WO2010060818A1 - Oligo- ou polyamines alcoxylées servant de stabilisateurs d'oxydation - Google Patents

Oligo- ou polyamines alcoxylées servant de stabilisateurs d'oxydation Download PDF

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WO2010060818A1
WO2010060818A1 PCT/EP2009/065188 EP2009065188W WO2010060818A1 WO 2010060818 A1 WO2010060818 A1 WO 2010060818A1 EP 2009065188 W EP2009065188 W EP 2009065188W WO 2010060818 A1 WO2010060818 A1 WO 2010060818A1
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polyamines
alkoxylated oligo
weight
oligo
groups
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PCT/EP2009/065188
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German (de)
English (en)
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Claudius Kormann
Klaus KÜHLING
Roman Benedikt Raether
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Basf Se
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/02—Polyamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/0206—Polyalkylene(poly)amines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/024—Polyamines containing oxygen in the form of ether bonds in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)
    • C10L1/2387—Polyoxyalkyleneamines (poly)oxyalkylene amines and derivatives thereof (substituted by a macromolecular group containing 30C)
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/003—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fatty acids with alcohols
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2215/042—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated derivatives thereof
    • 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
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/046—Polyamines, i.e. macromoleculars obtained by condensation of more than eleven amine monomers
    • 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
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants

Definitions

  • the present invention relates to the use of specific alkoxylated oligo- or polyamines for increasing the oxidation stability of oxidation-sensitive organic liquids, in particular fatty acid ester-based biofuel oils or mixtures of such biofuel oils with fatty acid ester-free middle distillates of fossil, vegetable or animal origin or petrol ,
  • the present invention relates to a mixture of specific representatives of such alkoxylated oligo- or polyamines and biofuel oils which are based on fatty acid esters.
  • the present invention relates to a fuel containing a larger proportion of a fuel oil
  • the present invention relates to a stabilizing formulation comprising such alkoxylated oligo- or polyamines as antioxidants and other stabilizing components.
  • biofuel oils which are usually also referred to as “biodiesel” and usually contain high levels of unsaturated fatty acid esters are sensitive due to their chemical structure more sensitive to oxidative decomposition by atmospheric oxygen as fuel oils of fossil origin, they are often to improve their Oxidationsstabili Kunststoff during storage with added small amounts of antioxidants.
  • Common antioxidants used herein are sterically hindered phenols, for example 2,6-di-tert-butyl-4-methylphenol (“BHT”), 3-tert-butyl-hydroxyanisole (“BHA”) and tert-butylhydroquinone ( “TBHQ”), as described in the literature article by Mittelbach and Schober in JAOCS, Vol. 80, No. 8 (2003), pp. 817-823.
  • succinimides obtainable by reacting C 4 - to C 29 -alkyl or -alkenyl succinic anhydride and primary amines, which may also be polyamines, are used as additives for improving the thermal stability of aircraft fuels, and furthermore also for biofuels such as vegetable oils and esters of vegetable oils are recommended.
  • WO 94/19430 describes reaction products of polyamines with acylating agents, in particular with fatty acids, as antifoams for mixtures of biofuel oil and middle distillates of fossil origin.
  • oligo- or polyamines having a number average molecular weight of 46 to 70,000, which are free of phenolic hydroxyl groups and have no Alkoxylatreste to increase the oxidation stability of fatty acid ester based biofuel oils or mixtures of such biofuel oils with fatty acid ester-free middle distillates fossil , of plant or animal origin.
  • DE 10 2004 024 532 A1 discloses fuel oils comprising a major proportion of a mixture of middle distillate fuel oil and biofuel oil and a minor proportion of oil-soluble polyethyleneimines which have been alkoxylated with C 2 -C 4 -alkylene oxides such as ethylene oxide, propylene oxide or butylene oxide, contain.
  • the determined by light scattering average molecular weight M w of these alkoxylated polyethyleneimines are always greater than 55,000 g / mol.
  • these alkoxylated polyethyleneimines act as demulsifiers for fuel and water mixtures.
  • the stabilizing effect of all the above-mentioned antioxidants in biofuel oil is usually not sufficient.
  • the necessary doses are too high.
  • the object was to provide more effective antioxidants in general for oxidation-sensitive organic liquids, but especially for biofuel oils and biofuel-containing fuels.
  • alkoxylated oligo- or polyamines having a number-average molecular weight of 90 to 70,000 which contain, on average for each molecule, 0.25 to 2.0 alkoxylate moieties of the formula - (C ⁇ H 2 ⁇ O) p -H in which Variable x for a number from 2 to 6 and the variable p for a number from 1 to 10 is, per nitrogen atom, dissolved to increase the oxidation stability of oxidation-sensitive organic liquids.
  • cationic structures in particular ammonium or substituted ammonium compounds, are excluded in the case of the alkoxylated oligo- or polyamines to be used according to the invention.
  • the number average molecular weight of the alkoxylated oligo- or polyamines is 90 [for the N-mono- (2-hydroxyethyl) -diaminomethane as the smallest possible representative] to 70,000, this upper limit not being critical in linear structures.
  • Preferred ranges for the number-average molecular weight are 100 to 40,000, especially 150 to 10,000, especially 200 to 5000, most preferably 300 to 2000.
  • the stated alkoxylated oligo- or polyamines preferably have 2 to 120, more preferably 2 to 60, in particular 2 to 30, especially 2 to 15, nitrogen atoms in the molecule. They can be linear or branched.
  • the present invention relates to the use according to the invention of linear alkoxylated oligo- or polyamines of general formula I. in the
  • the radicals R 1 to R 6 are independently alkoxylate groups of the formula - (C ⁇ H 2 ⁇ O) p -H, in which the variable x is a number from 2 to 6 and the variable p is a number from 1 to 10, hydrogen, d - to C3o-alkyl groups, Cs to Cs-cycloalkyl groups, d- to C29-alkylcarbonyl groups or C2 to Cs-cyanoalkyl groups, where the radicals R 1 and R 2 and / or R 5 and R 6 are each also together with the nitrogen atom carrying them is a five- or six-membered saturated or unsaturated ring which may contain further heteroatoms and / or carbonyl carbon atoms and may carry additional substituents, or together form a methylidene grouping represented by C 1 - to C 30 -alkyl groups and / or C ⁇ - to C12-aryl groups may be substituted,
  • the bridge members A 1 to A 3 independently denote d- to Ci2-alkylene groups and / or C ⁇ - to Ci2-arylene groups, wherein the radicals R 1 and / or R 5 each also together with the nitrogen atom carrying them and a carbon atom of an alkylene group A. 1 or A 3 may form a five- or six-membered saturated or unsaturated ring which may contain further heteroatoms and / or carbonyl carbon atoms and may carry additional substituents, and
  • n and m are each integers from 0 to 30,
  • the compounds of general formula I have on average for each molecule 0.25 to 2.0 alkoxylate moieties of the formula - (C ⁇ H 2 ⁇ O) p -H in which the variable x is a number from 2 to 6 and the Variable p is a number from 1 to 10, per nitrogen atom.
  • the average number of alkoxylate groups of the formula - (C x H 2 ⁇ O) p -H per nitrogen atom in the molecule is preferably 0.5 to 1.7, in particular 0.7 to 1.5, in particular 0.9 to 1.4 ,
  • the number of the alkylene oxide unit p per Alkoxylatgrupp ist is preferably 1 to 6, in particular 1 to 3, especially 1 to 2, wherein the variable p is a statistical average per molecule, p therefore represents no integer.
  • a single alkoxylate moiety may also contain various alkylene oxide moieties as building blocks.
  • Butylene oxide units can be derived from 2,3-butylene oxide or from 1, 2-butylene oxide; Longer-chain alkylene oxide units are usually derived from 1,2-alkylene oxides.
  • the said optional substituents on the five- or six-membered saturated or unsaturated rings may, for example, be longer-chain or shorter-chain hydrocarbyl radicals, in particular corresponding linear or branched alkyl radicals.
  • the linear alkoxylated oligo- or polyamines to be used in the context of the present invention can be radicals R 1 to R 6 which have at least one hydrocarbyl radical having 1 to 30 carbon atoms, especially 2 to 30 carbon atoms, more preferably 3 to 30 carbon atoms, especially 5 to 30 carbon atoms, included.
  • Longer chain hydrocarbyl radicals improve fuel solubility.
  • Suitable hydrocarbyl radicals of this kind and longer-chain hydrocarbyl radicals are, for example, pure aliphatic linear or branched hydrocarbon radicals which may be of synthetic or natural origin. Examples of these are methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, tert-butyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2.2- Dimethylpropyl, 1-ethylpropyl, n-hexyl, 1, 1-di- methyl-propyl, 1, 2-dimethyl-propyl, 1-methyl-pentyl, 2-methylpentyl, 3-methyl-pentyl, 4-methyl-pentyl, 1, 1-dimethyl-butyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl , 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-
  • Alicyclic hydrocarbyl radicals are also suitable as substituents on the linear aliphatic oligo- or polyamines in the context of the present invention. Examples of these are cyclopentyl, methylcyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, cycloheptyl and cyclooctyl.
  • linear or branched alkylcarbonyl radicals in particular radicals of corresponding fatty acids having 5 to 30, in particular 10 to 22, especially 12 to 18 carbon atoms.
  • these are formyl, acetyl, n-propanoyl, isopropanoyl, n-butanoyl, 2-butanoyl, isobutanoyl, tert-butanoyl, pentanoyl, 1-methylbutanoyl, 2-methylbutanoyl, 3-methylbutanoyl, 2,2- Dimethylpropanoyl, 1-ethylpropanoyl, n-hexanoyl, 1, 1-dimethylpropanoyl, 1, 2-dimethylpropanoyl, 1-methylpentanoyl, 2-methylpentanoyl, 3-methylpentanoyl, 4-methylpentanoyl, 1,1-dimethylbutanoyl, 1, 2-
  • longer-chain aliphatic hydrocarbon radicals or longer-chain alkylcarbonyl especially vegetable or animal fats or oils, eg. Coconut oil, tall oil, palm oil, rapeseed oil, soybean oil or jatropha oil.
  • the oligo or polyamines with longer-chain hydrocarbyl radicals based on these raw materials the latter are inevitably present as homolog mixtures and / or as mixtures of saturated and unsaturated chains.
  • Linear alkoxylated oligo- or polyamines substituted with the abovementioned alkylcarbonyl radicals can be prepared in a simple manner familiar to the person skilled in the art from the amine base and a reactive derivative of the associated fatty acid.
  • a lower alkyl, a halide such as the fatty acid chloride or the anhydride produce.
  • alkylcarbonyl radicals in the linear alkoxylated oligo- or polyamines can be converted, for example, by customary hydrogenation processes into the corresponding longer-chain aliphatic hydrocarbon radicals having the same carbon number.
  • Suitable bridge members A 1 to A 3 are in principle all divalent linear or branched aliphatic and divalent aromatic hydrocarbon bodies, but preferably polyalkylene groups of the formula - (CH 2) q -, in which q is a number from 1 to 12, in particular 2 to 6, especially 2 to 4, most preferably 2 or 3, stands. Thus, 1, 2-ethylene and 1, 3-propylene are particularly favorable.
  • bridge members having 2 or 3 carbon atoms in addition to the ⁇ , ⁇ -linking hydrocarbon bodies, it is also possible to use non-linear bridge members such as 1, 1-ethylene, 1, 1-propylene, 2,2-propylene and 1, 2 Propylene good.
  • divalent aromatic bridge members A 1 to A 3 are ortho, meta and para-phenylene.
  • the bridge members A 1 to A 3 may be the same or different.
  • n and m are each independently integers from 0 to 30, which upper limit is not critical.
  • n and m are each independently a number from 0 to 6, in particular 0 to 4, especially 0 to 2.
  • the present invention relates to the use of linear alkoxylated oligo- or polyamines of the general formula I in which
  • bridge members A 1 to A 3 independently of one another denote C 2 -C 3 -alkylene groups and
  • n and m are each the number from 0 to 2.
  • Typical examples of such linear alkoxylated oligo- or polyamines which can be used for the present invention are the following:
  • N-mono (hydroxybutyl) -1,3-propylenediamine • N, N'-di- (hydroxypropyl) -1,3-propylenediamine
  • substituted or heterocyclic-carrying representatives of the linear alkoxylated oligo- and polyamines of the general formula I which can be used for the present invention are the following:
  • N-propoxylated or N-butoxylated N-2-cyanoethyl-N ', N'-dimethyl-1,3-propylenediamine as a representative of a cyanoalkyl-substituted alkoxylated oligo- or polyamine • N- (3-amino-2,2-dimethylpropyl) -pyrrolidine, N- (3-aminopropyl) -pyrazate, N- (3-amino-propyl) -morpholine, propoxylated or butoxylated at the nitrogen atoms with still free hydrogen atoms , N- (3-aminopropyl) -N'-methylpyrazane, N- (3-aminopropyl) -N '- (2-hydroxyethyl) -pyrazane and N- (3-aminopropyl) -imidazole as representatives of alkoxylated oligo- or polyamines with radicals R 1 and R 2
  • R 1 and R 2 which together with the nitrogen atom carrying them, form a ring which still has carbonyl carbon atoms and can carry additional substituents
  • Propoxylated or butoxylated 4- (2-aminoethyl) imidazole as representatives of oligo- or polyamines, in which the radical R 1, together with the nitrogen atom carrying it and a carbon atom of the alkylene group A 1, has a five or more nitrogen atoms with free hydrogen atoms or six-membered ring which may have further heteroatoms
  • the present invention relates to the use according to the invention of branched alkoxylated oligo- or polyamines having a polyethyleneimine structure.
  • Polyethyleneimines also referred to as poly (iminomethylenes) which are suitable as base materials for the present invention are to be understood as meaning polyamines obtainable by acid-catalyzed homopolymerization of aziridine (ethyleneimine), usually having 6 to 700 ethyleneimine units. They usually have a number-average molecular weight of from 250 to 30,000, particularly preferably from 280 to 10,000, in particular from 300 to 5,000, in particular from 350 to 2,000. They are usually highly branched or crosslinked, so that they contain a high proportion of tertiary nitrogen atoms.
  • Typical ratios of primary to secondary to tertiary nitrogen atoms in the polyethylene imines are 1: 2: 1 to 3: 4: 3.
  • the alkoxylated polyethyleneimines used in the present invention may optionally further substituents or functional groups, such as C 1 - to C 30 -alkyl groups, C 5 - to C 6 -cycloalkyl groups, C 1 - to C 29 -alkylcarbonyl groups or C 2 - to C 5 -cycloalkyl groups.
  • branched alkoxylated oligo- or polyamines having a polyethyleneimine structure whose polyethyleneimine skeleton has a number-average molecular weight of from 300 to 5000, in particular from 300 to 3000, in particular from 350 to 2000.
  • a typical alkoxylated polyethylenimine for use in the present invention is a butoxylated polyethylenimine having a number average molecular weight for the polyethylenimine backbone of 400 to 1000 and an average of 0.9 to 1.2 dialkylate groups per nitrogen atom in the molecule.
  • alkoxylated oligo- and polyamines according to the invention in particular the linear alkoxylated oligo- or polyamines of the general formula I and the branched alkoxylated oligo- or polyamines having a polyethyleneimine structure used according to the invention have, on average, for each molecule
  • the alkoxylation of oligo- and polyamines to the alkoxylated oligo- and polyamines used according to the invention can be carried out by customary methods ,
  • the alkoxylation can be carried out with or without a catalyst.
  • catalysts are alkali metal or alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide or calcium hydroxide, alkali metal alkoxides such as sodium or potassium methoxide, alkali metal hydrides or alkali metal carbonates such as sodium or potassium carbonate, typically in amounts of 0.05 to 10 wt .-%, in particular of 0 , 5 to 2 wt .-%, based on the total amount of oligo- or polyamine plus alkylene oxide.
  • the alkoxylation is usually carried out in aqueous solution at temperatures of 70 to 200 0 C; It may be advantageous to carry out the reaction under pressure of up to 10 bar.
  • a two-stage reaction is recommended in which the oligo- or polyamine first - usually without catalyst - is reacted with up to one mole of alkylene oxide per secondary or primary amino group and then the intermediate - using a Catalyst - is reacted with further alkylene oxide to the desired degree of alkoxylation; the second stage of the reaction may, if desired, after dehydration in Vacuum at elevated temperature in bulk or in an aprotic organic Eisensmttel be performed.
  • the more recently developed alkoxylation process using double metal cyanides can also be used here.
  • the described alkoxylated oligo- and polyamines are generally suitable for increasing the oxidation stability of oxidation-sensitive organic liquids, but in particular for increasing the oxidation stability of oxidation-sensitive organic liquids selected from pure hydrocarbons and fuels and lubricants of fossil, vegetable or animal origin. Such organic liquids are especially sensitive to oxidation if they contain unsaturations, ie double or multiple bonds.
  • Pure hydrocarbons are, for example, large-scale hydrocarbon streams, such as those produced in refineries, for example C 4 -Khlenwasserst.0ff St.rome as raffinate I or raffinate II.
  • Fuels and lubricants are, for example, gasoline fuels, middle distillates such as diesel fuel of fossil origin or engine oils. Typical dosage rates for these purposes are 10 to 10,000 ppm by weight, in particular 20 to 2000 ppm by weight, especially 30 to 500 ppm by weight.
  • alkoxylated oligo- or polyamines is particularly preferred for increasing the oxidation stability of biofuel oils based on fatty acid esters or of mixtures of such biofuel oils with middle distillates of fossil origin and / or of vegetable and / or animal origin, which are described in US Pat represent essential hydrocarbon mixtures and are free of fatty acid esters, in an amount of 10 to 10,000 ppm by weight, based on the amount of biofuel.
  • the present invention furthermore relates to a mixture of linear alkoxylated oligo- or polyamines of the general formula I or branched alkoxylated oligo- or polyamines with a polyethyleneimine Structure whose polyethyleneimine skeleton has a number-average molecular weight of 300 to 5,000, and biofuel oils based on fatty acid esters in a weight ratio of 1: 100,000 to 1: 100, preferably 1: 50,000 to 1: 500, especially 1: 20,000 to 1: 1000, especially 1: 10,000 to 1: 2000.
  • the subject matter of the present invention is also a fuel which contains a larger proportion of a fuel oil
  • the fuel component (A) is usually referred to as "biodiesel".
  • This biofuel oil (A) is preferably substantially alkyl esters of fatty acids derived from vegetable and / or animal oils and / or fats.
  • Alkyl esters are usually lower alkyl esters, in particular C 1 to C 4 alkyl esters, understood by transesterification of occurring in vegetable and / or animal oils and / or fats glycerides, especially triglycerides, by means of
  • Examples of vegetable oils which are converted into corresponding alkyl esters and thus can serve as a basis for biodiesel are castor oil, olive oil, peanut oil, pear kernel oil, coconut oil, mustard oil, cottonseed oil, and in particular sunflower oil, palm oil, soybean oil and rapeseed oil.
  • Other examples include oils that can be extracted from wheat, jute, sesame and the shea nut; furthermore, arachis oil, jatropha oil and linseed oil are also usable. The recovery of these oils and their conversion to the alkyl esters are known in the art or may be derived therefrom.
  • Vegetable fats are also useful in principle as a source of biodiesel, but play a minor role.
  • animal fats and oils that are converted to corresponding alkyl esters and thus can serve as the basis for biodiesel include fish oil, beef tallow, swine tallow, and similar fats and oils derived from the slaughtering or recycling of farmed or wild animals.
  • saturated or unsaturated fatty acids which usually have from 12 to 22 carbon atoms and carry additional functional group such as hydroxyl groups
  • alkyl esters lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, elaidic acid, erucic acid and ricinoleic acid, especially in the form of mixtures of such fatty acids, can occur.
  • Typical lower alkyl esters based on vegetable and / or animal oils and / or fats which are used as biodiesel or biodiesel components are, for example, sunflower methyl ester, palm oil methyl ester ("PME”), soybean oil methyl ester (“SME”) and especially rapeseed oil methyl ester (“RME”). ).
  • fuel component (B) is to be understood as meaning middle distillate fuels boiling in the range from 120 to 450 ° C.
  • middle distillate fuels are used in particular as diesel fuel, heating oil or kerosene, with diesel fuel and heating oil being particularly preferred.
  • Middle distillate fuels fuels are referred to, can be obtained from crude oil distillation by DES and in the range from 120 to 450 0 C boil.
  • low-sulfur middle distillates are used, ie those containing less than 350 ppm sulfur, especially less than 200 ppm sulfur, especially less than 50 ppm sulfur. In special cases they contain less than 10 ppm sulfur, these middle distillates are also called "sulfur-free".
  • These are generally crude oil distillates, which have been subjected to a hydrogenating refining, and therefore contain only small amounts of polyaromatic and polar compounds.
  • those middle distillates which have 95% distillation points below 370 0 C, in particular below 350 0 C and in special cases below 330 0 C.
  • Low-sulfur and sulfur-free middle distillates can also be obtained from heavier petroleum fractions, which can no longer be distilled under atmospheric pressure.
  • Hydrocarbon cracking, thermal cracking, catalytic cracking, coker processes and / or visbreaking may be mentioned as typical conversion processes for the preparation of middle distillates from heavy petroleum fractions. Depending on the process, these middle distillates are low in sulfur or sulfur-free or are subjected to a hydrogenating refining.
  • middle distillates preferably have aromatics contents of less than 28% by weight, in particular less than 20% by weight.
  • the content of normal paraffins is between 5% and 50% by weight, preferably between 10 and 35% by weight.
  • middle distillates should also be understood here, which can be derived either indirectly from fossil sources such as crude oil or natural gas or else produced from biomass via gasification and subsequent hydrogenation.
  • a typical example of a middle distillate fuel derived indirectly from fossil sources is GTL (gas-to-liquid) diesel fuel produced by Fischer-Tropsch synthesis.
  • a middle distillate is produced via the BTL ("biomass-to-liquid") process, which can be used either alone or in admixture with other middle distillates as fuel component (B).
  • the middle distillates also include hydrocar- bons obtained by hydrogenating fats and fatty oils. They contain mostly n-paraffins.
  • the said middle distillate fuels have in common that they are essentially hydrocarbon mixtures and are free from fatty acid esters.
  • the described alkoxylated oligo- or polyamines are also particularly suitable for increasing the oxidation stability of gasolines.
  • gasoline fuels are all commercially available gasoline fuel compositions into consideration.
  • a typical representative here is the market-standard base oil from Eurosuper according to EN 228.
  • gasoline compositions of the specification according to WO 00/47698 are also suitable.
  • a gasoline composition having an aromatic content of at most 60% by volume, such as at most 42% by volume, and a sulfur content of at most 2000, such as at most 150 ppm by weight may be mentioned.
  • the aromatics content of the gasoline composition is preferably not more than 50% by volume, in particular from 1 to 45% by volume, especially from 5 to 40% by volume.
  • the sulfur content of the gasoline is preferably at most 500 ppm by weight, in particular 0.5 to 150 ppm by weight, especially 1 to 100 ppm by weight.
  • the gasoline composition for example, an olefin content up to 50 vol .-%, preferably from 0.1 to 21 vol .-%, in particular from 2 to 18 vol .-%, a benzene content of up to 5 vol .-%, preferably 0 to 1, 0 vol .-%, in particular 0.05 to 0.9 vol .-%, and / or an oxygen content of up to 47.5 wt .-%, such as 0.1 to 2.7 wt. % or, for example, from 2.7 to 47.5% by weight (for gasoline compositions containing predominantly lower alcohols).
  • gasoline fuel compositions may also be mentioned by way of example, which at the same time have an aromatics content of not more than 38% by volume, an olefin content of not more than 21% by volume, a sulfur content of not more than 50 ppm by weight, a benzene content of not more than 1.0% by volume. -% and have an oxygen content of 0.1 to 47.5 wt .-%.
  • the summer vapor pressure of the gasoline composition is usually maximum 70 kPa, in particular 60 kPa (each at 37 ° C).
  • the ROZ of the petrol fuel composition is usually 75 to 105.
  • a usual range for the corresponding MOZ is 65 to 95.
  • the specified specifications are determined by conventional methods (DIN EN 228).
  • said gasoline fuel compositions 0.1 to 95, more preferably 1 to 90, most preferably 5 to 90, especially 10 to 90, especially 50 to 90 vol .-% C r C 4 alkanols as low alcohol fuel components.
  • Such fuels are described, for example, in WO 2004/090079.
  • Suitable C 1 -C 6 -panolkanols are methanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol and, in particular, ethanol; Mixtures of the stated dC 4 -alkanols are possible as low-alcohol fuel components.
  • the gasoline fuel compositions may also contain ethers having 5 or more carbon atoms, for example methyl tert-butyl ether, in the molecule in an amount of up to 30% by volume.
  • the fuels described usually still contain additives customary for this purpose, such as flow improvers for improving the low-temperature behavior, in particular middle distillate flow improvers, nucleators, wax anti-settling additives and mixtures thereof, and furthermore conductivity improvers, corrosion protection additives , Lubricity additives, antioxidants, metal deactivators, anti-foaming agents, demulsifiers, detergents, cetane number improvers, solvents or diluents, dyes or fragrances or mixtures thereof.
  • additives customary for this purpose such as flow improvers for improving the low-temperature behavior, in particular middle distillate flow improvers, nucleators, wax anti-settling additives and mixtures thereof, and furthermore conductivity improvers, corrosion protection additives , Lubricity additives, antioxidants, metal deactivators, anti-foaming agents, demulsifiers, detergents, cetane number improvers, solvents or diluents, dyes or fragrances or mixtures thereof.
  • an accelerated oxidation test is also used.
  • air is passed through a certain amount of fuel, previously added in a defined manner traces of copper ions by immersion of a brass rod, at a constant elevated temperature for a fixed period of time.
  • sediment is formed, which is filtered off and weighed after defined aging. The less sediment is obtained, the better the thermal stability of the fuel.
  • the described alkoxylated oligo- or polyamines are typically added in an amount of 10 to 10,000 ppm by weight, based on the amount of biofuel oil (A) in the fuel according to the invention.
  • Preferred metering ranges are 20 to 2000 ppm by weight, in particular 50 to 1000 ppm by weight, especially 100 to 500 ppm by weight.
  • Most of the described alkoxylated oligo- or polyamines already meet the requirement of a long induction time in the ranzimat test with a dosage of 500 ppm by weight or less.
  • conventional antioxidants for example BHT, BHA, TBHQ, trimethylhydroquinone or bisphenol A
  • Suitable solvents here are, in particular, alcohols such as n-butanol tanol, n-pentanol, n-hexanol, n-heptanol, n-octanol, 2-ethylhexanol, 2-propylheptanol or n-heptadecanol, carbon or fatty acid esters such as rapeseed oil methyl ester or amines such as dimethylamine, trimethylamine, piperidine or morpholine.
  • the present invention also provides a stabilizing formulation which
  • This formulation can consist only of the components (i) to (v) or contain other components, which then usually provide no further contribution to the stabilization. However, it consists of at least 50 wt .-%, in particular at least 70 wt .-%, especially at least 90 wt .-%, of components (i) to (v).
  • the stabilization formulation mentioned serves to increase the stability, in particular the oxidation stability, of organic liquids requiring stabilization in general, but in particular to increase the stability, in particular the oxidation stability, but also, for example, the color stability of organic liquids requiring stabilization, which consist of pure hydrocarbons and starch - And lubricants of fossil, vegetable or animal origin are selected, especially if such organic liquids are unsaturates, ie Double or multiple bonds, included.
  • the addition of said stabilizing formulation causes an increase in color stability.
  • dispersants (ii) the customary detergents used in gasoline and / or diesel fuel are generally considered here, preferably polyisobutenyl-substituted succinimides are used.
  • Suitable metal deactivators (iii) are normally customary products available for this purpose on the market, for example N, N'-disalicylidene-1,2-diamino-propane.
  • demulsifiers or defoamers (iv) are normally used here commercially available products, such as Tolad® 2898 manufacturer Baker Petrolite.
  • solvent (v) is usually the above-mentioned solvents;
  • medium and long-chain aliphatic alcohols, in particular alkanols, with carbon chain lengths of 4 to 18 have proven to be particularly suitable.
  • the induction times [in hours] in pure biofuel oil and / or in the accelerated oxidation test were determined as a function of the metered dose in the ranzimat test in accordance with Euro Standard 1412 per liter of fuel] in a mixture of biofuel oil and diesel fuel of fossil origin.
  • TEPA tetraethylenepentamine (according to WO 2008/049822)
  • B2 mixture of 20 vol .-% B1 and 80 vol .-% of commercial diesel fuel of fossil origin
  • the doses are based on the active substance;
  • the oxidation-stabilizing additive was added in each case in the form of a 40% strength by weight or 50% strength by weight solution in an alcohol.
  • the doses are based on the active substance;
  • the oxidation-stabilizing additive was added in each case in the form of a 40% strength by weight or 50% strength by weight solution in an alcohol.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
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  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
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  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

L'invention porte sur l'utilisation d'oligo- ou de polyamines alcoxylées ayant une masse moléculaire moyenne en nombre de 90 à 70 000 pour augmenter la stabilité à l'oxydation de liquides organiques sensibles à l'oxydation tels que les hydrocarbures purs ou les carburants et lubrifiants, en particulier d'huiles biocombustibles et de carburants pour moteur à étincelles.
PCT/EP2009/065188 2008-11-25 2009-11-16 Oligo- ou polyamines alcoxylées servant de stabilisateurs d'oxydation WO2010060818A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP08169850 2008-11-25
EP08169850.8 2008-11-25

Publications (1)

Publication Number Publication Date
WO2010060818A1 true WO2010060818A1 (fr) 2010-06-03

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11969506B2 (en) 2017-03-15 2024-04-30 Modernatx, Inc. Lipid nanoparticle formulation

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB570232A (en) * 1941-01-15 1945-06-28 Us Rubber Co Improvements in anti-oxidants
DE102004024532A1 (de) * 2004-05-18 2005-12-15 Clariant Gmbh Demulgatoren für Mischungen aus Mitteldestillaten mit Brennstoffölen pflanzlichen oder tierischen Ursprungs und Wasser
WO2008049822A2 (fr) * 2006-10-27 2008-05-02 Basf Se Oligo- ou polyamine en tant que stabilisateurs d'oxydation pour huiles combustibles biologiques

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB570232A (en) * 1941-01-15 1945-06-28 Us Rubber Co Improvements in anti-oxidants
DE102004024532A1 (de) * 2004-05-18 2005-12-15 Clariant Gmbh Demulgatoren für Mischungen aus Mitteldestillaten mit Brennstoffölen pflanzlichen oder tierischen Ursprungs und Wasser
EP1609843A2 (fr) * 2004-05-18 2005-12-28 Clariant GmbH Désémulsifiants pour mélanges de distillats moyens, d'huiles combustibles d'origine végétale ou animale et d'eau
WO2008049822A2 (fr) * 2006-10-27 2008-05-02 Basf Se Oligo- ou polyamine en tant que stabilisateurs d'oxydation pour huiles combustibles biologiques

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11969506B2 (en) 2017-03-15 2024-04-30 Modernatx, Inc. Lipid nanoparticle formulation

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