Patent Application
20070149415
The present invention relates to fuel and lubricant additive concentrates which comprise at least one anthraquinone derivative as a marker, to the use of such concentrates for additizing mineral oils, and also to mineral oils which comprise such concentrates.
For mineral oil additization, additive concentrates (also referred to herein below, following the relevant terminology, as packages) are used which, in addition to a carrier oil and a mixture of different fuel additives, generally also comprise dyes and also, for invisible fiscal or manufacturer-specific marking, additionally markers. These packages enable the supply of different mineral oil distributors from a pool of unadditized mineral oil, to which the company-specific additization, color and marker are imparted only, for example, while the mineral oil is being filled into appropriate transport containers, with the aid of their individual packages.
The markers are usually substances which are either extracted from the mineral oil and subsequently converted to colored compounds by derivatization, or substances which exhibit absorption either in the visible or in the invisible wavelength region of the spectrum (for example in the NIR). Markers which have been proposed and find use per se, i.e. not just after preceding derivatization, include highly differing compound classes, for example 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 256 460 A1). Anthraquinone derivatives for coloring gasoline or mineral oils are described in the documents U.S. Pat. Nos. 2,611,772, 2,068,372, EP 1 001 003 A1 and EP 1 323 811 A2.
Experience has shown that many of the current markers are stable under the dilute conditions in the mineral oil, but not under the concentrated conditions in the packages; the action of the package components changes the characteristics (e.g. extinction) of the markers within a very short time.
It is thus an object of the present invention to provide fuel and lubricant additive concentrates which feature very good long-term storage stability, especially also with regard to the stability of the markers present therein against the action of the remaining components of these concentrates.
Accordingly, the fuel and lubricant additive concentrates (packages) mentioned at the outset have been found, which comprise at least one anthraquinone derivative as a marker.
The components of the inventive packages are in particular:
The component a) used is in particular anthraquinone derivatives which are selected from the group consisting of the compounds
R4 to R8 are each independently hydrogen, R or NHR and
C1-C20-Alkyl which is optionally interrupted by from 1 to 4 oxygen atoms in ether function include, 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 terms isooctyl, isononyl, isodecyl and isotridecyl are trivial names and stem from the alcohols obtained by the oxo process—on this subject, cf. Ullmanns Encyklopädie der technischen Chemie, 4th Edition, Volume 7, pages 215 to 217, and also Volume 11, pages 435 and 436), tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, 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-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.
Useful C5-C7-cycloalkyl radicals include cyclopentyl, cyclohexyl and cycloheptyl. These cycloalkyls are optionally substituted by one or more, in particular up to three, C1-C20-alkyl groups, and the latter may optionally be interrupted by from 1 to 4 oxygen atoms in ether function. Examples of such C1-C20-alkyl groups optionally interrupted by oxygen atoms have already been listed above.
Saturated, heterocyclic five- or six-membered radicals which are optionally substituted by one or more C1-C20-alkyl groups which are optionally interrupted by from 1 to 4 oxygen atoms in ether function are 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-(C1-C4-alkyl)piperazine such as 4-methyl- or 4-ethylpiperazine, morpholine, thiomorpholine or thiomorpholine S,S-dioxide.
When R, in the OR, NHR and NR2 groups of the definition of the variables Z1 and/or Z2, in the OR and NHR groups of the definition of the variables X, in the COOR group of the definition of the R9 and R10 radicals, in the NHR group of the definition of the variables R3 and also R4 to R8, corresponds to an appropriate, optionally substituted, saturated, heterocyclic five- or six-membered radical, it is bonded to the particular heteroatom of the group in question via a carbon atom of the heterocyclic five- or six-membered ring. The same applies when R alone in the definition of the variables R1 and R2 and the definition of the variables R3 corresponds to an appropriate, optionally substituted, saturated, heterocyclic five- or six-membered radical. In the other cases, the bonding may either be via a carbon atom or a heteroatom of the heterocyclic five- or six-membered radical which are suitable for bonding.
C6-C10-Aryls include in particular phenyl and naphthyl. These are optionally substituted by one or more halogen such as fluorine, chlorine or bromine, cyano, nitro, hydroxyl, amino, C1-C20-alkyl which is optionally interrupted by from 1 to 4 oxygen atoms in ether function, C1-C20-alkoxy, C1-C20-alkylamino or C1-C20-dialkylamino. Appropriate C1-C20-alkyl radicals which are optionally interrupted by from 1 to 4 oxygen atoms in ether function, and C1-C20-alkyl radicals which are present in the C1-C20-alkoxy, C1-C20-alkylamino or C1-C20-dialkylamino groups have already been listed above by way of example.
Heteroaryl radicals having from 3 to 12 carbon atoms which are optionally substituted by one or more C1-C20-alkyl which is optionally interrupted by from 1 to 4 oxygen atoms in ether function, C1-C20-alkoxy, C1-C20-alkylamino or C1-C20-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 also optionally the benzo or dibenzofused rings, for example 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. C1-C20-Alkyl substituents which are optionally interrupted by from 1 to 4 oxygen atoms in ether function have already been specified above by way of example.
When R, in the OR, NHR and NR2 groups of the definition of the variables Z1 and/or Z2, in the OR and NHR groups of the definition of the variables X, in the COOR group of the definition of the R9 and R10 radicals, in the NHR group of the definition of the variables R3 and also R4 to R8, corresponds to an appropriate, optionally substituted heteroaryl, it is bonded to the particular heteroatom of the group in question via a carbon atom of the heteroaryl. The same applies when R alone in the definition of the variables R1 and/or R2 and the definition of the variables R3 corresponds to an appropriate, optionally substituted heteroaryl. In the other cases, the bonding may either be via a carbon atom or a heteroatom of the heteroaryl which is suitable for bonding.
C6-C10-Aryl-C1-C4-alkyls which are optionally substituted in the aryl radical by one or more halogen, cyano, nitro, hydroxyl, amino, C1-C20-alkyl which is optionally interrupted by from 1 to 4 oxygen atoms in ether function, C1-C20-alkoxy, C1-C20-alkylamino or C1-C20-dialkylamino include in particular benzyl, phenylethyl, 3-phenylpropyl and 4-phenylbutyl. Appropriate C1-C20-alkyl radicals which are optionally interrupted by from 1 to 4 oxygen atoms in ether function, and C1-C20-alkyl radicals which are present in the C1-C20-alkoxy, C1-C20-alkylamino or C1-C20-dialkylamino groups have already been listed above by way of example.
Heteroaryl-C1-C4-alkyls having from 3 to 12 carbon atoms in the heteroaryl radical, the latter optionally being substituted by one or more C1-C20-alkyl which is optionally interrupted by from 1 to 4 oxygen atoms in ether function, C1-C20-alkoxy, C1-C20-alkyl-amino or C1-C20-dialkylamino are derived, for example, from the heteroaryl radicals specified above which are bonded to the C1-C4-alkyl radicals either via a carbon atom or a heteroatom of the heteroaryl which is suitable for bonding. Appropriate C1-C20-alkyl radicals which are optionally interrupted by from 1 to 4 oxygen atoms in ether function, and C1-C20-alkyl radicals which are present in the C1-C20-alkoxy, C1-C20-alkylamino or C1-C20-dialkylamino groups have already been listed above by way of example.
Preferred inventive fuel and lubricant additive concentrates comprise anthraquinone derivatives of the formulae I, II and III where
Anthraquinone derivatives of the formula I are in particular the compounds of the formulae Ia to If shown below:
In the formulae Ia to Ie, the variables R are in each case independently, and in formula If the variable R is, C1-C15-alkyl which is optionally interrupted by from 1 to 4 oxygen atoms in ether function, and C6-C10-aryl which is optionally substituted by one or more C1-C15-alkyl which is optionally interrupted by from 1 to 4 oxygen atoms in ether function.
In the definition of a C1-C15-alkyl which is optionally substituted by from 1 to 4 oxygen atoms in ether function, the variables R are preferably 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-tetramethylnonyl, 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 and 3,6,9,12-tetraoxatetradecyl.
In the definition of a C6-C10-aryl which is optionally substituted by one or more C1-C15-alkyl which is optionally interrupted by from 1 to 4 oxygen atoms in ether function, the variables R are preferably selected from the group consisting of unsubstituted phenyl, the 2-, 3- and 4-monosubstituted, the 2,3-, 2,4- and 3,4-disubstituted and the 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6- and 3,4,5-trisubstituted phenyl radicals which are substituted by the C1-C15-alkyl radicals which are optionally interrupted by oxygen in ether function and have been listed above by way of example.
The particular R radicals in the compounds of the formulae Ia to Ie are preferably the same.
Anthraquinone derivatives of the formula II are in particular the compounds of the formulae IIa to IIc shown below:
In the formulae IIa to IIc, the variables R, R1 and R2 are each independently C1-C15-alkyl which is optionally interrupted by from 1 to 4 oxygen atoms in ether function, and C6-C10-aryl which is optionally substituted by one or more C1-C15-alkyl which is optionally interrupted by from 1 to 4 oxygen atoms in ether function.
X in the formulae IIa to IIc either takes the meaning of two hydrogen atoms, two cyano groups in the 2,3- or 6,7-arrangement or two identical CH(R9)(R10) groups in the 2,3- or 6,7-arrangement of the anthraquinone structure. The latter two CH(R9)(R10) groups are either two CH(COOR)2, CH(CN)COOR or CH(CN)2 groups, where the R radicals are preferably C1-C15-alkyl which is optionally interrupted by from 1 to 4 oxygen atoms in ether function, or C6-C10-aryl which is optionally substituted by one or more C1-C15-alkyl which is optionally interrupted by from 1 to 4 oxygen atoms in ether function.
In the definition of a C1-C15-alkyl which is optionally interrupted by from 1 to 4 oxygen atoms in ether function, the variables R, R1 and R2 are preferably 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-tetramethylnonyl, 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 and 3,6,9,12-tetraoxatetradecyl.
In the definition of a C6-C10-aryl which is optionally substituted by one or more C1-C15-alkyl which is optionally interrupted by from 1 to 4 oxygen atoms in ether function, the variables R, R1 and R2 are preferably selected from the group consisting of unsubstituted phenyl, the 2-, 3- and 4-monosubstituted, 2,3-, 2,4- and 3,4-disubstituted and the 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6- and 3,4,5-trisubstituted phenyl radicals which are substituted by the C1-C15-alkyl radicals which are optionally interrupted by oxygen in ether function and are listed above by way of example.
Particular preference is given to compounds of the formulae IIa, IIb and IIc in which both variables R, R1 and R2, or R, R1 and R2, or R1 and R2 are the same as one another, i.e. corresponding compounds include:
and also the corresponding compounds 6,7-substituted by cyano groups or CH(R9)(R10) groups, the variables R corresponding to the selections listed above.
Anthraquinone derivatives of the formula III to be used in accordance with the invention are in particular the compounds of the formulae IIIa to IIId shown below:
where
R in the formulae IIIa to IIId is more preferably C1-C15-alkyl which is optionally interrupted by from 1 to 4 oxygen atoms in ether function, or C6-C10-aryl which is optionally interrupted by one or more C1-C15-alkyl which is optionally interrupted by from 1 to 4 oxygen atoms in ether function.
In particular, R in the formulae 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-tetramethylnonyl, 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-tetraoxatetradecyl, unsubstituted phenyl, the 2-, 3- and 4-monosubstituted, the 2,3-, 2,4- and 3,4-disubstituted and the 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6- and 3,4,5-trisubstituted phenyl radicals which are substituted by the C1-C15-alkyl radicals which are optionally interrupted by oxygen in ether function and have been listed above by way of example, 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-tetramethylnonyl, 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 and 3,6,9,12-tetraoxatetradecyl.
The carrier oils used are typically viscous, high-boiling and in particular thermally stable liquids. They cover the hot metal surfaces, for example the intake valves, with a thin liquid film and thus prevent or delay the formation and deposition of decomposition products on the metal surfaces.
Carrier oils useful as component b) of the inventive fuel and lubricant additive concentrates are, for example, mineral carrier oils (base oils), especially those of the Solvent Neutral (SN) 500 to 2000 viscosity class, synthetic carrier oils based on olefin polymers having MN=from 400 to 1800, in particular based on polybutene or polyisobutene (hydrogenated or nonhydrogenated), on poly-alpha-olefins or poly(internal olefins) and also synthetic carrier oils based on alkoxylated long-chain alcohols or phenols. According to the invention, adducts, to be used as carrier oils, of ethylene oxide, propylene oxide and/or butylene oxide to polybutyl alcohols or polyisobutene alcohols are described for instance, in EP 277 345 A1; further polyalkene alcohol polyalkoxylates to be used in accordance with the invention are described in WO 00/50543 A1. Further carrier oils to be used in accordance with the invention also include polyalkene alcohol polyether amines, as detailed in WO 00/61708.
It will be appreciated that mixtures of different carrier oils may also be used, as long as they are compatible with one another and with the remaining components of the inventive packages.
Carburetors and intake systems of internal combustion engines, but also injection systems for fuel metering, are being contaminated to an increasing degree by impurities which are caused, for example, by dust particles from the air and uncombusted hydrocarbons from the combustion chamber.
To reduce or prevent these contaminations, additives (“detergents”) are added to the fuel to keep valves and carburetors or injection systems clean. Such detergents are generally used in combination with one or more carrier oils. The carrier oils exert an additional “wash function”, support and often promote the detergents in their action of cleaning and keeping clean, and can thus contribute to the reduction in the amount of detergents required.
It should also be mentioned here that many of the substances typically used as carrier oils display additional action as detergents and/or dispersants, which is why the proportion of the latter can be reduced in such a case. Such carrier oils having detergentidispersant action are detailed, for instance, in the last-mentioned WO document.
It is also often impossible to clearly delimit the mode of action of detergents, dispersants and valve seat wear-inhibiting additives, which is why these compounds are listed in summary under component c). Customary detergents which find use in the inventive packages are listed, for example, in WO 00/50543 A1 and WO 00/61708 A1 and include:
Further detergents and/or valve seat wear-inhibiting additives to be used in accordance with the invention are listed, for example, in WO 00/47698 A1 and include compounds which have at least one hydrophobic hydrocarbon radical having a number-average molecular weight (MN) of from 85 to 20 000 and at least one polar moiety, and which are selected from:
Additives containing mono- or polyamino groups (i) are preferably polyalkenemono- or polyalkenepolyamines based on polypropene or on highly reactive (i.e. having predominantly terminal double bonds, usually in the β- and γ-positions) or conventional (i.e. having predominantly internal double bonds) polybutene or polyisobutene having MN=from 300 to 5000. Such additives based on highly reactive polyisobutene, which can be prepared 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, are disclosed in particular in EP 244 616 A2. When polybutene or polyisobutene having predominantly internal double bonds (usually in the β- and γ-positions) are used as starting materials in the preparation of the additives, a possible preparative route is by chlorination and subsequent amination or by oxidation of the double bond with air or ozone to give the carbonyl or carboxyl compound and subsequent amination under reductive (hydrogenating) conditions. The amines used here for the amination may be the same as those used above for the reductive amination of the hydroformylated highly reactive polyisobutene. Corresponding additives based on polypropene are described in particular in WO 94/24231 A1.
Further preferred additives containing monoamino groups (i) are the hydrogenation products of the reaction products of polyisobutenes having an average degree of polymerization P=from 5 to 100 with nitrogen oxides or mixtures of nitrogen oxides and oxygen, as described in particular in WO 97/03946 A1.
Further preferred additives containing monoamino groups (i) 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 DE 196 20 262 A1.
Additives containing nitro groups (ii), optionally in combination with hydroxyl groups, are preferably reaction products of polyisobutenes having an average degree of polymerization P of from 5 to 100 or from 10 to 100 with nitrogen oxides or mixtures of nitrogen oxides and oxygen, as described in particular in WO 96/03367 A1 and
WO 96/03479 A1. These reaction products are generally mixtures of pure nitropolyisobutanes (e.g. α,β-dinitropolyisobutane) and mixed hydroxynitropolyisobutanes (e.g. α-nitro-β-hydroxypolyisobutane).
Additives containing hydroxyl groups in combination with mono- or polyamino groups (iii) are in particular reaction products of polyisobutene epoxides obtainable from polyisobutene having preferably predominantly terminal double bonds and MN=from 300 to 5000, with ammonia or mono- or polyamines, as described in particular in EP 476 485 A1.
Additives containing carboxyl groups or their alkali metal or alkaline earth metal salts (iv) are preferably copolymers of C2-C40-olefins with maleic anhydride which have a total molar mass of from 500 to 20 000 and of whose carboxyl groups some or all have been converted to the alkali metal or alkaline earth metal salts and any remainder of the carboxyl groups has been reacted with alcohols or amines. Such additives are disclosed in particular by EP 307 815 Al. Such additives serve mainly to prevent valve seat wear and can, as described in WO 87/01126 A1, advantageously be used in combination with customary detergents such as poly(iso)butenamines or polyetheramines.
Additives containing sulfonic acid groups or their alkali metal or alkaline earth metal salts (v) are preferably alkali metal or alkaline earth metal salts of an alkyl sulfosuccinate, as described in particular in EP 639 632 A1. Such additives serve mainly to prevent valve seat wear and can be used advantageously in combination with customary detergents such as poly(iso)butenamines or polyetheramines.
Additives containing polyoxy-C2-C4-alkylene moieties (vi) are preferably polyethers or polyetheramines which are obtainable by reaction of C2- to C60-alkanols, C6- to C30-alkanediols, mono- or di-C2-C30-alkylamines, C1-C30-alkylcyclohexanols or C1-C30-alkylphenols with from 1 to 30 mol of ethylene oxide and/or propylene oxide and/or butylene oxide per hydroxyl group or amino group and, in the case of 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 U.S. Pat. No. 4, 877,416. In the case of polyethers, such products also have carrier oil properties. Typical examples of these are tridecanol butoxylates, isotridecanol butoxylates, isononylphenol butoxylates and polyisobutenol butoxylates and propoxylates and also the corresponding reaction products with ammonia.
Additives containing carboxylic ester groups (vii) are preferably esters of mono-, di- or tricarboxylic acids with long-chain alkanols or polyols, in particular those having a minimum viscosity of 2 mm2/s at 100° C., as described in particular in DE 38 38 918 A1. The mono-, di- or tricarboxylic acids used may be aliphatic or aromatic acids, and particularly suitable ester alcohols or ester polyols are long-chain representatives having, for example, from 6 to 24 carbon atoms. Typical representatives of the esters are adipates, phthalates, isophthalates, terephthalates and trimellitates of isooctanol, of isononanol, of isodecanol and of isotridecanol. Such products also have carrier oil properties.
Additives containing moieties derived from succinic anhydride and having hydroxyl and/or amino and/or amido and/or imido groups (viii) are preferably corresponding derivatives of polyisobutenylsuccinic anhydride which are obtainable by reacting conventional or highly reactive polyisobutene having MN=from 300 to 5000 with maleic anhydride by a thermal route or via the chlorinated polyisobutene. Particular interest attaches to derivatives with aliphatic polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine. Such gasoline fuel additives are described in particular in U.S. Pat. No. 4, 849, 572.
Additives containing moieties obtained by Mannich reaction of phenolic hydroxyl groups with aldehydes and mono- or polyamines (ix) 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 may stem from conventional or highly reactive polyisobutene having MN=from 300 to 5000. Such “polyisobutene-Mannich bases” are described in particular in EP 831 141 A1.
For a more precise definition of the additives detailed individually, reference is explicitly made here to the disclosures of the abovementioned prior art documents.
Dispersants as component c) are, for example, imides, amides, esters and ammonium and alkali metal salts of polyisobutenesuccinic anhydrides. These compounds find use especially in lubricant oils, but sometimes also as detergents in fuel compositions.
Further additives and assistants which may, if desired, be present as component d) of the inventive packages are
The concentration of component a), i.e. the at least one anthraquinone derivative, in the inventive packages is typically selected in such a magnitude that, after addition of the package to the mineral oil, the desired concentration of marker(s) is present therein. Typical concentrations of the markers in the mineral oil are, for instance, in the range from 0.01 up to a few 10s of ppm by weight.
Component b), i.e. the at least one carrier oil, is present in the inventive packages typically in a concentration of from 1 to 50% by weight, in particular from 5 to 30% by weight, and
When, as component d), corrosion inhibitors, antioxidants or stabilizers, demulsifiers, antistats, metallocenes, lubricity improvers and amines to reduce the pH of the fuel are present in the inventive packages, the sum of their concentrations typically does not exceed 10% by weight, based on the total weight of the package (i.e. the total amount of components a) to c) and d)), the concentration of the corrosion inhibitors and demulsifiers being typically in the range of from in each case about 0.01 to 0.5% by weight of the total amount of the package.
When, as component d), additional organic solvents (i.e. not already introduced with the remaining components) are present in the inventive packages, the sum of their concentrations typically does not exceed 20% by weight, based on the total amount of the package. These solvents generally stem from solutions of the markers and/or dyes, which are added to the packages instead of the pure markers and/or dyes with a view to more precise meterability.
When, as component d), further markers other than anthraquinone derivatives are present in the inventive packages, their concentration is in turn based on the content that they are to have after addition of the packages in mineral oil. That which was stated for component a) applies mutatis mutandis.
When, as component d), dyes are present in the inventive packages, their concentration is typically, for instance, between 0.1 to 5% by weight, based on the total amount of the package.
Anthraquinone derivatives shown below were investigated. The compounds 1 to 9 were synthesized starting from 1,4,5,8-tetrachloroanthraquinone and the appropriately substituted anilines by the method described in the document EP 0 323 184 A1.
The trisubstituted compound was obtained as a by-product in the preparation of compound 8.
S.G. 33 (commercially available from BASF Aktiengesellschaft)
(commercially available from BASF Aktiengesellschaft)
S.B. 79 (commercially available from BASF Aktiengesellschaft) Comparison (λmax=770 nm, THF):
The comparative compound used was the phthalocyanine of the following formula:
(prepared according to Example 1 of WO 98/52950 A1)
Experiments on Storage Stability:
The test mixture used, of a fuel and lubricant additive concentrate with the components contained therein and their particular proportions, is detailed below in Table 1:
(Detergent, carrier oil, corrosion protection and demulsifier are commercially available, for example, from or via BASF Aktiengesellschaft)
The samples were transferred to 10 ml ampules, sealed in an airtight manner and stored in a water bath at 50° C.
The results are reproduced in Tables 2 and 3. All experiments were normalized to the starting extinction.
In the presence of carrier oil, the comparative compound exhibited a distinctly sharper decrease in the normalized extinction as a function of time than in the case of the presence of detergent. The values were therefore not reproduced.
Detergent at room temperature: after storage times of 4, 12, 28 and 42 days, substantially no change could be detected in the normalized extinction. The results are shown by the following table:
Detergent at 40° C.: after storage times of 4, 12, 28 and 42 days, substantially no change could be detected in the normalized extinction. The results are shown by the following table:
| Number | Date | Country | Kind |
|---|---|---|---|
| 10361504.0 | Dec 2003 | DE | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/EP04/14587 | 12/22/2004 | WO | 6/23/2006 |
