis von hochreaktivem Polyisobuten, welche aus dem Polyisobuten, welches bis zu 20 Gew.-% n-Buten-Einheiten enthalten kann, durch Hydroformylierung und reduktive Aminierung mit Ammoniak, Monoaminen oder Polyaminen wie Dimethylaminopropyla- min, Ethylendiamin, Diethylentriamin, Triethylentetramin oder Tetraethylenpentamin hergestellt werden können, sind insbesondere aus der Schrift EP 244616 A2 bekannt. Geht man bei der Herstellung der Additive von Polybuten oder Polyisobuten mit überwiegend mittenständigen Doppelbindungen (meist in der ß- und γ-Position) aus, bietet sich der Herstellweg durch Chlorierung und anschließende Aminierung oder durch Oxi- dation der Doppelbindung mit Luft oder Ozon zur Carbonyl- oder Carboxylverbindung und anschließende Aminierung unter reduktiven (hydrierenden) Bedingungen an. Zur Aminierung können hier die gleichen Amine wie oben für die reduktive Aminierung des hydroformylierten hochreaktiven Polyisobutens eingesetzt werden. Entsprechende Additive auf Basis von Polypropen sind insbesondere in der Schrift WO 94/24231 A1 beschrieben.Mono- or polyamino (i) -containing additives are preferably polyalkylene mono- or Polyalkenpolyamine based on polypropene or highly reactive (ie with predominantly terminal double bonds - usually in the ß and γ position) or conventional (ie with predominantly middle Double bonds) polybutene or polyisobutene with M n = 300 to 5000. 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. If one starts with the preparation of the additives of polybutene or polyisobutene with predominantly intermediate double bonds (usually in the β and γ position), 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. For 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.
Weitere bevorzugte Monoaminogruppen (i) enthaltende Additive sind die Hydrierungsprodukte der Umsetzungsprodukte aus Polyisobutenen mit einem mittleren Polymerisationsgrad P = 5 bis 100 mit Stickoxiden oder Gemischen aus Stickoxiden und Sauerstoff, wie sie insbesondere in der Schrift WO 97/03946 A1 beschrieben sind.Further preferred monoamino groups (i) containing additives are the hydrogenation products of the reaction products of polyisobutenes having an average degree of polymerization P = 5 to 100 with nitrogen oxides or mixtures of nitrogen oxides and oxygen, as described in particular in the document WO 97/03946 A1.
Weitere bevorzugte Monoaminogruppen (i) enthaltende Additive sind die aus Polyisobutenepoxiden durch Umsetzung mit Aminen und nachfolgende Dehydratisierung und Reduktion der Aminoalkohole erhältlichen Verbindungen, wie sie insbesondere in der Schrift DE 19620262 A1 beschrieben sind.Further preferred 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.
Nitrogruppen, ggf. in Kombination mit Hydroxylgruppen, (ii) enthaltende Additive sind vorzugsweise Umsetzungsprodukte aus Polyisobutenen des mittleren Polymerisationsgrades P = 5 bis 100 oder 10 bis 100 mit Stickoxiden oder Gemischen aus Stickoxiden und Sauerstoff, wie sie insbesondere in den Schriften WO 96/03367 A1 und WO 96/03479 A1 beschrieben sind. Diese Umsetzungsprodukte stellen in der Regel Mischungen aus reinen Nitropolyisobutanen (z.B. α,ß-Dinitropolyisobutan) und gemischten Hydroxynitropolyisobutanen (z.B. α-Nitro-ß-hydroxypolyisobutan) dar.Nitro groups, optionally in combination with hydroxyl groups, (ii) containing additives are preferably reaction products of polyisobutenes of average degree of polymerization P = 5 to 100 or 10 to 100 with nitrogen oxides or mixtures of nitrogen oxides and oxygen, as described in particular in the publications WO 96/03367 A1 and WO 96/03479 A1 are described. These reaction products typically are mixtures of pure nitropolyisobutanes (e.g., α, β-dinitropolyisobutane) and mixed hydroxynitropolyisobutanes (e.g., α-nitro-β-hydroxy polyisobutane).
Hydroxylgruppen in Kombination mit Mono- oder Polyaminogruppen (iii) enthaltende Additive sind insbesondere Umsetzungsprodukte von Polyisobutenepoxiden, erhältlich aus vorzugsweise überwiegend endständige Doppelbindungen aufweisendem Polyisobuten mit MN = 300 bis 5000, mit Ammoniak, Mono- oder Polyaminen, wie sie insbesondere in der Schrift EP 476485 A1 beschrieben sind. Carboxylgruppen oder deren Alkalimetall- oder Erdalkalimetallsalze (iv) enthaltende Additive sind vorzugsweise Copolymere von C2-C40-Olefinen mit Maleinsäureanhydrid mit einer Gesamt-Molmasse von 500 bis 20 000, deren Carboxylgruppen ganz oder teilweise zu den Alkalimetall- oder Erdalkalimetallsalzen und ein verbleibender Rest der Carboxylgruppen mit Alkoholen oder Aminen umgesetzt sind. Solche Additive sind insbesondere aus der Schrift EP 307815 A1 bekannt. Derartige Additive dienen hauptsächlich zur Verhinderung von Ventilsitzverschleiß und können, wie in der Schrift WO 87/01126 A1 beschrieben, mit Vorteil in Kombination mit üblichen Detergenzien, wie Poly(iso)butenaminen oder Polyetheraminen, eingesetzt werden.Hydroxyl groups in combination with mono- or polyamino groups (iii) containing additives are in particular reaction products of polyisobutene epoxides obtainable from preferably predominantly terminal double bonds having polyisobutene with M N = 300 to 5000, with ammonia, mono- or polyamines, as described in particular in EP 476485 A1 are described. 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.
Sulfonsäuregruppen oder deren Alkalimetall- oder Erdalkalimetallsalze (v) enthaltende Additive sind vorzugsweise Alkalimetall- oder Erdalkalimetallsalze eines Sulfobern- steinsäurealkylesters, wie er insbesondere in der Schrift EP 639632 A1 beschrieben ist. Derartige Additive dienen hauptsächlich zur Verhinderung von Ventilsitzverschleiß und können mit Vorteil in Kombination mit üblichen Detergenzien, wie Poly(iso)buten- aminen oder Polyetheraminen, eingesetzt werden.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- steinsäurealkylesters, 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-C2- bis C -alkylengruppierungen (vi) enthaltende Additive sind vorzugsweise Polyether oder Polyetheramine, welche durch Umsetzung von C2- bis C60-Alkanolen, C6- bis C3o-Alkandiolen, Mono- oder Di-C2-C30-alkylaminen, Cι-C3o-Alkylcyclohexa- nolen oder C -C30-Alkylphenolen mit 1 bis 30 mol Ethylenoxid und/oder Propylenoxid und/oder Butylenoxid pro Hydroxylgruppe oder Aminogruppe und, im Falle der Polyetheramine, durch anschließende reduktive Aminierung mit Ammoniak, Monoaminen oder Polyaminen erhältlich sind. Derartige Produkte werden insbesondere in den Schriften EP 310 875 A1, EP 356725 A1, EP 700985 A1 und US 4,877,416 beschrieben. Im Falle von Polyethern erfüllen solche Produkte auch Trägeröleigenschaften. Typische Beispiele hierfür sind Tridecanol- oder Isotridecanolbutoxylate, Isononylphe- nolbutoxylate sowie Polyisobutenolbutoxylate und -propoxylate sowie die entsprechenden Umsetzungsprodukte mit Ammoniak.Polyoxy-C 2 - to C -alkylene additives (vi) 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. In the case of 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.
Carbonsäureestergruppen (vii) enthaltende Additive sind vorzugsweise Ester aus Mono-, Di- oder Tricarbonsäuren mit langkettigen Alkanolen oder Polyolen, insbesondere solche mit einer Mindestviskosität von 2 mm /s bei 100°C, wie sie insbesondere in der Schrift DE 38 38 918 A1 beschrieben sind. Als Mono-, Di- oder Tricarbonsäuren kön- nen aliphatische oder aromatische Säuren eingesetzt werden, als Esteralkohole bzw.- polyole eignen sich vor allem langkettige Vertreter mit beispielsweise 6 bis 24 C-Atomen. Typische Vertreter der Ester sind Adipate, Phthalate, iso-Phthalate, Terephthalate und Trimellitate des iso-Octanols, iso-Nonanols, iso-Decanols und des iso-Tridecanols. Derartige Produkte erfüllen auch Trägeröleigenschaften. Aus Bernsteinsäureanhydrid abgeleitete Gruppierungen mit Hydroxy- und/oder Amino- und/oder Amido- und/oder Imidogruppen (viii) enthaltende Additive sind vorzugsweise entsprechende Derivate von Polyisobutenylbernsteinsäureanhydrid, welche durch Umsetzung von konventionellem oder hochreaktivem Polyisobuten mit MN = 300 bis 5000 mit Maleinsäureanhydrid auf thermischen Wege oder über das chlorierte Polyisobuten erhältlich sind. Von besonderem Interesse sind hierbei Derivate mit aliphati- schen Polyaminen wie Ethylendiamin, Diethylentriamin, Triethylentetramin oder Tetra- ethylenpentamin. Derartige Ottokraftstoffadditive sind insbesondere in der Schrift US 4,849,572 beschrieben.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. As 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. Succinic anhydride-derived groupings containing hydroxyl and / or amino and / or amido and / or imido groups (viii) additives are preferably corresponding derivatives of polyisobutenyl succinic anhydride obtained by reacting conventional or highly reactive polyisobutene with M n = 300 to 5000 with maleic anhydride are obtainable by thermal means or via the chlorinated polyisobutene. Of particular interest here are derivatives with aliphatic polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine. Such Otto fuel additives are described in particular in the document US 4,849,572.
Durch Mannich-Umsetzung von phenolischen Hydroxylgruppen mit Aldehyden und Mono- oder Polyaminen erzeugte Gruppierungen (ix) enthaltende Additive sind vorzugsweise Umsetzungsprodukte von polyisobutensubstituierten Phenolen mit Formaldehyd und Mono- oder Polyaminen wie Ethylendiamin, Diethylentriamin, Triethylen- tetramin, Tetraethylenpentamin oder Dimethylaminopropylamin. Die polyisobutenyl- substituierten Phenole können aus konventionellem oder hochreaktivem Polyisobuten mit MN = 300 bis 5000 stammen. Derartige „Polyisobuten-Mannichbasen" sind insbesondere in der Schrift EP 831 141 A1 beschrieben.By 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. The polyisobutenyl-substituted phenols can be derived from conventional or highly reactive polyisobutene having M N = 300 to 5,000. Such "polyisobutene-Mannich bases" are described in particular in document EP 831 141 A1.
Zur genaueren Definition der einzelnen aufgeführten Additive wird hier auf die Offenbarungen der obengenannten Schriften des Standes der Technik ausdrücklich Bezug genommen.For a more detailed definition of the individual listed additives, reference is expressly made to the disclosures of the above-mentioned documents of the prior art.
Dispergatoren als Komponente c) sind beispielsweise Imide, Amide, Ester und Ammo- nium- und Alkalimetallsalze von Polyisobutenbernsteinsäureanhydriden. Diese Verbindungen finden insbesondere Einsatz in Schmierölen, teilweise jedoch auch als Detergenzien in Kraftstoffzusammensetzungen.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.
Weitere Additive und Hilfsmittel, welche gegebenenfalls als Komponente d) der erfin- dungsgemäßen Packages vorhanden sein können, sindFurther additives and auxiliaries which may optionally be present as component d) of the packages according to the invention are
organische Lösungsmittel, z.B. Alkohole, wie Methanol, Ethanol, Propanol, Isopropa- nol, Butanol, Isobutanol, sec-Butanol, Pentanol, Isopentanol, Neopentanol oder Hexa- nol, z.B. Glykole, wie 1 ,2-Ethylenglykol, 1,2- oder 1 ,3-Propylenglykol, 1,2-, 2,3- oder 1 ,4-Butylenglykol, Di- oder Triethylenglykol oder Di- oder Tripropylenglykol, z.B. Ether, wie Methyltertbutylether, 1 ,2-Ethylenglykolmono- oder -dimethylether, 1 ,2-Ethylengly- kolmono- oder -diethylether, 3-Methoxypropanol, 3-lsopropoxypropanol, Tetrahydrofu- ran oder Dioxan, z.B. Ketone, wie Aceton, Methylethylketon oder Diacetonalkohol, z.B. Ester, wie Essigsäuremethylester, Essigsäureethylester, Essigsäurepropylester oder Essigsäurebutylester, z.B. Laktame, wie N-Methylpyrrolidinon (NMP), z.B. aliphatische oder aromatische Kohlenwasserstoffe sowie deren Gemische, wie Pentan, Hexan, Heptan, Octan, Isooctan, Petrolether, Toluol, Xylol, Ethylbenzol, Tetralin, Dekalin, Di- methylnaphthalin oder Testbenzin und z.B. Mineralöl, wie Benzin, Kerosin, Dieselöl oder Heizöl,organic solvents, for example alcohols, such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, pentanol, isopentanol, neopentanol or hexanol, for example 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, for example 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, eg ketones, such as acetone, methyl ethyl ketone or diacetone alcohol, for example esters, such as methyl acetate, ethyl acetate, propyl acetate or butyl acetate, eg lactams, such as N-methylpyrrolidinone (NMP), eg aliphatic or aromatic hydrocarbons and mixtures thereof, such as pentane, hexane, heptane, octane, isooctane, petroleum ether, toluene, xylene, ethylbenzene, tetralin, decalin, dimethylnaphthalene or white spirit and, for example, mineral oil, such as gasoline, kerosene, diesel oil or heating oil,
Korrosionsinhibitoren, beispielsweise auf Basis von zur Filmbildung neigenden Ammoniumsalzen organischer Carbonsäuren oder von heterocyclischen Aromaten bei Buntmetallkorrosionsschutz,Corrosion inhibitors, for example based on film-forming ammonium salts of organic carboxylic acids or of heterocyclic aromatics in non-ferrous metal corrosion protection,
Antioxidantien oder Stabilisatoren, beispielsweise auf Basis von Aminen wie p-Phenyl- endiamin, Dicyclohexylamin oder Derivaten hiervon oder von Phenolen wie 2,4-Di-tert- butylphenol oder 3,5-Di-tert.-butyl-4-hydroxyphenylpropionsäure, Demulgatoren,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-hydroxyphenylpropionsäure, demulsifiers .
Antistatikmittel,Antistatic agents,
Metallocene wie Ferrocen oder Methylcyclopentadienylmangantricarbonyl,Metallocenes such as ferrocene or methylcyclopentadienyl manganese tricarbonyl,
Schmierfähigkeitsverbesserer (Lubricity-Additive) wie bestimmte Fettsäuren, Alkenyl- bernsteinsäureester, Bis(hydroxyalkyl)fettamine, Hydroxyacetamide oder Ricinusöl,Lubricity additives such as certain fatty acids, alkenylsuccinic acid esters, bis (hydroxyalkyl) fatty amines, hydroxyacetamides or castor oil,
Amine zur Absenkung des pH-Wertes des Kraftstoffes,Amines for lowering the pH of the fuel,
weitere, von Anthrachinonderivaten verschiedene Markierungsstoffe sowieother, different from anthraquinone markers and
Farbstoffe.Dyes.
Die Konzentration der Komponente a), d.h. das mindestens eine Anthrachinonderivat, in den erfindungsgemäßen Packages wird üblicherweise in einer solchen Höhe ge- wählt, dass nach Zugabe des Packages zum Mineralöl die gewünschte Konzentration an Markierungsstoff(en) darin enthalten ist. Übliche Konzentrationen der Markierungsstoffe im Mineralöl liegen etwa im Bereich von 0,01 bis zu einigen 10 Gew.-ppm.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.
Komponente b), d.h. das mindestens eine Trägeröl, ist in den erfindungsgemäßen Pa- ckages üblicherweise in einer Konzentration von 1 bis 50, insbesondere 5 bis 30 Gew.-%, undComponent 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
Komponente c), d.h. das mindestens eine Detergens und/oder der mindestens eine Dispergator, üblicherweise in einer Konzentration von 25 bis 90 Gew.-%, insbesondere 30 bis 80 Gew.-%, enthalten, jeweils bezogen auf die Gesamtmenge der Komponenten a) bis c) und gegebenenfalls d), wobei die Summe der Einzelkonzentrationen der Komponenten a) bis c) und gegebenenfalls d) sich zu 100 Gew.-% ergänzt.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 .-%.
Sofern als Komponente d) Korrosionsinhibitoren, Antioxidantien oder Stabilisatoren, Demulgatoren, Antistatikmittel, Metallocene, Schmierfähigkeitsverbesserer und Amine zur Absenkung des pH-Wertes des Kraftstoffes, in den erfindungsgemäßen Packages enthalten sind, beläuft sich deren Konzentration in der Summe üblicherweise auf nicht mehr als 10 Gew.-%, bezogen auf die Gesamtmenge des Packages (d.h. die Gesamt- menge der Komponenten a) bis c) und d)), wobei die Konzentration der Korrosionsinhibitoren und Demulgatoren üblicherweise im Bereich von jeweils etwa 0,01 bis 0,5 Gew.-% der Gesamtmenge des Packages liegt.If, as component d), corrosion inhibitors, antioxidants or stabilizers, demulsifiers, antistatic agents, metallocenes, lubricity improvers and amines 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.
Sofern als Komponente d) zusätzliche (d.h. nicht bereits mit den übrigen Komponenten eingebrachte) organische Lösungsmittel in den erfindungsgemäßen Packages enthalten sind, beläuft sich deren Konzentration in der Summe üblicherweise auf nicht mehr als 20 Gew.-%, bezogen auf die Gesamtmenge des Packages. Diese Lösungsmittel stammen in der Regel von Lösungen der Markierungsstoffe und/oder Farbstoffe, welche im Hinblick auf eine genauere Dosierbarkeit -anstelle der reinen Markierungsstoffe und/oder Farbstoffe- den Packages zugegeben werden.If, as component d), additional (i.e., not already introduced with the other components) 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. As a rule, 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.
Sofern als Komponente d) weitere, von Anthrachinonderivaten verschiedene Markierungsstoffe in den erfindungsgemäßen Packages enthalten sind, bemisst sich deren Konzentration wiederum am Gehalt, welchen diese nach Zugabe der Packages im Mi- neralöl aufweisen sollen. Sinngemäß gilt das zu Komponente a) Gesagte.If, as 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).
Sofern als Komponente d) Farbstoffe in den erfindungsgemäßen Packages enthalten sind, liegt deren Konzentration üblicherweise etwa zwischen 0,1 bis 5 Gew.-%, bezogen auf die Gesamtmenge des Packages. If 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.
Beispiele:Examples:
Nachfolgend gezeigte Anthrachinonderivate wurden untersucht. Die Synthese der Verbindungen 1 bis 9 erfolgte ausgehend von 1,4,5,8-Tetrachloranthrachinon und den entsprechend substituierten Anilinen gemäß der in der Schrift EP 0323 184 A1 beschriebenen Methode.Anthraquinone derivatives shown below were investigated. The synthesis of compounds 1 to 9 was carried out starting from 1,4,5,8-tetrachloroanthraquinone and the correspondingly substituted anilines according to the method described in EP 0323 184 A1.
Verbindung 1 (λmax= 753 nm, THF):Compound 1 (λ max = 753 nm, THF):
Figure imgf000023_0001
Figure imgf000023_0001
Verbindung 2 (λmax= 750 nm, THF):Compound 2 (λ max = 750 nm, THF):
Figure imgf000023_0002
Figure imgf000023_0002
Verbindung 3 (λmax= 673 nm, THF):Compound 3 (λ max = 673 nm, THF):
Figure imgf000023_0003
Verbindung 4 (λmax= 758 nm, THF):
Figure imgf000023_0003
Compound 4 (λ max = 758 nm, THF):
Figure imgf000024_0001
Verbindung 5 (λmax= 756 nm, THF):
Figure imgf000024_0001
Compound 5 (λ max = 756 nm, THF):
Figure imgf000024_0002
Figure imgf000024_0002
Verbindung 6 (λmax= 756 nm, THF):Compound 6 (λ max = 756 nm, THF):
Figure imgf000024_0003
Figure imgf000024_0003
Verbindung 7 (λmax= 756 nm, THF):Compound 7 (λ max = 756 nm, THF):
Figure imgf000025_0001
Figure imgf000025_0001
Verbindung 8:Compound 8:
Figure imgf000025_0002
Figure imgf000025_0002
Verbindung 9 (λmax= 670 nm, THF):Compound 9 (λ max = 670 nm, THF):
Figure imgf000025_0003
Figure imgf000025_0003
Die trisubstituierte Verbindung wurde als Nebenprodukt bei der Herstellung von Verbindung 8 erhalten. Verbindung 10 (λmax= 643 nm, THF):The trisubstituted compound was obtained as a by-product in the preparation of compound 8. Compound 10 (λ max = 643 nm, THF):
Figure imgf000026_0001
Figure imgf000026_0001
S.G. 33 (kommerziell erhältlich von BASF Aktiengesellschaft)S.G. 33 (commercially available from BASF Aktiengesellschaft)
Verbindung 11 (λmax= 328 nm, THF):Compound 11 (λ max = 328 nm, THF):
Figure imgf000026_0002
Figure imgf000026_0002
(kommerziell erhältlich von BASF Aktiengesellschaft)(commercially available from BASF Aktiengesellschaft)
Verbindung 12 (λmax= 648 nm, THF):Compound 12 (λ max = 648 nm, THF):
R: Mischung der ResteR: mixture of the radicals
Figure imgf000026_0003
Figure imgf000026_0003
S.B. 79 (kommerziell erhältlich von BASF Aktiengesellschaft) SB 79 (commercially available from BASF Aktiengesellschaft)
Vergleich (λmax= 770 nm, THF):Comparison (λ max = 770 nm, THF):
Als Vergleichsverbindung diente das Phthalocyanin der nachfolgenden Formel:As a comparative compound, the phthalocyanine of the following formula was used:
Figure imgf000027_0001
(hergestellt gemäß Beispiel 1 von WO 98/52950 A1 )
Figure imgf000027_0001
(prepared according to Example 1 of WO 98/52950 A1)
Versuche zur Lagerbeständigkeit:Tests for storage stability:
Die verwendete Testmischung eines Kraft- und Schmierstoffadditiv-Konzentrats mit den darin enthaltenen Komponenten und ihren jeweilige Anteilen ist nachfolgend in Tabelle 1 aufgeführt:The 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:
Tabelle 1:Table 1:
Figure imgf000027_0002
Figure imgf000027_0002
(Detergens, Trägeröl, Korrosionsschutz und Demulgator sind z.B. von bzw. über BASF Aktiengesellschaft kommerziell erhältlich) Die Lagerbeständigkeit der Verbindungen 1 bis 9 und der Vergleichsverbindung gegenüber den in Tabelle 1 genannten Hauptbestandteilen Detergens und Trägeröl wurde untersucht. Hierzu wurden 50 bis 100 mg der jeweiligen Verbindung in 50 ml Shellsol AB gelöst oder, sofern die Löslichkeit der Verbindung in Shellsol AB nicht ausreichend war, diese erst mit ca. 5 ml Isopropanol oder NMP angelöst und dann mit Shellsol AB auf 50 ml aufgefüllt. Anschliessend wurde die Lösung durch einen Papier-Faltenfilter filtriert.(Detergent, carrier oil, corrosion protection and demulsifier are commercially available, for example, from or via BASF Aktiengesellschaft) The storage stability of the compounds 1 to 9 and the comparative compound with respect to the main constituents detergent and carrier oil mentioned in Table 1 was investigated. For this purpose, 50 to 100 mg of the respective compound were dissolved in 50 ml of Shellsol AB or, if the solubility of the compound in Shellsol AB was insufficient, first solubilized with about 5 ml of isopropanol or NMP and then made up to 50 ml with Shellsol AB. Subsequently, the solution was filtered through a paper-folded filter.
1 bis 3 ml des Filtrats wurden mit Detergens oder Trägeröl auf 10 ml aufgefüllt (entsprechend einer Konzentration der jeweiligen Verbindung von 0,01 bis 0,08 %) und in 1mm-Küvetten gegen die entsprechende nicht-additivierte Referenz gemessen.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.
Die Proben wurden in 10-ml-Ampullen gefüllt, luftdicht verschlossen und bei 50°C im Wasserbad gelagert.The samples were filled in 10 ml ampoules, sealed airtight and stored at 50 ° C in a water bath.
Die Ergebnisse sind in den Tabellen 2 und 3 wiedergegeben. Bei allen Versuchen wurden auf die Anfangsextinktion normiert.The results are shown in Tables 2 and 3. All experiments normalized to the initial absorbance.
Tabelle 2: Vergleich der Lagerbeständigkeit bei 50°C gegenüber dem DetergensTable 2: Comparison of the shelf life at 50 ° C versus the detergent
Figure imgf000028_0001
Tabelle 3: Vergleich der Lagerbeständigkeit bei 50°C gegenüber dem Trägeröl
Figure imgf000028_0001
Table 3: Comparison of the storage stability at 50 ° C compared to the carrier oil
Figure imgf000029_0001
Figure imgf000029_0001
Die Vergleichsverbindung zeigte bei Anwesenheit von Trägeröl einen deutlich schnelleren Abfall der normierten Extinktion in Abhängigkeit von der Zeit als imIn the presence of carrier oil, the comparison compound showed a significantly faster decrease in the normalized extinction as a function of time
Falle der Anwesenheit von Detergens. Die Werte wurden daher nicht wiedergegeben.Case of the presence of detergent. The values were therefore not reproduced.
B) Die Lagerbeständigkeit der Verbindungen 10 bis 12 gegenüber Detergens und dem Kraft- und Schmierstoffadditiv-Konzentrat aus Tabelle 1 wurde untersucht.B) The shelf life of compounds 10 to 12 over detergent and the Kraft and lubricant additive concentrate from Table 1 was examined.
Hierzu stellte man Lösungen mit einem Gehalt von 1 Gew.-% der Verbindungen 10 bis 12 im Detergens bzw. dem Kraft- und Schmierstoffadditiv-Konzentrat her und bestimmte die normierte Extinktion in Abhängigkeit von der Lagerzeit sowohl bei Raumtemperatur als auch bei 40°C. Die Normierung erfolgte auf den Extink- tionswert bei Start der Lagerung (d.h. unmittelbar nach Herstellung der entsprechenden Lösung). Die Ergebnisse sind nachfolgend aufgeführt.For this purpose, 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.
Verbindung 10:Connection 10:
Detergens bei Raumtemperatur: nach Lagerzeiten von 7 und 14 Tagen konnte keine Veränderung der normierten Extinktion festgestellt werden.Detergent at room temperature: after storage times of 7 and 14 days, no change in the normalized extinction could be detected.
Detergens bei 40°C: nach Lagerzeiten von 7 und 14 Tagen konnte keine Veränderung der normierten Extinktion festgestellt werden.Detergent at 40 ° C: after storage times of 7 and 14 days, no change in the normalized extinction could be detected.
Kraft- und Schmierstoffadditiv-Konzentrat bei Raumtemperatur: nach Lagerzeiten von 7 und 14 Tagen konnte keine Veränderung der normierten Extinktion festgestellt werden.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- und Schmierstoffadditiv-Konzentrat bei 40°C: nach Lagerzeiten von 7 und 14 Tagen konnte keine Veränderung der normierten Extinktion festgestellt werden. Verbindung 11 :Fuel and lubricant additive concentrate at 40 ° C: after storage times of 7 and 14 days, no change in the normalized extinction could be detected. Connection 11:
Detergens bei Raumtemperatur: nach Lagerzeiten von 4, 12, 28 und 42 Tagen konnte keine Veränderung der normierten Extinktion festgestellt werden.Detergent at room temperature: after storage times of 4, 12, 28 and 42 days, no change in the normalized extinction could be detected.
Detergens bei 40°C: nach Lagerzeiten von 4, 12, 28 und 42 Tagen konnte keine Veränderung der normierten Extinktion festgestellt werden.Detergent at 40 ° C: after storage times of 4, 12, 28 and 42 days, no change in the normalized extinction could be detected.
Kraft- und Schmierstoffadditiv-Konzentrat bei Raumtemperatur: nach Lagerzeiten von 21 und 28 Tagen konnte keine Veränderung der normierten Extinktion festgestellt werden.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.
Kraft- und Schmierstoffadditiv-Konzentrat bei 40°C: nach Lagerzeiten von 21 und 28 Tagen konnte keine Veränderung der normierten Extinktion festgestellt werden.Fuel and lubricant additive concentrate at 40 ° C: after storage times of 21 and 28 days, no change in the normalized extinction could be detected.
Verbindung 12:Connection 12:
Detergens bei Raumtemperatur: nach Lagerzeiten von 4, 12, 28 und 42 Tagen konnte im Wesentlichen keine Veränderung der normierten Extinktion festgestellt werden. Die Ergebnisse zeigt nachfolgende Tabelle:Detergent at room temperature: after storage times of 4, 12, 28 and 42 days, essentially no change in the normalized extinction could be detected. The results are shown in the following table:
Figure imgf000030_0001
Figure imgf000030_0001
Detergens bei 40°C: nach Lagerzeiten von 4, 12, 28 und 42 Tagen konnte im Wesentlichen keine Veränderung der normierten Extinktion festgestellt werden. Die Ergebnis- se zeigt nachfolgende Tabelle:Detergent at 40 ° C: after storage times of 4, 12, 28 and 42 days, essentially no change in the normalized extinction could be detected. The results are shown in the following table:
Figure imgf000030_0002
Figure imgf000030_0002

Claims

Patentansprüche claims
Kraft- und Schmierstoffadditiv-Konzentrate, enthaltend mindestens ein Anthrachinonderivat als Markierungsstoff.Kraft and lubricant additive concentrates containing at least one anthraquinone derivative as a marker.
Konzentrate nach Anspruch 1 , enthaltend mindestens ein Anthrachinonderivat ausgewählt aus der Gruppe bestehend aus den Verbindungen der Formel IConcentrates according to Claim 1, containing at least one anthraquinone derivative selected from the group consisting of the compounds of the formula I.
Figure imgf000031_0001
der Formel II
Figure imgf000031_0001
of formula II
Figure imgf000031_0002
und der Formel
Figure imgf000031_0002
and the formula
Figure imgf000031_0003
worin bedeuten
Figure imgf000031_0003
in which mean
Z , Z^ unabhängig voneinander Wasserstoff, Hydroxy, OR, NHR oder NR2) Z, Z ^ independently of one another hydrogen, hydroxy, OR, NHR or NR 2)
R , R unabhängig voneinander R oder COR, X Wasserstoff, Cyano, Nitro, Hydroxy, OR, Amino, NHR, R oderR, R independently of one another R or COR, X is hydrogen, cyano, nitro, hydroxy, OR, amino, NHR, R or
CH(R9)(R10)CH (R 9 ) (R 10 )
n, m 0, 1 , 2, 3 oder 4, wobei jeweils für n bzw. m größer als 1 die Reste R bzw. X gleich oder voneinander verschieden sind,n, m is 0, 1, 2, 3 or 4, wherein in each case for n or m greater than 1 the radicals R and X are the same or different from one another,
R9, R10 unabhängig voneinander Cyano, COOH oder COOR,R 9 , R 10 independently of one another cyano, COOH or COOR,
R3 Wasserstoff, R oder NHR,R 3 is hydrogen, R or NHR,
R4 bis R8 unabhängig voneinander Wasserstoff, R oder NHRR 4 to R 8 are independently hydrogen, R or NHR
undand
R CrC2o-Alkyl, das gegebenenfalls durch 1 bis 4 Sauerstoffatome inR is CrC 2 o-alkyl optionally substituted by 1 to 4 oxygen atoms in
Etherfunktion unterbrochen ist, C5-C -Cycloalkyl, das gegebenenfalls mit einer oder mehreren Cι-C2o-Alkylgruppen, die gegebenenfalls durch 1 bis 4 Sauerstoffatome in Etherfunktion unterbrochen sind, substituiert ist, gesättigter heterocyclischer fünf- oder sechsgliedrigerEther function is interrupted, C 5 -C -cycloalkyl which is optionally substituted by one or more -CC 2 o-alkyl groups which are optionally interrupted by 1 to 4 oxygen atoms in ether function, saturated heterocyclic five- or six-membered
Rest, der gegebenenfalls mit einer oder mehreren Cι-C20-Alkyl- gruppen, die gegebenenfalls durch 1 bis 4 Sauerstoffatome in Etherfunktion unterbrochen sind, substituiert ist, C6-Cι0-Aryl, das gegebenenfalls mit einem oder mehreren Halogen, Cyano, Nitro, Hydroxy, Amino, Cι-C20-Alkyl, das gegebenenfalls durch 1 bis 4 Sauerstoffatome in Etherfunktion unterbrochen ist, d-C2o-Alkoxy, CrC2o-Alkyl- amino oder Cι-C2o-Dialkylamino substituiert ist, Heteroaryl mit 3 bis 12 Kohlenstoffatomen, das gegebenenfalls mit einem oder mehreren CrC∑o-Alkyl, das gegebenenfalls durch 1 bis 4 Sauerstoffatome in Etherfunktion unterbrochen ist, Cι-C20-Alkoxy, C -C20-Alkylamino oderRadical which is optionally substituted with one or more Cι-C groups 20 -alkyl, which are optionally interrupted by from 1 to 4 oxygen atoms in ether function, C 6 -Cι 0 aryl, optionally substituted with one or more halogen, cyano, Nitro, hydroxy, amino, -CC 20 alkyl which is optionally interrupted by 1 to 4 oxygen atoms in ether function, dC is 2 o-alkoxy, CrC 2 o-alkyl-amino or -CC 2 o-dialkylamino substituted, heteroaryl with 3 to 12 carbon atoms, optionally with one or more CrC Σ o-alkyl, which is optionally interrupted by 1 to 4 oxygen atoms in ether function, -C-C 20 alkoxy, C -C 20 alkylamino or
Cι-C2o-Dialkylamino substituiert ist, C6-Cι0-Aryl-Cι-C4-alkyl, das im Arylrest gegebenenfalls mit einem oder mehreren Halogen, Cyano, Nitro, Hydroxy, Amino, CrC2o-Alkyl, das gegebenenfalls durch 1 bis 4 Sauerstoffatome in Etherfunktion unterbrochen ist,
Figure imgf000032_0001
Cι-C20-Alkylamino oder Cι-C20-Dialkylamino substituiert ist, oder He- teroaryl-C -C -alkyl mit 3 bis 12 Kohlenstoffatomen im Heteroarylrest, wobei letzterer gegebenenfalls mit einem oder mehreren CrC2o-Alkyl, das gegebenenfalls durch 1 bis 4 Sauerstoffatome in Etherfunktion unterbrochen ist, Cι-C20-Alkoxy, C1-C20-Alkylamino oder C C2o-Di- alkylamino substituiert ist. Konzentrate nach Anspruch 2, dadurch gekennzeichnet, dass in Formel I und Formel II bedeutenCι-C 2 is substituted o-dialkylamino, C 6 -aryl -Cι 0-Cι-C 4 -alkyl, which in the aryl radical optionally substituted by one or more halogen, cyano, nitro, hydroxy, amino, CrC 2 O-alkyl optionally interrupted by 1 to 4 oxygen atoms in ether function,
Figure imgf000032_0001
Cι-C 20 alkylamino or Cι-C 20 -dialkylamino groups, or He-teroaryl-C -C alkyl having 3 to 12 carbon atoms in the heteroaryl radical, the latter optionally being substituted by one or more C 2 o-alkyl optionally substituted by 1 is interrupted in ether function to 4 oxygen atoms, Cι-C 20 alkoxy, C 1 -C 20 alkylamino or C 2 o-di- alkylamino. Concentrates according to claim 2, characterized in that in formula I and formula II mean
Z1 , Z2 unabhängig voneinander Wasserstoff oder NHR,Z 1 , Z 2 independently of one another are hydrogen or NHR,
R1, R2 unabhängig voneinander R,R 1 , R 2 independently of one another R,
X Wasserstoff, Cyano oder CH(R9)(R10),X is hydrogen, cyano or CH (R 9 ) (R 10 ),
n, m 0, 1 , n, m 0, 1,
2, 2,
3 oder 4, wobei für n bzw. m größer als 1 die Reste R bzw. X gleich oder voneinander verschieden sind,3 or 4, where, for n or m greater than 1, the radicals R and X are the same or different from each other,
R9, R10 unabhängig voneinander Cyano oder COOR,R 9 , R 10 independently of one another cyano or COOR,
R3 Wasserstoff, R oder NHR,R 3 is hydrogen, R or NHR,
R4 bis R7 Wasserstoff oder NHR,R 4 to R 7 are hydrogen or NHR,
R8 NHRR 8 NHR
undand
R Ci-Cis-Alkyl, das gegebenenfalls durch 1 bis 4 Sauerstoffatome in E- therfunktion unterbrochen ist, Cyclohexyl, das gegebenenfalls mit einer oder mehreren Cι-Cι5-Alkylgruppen, die gegebenenfalls durch 1 bis 4 Sauerstoffatome in Etherfunktion unterbrochen sind, substituiert ist, gesättigter heterocyclischer fünf- oder sechsgliedriger Rest, der gegebenenfalls mit einer oder mehreren Cι-C 5-Alkylgruppen, die gegebenenfalls durch 1 bis 4 Sauerstoffatome in Etherfunktion unterbrochen sind, substituiert ist, C6-Cι0-Aryl, das gegebenenfalls mit einem oder mehreren Cι-C 5-Alkyl, das gegebenenfalls durch 1 bis 4 Sauerstoffatome in Etherfunktion unterbrochen ist, CrCι5-Alkoxy, Cι-Ci5-Alkylamino oder C Cι5-Dialkylamino substituiert ist, Hetero- aryl mit 3 bis 5 Kohlenstoffatomen, das gegebenenfalls mit einem o- der mehreren C -C15-Alkyl, das gegebenenfalls durch 1 bis 4 Sauerstoffatome in Etherfunktion unterbrochen ist, CrC15-Alkoxy, Cι-Cι5-Alkylamino oder C C 5-Dialkylamino substituiert ist, Phenyl- Cι-C -alkyl, das im Phenylrest gegebenenfalls mit einem oder mehre- ren CrC15-Alkyl, das gegebenenfalls durch 1 bis 4 Sauerstoffatome in Etherfunktion unterbrochen ist, Cι-C15-Alkoxy, Cι-Cι5-Alkylamino oder Cι-Cι5-Dialkylamino substituiert ist, oder Heteroaryl-Cι-C4-alkyl mit 3 bis 5 Kohlenstoffatomen im Heteroarylrest, wobei letzterer gegebe- nenfalls mit einem oder mehreren Cι-Cι5-Alkyl, das gegebenenfalls durch 1 bis 4 Sauerstoffatome in Etherfunktion unterbrochen ist, Ci-C s-Alkoxy, Cι-Cι5-Alkylamino oder C -Cι5-Dialkylamino substituiert ist.R Ci-Cis-alkyl, which is optionally interrupted by 1 to 4 oxygen atoms in ether function, cyclohexyl, 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 , 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 0 -aryl which is optionally substituted by one or more more Cι-C 5 -alkyl which is optionally interrupted by 1 to 4 oxygen atoms in ether function, CrCι 5 -alkoxy, Ci5-alkylamino or C Cι substituted 5 dialkylamino, hetero aryl having 3 to 5 carbon atoms which is optionally substituted with one or more C -C 15 -alkyl which is optionally interrupted by 1 to 4 oxygen atoms in ether function, -C 15 -alkoxy, Cι 5 alkylamino or C 5 -di alkylamino, phenyl-C 1 -C 4 -alkyl which is optionally substituted in the phenyl radical by one or more ren C 1 -C 15 -alkyl, which is optionally interrupted by 1 to 4 oxygen atoms in ether function, -CC 15 alkoxy, -CC 5 alkylamino or -CC 5- dialkylamino is substituted, or heteroaryl-C 4 -alkyl with 3 to 5 carbon atoms in the heteroaryl radical, the latter optionally with one or more -CC 5 alkyl, which is optionally interrupted by 1 to 4 oxygen atoms in ether function, Ci-C s-alkoxy, -CC 5 alkylamino or C -C 5 -dialkylamino is substituted.
4. Verwendung der Konzentrate nach einem oder mehreren der Ansprüche 1 bis 3 zur Additivierung von Mineralölen.4. Use of the concentrates according to one or more of claims 1 to 3 for the additive of mineral oils.
5. Mineralöle, enthaltend Konzentrate nach einem oder mehreren der Ansprüche 1 bis 3. 5. mineral oils containing concentrates according to one or more of claims 1 to 3.
PCT/EP2004/014587 2003-12-23 2004-12-22 Power and lubricant additive concentrates containing at least one anthrachinone derivative as a marking substance WO2005063942A1 (en)

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AU2004309053A AU2004309053B2 (en) 2003-12-23 2004-12-22 Power and lubricant additive concentrates containing at least one anthrachinone derivative as a marking substance
JP2006546049A JP2007515532A (en) 2003-12-23 2004-12-22 Concentrate of fuel and lubricant additive containing at least one anthraquinone derivative as labeling 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
CA002549647A CA2549647A1 (en) 2003-12-23 2004-12-22 Fuel and lubricant additive concentrates comprising at least one arthraquinone derivative as a marker
MXPA06006135A MXPA06006135A (en) 2003-12-23 2004-12-22 Power and lubricant additive concentrates containing at least one anthrachinone derivative as a marking substance.
EP04804183A EP1699907A1 (en) 2003-12-23 2004-12-22 Power and lubricant additive concentrates containing at least one anthrachinone derivative as a marking substance
BRPI0417837-8A BRPI0417837A (en) 2003-12-23 2004-12-22 fuel and lubricant additive concentrate, concentrate use, and, mineral oil

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WO2020239942A1 (en) * 2019-05-31 2020-12-03 Katholieke Universiteit Leuven Multi-electron redox-active organic molecules for high-energy-density nonaqueous redox flow batteries
WO2022026225A1 (en) * 2020-07-29 2022-02-03 Dow Global Technologies Llc Aromatic hydrocarbon-soluble anthraquinone
ES2957535A1 (en) * 2022-06-08 2024-01-22 Kemegal Quim S L FUEL ADDITIVE FOR INTERNAL COMBUSTION ENGINES (Machine-translation by Google Translate, not legally binding)

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US8664442B2 (en) * 2008-09-09 2014-03-04 Chemtura Corporation Anti-oxidants
WO2011032857A2 (en) 2009-09-15 2011-03-24 Basf Se Use of derivatives of aromatic compounds as markers for liquids
FR2971254B1 (en) 2011-02-08 2014-05-30 Total Raffinage Marketing LIQUID COMPOSITIONS FOR MARKING LIQUID HYDROCARBON FUELS AND FUELS, FUELS AND FUELS CONTAINING THEM, AND METHOD OF DETECTING MARKERS

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WO2020239942A1 (en) * 2019-05-31 2020-12-03 Katholieke Universiteit Leuven Multi-electron redox-active organic molecules for high-energy-density nonaqueous redox flow batteries
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