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EP1996549A1 - Utilisation de phtalocyanines substituees par de l'aryle ou de l'alkyloxy en tant que materiau de marquage pour liquides - Google Patents

Utilisation de phtalocyanines substituees par de l'aryle ou de l'alkyloxy en tant que materiau de marquage pour liquides

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Publication number
EP1996549A1
EP1996549A1 EP07726680A EP07726680A EP1996549A1 EP 1996549 A1 EP1996549 A1 EP 1996549A1 EP 07726680 A EP07726680 A EP 07726680A EP 07726680 A EP07726680 A EP 07726680A EP 1996549 A1 EP1996549 A1 EP 1996549A1
Authority
EP
European Patent Office
Prior art keywords
formula
different
same
alkyl
symbols
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
EP07726680A
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German (de)
English (en)
Inventor
Thomas Gessner
Sophia Ebert
Rüdiger Sens
Martin KÖNEMANN
Wolfgang Ahlers
Christos Vamvakaris
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BASF SE
Original Assignee
BASF SE
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Priority to EP07726680A priority Critical patent/EP1996549A1/fr
Publication of EP1996549A1 publication Critical patent/EP1996549A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C255/54—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and etherified hydroxy groups bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C255/50—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton to carbon atoms of non-condensed six-membered aromatic rings
    • C07C255/51—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton to carbon atoms of non-condensed six-membered aromatic rings containing at least two cyano groups bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/44—Iso-indoles; Hydrogenated iso-indoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
    • 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
    • C09B47/00—Porphines; Azaporphines
    • C09B47/04—Phthalocyanines abbreviation: Pc
    • C09B47/06—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide
    • C09B47/067—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide from phthalodinitriles naphthalenedinitriles, aromatic dinitriles prepared in situ, hydrogenated phthalodinitrile
    • C09B47/0675—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide from phthalodinitriles naphthalenedinitriles, aromatic dinitriles prepared in situ, hydrogenated phthalodinitrile having oxygen or sulfur linked directly to the skeleton
    • 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
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/52—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of 30 or more atoms
    • C10M133/58—Heterocyclic compounds
    • 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
    • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12—Reaction products
    • C10M159/18—Complexes with metals
    • 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
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/56—Ring systems containing bridged rings
    • C07C2603/58—Ring systems containing bridged rings containing three rings
    • C07C2603/70—Ring systems containing bridged rings containing three rings containing only six-membered rings
    • C07C2603/74—Adamantanes
    • 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
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/225—Heterocyclic nitrogen compounds the rings containing both nitrogen and oxygen
    • C10M2215/227—Phthalocyanines
    • 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
    • C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
    • C10M2227/09—Complexes with metals
    • 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 invention relates to the use of specific aryl- or alkyloxy-substituted phthalocyanines as markers for liquids, in particular mineral oils, liquids, in particular mineral oils, which contain at least one such phthalocyanine as a marker, a method for labeling liquids and for the detection of labeled liquids and special aryl or alkyloxy-substituted phthalocyanines.
  • phthalocyanine derivatives are proposed in WO 94/02570 A1 in addition to other compounds.
  • WO 98/52950 A1 are described as markers for liquids, in particular mineral oils, phthalocyanines which contain as substituents five- or six-membered saturated nitrogen-containing heterocyclic radicals which are bonded via a ring nitrogen atom to the Phthalocyaningrundgerüst.
  • WO 2005/070935 describes phthalocyanines which carry substituents attached to the phthalocyanine skeleton via methylene groups as marking agents for liquids, in particular mineral oils.
  • the object of the invention is to provide phthalocyanines which are distinguished not only by good solubility but also by good long-term stability in the liquids to be marked, in particular mineral oils.
  • phthalocyanines of the formula (I) have both a good solubility and a very good long-term stability, especially against conventional fuel additives.
  • the invention accordingly provides the use of phthalocyanines of the formula (I) as markers for liquids,
  • M is hydrogen twice, lithium, magnesium, zinc, copper, nickel, VO, TiO, AICI, AlOCOCH 3 , AlOCOCF 3 , SiCl 2 or Si (OH) 2 twice;
  • n 1, 2, 3 or 4;
  • n is the same or different O, 1, 2, 3 or 4;
  • r is the same or different 0, 1, 2, 3 or 4;
  • n + r is 1, 2, 3 or 4;
  • n + r is O, 1, 2, 3 or 4; R is the same or different
  • R 1 is the same or different H, halogen or R 2 ;
  • R 2 is identical or different (Ci-C 8) -alkyl, (C 4 -C 8) cycloalkyl, (C2-Ci2) alkenyl, (C6 -Cio) aryl, (C 7 -C 2 o) aralkyl or (C 2 -C 2) -alkynyl, wherein aryl is unsubstituted or substituted with 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 1 -C 20 alkoxy, C 1 -C 20 alkylamino or C 1 -C 20 dialkylamino;
  • R 3 is identical or different R 1 or two radicals R 3 or a radical R 1 and a radical R 3 together form a further ring system;
  • R 4 , R 5 , R 6 are identical or different H, halogen, CH 3 or C 2 H 5 Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 are identical or different (C r C 4 ) Alkylene which is unsubstituted or substituted by one or more halogen atoms;
  • s 0, 1, 2, 3, 4, 5, or 6;
  • t is O, 1, 2, 3.
  • -C 8 alkyl for example, be mentioned 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 trivial names and are derived from the alcohols obtained
  • Suitable C 4 -C 8 -cycloalkyl radicals are cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.
  • C 6 -C 0 -Aryle in particular phenyl and naphthyl are mentioned. These are optionally substituted with one or more halogen atoms such as fluorine, chlorine or bromine, Cy to, nitro, hydroxy, amino, -C 2 -alkyl, which is optionally interrupted by 1 to 4 oxygen atoms in ether function, dC 2 -alkoxy, dC 2 o-alkylamino or C 1 -C 2 0-dialkyl-amino substituted.
  • halogen atoms such as fluorine, chlorine or bromine
  • Cy to, nitro, hydroxy, amino, -C 2 -alkyl, which is optionally interrupted by 1 to 4 oxygen atoms in ether function, dC 2 -alkoxy, dC 2 o-alkylamino or C 1 -C 2 0-dialkyl-amino substituted.
  • (C 7 -C 2 o) aralkyls which lie optionally substituted with one or more Ha- in the aryl radical, 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 0-Al koxy, CrC 2 o-alkyl-amino or CrC 2 o-dialkylamino are substituted, in particular benzyl, phenyl-ethyl, 3-phenylpropyl and 4-phenylbutyl mentioned.
  • (C2-Ci2) alkenyl which may be mentioned with their various positional isomers, in particular propenyl, butenyl, pentenyl, and hexenyl.
  • (C2-Ci2) alkynyl are, in particular propynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decynyl, undecynyl and dodecynyl be mentioned isomers with their various positional.
  • halogens to be mentioned in particular fluorine, chlorine, bromine and iodine.
  • M is preferably twice hydrogen, twice lithium, magnesium, zinc, copper, nickel, VO, TiO, SiCl 2 or Si (OH) 2 .
  • n is preferably 0, 1 or 2.
  • R is preferably the same or different
  • R 1 is preferably identical or different H or R 2 .
  • R 2 is preferably equal to or different from (d-Ci2) alkyl, (C 5 -C 7) -cycloalkyl, phenyl, (C 7 -C 6) aralkyl, wherein the phenyl is unsubstituted or substituted by one or more halogen, ( CrCi 2 ) alkyl or (CrCi 2 ) alkoxy substituted.
  • R 3 is preferably the same or different R 1 .
  • s is preferably 0, 1 or 2.
  • t is preferably 0, 1 or 2.
  • M is particularly preferably twice hydrogen.
  • m is more preferably 1 or 2.
  • n is more preferably 1 or 2.
  • R is particularly preferably the same or different
  • R 1 is more preferably identical or different to H or R 2
  • R 2 is more preferably identical or different (C 1 -C 2 -) -alkyl, phenyl, (C 5 -C 6 ) -cycloalkyl, where phenyl is unsubstituted or substituted by one to three radicals from the group F, Cl, (C r C 6 ) Alkyl and (C r C 6 ) alkoxy substituted.
  • R 3 is more preferably the same or different R 1 .
  • s is more preferably 0 or 1.
  • t is more preferably 0 or 1.
  • n is very particularly preferred 1.
  • r is most preferably 0.
  • M is most preferably H.
  • R is especially preferred
  • R 1 is very particularly preferably identical or different H or R 2 .
  • R 2 is most preferably (C 1 -C 2 ) alkyl or phenyl.
  • R 3 is very particularly preferably H or (d-Ci 2) -alkyl.
  • X 1 "7 are identical or different R or R 1 ,
  • X 1 -X 6 , R and R 1 have the meanings given above.
  • Preferred compounds of the formula (Iaa) are those where all four radicals R have the same meaning.
  • R 1 has the meaning H.
  • Particularly preferred compounds of the formula (Iaa) are therefore those in which all four radicals R have the same meaning and R 1 has the meaning H.
  • the invention therefore also relates to compounds of the formula (I) in which the symbols and indices have the following meanings:
  • R is a group
  • the compounds of the formula (I) can be prepared by known methods known to the person skilled in the art, as described, for example, in FH Moser and AL Thomas in Phthalocyanine Compounds, ACS Monograph Series, Chapman & Hall, New York, 1963, FH Moser and AL Thomas in The Phthalocyanines, Manufacture and Applications, Vol. 2, CRC Press, Boca Raton, 1983, CC Leznoff in Phthalocyanines, Properties and Application (Eds .: CC Leznoff and ABP Lever), Vol. 1, VCH, New York, Weinheim , Cambridge, 1989, M. Hanack, H. Heckmann and R. Polley in Houben-Weyl, Methods of Organic Chemistry (Ed .: E.
  • the invention also provides a process for the preparation of the abovementioned novel compounds of the formula (I), where a phthalonitrile of the formula (II)
  • Suitable reducing agents are, for example, hydroquinone, resorcinol, catechol and pyrogallol (1,3,3-trihydroxybenzene) or mixtures thereof, hydroquinone being preferred.
  • Suitable bases are, for example, alkali metal hydroxides, oxides and carbonates, preference being given to NaOH.
  • the molar ratio of phthalonitrile to reducing agent is generally 0.1 to 10: 1, preferably 0.5 to 2: 1.
  • the reaction is carried out in the melt, preferably at temperatures of 140 to 250 ° C, more preferably from 150 to 200 ° C.
  • the reaction time is generally 1 to 24 hours.
  • the reaction is generally carried out under atmospheric pressure, but may optionally also be carried out at overpressure or underpressure.
  • the phthalonitriles of the formula (II) are also new and subject of the invention.
  • reaction of the phthalonitriles (II) to give the phthalocyanines of the formula (I) can, if appropriate, also be carried out via the imino-aminoisoindolines (III a / b) as isolated intermediates, according to the cited methods,
  • Suitable liquids which can be labeled by means of the phthalocyanines of the formula (I) 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- o the 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,
  • the phthalocyanines of the formula (I) are used to particular advantage for the marking of oils, in particular mineral oils.
  • the invention furthermore relates to liquids, preferably oils, in particular mineral oils, which contain at least one phthalocyanine of the formula (I) as a marker.
  • the compounds of the formula (I) to be used as markers are added to the liquids in amounts such that reliable detection is ensured.
  • the (weight-related) total content of markers in the labeled liquid is about 0.1 to 5000 ppb, preferably 1 to 2000 ppb and particularly preferably 1 to 1000 ppb.
  • the compounds are generally added in the form of solutions (stock solutions).
  • suitable solvents for preparing these stock solutions are preferably aromatic hydrocarbons, such as toluene, xylene or higher-boiling aromatic mixtures.
  • a total concentration of the marking substances of from 0.5 to 50% by weight, based on the total weight of these stock solutions, is generally selected.
  • the compounds of the formula (I) can also be used in a mixture with other markers / dyes, as described, for example, in the beginning become.
  • the total amount of the marking substances in the liquids is then usually in the range described above.
  • the invention also provides a process for the marking of liquids, preferably oils, in particular mineral oils, wherein the liquid is a compound of formula (I) is added.
  • the detection of the compounds of formula (I) in the liquids is carried out by conventional methods. Since these compounds usually have high absorbency and / or fluorescence, in the given case, e.g. a spectroscopic detection.
  • the compounds of the formula (I) generally have their absorption maximum in the range from 600 to 800 nm and / or fluoresce in the range from 600 to 900 nm and can thus easily be detected with suitable instruments.
  • the detection can be carried out in a manner known per se, for example by measuring the absorption spectrum of the liquids to be examined.
  • ⁇ max means the wavelength of the absorption maximum of the marking substance.
  • the wavelength of the maximum emission is in the range of 620 to 900 nm.
  • the fluorescent light thus generated is advantageously detected with a semiconductor detector, in particular with a silicon photodiode or a germanium photodiode.
  • Detection is particularly advantageous when there is an interference filter and / or an edge filter (with a short-wave transmission edge in the range from ⁇ max to ⁇ max +80 nm) in front of the detector and / or a polarizer.
  • the invention also provides a process for the identification of liquids, preferably oils, in particular mineral oils, which contain a compound of the formula (I) in an amount sufficient to excite detectable fluorescence upon irradiation with a suitable wavelength,
  • the liquid is irradiated with electromagnetic radiation of a wavelength of 600 to 800 nm
  • the excited fluorescence radiation is detected with a device for detecting radiation in the long-wave visible range or in the near infrared range.
  • the phthalocyanines of the formula (I) can also be used as a component in additive concentrates (hereinafter also referred to as "packagings"), which in addition to a carrier oil and a mixture of various fuel additives generally also include dyes , for invisible fiscal or manufacturer-specific marking, additionally contain markers.
  • 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.
  • the carrier oils used are usually viscous, high-boiling and, in particular, thermostable liquids. They coat the hot metal surfaces, eg. As the inlet 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, in particular based on polybutene or polyisobutene (hydrogenated or non-hydrogenated), of polyalphaolefins or polyinteralalefins 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 are obtainable 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,
  • Poly (iso) buteneamines which are obtainable by chlorination of polybutenes or polyisobutenes having double bonds predominantly in the ⁇ and ⁇ 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 -C 3 o-alkanols, C 6 -C 3 o-alkanediols, mono- or di-C 2 -C 3 o-alkylamines, dC 3 o-Alkylcyclohexa-nolen or dC 3 o- Alkyl phenols with 1 to 30 moles 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 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.
  • Further detergents and / or valve seat wear-inhibiting additives to be used are listed, for example, in WO 00/47698 A1 and comprise compounds which have at least one hydrophobic hydrocarbon radical having a number-average molecular weight (M N ) of from 85 to 20,000 and at least one polar Have grouping, and which are selected from:
  • polyoxy-C 2 -C 4 -alkylene groups terminated by hydroxyl groups, mono- or polyamino groups, wherein at least one nitrogen atom has basic properties, or terminated by carbamate groups,
  • Amination with ammonia, monoamines or polyamines such as dimethylaminopropylamine, ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine can be prepared, are known in particular from the 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 of the double bond with air or ozone to carbonyl - or carboxyl compound and subsequent amination under reductive (hydrogenating) conditions.
  • 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 in particular from document EP 307 815 A1.
  • Such additives are mainly used to prevent valve seat wear and, as described in document WO 87/01 126 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 -C 4 -alkylene (vi) additives are preferably polyethers or polyetheramines which are obtainable by reaction of kanolen C 2 -C 6O -AI, C 6 -C 30 - alkanediols, mono- or di-C 2 -C alkylamines 30, CrC 30--Alkylcyclo hexanols d- or C 30 alkyl phenols having 1 to 30 mol ethylene oxide and / or propylene oxide and / or butylene oxide per hydroxyl group or amino group and, in the case of the polyetheramines, by subsequent reductive amination with ammonia, monoamines or polyamines.
  • Such products are described in particular in EP 310 875 A1, EP 356 725 A1, EP 700 985 A1 and US Pat. No. 4,877,416.
  • polyethers such products also meet carrier oil properties. Typical examples of these are tridecanol or Isotridecanolbutoxylate, Isononylphenolbutoxylate and Polyisobutenolbutoxylate and propoxylates and the corresponding reaction products with ammonia.
  • 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.
  • mono-, di- or tricarboxylic acids it is possible to use aliphatic or aromatic acids; as ester alcohols or polyols, especially long-chain representatives having, for example, 6 to 24 carbon atoms are suitable.
  • Typical representatives of the esters are adipates, phthalates, isophthalates, terephthalates and trimellitates of iso-octanol, iso-nonanol, iso-decanol and of isotridecanol.
  • 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 a
  • 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. the at least one phthalocyanine of the formula (I) or its preferred embodiments, in the packages is usually chosen in such a height that after addition of the package to the mineral oil, the desired concentration of marker (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), ie 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), ie the at least one detergent and / or the at least one dispersant, usually in a concentration of 25 to 90% by weight, in particular 30 to 80% by weight, in each case based on the total amount of components a) to c) and optionally d), where 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 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 Total amount of the package is.
  • 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 If, as component d), other labeling substances other than phthalocyanines of the formula (I) 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.
  • Example 1 1 (4), 8 (11), 15 (18), 22 (25) tetrakis (2,6-diisopropylphenoxy) phthalocyanine
  • Example 2 1 (4), 8 (11), 15 (18), 22 (25) tetrakis (2,4-di-tert-pentylphenoxy) phthalocyanine
  • Example 3 1 (4), 8 (11), 15 (18), 22 (25) tetrakis (2,4,6-trimethylphenoxy) phthalocyanine a) 3- (2,4,6-trimethylphenoxy) -phthalodinitrile
  • Example 4 1 (4), 8 (11), 15 (18), 22 (25) tetrakis (2,6-diphenylphenoxy) phthalocyanine
  • Example 6 2 (3), 9 (10), 16 (17), 23 (24) tetrakis (2,6-diisopropylphenoxy) phthalocyanine
  • Example 7 1 (4), 8 (11), 15 (18), 22 (25) tetra (1-adamantanoxy) phthalocyanine
  • Example 8 (Comparative Example): 1 (4), 8 (11), 15 (18), 22 (25) -tetra (4-nonylphenoxy) phthalocyanine
  • the solution was filtered and added dropwise to 700 ml of methanol. After one hour of stirring, the solid was filtered off, washed with 700 ml of methanol, then with water and dried at 60 ° C in a vacuum oven (19.4 g). The solid was recrystallized in 194 ml of butyl glycol. The solid was filtered off, washed with 40 ml of butyl glycol, then with 390 ml of methanol, sucked dry and dried in a vacuum oven at 60 ° C. 15.4 g (44% of theory) of analytically pure green microcrystals having a melting point of 168.5 to 170 ° C. were obtained.
  • Example 9 Storage stability test in the presence of mineral oil additives Approximately 20 mg of the respective substance were dissolved in 25 ml of Shellsol naphtha. Any insoluble components were separated by filtration (pleated filter). The concentration of the dissolved substance was chosen so that the extinctions of the longest wavelength absorption bands to be measured were between 0.8 and 1.5. 5 ml of the filtrate were made up to 10 ml with a commercial polyisobutene (PIBA) -based additive, mixed and stored in an airtight ampule at 40 ° C. After the storage times listed in the table below, samples were taken from the ampoules and measured in 1 mm cuvettes. In order to obtain a better comparability of the different samples, the table shows 1 standardized extinctions (extinction equal to 1 at the beginning of the storage period).
  • PIBA polyisobutene

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  • Chemical & Material Sciences (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Lubricants (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
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Abstract

L'invention concerne la phtalocyanine de formule (I), dans laquelle les symboles et les indices sont tels que définis dans la description, utilisée en tant que matériau de marquage pour liquides, notamment pour huiles minérales.
EP07726680A 2006-03-15 2007-03-07 Utilisation de phtalocyanines substituees par de l'aryle ou de l'alkyloxy en tant que materiau de marquage pour liquides Withdrawn EP1996549A1 (fr)

Priority Applications (1)

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EP07726680A EP1996549A1 (fr) 2006-03-15 2007-03-07 Utilisation de phtalocyanines substituees par de l'aryle ou de l'alkyloxy en tant que materiau de marquage pour liquides

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EP06111161 2006-03-15
PCT/EP2007/052122 WO2007104685A1 (fr) 2006-03-15 2007-03-07 Utilisation de phtalocyanines substituees par de l'aryle ou de l'alkyloxy en tant que materiau de marquage pour liquides
EP07726680A EP1996549A1 (fr) 2006-03-15 2007-03-07 Utilisation de phtalocyanines substituees par de l'aryle ou de l'alkyloxy en tant que materiau de marquage pour liquides

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WO2009024512A1 (fr) 2007-08-17 2009-02-26 Basf Se Dérivés halogénés d'acide tétracarboxylique de pérylène, et leur utilisation
CA2702921C (fr) * 2007-11-09 2016-06-28 Basf Se Polyalkyleneimines alcoxyles amphiphiles solubles dans l'eau presentant un bloc interne d'oxyde de polyethylene et un bloc externe d'oxyde de polypropylene
JP5725863B2 (ja) * 2007-11-09 2015-05-27 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ アルコキシル化されたポリアルカノールアミン
CN101580506B (zh) * 2009-05-26 2012-11-07 福建师范大学 1-3代芳醚树枝状酞菁配合物及其聚合物纳米粒子
WO2010136420A1 (fr) * 2009-05-26 2010-12-02 Basf Se Utilisation de composés de phthalocyanine avec substituants aryles ou hétaryles dans des piles solaires organiques
JP2011094127A (ja) * 2009-09-29 2011-05-12 Nippon Shokubai Co Ltd 熱線吸収材
US9995681B2 (en) 2010-09-28 2018-06-12 Authentix, Inc. Determining the quantity of a taggant in a liquid sample
JP5790546B2 (ja) * 2012-03-07 2015-10-07 コニカミノルタ株式会社 光電変換素子用色素、光電変換素子及びその製造方法
US9068147B2 (en) 2012-05-11 2015-06-30 Basf Se Quaternized polyethylenimines with a high quaternization degree
CN104614132A (zh) * 2015-02-05 2015-05-13 广西柳工机械股份有限公司 工程机械整机润滑油泄漏检测方法
JP6548221B2 (ja) * 2015-02-12 2019-07-24 株式会社日本触媒 フタロシアニン化合物
PT3325947T (pt) 2015-07-24 2024-12-10 Authentix Inc Determinação da quantidade de um elemento de marcação numa amostra líquida
KR101816232B1 (ko) * 2015-10-16 2018-01-08 삼성에스디아이 주식회사 신규한 화합물, 이를 포함하는 감광성 수지 조성물 및 컬러필터
CN106243115B (zh) * 2016-07-28 2018-03-30 北京化工大学 含金刚烷结构的双核金属酞菁催化剂及其制备方法
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CN109959626B (zh) * 2019-04-08 2022-05-03 天津农学院 一种定量总脂含量的分光光度法及应用
CN110951071B (zh) * 2019-12-11 2022-05-13 南通北风橡塑制品有限公司 一种酞菁金属盐改性多元醇及其制备方法和应用
CN114136943B (zh) * 2021-11-30 2024-01-05 厦门大学 一种以空壳酞菁为分子探针测定锂离子的荧光分析法
WO2023241950A1 (fr) 2022-06-13 2023-12-21 Basf Se Mélanges de composés ayant une solubilité améliorée destinés à être utilisés en tant que marqueurs
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ZA200808721B (en) 2009-12-30
NO20083763L (no) 2008-10-14
KR20090008228A (ko) 2009-01-21
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TW200745131A (en) 2007-12-16
UA88747C2 (ru) 2009-11-10
US20090189086A1 (en) 2009-07-30
CA2646205A1 (fr) 2007-09-20
AR059897A1 (es) 2008-05-07
CN101421236A (zh) 2009-04-29
EA200801986A1 (ru) 2009-02-27
WO2007104685A1 (fr) 2007-09-20

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