EP1861482A2 - Utilisation de derives dibenzanthrone et isodibenzanthrone en tant que marqueurs de liquides - Google Patents

Utilisation de derives dibenzanthrone et isodibenzanthrone en tant que marqueurs de liquides

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Publication number
EP1861482A2
EP1861482A2 EP06708710A EP06708710A EP1861482A2 EP 1861482 A2 EP1861482 A2 EP 1861482A2 EP 06708710 A EP06708710 A EP 06708710A EP 06708710 A EP06708710 A EP 06708710A EP 1861482 A2 EP1861482 A2 EP 1861482A2
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EP
European Patent Office
Prior art keywords
alkyl
alkylamino
optionally
substituted
oxygen atoms
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP06708710A
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German (de)
English (en)
Inventor
Sophia Ebert
Rüdiger Sens
Christos Vamvakaris
Wolfgang Ahlers
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BASF SE
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BASF SE
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Publication of EP1861482A2 publication Critical patent/EP1861482A2/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B3/00—Dyes with an anthracene nucleus condensed with one or more carbocyclic rings
    • C09B3/02—Benzathrones
    • C09B3/06—Preparation from starting materials already containing the benzanthrone nucleus
    • 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
    • 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
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2070/00—Specific manufacturing methods for lubricant compositions
    • C10N2070/02—Concentrating of additives

Definitions

  • the present invention relates to the use of dibenzanthrone derivatives of general formula Ia
  • X Y 2 independently of one another are -O-, -S-, -NH-, -NY-, -CO-, -O-CO-, -CO-O-, -S-CO-, -CO-S-, -NH-CO-, -CO-NH-, -NY-CO-, -CO-NY-, -CH 2 -NH-, -CH 2 -NY-, -CH 2 -NH-CO- or -CH 2 -NY-CO-, where the four last-mentioned groups are each attached via the CH 2 group to the dibenzanthrone or isodibenzanthrone skeleton,
  • C 5 -C 7 -cycloalkyl which is optionally substituted by one or more C 1 -C 20 -alkyl groups which are optionally interrupted by 1 to 4 oxygen atoms in ether function; saturated heterocyclic five- or six-membered radical optionally substituted with one or more C 1 -C 4 -alkyl groups optionally interrupted by 1 to 4 oxygen atoms in ether function;
  • C 6 -C 0 aryl optionally substituted with one or more halogen, cyano, nitro, hydroxy, amino, C 1 -C 20 -AIRyI, which is optionally interrupted by 1 to 4 oxygen atoms in ether function, C 1 -C 2O - AIkOXy, Ci-C 20 -alkylamino or di (C 1 -C 20 -alkyl) amino substituted;
  • C 6 -C 10 aryl-Ci-C 4 alkyl which in the aryl radical optionally substituted by one or more halogen, cyano, nitro, hydroxy, amino, C r C 20 -alkyl which may be interrupted by 1 to 4 oxygen atoms in ether function is C 1 -C 2O -alkoxy, C ⁇ C ⁇ alkylamino or di (alkyl -C 20) amino group;
  • n, m are integer values from 1 to 16, where, for n> 1 or m> 1, the n groupings (X 1 -R 1 ) or the m groups (X 2 -R 2 ) may be identical or different.
  • the present invention relates to fuel and lubricant additive concentrates which contain at least one dibenzanthrone derivative of the general formula Ia or an isodibenzanthrone derivative of the general formula Ib, and mineral oils which contain at least one dibenzanthrone derivative of the general formula Ia or an isodibenzenthrone derivative.
  • Derivative of the general formula Ib or inventive fuel and lubricant additive concentrates 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.
  • packages allow various mineral oil distribution companies to supply themselves from a "pool” of unadditized mineral oil and only with the help of their individual packages give the mineral oil, eg during filling into appropriate transport containers, the company-specific additives, colouration and marking.
  • the markers for liquids and in particular for mineral oils are usually substances which are either extracted from the liquid or the mineral oil and then converted by derivatization into colored compounds, or to substances which are visible both in the visible and in the non-visible wavelength range of the spectrum show absorption (eg 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 (e.g., WO
  • Anthraquinone derivatives for coloring petrol or mineral oils are described in US Pat. Nos. 2,611,772, 2,068,372, EP 1 001 003 A1 and EP 1 323 811 A2.
  • Fluorescent isodibenzanthracene and dibenz-anthracene derivatives (hereinafter these compounds are also referred to as "(iso) dibenzanthracenes” and their corresponding diketo compounds as “(iso) dibenzanthrones”) and their preparation from suitably substituted (iso) dibenzanthrone precursor compounds are disclosed in U.S. Pat Document US 6,215,008 described.
  • (iso) -Dibenzanthracen derivatives for the marking of individual liquid flows in complex installations with a variety of liquid-conducting pipelines and generally for marking liquids, in particular mineral oils referenced.
  • markers are sufficiently stable in the pure liquids which they are intended to mark and in the normally low concentration in which they are present. However, if other ingredients are present in addition to the markers, it may lead to unwanted degradation reactions of the marker - the marking is lost.
  • the object of the present invention was therefore to provide marking substances which are distinguished by very good long-term stability in the liquids to be marked, in particular mineral oils, especially in the presence of further components present in the liquids, in particular mineral oils.
  • linking groups X 1 and X 2 in the formulas Ia and Ib mean the meaning
  • all n or m groups X 1 or X 2 are attached to the (iso) dibenzanthrone skeleton either via the carbonyl group or via the heteroatom.
  • linking groups X 1 and X 2 in formulas Ia and Ib have the meaning -CH 2 -NH-, -CH 2 -NY-, -CH 2 -NH-CO- or -CH 2 -NY-CO-, their attachment to the (iso) dibenzanthrone skeleton occurs via the CH 2 group.
  • n or m groups X 1 or X 2 in the respective formulas Ia and Ib may be different from one another.
  • the n or m groups X 1 and X 2 in the respective formulas Ia and Ib are the same and, if different connections to the (iso) dibenzanthrone skeleton are possible, connected in the same way.
  • n or m radicals R 1 or R 2 in the respective formulas Ia and Ib may be different from one another.
  • n or m groups R 1 and R 2 in the respective formulas Ia and Ib are the same.
  • n or m groups X 1 R 1 or X 2 R 2 in the respective formulas Ia and Ib may be different from one another.
  • n or m groups X 1 R 1 or X 2 R 2 in the respective formulas Ia and Ib are preferably the same. This means that the respectively n or m identical radicals R 1 and R 2 in the same way via the linking groups X 1 and X 2 are attached to the (iso) - dibenzanthrone skeleton, if there are different possibilities in the latter groups the connection gives.
  • R 1 , R 2 and Y are: as CrC 2 o-alkyl which is optionally interrupted by 1 to 4 oxygen atoms in ether function, 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 Designations isooctyl, isononyl, isodecyl and isotri
  • Tetradecyl pentadecyl, hexadecyl, heptadecyl, octadecyl, imonadecyl, 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-butoxypropyl, 2- or 4-M ethoxybutyl, 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-dioxan
  • C 5 -C 7 -cycloalkyl radicals cyclopentyl, cyclohexyl and cycloheptyl.
  • These cycloalkyls are optionally substituted by one or more, in particular up to three C 1 -C 2 O-alkyl groups, the latter being optionally interrupted by 1 to 4 oxygen atoms in ether function. Examples of such optionally interrupted by oxygen atoms C r C 2 o-alkyl groups have already been mentioned previously;
  • C 6 -C 10 -aryl in particular phenyl and naphthyl.
  • phenyl and naphthyl are optionally xy with one or more halogen, such as fluorine, chlorine or bromine, cyano, nitro, hydro-, amino, C r C 20 alkyl, which is optionally interrupted by 1 to 4 oxygen atoms in ether function, C 1 -C 20- alkoxy, substituted.
  • halogen such as fluorine, chlorine or bromine, cyano, nitro, hydro-, amino, C r C 20 alkyl, which is optionally interrupted by 1 to 4 oxygen atoms in ether function, C 1 -C 20- alkoxy, substituted.
  • C 1 -C 4 -alkyl substituents which may be replaced by 1 to 4 oxygen atoms are interrupted in ether function, or Ci-C 2 o-alkyl radicals, which in the Ci-C 20 -Aikoxy-, Ci-C 20 -Alkylamino- or Ci-C 20 -Dialkylaminosubstienten are included, were already listed by way of example.
  • heteroaryl radicals having 3 to 12 carbon atoms which are optionally interrupted by one or more C 1 -C 20 -alkyl which is optionally interrupted by 1 to 4 oxygen atoms in ether function, C 1 -C 20 -alkoxy, C 1 -C 20 -alkylamino or C 1 -C 4 - Dialkylamino are substituted, such radicals, for example, derived from pyrrole, furan, thiophene, pyrazole, isoxazole, isothiazole, imidazole, 1 H-1, 2,3-triazole, 1H-1, 2,4-triazole, pyridine , Pyrazine, pyridazine, 1 H-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 faced rings such as quinoline, isoquinoline, indole, benzo [b] furan (coumarone) , Benzo [b] thiophene (thionaphthene), carbazole, dibenzofuran, dibenzothiophene, 1H-indazole, indoxazole, benzo [d] isothiazole, anthranil, benzimidazole, benzoxazole, benzothiazole, cinnoline, phthalazine, quinazoline, quinoxaline or phenazine.
  • C 1 -C 20 -alkyl substituents which are optionally interrupted by 1 to 4 oxygen atoms in ether function, or C r C 20 -alkyl radicals which in the Ci-C 20 alkoxy, C 1 - C 20 -Alkylamino- or Ci-C 2o -Dialkylaminosubstituenten are included, have already been listed by way of example;
  • aryl radical when which in the aryl radical optionally substituted by one or more halogen, cyano, nitro, hydroxy, amino, CrC 20-alkyl, which is optionally interrupted by 1 to 4 oxygen atoms in ether function, C r C 2 -alkoxy, C r C 20 alkyl amino or C r C 20 dialkylamino, in particular benzyl, phenylethyl, 3-phenylpropyl and 4-phenylbutyl.
  • C 1 -C 4 -alkyl radicals which are optionally interrupted by 1 to 4 oxygen atoms in ether function, or C 1 -C 20 -alkyl radicals which are bonded to the C 1 -C 20 -alkoxy, C 1 -C 4 -alkylamino or C 1 -C 20 -alkyl radicals.
  • C 20 -Dialkylamino- groups are included, have already been listed by way of example;
  • heteroaryl-C 1 -C 4 alkyls having 3 to 12 carbon atoms in the heteroaryl radical, the latter optionally substituted by one or more Ci-C 20 alkyl, which is optionally interrupted by 1 to 4 oxygen atoms in ether function, C 1 -C 20 - AIkOXy, C 1 -C 20 - alkylamino or Ci-C 20 -Dialkylamino are derived, for example, from the above-mentioned heteroaryl, those which are attached to the C 1 -C 4 - alkyl radicals either via a carbon atom or a to Bonding suitable heteroatom of the heteroaryl are attached.
  • X 1 , X 2 independently of one another are -O-, -S-, -NH-, -NY-, -CO-, -O-CO-, -CO-O-, -S-CO-, -CO-S-, -NH-CO-, -CO-NH-, -NY-CO- or -CO-NY-
  • Cyclohexyl which is optionally substituted by one or more C 1 -C 15 -AlkVIgOIp- pen, which are optionally interrupted by 1 to 4 oxygen atoms in ether function, is substituted;
  • C 6 -C 10 aryl which is optionally substituted with one or more C 1 -C 15 -alkyl, which is optionally interrupted by 1 to 4 oxygen atoms in ether function, C 1 -C 15 -alkoxy, C r C 15 alkylamino or di (C r C 15) alkylamino;
  • Phenyl-d ⁇ -alkyl which in the phenyl radical optionally substituted with one or more C 15 -alkyl which is optionally interrupted by 1 to 4 oxygen atoms in ether function, C 1 -C 15 -alkoxy 1 CrC ⁇ alkylamino or di (Ci-C 15 ) alkylamino is substituted;
  • n, m are integer values from 1 to 8, where, for n> 1 or m> 1, the n groupings (X 1 -R 1 ) or the m groups (X 2 -R 2 ) may be identical or different.
  • X 1 , X 2 are independently -O-, -NH-, -NY-, -CO-, -O-CO-, -CO-O-
  • Cyclohexyl optionally substituted with one or more C 1 -C 15 alkyl groups
  • Phenyl which r C 15 alkyl, C 1 -C 15 optionally substituted with one or more C - alkoxy, CrC ⁇ alkylamino or di (C r C 15) alkylamino group;
  • Phenyl-Ci-C4-alkyl which is substituted in the phenyl radical optionally substituted with one or more C r C 15 alkyl, C 1 -C 15 -alkoxy, CrC ⁇ alkylamino or di (C r C 15) alkyl amino;
  • Heteroaryl-C 1 -C 4 -alkyl having 3 to 5 carbon atoms in the heteroaryl radical the latter optionally with one or more dC 15 alkyl, C 1 -C 15 alkoxy, C r C 15 alkylamino or di (C r Ci 5 ) alkylamino is substituted,
  • n, m are integer values from 1 to 8, where, for n> 1 or m> 1, the n groupings (X 1 -R 1 ) or the m groups (X 2 -R 2 ) may be identical or different.
  • n or m assumes values of 1 to 4, in particular values of 2 or 3.
  • the compounds of the formulas Ia and Ib to be used according to the invention can be prepared by the customary methods of organic synthesis, it being sensible to start from corresponding starting materials with (iso) dibenzanthrone skeleton.
  • the alkoxy-substituted (iso) dibenzanthrones can be prepared from the corresponding hydroxy compounds by etherification under the customary conditions known to the person skilled in the art.
  • the preparation of 3,4,11,12-tetrahydroxydibenzanthrone and 1,2,10,11-tetrahydroxyisodibenzanthrone as possible starting compounds are described, for example, in KS Nair, KH Shah, Bull. Chem. Soc. Japan, 39, (1966), 2023-2026.
  • the preparation of further alkoxy-substituted and substituted (iso) dibenzanthrones containing other Group-linking groups X 1 and X 2 contained in the substituents is for example described in US 4,486,587.
  • Alkylthio, arylthio, alkylamino, dialkylamino or arylamino-substituted (iso) dibenzanthrones are, for example, by reacting the corresponding halogenated, usually chlorinated or brominated, or nitrated compounds with the respective alkylthiols, arylthiols, alkylamines, dialkylamines or Arylaminen under the usual, known in the art conditions of nucleophilic aromatic substitution accessible.
  • Dibenzanthrones which have substituents -CH 2 -NY-CO-R can be prepared by reacting the (iso) dibenzanthrones with paraformaldehyde and the corresponding acid amides (or lactams) in polyphosphoric acid or sulfuric acid. This can be done, for example, in analogy to the methods described in EP 343 108 A2 and the earlier German patent application 10 2004 003791.4 for the synthesis of correspondingly substituted phthalocyanines.
  • the substituents -CH 2 -NY-CO-R 1 or -CH 2 -NY-CO-R 2 can also be introduced by reaction of the unsubstituted (iso) dibenzanthrones with the corresponding hydroxymethylated compounds in the presence of a concentrated acid (for example analogously to the preparation of correspondingly substituted phthalocyanines, as described in the earlier German patent application mentioned above), the hydroxymethylated compounds being obtainable by general methods known to the person skilled in the art.
  • the preparation of hydroxymethyllactams from lactams is described, for example, in US Pat. Nos. 4,769,454 and 3,073,843.
  • the degree of substitution of (iso) dibenzanthrones and thus their solubility is controlled.
  • the degree of substitution can be determined, for example, by mass spectroscopy.
  • Liquids which can be labeled according to the invention with the (iso) dibenzanthrones of the formulas Ia and Ib and their preferred embodiments are, in particular, organic liquids, 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 monomethyl or dimethyl ether, 1,2-ethylene glycol mono- or diethyl ether, 3-methoxypropanol, 3-isopropoxypropanol, tetrahydrofuran or dioxane
  • the (iso) dibenzanthrones of the formulas Ia and Ib and their preferred embodiments are used for marking mineral oils.
  • the liquids, in particular the mineral oils also several different dibenzanthrones of formula Ia and their preferred embodiments, several different Isodibenzanthrone the formula Ib and their preferred embodiments or mixtures of dibenzanthrones and isodibenzanthrones may be added.
  • the (iso) dibenzanthrones of the formulas Ia and Ib and their preferred embodiments can also be used as a component in fuel and lubricant additive concentrates ("packages"), which in addition to a carrier oil and a mixture of different fuel additives usually also dyes and additionally contain markers.
  • packages which in addition to a carrier oil and a mixture of different fuel additives usually also dyes and additionally contain markers.
  • the present invention therefore also claims those fuel and lubricant additive concentrates which contain at least one dibenzanthrone derivative of the general formula Ia or an isodibenzene-anthrone derivative of the general formula Ib or preferred embodiments of these (iso) dibenzanthrones listed above.
  • 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 bis 1800, especially based on polybutene or polyisobutene (hydrogenated or non-hydrogenated), polyalphaolefins or polyinter- nalolefins 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 as carrier oils are described, for example, in document EP 277 345 A1, further polyalkene alcohol polyalkoxylates to be used in WO 00/50543 A1.
  • Other carrier oils to be used are also polyalkene alcohol-polyetheramines, 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.
  • 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.
  • Polyisobuteneamines which according to EP-A 244 616 by hydroformylation of highly reactive polyisobutene and subsequent reductive amination with ammonia, Monoamines or polyamines such as dimethyleneaminopropylamine, ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine are obtainable,
  • Poly (iso) buteneamines which are obtainable by chlorination of polybutenes or polyisobutenes having double bonds predominantly in the .beta. And .gamma. Position and subsequent amination with ammonia, monoamines or the abovementioned polyamines,
  • Polyisobuteneamines which are obtainable according to DE-A 196 20 262 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 476 485 by reacting polyisobutene epoxides with ammonia, monoamines or the abovementioned polyamines,
  • Polyetheramines which by reacting C 2 - to C 30 alkanols, C 6 - to C 30 -alkanediols, mono- or di-C 2 - to C 30 -alkylamines, C 1 - to C 30 -alkylcyclohexa-noles or C 1 - to C 30 -alkylphenols with 1 to 30 mol of ethylene oxide and / or propylene oxide and / or butylene oxide per hydroxyl or amino group and subsequent reductive amination with ammonia, monoamines or the abovementioned polyamines are obtainable, 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 are listed, for example, in the document WO 00/47698 A1 and comprise compounds which have at least one hydrophobic hydrocarbon radical with one have 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 may contain from the polyisobutene, which may contain up to 20% by weight of n-butene units, by hydroformylation and reductive amination with ammonia
  • Monoamines or polyamines such as dimethylaminopropylamine, ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine can be prepared, are known in particular from document EP 244 616 A2. If one starts with the preparation of the additives of polybutene or polyisobutene with predominantly intermediate double bonds (usually in the ⁇ and ⁇ position), the preparation route is afforded by chlorination and subsequent amination or by oxidation.
  • monoamino groups (i) containing additives are the polyisobutene epoxides by reaction with amines and subsequent dehydration and reduction of the amino alcohols obtainable compounds, as described in particular in the document DE 196 20 262 A1.
  • These reaction products typically are mixtures of pure nitropolyisobutanes (e.g., ⁇ , ⁇ -dinitropolyisobutane) and mixed hydroxynitropolyisobutanes (e.g., ⁇ -nitro- ⁇ -hydroxy polyisobutane).
  • 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 307 815 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 639 632 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 4 -alkylene (vi) containing additives are preferably polyethers or polyetheramines which are obtainable by reaction of C 2 - to C 60 alkanols, C 6 - to C 30 alkanediols, mono- or di-C 2 C 30 -alkylamines, Ci-C 30 -alkylcyclo-hexanoles or Ci-Cao-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 used in particular in the
  • 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, especially those having a minimum viscosity of 2 mm 2 / s at 100 0 C, as described in particular in DE 38 38 918 A1 are described.
  • Aliphatic or aromatic acids can be used as the mono-, di- or tricarboxylic acids, especially suitable as ester alcohols or polyols are long-chain representatives with, for example, 6 to 24 C atoms.
  • esters are adipates, phthalates, isophthalates, terephthalates and trimellitates of iso-octanol, iso-nonanol, iso-decanol and of isotridecanol. Such products also meet carrier oil properties.
  • derivatives with aliphatic polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine.
  • Such Otto fuel additives are described in particular in the document US 4,849,572.
  • 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 e.g. Alcohols, such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, pentanol, isopentanol, neopentanol or hexanol, e.g. 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, e.g.
  • 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
  • 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, e.g. Ketones such as acetone, methyl ethyl ketone or diacetone alcohol, e.g. Esters such as methyl acetate, ethyl acetate, propyl acetate or butyl acetate, e.g. Lactams, such as N-methylpyrrolidinone (NMP), e.g.
  • NMP N-methylpyrrolidinone
  • 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 e.g. Mineral oil, such as gasoline, kerosene, diesel oil or fuel oil,
  • 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-phenylenediamine, dicyclohexylamine or derivatives thereof or of phenols such as 2,4-di-tert-butylphenol or 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid,
  • 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. of the at least one dibenzanthrone of the formula Ia or isodibenzanthrone of the formula Ib or of the preferred embodiment of this (iso) dibenzanthrone, in the packages it is customary to select such a height that after addition of the package to the mineral oil the desired concentration of marking substance (s) 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 in the packages in a concentration of 1 to 50, in particular 5 to 30 wt .-%, and component c), i. 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 the components a) to c) and optionally d) to 100 wt .-% complements.
  • 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, their concentration in the sum is usually not more than 10 wt .-%, 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 contained in the packages, their concentration in the sum usually amounts to not more than 20 wt .-%, based on the total amount of the package.
  • solvents are usually derived from solutions of the markers and / or dyes which are added to the packages in the interests of more accurate metering, in place of the pure tags and / or dye.
  • component d further different marker substances from the dibenzanthrones of the formula Ia, isodibenzanthrones of the formula Ib or their preferred embodiments are contained in the packages, 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.
  • mineral oils which contain at least one dibenzanthrone derivative of the general formula Ia or at least one isodibenzanthrone derivative of the general formula Ib or its preferred embodiments or force and lubricant additive concentrates according to the invention containing such (iso) dibenzanthrones of the formula Ia or Ib.
  • Compounds 2 and 3 were prepared in an analogous manner using 1-isotridecyl bromide and 6,15-dihydroxyisodibenzanthrone (Compound 2) and 1-dodecylbromide and 16,17-dihydroxydibenzanthrone, respectively.
  • the comparative compound was prepared according to Example 3 of the specification US 6,215,008.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Lubricants (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Fats And Perfumes (AREA)

Abstract

La présente invention concerne l'utilisation de dérivés dibenzanthrone et isodibenzanthrone sélectionnés en tant que marqueurs de liquides, notamment d'huiles minérales. L'invention concerne également des concentrés d'additifs de carburants et de lubrifiants, ainsi que des huiles minérales contenant au moins un tel dérivé dibenzanthrone ou isodibenzanthrone.
EP06708710A 2005-03-15 2006-03-09 Utilisation de derives dibenzanthrone et isodibenzanthrone en tant que marqueurs de liquides Withdrawn EP1861482A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005012211A DE102005012211A1 (de) 2005-03-15 2005-03-15 Verwendung von Dibenzanthron- und Isodibenzanthron-Derivaten als Markierungsstoffe für Flüssigkeiten
PCT/EP2006/060609 WO2006097434A2 (fr) 2005-03-15 2006-03-09 Utilisation de derives dibenzanthrone et isodibenzanthrone en tant que marqueurs de liquides

Publications (1)

Publication Number Publication Date
EP1861482A2 true EP1861482A2 (fr) 2007-12-05

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EP06708710A Withdrawn EP1861482A2 (fr) 2005-03-15 2006-03-09 Utilisation de derives dibenzanthrone et isodibenzanthrone en tant que marqueurs de liquides

Country Status (6)

Country Link
US (1) US20080194446A1 (fr)
EP (1) EP1861482A2 (fr)
AR (1) AR053829A1 (fr)
DE (1) DE102005012211A1 (fr)
TW (1) TW200720422A (fr)
WO (1) WO2006097434A2 (fr)

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Publication number Priority date Publication date Assignee Title
US8129190B2 (en) * 2006-11-17 2012-03-06 Applied Nanotech Holdings, Inc. Tagged petroleum products and methods of detecting same
US9995681B2 (en) 2010-09-28 2018-06-12 Authentix, Inc. Determining the quantity of a taggant in a liquid sample
GB2497477B (en) 2010-09-28 2017-03-15 Authentix Inc Determining the quantity of a taggant in a liquid sample
WO2017019337A1 (fr) 2015-07-24 2017-02-02 Authentix, Inc. Détermination de la quantité d'un traceur dans un échantillon liquide
US10705018B2 (en) 2017-12-28 2020-07-07 Authentix, Inc. Fluorescence based global fuel analysis method
WO2022223384A1 (fr) 2021-04-20 2022-10-27 Basf Se Procédé de détection d'un ou de plusieurs marqueurs dans un carburant pétrolier à l'aide d'un détecteur photoacoustique

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GB495460A (en) * 1936-02-07 1938-11-11 Ig Farbenindustrie Ag Improvements in the manufacture and production of carbon compounds of high molecular weight
US2135259A (en) * 1936-03-04 1938-11-01 Gen Aniline Works Inc Esters of high molecular weight
US2238940A (en) * 1939-07-22 1941-04-22 Du Pont Condensation products from high molecular weight carbocyclic ketones
DE3133390A1 (de) * 1981-08-24 1983-03-10 Basf Ag, 6700 Ludwigshafen Verfahren zur flaechenmaessigen konzentrierung von licht und neue fluoreszierende verbindungen

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Title
See references of WO2006097434A2 *

Also Published As

Publication number Publication date
TW200720422A (en) 2007-06-01
DE102005012211A1 (de) 2006-09-28
WO2006097434A3 (fr) 2006-11-30
AR053829A1 (es) 2007-05-23
US20080194446A1 (en) 2008-08-14
WO2006097434A2 (fr) 2006-09-21

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