EP0398100A1 - Fuel compositions containing alkoxylation products - Google Patents

Fuel compositions containing alkoxylation products Download PDF

Info

Publication number
EP0398100A1
EP0398100A1 EP90108498A EP90108498A EP0398100A1 EP 0398100 A1 EP0398100 A1 EP 0398100A1 EP 90108498 A EP90108498 A EP 90108498A EP 90108498 A EP90108498 A EP 90108498A EP 0398100 A1 EP0398100 A1 EP 0398100A1
Authority
EP
European Patent Office
Prior art keywords
oxo
oils
alkoxylation products
alcohols
fuels
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.)
Granted
Application number
EP90108498A
Other languages
German (de)
French (fr)
Other versions
EP0398100B1 (en
Inventor
Hans Peter Dr. Rath
Herwig Dr. Hoffmann
Volker Dr. Vogt
Hans Dr. Horler
Helmut Dr. Mach
Jürgen Dr. Thomas
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP0398100A1 publication Critical patent/EP0398100A1/en
Application granted granted Critical
Publication of EP0398100B1 publication Critical patent/EP0398100B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
    • C10L1/1985—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid polyethers, e.g. di- polygylcols and derivatives; ethers - esters
    • 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
    • C10L1/146—Macromolecular compounds according to different macromolecular groups, mixtures 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
    • C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)

Definitions

  • the invention relates to fuels for internal combustion engines with improved properties, containing alkoxylation products, by the reaction of oxo oils, fractions of these oxo oils or partially esterified carboxylic acids with oxo oils or oxo oil fractions, with alkylene oxides with 2 to 4 carbon atoms, in particular with propene oxide and / or butene oxides and / or be obtained in minor amounts of ethene oxide.
  • the invention relates to fuel compositions for gasoline engines.
  • additive packages are added to gasoline in amounts of up to 2,500 mg / kg. These mostly consist of fuel detergents, corrosion inhibitors, oxidation inhibitors, anti-icing agents, carrier oils and solvents.
  • Carrier oils primarily have the task of preventing the so-called valve plugging and ensuring a better distribution of the detergents.
  • polyethers and esters as carrier oils should reduce the increase in the octane requirement of engines with increasing number of operating hours and ultimately set the lowest possible level of octane requirement.
  • esters as a gasoline additive has long been known and is described, for example, in DE-OS 21 29 461, DE-OS 19 64 785, DE-OS 23 16 535 or GB 21 17 468.
  • Esters with more than 35 carbon atoms have a particularly good effect, in particular if the alcohol component is highly branched, that is to say has been prepared by oxidizing oligomers of propene and butenes, in particular of n-butenes.
  • aromatic tri- and tetracarboxylic acids are used, relatively short-chain alcohols can be used to achieve the desired molecular weight in acceptable condensation times and with normal catalyst removal. However, the high price of these poorly accessible acids is a serious economic disadvantage.
  • aromatic dicarboxylic acids such as phthalic acid is far more economical, but long-chain alcohols which are difficult to access are then required for the preparation of effective esters. High condensation temperatures give acceptable condensation times, but processing is very difficult and time-consuming.
  • alkene oxide-based polyethers have also been known for a long time and e.g. described in DE-OS 21 29 461. Alkene oxides such as propene oxide and butene oxides are preferred here. However, only special polyethers containing predominantly butene oxides are infinitely miscible with polyisobutene and polyisobutene derivatives. Butene oxides are only available to a limited extent and the market price is correspondingly high.
  • the task was therefore to synthesize a highly effective, at least equivalent carrier oil at significantly lower costs and to avoid the disadvantages of ester synthesis with complete esterification or polyether production with an excess of alkoxide.
  • alkoxylation products from reaction products of alkene oxides with oxo oils, oxo oil fractions and carboxylic acids partially esterified with oxo oils combine all the advantages of esters and / or polyethers, and the cost of starting materials can be drastically reduced.
  • the products are excellent carrier oils with partly high molecular weight, whereby up to 30% of the usual detergents can be saved without the gasoline quality, i.e. the purifying effect in the intake and mixture formation system deteriorates.
  • the invention relates to fuel compositions which contain small amounts, e.g. Contain 0.005 to 0.2% by weight of alkoxylation products, obtainable by reacting alkylene oxides with 2 to 4 carbon atoms, in particular propene oxide and / or butene oxides and / or in minor amounts of ethene oxide with oxo oils, oxo oil fractions and carboxylic acids partially esterified with oxo oils or oxo oil fractions, where the oxo oils are distillation residues from the production of oxo alcohols with more than 8 carbon atoms and the molar ratio of the alkylene oxides to the OH groups and free carboxyl groups in the oxo oil or ester is preferably from 0.2 to 30.
  • the amount of alkoxides must be at least so large that all free carboxyl groups are alkoxylated, i.e. a molar ratio of alkene oxide to carboxyl groups of at least 2.
  • alkene oxides in particular 1 2-butene oxide.
  • minor amounts for example up to 50 mol%, based on the total amount of carboxyl and hydroxyl groups of ethene oxide can also be incorporated, as long as the compatibility of the components of gasoline additive packages is not impaired thereby. This is the case in particular in the production according to Example D.
  • the use of pure ethylene oxide may even be economical here.
  • the reaction with alkene oxides takes place in a manner known per se and is described, for example, in DE patent application P 38 26 608.3, preparation example 1.
  • the oxo oils or fractions used are distillation residues from the production of oxo alcohols with more than 8 carbon atoms.
  • the oxo alcohols on which the oxo oils are based should in particular be branched with 13, 17, 21, 25, 29 and 33 carbon atoms and derive from oligomers of propene and from butenes, in particular from n-butenes, in order to ensure that the oxo oils are in a liquid state at room temperature.
  • a low melting point well below zero ° C is an advantage, since the oxo oil behaves largely like its alcohol in this respect.
  • the oxo oils are mixtures of substances with far more than 20 compounds, some of which are only isomers.
  • the oxo oil of a di-butene contains acids, nonanols, decanediols, di-isononyl ethers, isononanoic acid nyl esters and large amounts of ether alcohols of the empirical formula C19H40O2.
  • the ether alcohols of the oxo oils have the general formula C 2n + 1 H 4n + 2 O2, where n stands for the number of carbon atoms of the oxo alcohol.
  • ether alcohols are probably formed by etherification of a diol with an alcohol, ie in the case of dibutene from decanediol and nonanol. This leads to the presumed general formula of ether alcohol: where n has the aforementioned meaning and generally means the numbers 9 to 33.
  • ether alcohols are usually present in the oxo oils in amounts of 30-60% and can optionally be separated off by distillation. For economic reasons, however, isolation of the ether alcohols with subsequent esterification and / or etherification is not recommended for the present application, unless there are qualitative reasons for this.
  • the partial esterification of the previously characterized oxo oils or oxo oil fractions can be carried out according to conventional esterification processes with aliphatic and aromatic carboxylic acids.
  • Suitable aliphatic carboxylic acids are isononanoic acid, succinic acid, maleic acid and adipic acid, but also carboxylic acid mixtures, such as the dicarboxylic acid mixture of the production of adipic acid (mixture of adipic acid, succinic acid and glutaric acid) or the stripping acid of cyclohexane oxidation (mixture of adipic acid) and hydroxyapronic acid and hydroxyapronic acid.
  • Aromatic di-, tri- or tetracarboxylic acids are o-phthalic acid, isophthalic acid, terephthalic acid, trimesic acid, trimellitic acid, pyromellitic acid and benzene tetracarboxylic acid.
  • Esterification with acid anhydrides is particularly preferred.
  • the acids or acid anhydrides are generally added during the esterification in amounts of 0.5 to 1.3 equivalents based on the hydroxyl number and with acid catalysts, such as titanium acid esters, but also without a catalyst at temperatures of 150 to 250 ° C. under vacuum or with Fumigation with nitrogen esterified. Processing by neutralization and washing is carried out according to conventional methods.
  • the oxo oils are esterified, preferably in the presence of KOH, with 0.4 to 0.6 mol of phthalic anhydride, based on the 0H number, and the condensation is terminated at acid numbers between 10 and 50 and, as previously described, with alkene oxides without further KOH addition or drainage. In this way, time and cost-intensive neutralization and washing steps are avoided and alkene oxide consumption is minimized.
  • Fuels for internal combustion engines are organic, mostly hydrocarbon-containing liquids that are suitable for the operation of Otto, Wankel and diesel engines.
  • hydrocarbons from coal hydrogenation hydrocarbons from coal hydrogenation, alcohols of various origins and compositions and ethers such as Methyl tertiary butyl ether contained therein.
  • the admissible mixtures are mostly nationally defined worldwide.
  • the alkoxylation products to be used according to the invention are usually the fuels together with fuel detergents, such as amines of oleic acid or ethylenediaminetetraacetic acid according to EP-A-6527, or the polyisobutenylsuccinic acid furthermore polyether polyamine carbamates, and in particular polybutenamines, obtained by reacting the alcohols or the corresponding halogen compounds with NH3 , Aminoethylethanolamine, dimethylaminopropylamine, triethylene tetramine or tetraethylene pentamine, as described in US Pat. No.
  • fuel detergents such as amines of oleic acid or ethylenediaminetetraacetic acid according to EP-A-6527
  • polyisobutenylsuccinic acid furthermore polyether polyamine carbamates, and in particular polybutenamines, obtained by reacting the alcohols or the corresponding halogen compounds with NH3 , Aminoethylethanolamine
  • the distillation residue of a C9-oxo alcohol, obtained from the cobalt-catalyzed oxidation of dibutene, is used to produce the alkoxylation product.
  • the dibutene is produced from the so-called raffinate II, a mixture of approximately 30% butanes, 45% butene-1 and 25% cis and trans-butene-2.
  • 1,000 g of this distillation residue which has an OH number of 132, an acid number of 10, a density of 0.872 g / cm3 at 20 ° C and a viscosity of 27 mm2 / s at 20 ° C, are in a stirred tank with 5 g of KOH flakes are added, the reaction vessel is flushed with nitrogen, evacuated to 10 mbar and heated to 120 ° C. under vacuum and the mixture is stirred for 2 hours. At 1.1 bar nitrogen pressure, the mixture is heated to 160 to 170 ° C. and 1,000 g of 1,2-butene oxide are gassed in so slowly that a pressure of 4.5 bar is not exceeded.
  • the polyether-containing mixture obtained has an OH number of 75, a density of 0.917 g / cm3 at 20 ° C and a viscosity of 71 mm2 / s at 20 ° C.
  • the procedure is as in Preparation A, but 400 g of distillation residue, 2 g of KOH flakes and 1,600 g of 1,2-butene oxide are used.
  • the product has an OH number of 37, a density of 0.948 g / cm3 at 20 ° C and a viscosity of 385 mm2 / s at 20 ° C.
  • an ether alcohol C21H44O2 is isolated by distillation and analogous to Preparation A with a mixture of 1,2-propene oxide and 1,2-butene oxide implemented.
  • the OH number of the alcohol is 171, its density at 20 ° C 0.87 g / cm3 and its viscosity at 20 ° C 75 mm2 / s.
  • 500 g of the ether alcohol, 2.5 g of KOH, 500 g of 1,2-propene oxide and 1,000 g of 1,2-butene oxide are used for the reaction.
  • the OH number of the reaction product is 48, its viscosity at 20 ° C was 320 mm2 / s.
  • the following table shows the effect of known carrier oils and the alkoxylation products to be used according to the invention in combination with known detergents in gasoline for internal combustion engines.
  • the quantities shown in the table were added unleaded premium petrol (RON 95; DIN 51 607) and tested in test bench tests with a 1.2 Opel Kadett engine in accordance with CEC-F-02-T-79.
  • the reference oil RL 51 was used as engine oil.
  • the table shows a significantly better effect of the alkoxylation products according to the invention compared to the prior art, i.e. less deposits on the intake valves of the 1.2 l Opel Kadett engine.
  • the carrier oils to be used according to the invention were combined with commercially available polybutenamine, produced from polybutene MG 1300 and aminoethylethanolamine, active substance content 50%.
  • the recommended dosage of the commercial polybutenamine for formulations with mineral oil is 350 mg / kg.
  • the carrier oils according to the invention enable a saving of about 30% in polymeric detergents. Results with other higher viscosity detergents are comparable.
  • Another advantage of the new carrier oils is their compatibility with polyisobutene with a molecular weight of 800 to 2,000, which is contained in most of the detergents used for gasoline additives.
  • Propene oxide-based polyethers are not very compatible; i.e. higher amounts of solvent are required to produce an additive package.
  • the carrier oils according to the invention are significantly cheaper to produce than polyethers, especially if the latter are produced on the basis of butene oxide based on polyisobutene. Since the substance mixtures contain a number of low molecular weight compounds, particularly in the case of partial esterification, they are more suitable for combating valve plugging than pure polyethers with higher molecular weights.

Abstract

Fuel compositions contain alkoxylation products of oxo-oils or fractions or esters thereof, which have been alkoxylated with propene oxide and/or butene oxides and/or at most minor quantities of ethene oxide.

Description

Die Erfindung betrifft Kraftstoffe für Verbrennungsmaschinen mit verbes­serten Eigenschaften, mit einem Gehalt an Alkoxylierungsprodukten, die durch Umsetzung von Oxoölen, Fraktionen dieser Oxoöle oder teilveresterten Carbonsäuren mit Oxoölen oder Oxoölfraktionen, mit Alkylenoxiden mit 2 bis 4 C-Atomen insbesondere mit Propenoxid und/oder Butenoxiden und/oder in untergeordneten Mengen Ethenoxid erhalten werden. Insbesondere betrifft die Erfindung Kraftstoffzusammensetzungen für Ottomotoren.The invention relates to fuels for internal combustion engines with improved properties, containing alkoxylation products, by the reaction of oxo oils, fractions of these oxo oils or partially esterified carboxylic acids with oxo oils or oxo oil fractions, with alkylene oxides with 2 to 4 carbon atoms, in particular with propene oxide and / or butene oxides and / or be obtained in minor amounts of ethene oxide. In particular, the invention relates to fuel compositions for gasoline engines.

Es ist bekannt, daß man durch Zusatz verschiedener Additive zum Benzin die Reinhaltung von Vergasern, Einspritzdüsen, Ansaugrohren und Einlaßventilen verbessern und die Emissionen unerwünschter Bestandteile der Auspuffgase dadurch verringern kann. Im allgemeinen setzt man dem Benzin sogenannte Additivpakete in Mengen bis zu 2 500 mg/kg zu. Diese bestehen meist aus Kraftstoffdetergentien, Korrosionsinhibitoren, Oxidationsinhibitoren, Vereisungsverhinderern, Trägerölen und Lösemitteln.It is known that the addition of various additives to gasoline can improve the cleanliness of carburetors, injectors, intake pipes and intake valves and thereby reduce the emissions of undesirable components of the exhaust gases. In general, additive packages are added to gasoline in amounts of up to 2,500 mg / kg. These mostly consist of fuel detergents, corrosion inhibitors, oxidation inhibitors, anti-icing agents, carrier oils and solvents.

Trägeröle haben vor allem die Aufgabe, das sogenannte Ventilstecken zu verhindern und für eine bessere Verteilung der Detergentien zu sorgen. Darüber hinaus sollen Polyether und Ester als Trägeröle die Zunahme des Oktanzahlbedarfs von Motoren bei steigender Betriebsstundenzahl verringern und schließlich ein möglichst niedriges Niveau des Oktanzahlbedarfs ein­stellen.Carrier oils primarily have the task of preventing the so-called valve plugging and ensuring a better distribution of the detergents. In addition, polyethers and esters as carrier oils should reduce the increase in the octane requirement of engines with increasing number of operating hours and ultimately set the lowest possible level of octane requirement.

Die Verwendung von Estern als Benzinzusatz ist seit langem bekannt und z.B. in der DE-OS 21 29 461, DE-OS 19 64 785, DE-OS 23 16 535 oder GB 21 17 468 beschrieben. Besonders gute Wirkung haben Ester mit mehr als 35 Kohlenstoffatomen insbesondere dann, wenn die Alkoholkomponente stark verzweigt ist, d.h. durch Oxierung von Oligomeren von Propen und Butenen, insbesondere von n-Butenen hergestellt worden ist. Bei Verwendung von aromatischen Tri- und Tetracarbonsäuren kann man mit relativ kurzkettigen Alkoholen zu dem gewünschten Molekulargewicht in vertretbaren Kondensa­tionszeiten und mit normalem Aufwand für die Katalysatorentfernung gelan­gen. Der hohe Preis dieser schlecht zugänglichen Säuren ist jedoch ein Gravierender wirtschaftlicher Nachteil. Weitaus wirtschaftlicher ist die Verwendung von aromatischen Dicarbonsäuren wie Phthalsäure, doch benötigt man für die Herstellung wirksamer Ester dann schwer zugängliche langketti­ge Alkohole. Durch hohe Kondensationstemperaturen erhält man zwar durchaus vertretbare Kondensationszeiten, doch ist die Aufarbeitung sehr schwierig und zeitintensiv.The use of esters as a gasoline additive has long been known and is described, for example, in DE-OS 21 29 461, DE-OS 19 64 785, DE-OS 23 16 535 or GB 21 17 468. Esters with more than 35 carbon atoms have a particularly good effect, in particular if the alcohol component is highly branched, that is to say has been prepared by oxidizing oligomers of propene and butenes, in particular of n-butenes. If aromatic tri- and tetracarboxylic acids are used, relatively short-chain alcohols can be used to achieve the desired molecular weight in acceptable condensation times and with normal catalyst removal. However, the high price of these poorly accessible acids is a serious economic disadvantage. The use of aromatic dicarboxylic acids such as phthalic acid is far more economical, but long-chain alcohols which are difficult to access are then required for the preparation of effective esters. High condensation temperatures give acceptable condensation times, but processing is very difficult and time-consuming.

Auch die Verwendung von Polyethern auf Alkenoxidbasis ist seit langem be­kannt und z.B. in der DE-OS 21 29 461 beschrieben. Hierbei sind Alkenoxide wie Propenoxid und Butenoxide bevorzugt. Unbegrenzt mischbar mit Polyiso­buten und Polyisobutenderivaten sind jedoch nur spezielle, überwiegend Butenoxide enthaltende Polyether. Butenoxide sind jedoch nur begrenzt ver­fügbar und der Marktpreis ist entsprechend hoch.The use of alkene oxide-based polyethers has also been known for a long time and e.g. described in DE-OS 21 29 461. Alkene oxides such as propene oxide and butene oxides are preferred here. However, only special polyethers containing predominantly butene oxides are infinitely miscible with polyisobutene and polyisobutene derivatives. Butene oxides are only available to a limited extent and the market price is correspondingly high.

Es bestand daher die Aufgabe, ein hochwirksames, mindestens gleichwertiges Trägeröl mit deutlich niedrigeren Kosten zu synthetisieren und die Nach­teile der Estersynthese mit vollständiger Veresterung bzw. Polyetherher­stellung mit Alkoxidüberschuß zu umgehen. Überraschenderweise vereinigen Alkoxylierungsprodukte aus Umsetzungsprodukten von Alkenoxiden mit Oxo­ölen, Oxoölfraktionen und mit Oxoölen teilveresterten Carbonsäuren alle Vorteile von Estern und/oder Polyethern in sich, wobei die Einsatzstoff­kosten drastisch gesenkt werden können. Die Produkte stellen ausgezeich­nete Trägeröle mit z.T. hohem Molekulargewicht dar, wodurch bis zu 30 % der üblichen Detergentien eingespart werden können, ohne daß sich die Benzinqualität, d.h. die reinhaltende Wirkung im Einlaß- und Gemischbil­dungssystem, verschlechtert.The task was therefore to synthesize a highly effective, at least equivalent carrier oil at significantly lower costs and to avoid the disadvantages of ester synthesis with complete esterification or polyether production with an excess of alkoxide. Surprisingly, alkoxylation products from reaction products of alkene oxides with oxo oils, oxo oil fractions and carboxylic acids partially esterified with oxo oils combine all the advantages of esters and / or polyethers, and the cost of starting materials can be drastically reduced. The products are excellent carrier oils with partly high molecular weight, whereby up to 30% of the usual detergents can be saved without the gasoline quality, i.e. the purifying effect in the intake and mixture formation system deteriorates.

Demgemäß sind Gegenstand der Erfindung Kraftstoffzusammensetzungen, die geringe Mengen, z.B. 0,005 bis 0,2 Gew.% Alkoxylierungsprodukte enthalten, erhältlich durch Umsetzung von Alkylenoxiden mit 2 bis 4 C-Atomen, insbe­sondere Propenoxid und/oder Butenoxiden und/oder in untergeordneten Mengen Ethenoxid mit Oxoölen, Oxoölfraktionen und mit Oxoölen oder Oxoölfraktio­nen teilveresterten Carbonsäuren, wobei die Oxoöle Destillationsrückstände der Herstellung von Oxoalkoholen mit mehr als 8 Kohlenstoffatomen sind und wobei bevorzugt das Molverhältnis der Alkylenoxide zu den OH-Gruppen und freien Carboxylgruppen im Oxoöl oder Ester 0,2 bis 30 beträgt. Dabei muß die Menge der Alkoxide mindestens so groß sein, daß alle freien Carboxyl­gruppen alkoxyliert sind, d.i. ein Molverhältnis Alkenoxid zu Carboxyl­gruppen von mindestens 2.Accordingly, the invention relates to fuel compositions which contain small amounts, e.g. Contain 0.005 to 0.2% by weight of alkoxylation products, obtainable by reacting alkylene oxides with 2 to 4 carbon atoms, in particular propene oxide and / or butene oxides and / or in minor amounts of ethene oxide with oxo oils, oxo oil fractions and carboxylic acids partially esterified with oxo oils or oxo oil fractions, where the oxo oils are distillation residues from the production of oxo alcohols with more than 8 carbon atoms and the molar ratio of the alkylene oxides to the OH groups and free carboxyl groups in the oxo oil or ester is preferably from 0.2 to 30. The amount of alkoxides must be at least so large that all free carboxyl groups are alkoxylated, i.e. a molar ratio of alkene oxide to carboxyl groups of at least 2.

Bei der Herstellung der Alkoxylierungsprodukte sind als Alkenoxide Propen­oxid und Butenoxide bevorzugt, insbesondere 1 2-Butenoxid. Allerdings können auch in untergeordneten Mengen, z.B. bis zu 50 Mol%, bezogen auf die Gesamtmenge der Carboxyl- und Hydroxylgruppen an Ethenoxid eingebaut werden, solange davon nicht die Verträglichkeit der Komponenten von Ben­zinadditivpaketen beeinträchtigt wird. Dies ist insbesondere bei Herstel­lung gemäß Beispiel D der Fall. Hier ist sogar der Einsatz reinen Ethy­lenoxids gegebenenfalls wirtschaftlich. Die Umsetzung mit Alkenoxiden erfolgt in an sich bekannter Weise und ist z.B. in DE-Patentanmeldung P 38 26 608.3, Herstellungsbeispiel 1, beschrieben.In the preparation of the alkoxylation products, propene oxide and butene oxides are preferred as alkene oxides, in particular 1 2-butene oxide. However, minor amounts, for example up to 50 mol%, based on the total amount of carboxyl and hydroxyl groups of ethene oxide can also be incorporated, as long as the compatibility of the components of gasoline additive packages is not impaired thereby. This is the case in particular in the production according to Example D. The use of pure ethylene oxide may even be economical here. The reaction with alkene oxides takes place in a manner known per se and is described, for example, in DE patent application P 38 26 608.3, preparation example 1.

Die verwendeten Oxoöle oder Oxoölfraktionen sind Destillationsrückstände der Herstellung von Oxoalkoholen mit mehr als 8 Kohlenstoffatomen. Die den Oxoölen zugrundeliegenden Oxoalkohole sollten insbesondere mit 13, 17, 21, 25, 29 und 33 Kohlenstoffatomen verzweigt sein und sich von Oligomeren des Propens und von Butenen, insbesondere von n-Butenen ableiten, um bei Raumtemperatur einen flüssigen Zustand der Oxoöle zu gewährleisten. Ein niedriger Schmelzpunkt weit unter Null °C ist von Vorteil, da sich das Oxoöl in dieser Hinsicht weitgehend wie sein Alkohol verhält.The oxo oils or fractions used are distillation residues from the production of oxo alcohols with more than 8 carbon atoms. The oxo alcohols on which the oxo oils are based should in particular be branched with 13, 17, 21, 25, 29 and 33 carbon atoms and derive from oligomers of propene and from butenes, in particular from n-butenes, in order to ensure that the oxo oils are in a liquid state at room temperature. A low melting point well below zero ° C is an advantage, since the oxo oil behaves largely like its alcohol in this respect.

Die Oxoöle stellen, insbesondere wenn sie sich von Oligomeren von Propen oder Butenen ableiten, Stoffgemische mit weit mehr als 20 Verbindungen dar, die nur z.T. Isomere sind. So enthält z.B. das Oxoöl eines Di-butens neben Säuren, Nonanolen, Dekandiolen, Di-isononylethern, Isononansäure­nonylester und größere Mengen von Etheralkoholen der Summenformel C₁₉H₄₀O₂. Die Etheralkohole der Oxoöle haben die allgemeine Formel C2n+1 H4n+2O₂, wobei n für die Anzahl der Kohlenstoffatome des Oxoalkohols steht. Wahrscheinlich entstehen diese Etheralkohole durch Veretherung eines Diols mit einem Alkohol, d.h. im Falle des Dibutens aus Dekandiol und Nonanol. Daraus ergibt sich die vermutete allgemeine Formel des Etheralkohols:

Figure imgb0001
wobei n vorgenannte Bedeutung hat und in der Regel die Zahlen 9 bis 33 bedeutet. Diese Etheralkohole sind meist in Mengen von 30-60 % in den Oxoölen vorhanden und können gegebenenfalls destillativ abgetrennt werden. Aus wirtschaftlichen Gründen empfiehlt sich eine Isolierung der Etheral­kohole mit nachfolgender Veresterung und/oder Veretherung für den vorlie­genden Anwendungszweck jedoch nicht, es sei denn, qualitative Gründe sprechen dafür.The oxo oils, especially if they are derived from oligomers of propene or butenes, are mixtures of substances with far more than 20 compounds, some of which are only isomers. For example, the oxo oil of a di-butene contains acids, nonanols, decanediols, di-isononyl ethers, isononanoic acid nyl esters and large amounts of ether alcohols of the empirical formula C₁₉H₄₀O₂. The ether alcohols of the oxo oils have the general formula C 2n + 1 H 4n + 2 O₂, where n stands for the number of carbon atoms of the oxo alcohol. These ether alcohols are probably formed by etherification of a diol with an alcohol, ie in the case of dibutene from decanediol and nonanol. This leads to the presumed general formula of ether alcohol:
Figure imgb0001
 where n has the aforementioned meaning and generally means the numbers 9 to 33. These ether alcohols are usually present in the oxo oils in amounts of 30-60% and can optionally be separated off by distillation. For economic reasons, however, isolation of the ether alcohols with subsequent esterification and / or etherification is not recommended for the present application, unless there are qualitative reasons for this.

Die Teilveresterung der zuvor charakterisierten Oxoöle oder Oxoölfraktio­nen kann nach herkömmlichen Veresterungsverfahren mit aliphatischen und aromatischen Carbonsäuren erfolgen. Als aliphatische Carbonsäuren sind Isononansäure, Bernsteinsäure, Maleinsäure und Adipinsäure aber auch Car­bonsäuregemische, wie das Dicarbonsäuregemisch der Adipinsäureherstellung (Mischung aus Adipinsäure, Bernsteinsäure und Glutarsäure) oder der Ab­streifsäure der Cyclohexanoxidation (Mischung aus Adipinsäure und Hydroxi­capronsäure) geeignet. Als aromatische Di-, Tri-oder Tetracarbonsäuren kommen o-Phthalsäure, Isophthalsäure, Terephthalsäure, Trimesinsäure, Trimellitsäure, Pyromellithsäure und Benzoltetracarbonsäure in Betracht.The partial esterification of the previously characterized oxo oils or oxo oil fractions can be carried out according to conventional esterification processes with aliphatic and aromatic carboxylic acids. Suitable aliphatic carboxylic acids are isononanoic acid, succinic acid, maleic acid and adipic acid, but also carboxylic acid mixtures, such as the dicarboxylic acid mixture of the production of adipic acid (mixture of adipic acid, succinic acid and glutaric acid) or the stripping acid of cyclohexane oxidation (mixture of adipic acid) and hydroxyapronic acid and hydroxyapronic acid. Aromatic di-, tri- or tetracarboxylic acids are o-phthalic acid, isophthalic acid, terephthalic acid, trimesic acid, trimellitic acid, pyromellitic acid and benzene tetracarboxylic acid.

Besonders bevorzugt ist die Veresterung mit Säureanhydriden, insbesondere Phthalsäureanhydrid. Die Säuren oder Säureanhydride werden bei der Ver­esterung in der Regel in Mengen von 0,5 bis 1,3 Äquivalent bezogen auf die Hydroxyzahl zugesetzt und mit Säurekataysatoren, wie Titansäureestern, aber auch ohne Katalysator bei Temperaturen von 150 bis 250 °C unter Vaku­um oder mit Begasung durch Stickstoff verestert. Die Aufarbeitung durch Neutralisation und Wäsche erfolgt nach herkömmlichen Verfahren. In einer bevorzugten Ausführungsform verestert man die Oxoöle bevorzugt in Gegen­wart von KOH mit 0,4 bis 0,6 Mol Phthalsäureanhydrid bezogen auf die 0H-Zahl und bricht die Kondensation bei Säurezahlen zwischen 10 und 50 ab und setzt, wie vorher beschrieben, mit Alkenoxiden ohne weitere KOH-Zugabe oder Entwässerung um. Auf diese Weise umgeht man zeit- und kostenintensive Neutralisations- und Waschstufen und minimiert den Alkenoxidverbrauch.Esterification with acid anhydrides, in particular phthalic anhydride, is particularly preferred. The acids or acid anhydrides are generally added during the esterification in amounts of 0.5 to 1.3 equivalents based on the hydroxyl number and with acid catalysts, such as titanium acid esters, but also without a catalyst at temperatures of 150 to 250 ° C. under vacuum or with Fumigation with nitrogen esterified. Processing by neutralization and washing is carried out according to conventional methods. In a preferred embodiment, the oxo oils are esterified, preferably in the presence of KOH, with 0.4 to 0.6 mol of phthalic anhydride, based on the 0H number, and the condensation is terminated at acid numbers between 10 and 50 and, as previously described, with alkene oxides without further KOH addition or drainage. In this way, time and cost-intensive neutralization and washing steps are avoided and alkene oxide consumption is minimized.

Unter Kraftstoffen für Verbrennungsmaschinen versteht man organische, meist überwiegend kohlenwasserstoffhaltige Flüssigkeiten, die für den Be­trieb von Otto-, Wankel- und Dieselmotoren geeignet sind. Neben Fraktionen der Rohölverarbeitung sind auch Kohlenwasserstoffe der Kohlehydrierung, Alkohole unterschiedlichster Herkunft und Zusammensetzung und Ether wie z.B. Methyltertiärbutylether darin enthalten. Die zulässigen Gemische sind weltweit meist national festgelegt.Fuels for internal combustion engines are organic, mostly hydrocarbon-containing liquids that are suitable for the operation of Otto, Wankel and diesel engines. In addition to fractions from crude oil processing, hydrocarbons from coal hydrogenation, alcohols of various origins and compositions and ethers such as Methyl tertiary butyl ether contained therein. The admissible mixtures are mostly nationally defined worldwide.

Die erfindungsgemäß zu verwendenden Alkoxylierungsprodukte werden den Kraftstoffen in der Regel zusammen mit Kraftstoffdetergentien, wie Aminen der Ölsäure oder Ethylendiamintetraessigsäure gemäß EP-A-6527, oder der Polyisobutenylbernsteinsäure ferner Polyetherpolyamincarbamaten, sowie insbesondere Polybutenaminen, erhalten durch Umsetzung der Alkohole oder der entsprechenden Halogenverbindungen, mit NH₃, Aminoethylethanolamin, Dimethylaminopropylamin, Triethylentetramin oder Tetraethylenpentamin, wie in US 3,275,354, DE-A-21 25 039, EP 244 616 beschrieben, Korrosionsinhi­bitoren, das sind meist niedermolekulare iserbindungen mit Amid- und/oder Ammonium- und/oder Amin-und/oder Säuregruppierungen oder Triazol- sowie Imidazolderivate, ferner phenolischen oder aminischen Antioxydantien, wie Di-tert.-butylphenol oder para-phenylendiamin und schließlich Vereisungs­verhinderern, wie Alkoholen oder Diolen zugesetzt. Hierbei ist die Kombi­nation der erfindungsgemäß zu verwendenden Alkoxylierungsprodukte mit ­Polybutenaminen bevorzugt, wobei das Mengenverhältnis der Alkoxylierungs­produkte zu den Polybutenaminen in der Regel 1 : 2 bis 3 : 1 beträgt. Auch eine Trägerölkombination mit Polyethern oder Mineralöl kommt in Betracht; dies ermöglicht eine Verringerung des Anteils der Alkoxylierungsprodukte im Verhältnis zu den Polybutenaminen, Polyetherpolyamincarbamaten oder Amiden.The alkoxylation products to be used according to the invention are usually the fuels together with fuel detergents, such as amines of oleic acid or ethylenediaminetetraacetic acid according to EP-A-6527, or the polyisobutenylsuccinic acid furthermore polyether polyamine carbamates, and in particular polybutenamines, obtained by reacting the alcohols or the corresponding halogen compounds with NH₃ , Aminoethylethanolamine, dimethylaminopropylamine, triethylene tetramine or tetraethylene pentamine, as described in US Pat. No. 3,275,354, DE-A-21 25 039, EP 244 616, corrosion inhibitors, these are mostly low molecular weight isocyanate compounds with amide and / or ammonium and / or amine and / or Acid groups or triazole and imidazole derivatives, also phenolic or aminic antioxidants, such as di-tert-butylphenol or para-phenylenediamine, and finally icing inhibitors, such as alcohols or diols, are added. The combination of the alkoxylation products to be used according to the invention with polybutenamines is preferred, the quantitative ratio of the alkoxylation products to the polybutenamines generally being 1: 2 to 3: 1. A carrier oil combination with polyethers or mineral oil is also possible; this enables a reduction in the proportion of the alkoxylation products in relation to the polybutenamines, polyetherpolyamine carbamates or amides.

Obgleich die Gründe für die Wirkung der zu verwendenden Alkoxylierungs­produkte nicht in einzelnen bekannt sind, kann festgestellt werden, daß die Wirksamkeit sich mit zunehmender Viskosität erhöht. Demzufolge ist die untere Grenze der Zahl der C-Atome nicht scharf und eine obere Begrenzung allein durch die Viskosität, d.h. Handhabbarkeit, Kältestabilität (Schmelzpunkt) und die Verfügbarkeit der Oxoöle bestimmt.Although the reasons for the action of the alkoxylation products to be used are not known in detail, it can be stated that the effectiveness increases with increasing viscosity. As a result, the lower limit of the number of C atoms is not sharp and an upper limit solely by the viscosity, i.e. Manageability, cold stability (melting point) and the availability of the oxo oils are determined.

In den folgenden Beispielen wird die Herstellung einiger repräsentativer Alkoxylierungsprodukte gemäß der Erfindung sowie ihre motorische Wirkung im Vergleich zu bekannten Zusätzen beschrieben.The following examples describe the production of some representative alkoxylation products according to the invention and their motor action in comparison to known additives.

Herstellungsbeispiel AProduction example A

Zur Herstellung des Alkoxylierungsproduktes wird der Destillationsrück­stand eines C₉-Oxoalkohols, erhalten aus der Kobalt-Katalysierten Oxierung von Dibuten, eingesetzt. Das Dibuten wird aus dem sogenannten Raffinat II, einer Mischung aus annähernd 30 % Butanen, 45 % Buten-1 und 25 % cis- und trans-Buten-2 hergestellt. 1 000 g dieses Destillationsrückstandes, der eine OH-Zahl von 132, eine Säurezahl von 10, eine Dichte von 0,872 g/cm³ bei 20°C und eine Viskosität von 27 mm²/s bei 20°C hat, werden in einem Rührkessel mit 5 g KOH Schuppen versetzt, das Reaktionsgefäß mit Stick­stoff gespült, auf 10 mbar evakuiert und unter Vakuum auf 120°C aufgeheizt und die Mischung 2 h gerührt. Bei 1,1 bar Stickstoffdruck wird auf 160 bis 170°C aufgeheizt und 1 000g Butenoxid-1,2 so langsam eingegast, daß ein Druck von 4,5 bar nicht überschritten wird. Ist die Begasung beendet, wartet man bis sich Druckkonstanz einstellt, entspannt, wobei unumge­setztes Butenoxid abdestilliert und kühlt auf Raumtemperatur ab. Die KOH wird nun durch übliche Verfahren, wie Zugabe von Ionenaustauschern, Phos­phorsäure oder Phospaten gebunden, und der Niederschlag abfiltriert. Das erhaltene polyetherhaltige Stoffgemisch hat eine OH-Zahl von 75, eine Dichte von 0,917 g/cm³ bei 20°C und eine Viskosität von 71 mm²/s bei 20°C.The distillation residue of a C₉-oxo alcohol, obtained from the cobalt-catalyzed oxidation of dibutene, is used to produce the alkoxylation product. The dibutene is produced from the so-called raffinate II, a mixture of approximately 30% butanes, 45% butene-1 and 25% cis and trans-butene-2. 1,000 g of this distillation residue, which has an OH number of 132, an acid number of 10, a density of 0.872 g / cm³ at 20 ° C and a viscosity of 27 mm² / s at 20 ° C, are in a stirred tank with 5 g of KOH flakes are added, the reaction vessel is flushed with nitrogen, evacuated to 10 mbar and heated to 120 ° C. under vacuum and the mixture is stirred for 2 hours. At 1.1 bar nitrogen pressure, the mixture is heated to 160 to 170 ° C. and 1,000 g of 1,2-butene oxide are gassed in so slowly that a pressure of 4.5 bar is not exceeded. When the gassing has ended, you wait until the pressure is constant, the pressure is released, unreacted butene oxide is distilled off and the mixture is cooled to room temperature. The KOH is then bound by customary methods, such as the addition of ion exchangers, phosphoric acid or phosphates, and the precipitate is filtered off. The polyether-containing mixture obtained has an OH number of 75, a density of 0.917 g / cm³ at 20 ° C and a viscosity of 71 mm² / s at 20 ° C.

Herstellungsbeispiel BProduction example B

Man verfährt wie bei Herstellungsbeispiel A, jedoch verwendet man 400 g Destillationsrückstand, 2 g KOH-Schuppen und 1 600 g Butenoxid-1,2. Das Produkt hat eine OH-Zahl von 37, eine Dichte von 0,948 g/cm³ bei 20°C und eine Viskosität von 385 mm²/s bei 20°C.The procedure is as in Preparation A, but 400 g of distillation residue, 2 g of KOH flakes and 1,600 g of 1,2-butene oxide are used. The product has an OH number of 37, a density of 0.948 g / cm³ at 20 ° C and a viscosity of 385 mm² / s at 20 ° C.

Herstellungsbeispiel CProduction example C

Aus dem Destillationsrückstand eines C₁₀-Oxoalkohols auf Basis Trimerpro­pen wird destillativ ein Etheralkohol C₂₁H₄₄O₂ isoliert und analog Her­stellbeispiel A mit einer Mischung aus Propenoxid-1,2 und Butenoxid-1,2 umgesetzt. Die OH-Zahl des Alkohols ist 171, seine Dichte bei 20°C 0,87 g/cm³ und seine Viskosität bei 20°C 75 mm²/s. Für die Umsetzung wer­den 500 g des Etheralkohols, 2,5 g KOH, 500 g Propenoxid-1,2 und 1 000 g Butenoxid-1,2 verwendet. Die OH-Zahl dem Umsetzungsproduktes beträgt 48, seine Viskosität bei 20°C war 320 mm²/s.From the distillation residue of a C₁₀ oxo alcohol based on trimer propene, an ether alcohol C₂₁H₄₄O₂ is isolated by distillation and analogous to Preparation A with a mixture of 1,2-propene oxide and 1,2-butene oxide implemented. The OH number of the alcohol is 171, its density at 20 ° C 0.87 g / cm³ and its viscosity at 20 ° C 75 mm² / s. 500 g of the ether alcohol, 2.5 g of KOH, 500 g of 1,2-propene oxide and 1,000 g of 1,2-butene oxide are used for the reaction. The OH number of the reaction product is 48, its viscosity at 20 ° C was 320 mm² / s.

Herstellungsbeispiel DProduction example D

400 g eines Destillationsrückstandes der C₁₃-Oxoalkoholsynthese aus dem Trimeren eines n-Butengemischs, wie es in Herstellungsbeispiel A be­schrieben ist, mit einer OH-Zahl von 144, einer Säurezahl von 1,5, einer Dichte bei 20°C von 0,863 g/cm³ und einer Viskosität bei 20°C von 105 mm²/s werden mit 75 g Phthalsäureanhydrid und 2 g geschuppter KOH ver­setzt und bei 180°C im Stickstoffstrom 5 h lang kondensiert. Dabei fällt die Säurezahl auf 20. Man stoppt die Stickstoffzufuhr, schließt den Auto­klav und gast bei 160 bis 170°C 150 g Butenoxid-1,2 so zu, daß 4,5 bar nicht überschritten werden. Nachdem man weiter verfahren hat, wie in Her­stellungsbeispiel A angegeben und 75 g Butenoxid abdestilliert hat, erhält man nach dem Entfernen der KOH ein Produkt mit einer Dichte von 0,924 g/cm³ bei 20°C und einer Viskosität von 398 mm²/s bei 20°C.400 g of a distillation residue of C₁₃-oxo alcohol synthesis from the trimers of an n-butene mixture, as described in Preparation A, with an OH number of 144, an acid number of 1.5, a density at 20 ° C of 0.863 g / cm³ and a viscosity at 20 ° C of 105 mm² / s are mixed with 75 g phthalic anhydride and 2 g scaled KOH and condensed at 180 ° C in a nitrogen stream for 5 h. The acid number drops to 20. The nitrogen supply is stopped, the autoclave is closed and 150 g of 1,2-butene oxide 1,2 are added at 160 to 170 ° C. so that 4.5 bar are not exceeded. After proceeding as described in Preparation A and distilling off 75 g of butene oxide, a product with a density of 0.924 g / cm³ at 20 ° C. and a viscosity of 398 mm² / s at 20 ° is obtained after removing the KOH C.

In der folgenden Tabelle ist die Wirkung bekannter Trägeröle und der er­findungsgemäß zu verwendenden Alkoxylierungsprodukte in Kombination mit bekannten Detergentien in Benzin für Verbrennungsmaschinen gezeigt. Die in der Tabelle angegebenen Mengen wurden Superbenzin unverbleit (ROZ 95; DIN 51 607) zugesetzt und in Prüfstandsversuchen mit einem 1,2 Opel-­Kadett-Motor gemäß CEC-F-02-T-79 geprüft. Als Motorenöl wurde das Refe­renzöl RL 51 verwendet.

Figure imgb0002
The following table shows the effect of known carrier oils and the alkoxylation products to be used according to the invention in combination with known detergents in gasoline for internal combustion engines. The quantities shown in the table were added unleaded premium petrol (RON 95; DIN 51 607) and tested in test bench tests with a 1.2 Opel Kadett engine in accordance with CEC-F-02-T-79. The reference oil RL 51 was used as engine oil.
Figure imgb0002

Die Tabelle zeigt eine deutlich bessere Wirkung der erfindungsgemäßen Alkoxylierungsprodukte gegenüber dem Stand der Technik, d.h. geringere Ablagerungen auf den Einlaßventilen des 1,2 l Opel-Kadett-Motors.The table shows a significantly better effect of the alkoxylation products according to the invention compared to the prior art, i.e. less deposits on the intake valves of the 1.2 l Opel Kadett engine.

Hierbei wurden die erfindungegemäß zu verwendenden Trägeröle mit handels­üblichem Polybutenamin, hergestellt aus Polybuten MG 1300 und Aminoethyl­ethanolamin, Wirksubstanzgehalt 50 % kombiniert. Die empfohlene Dosierung des handelsüblichen Polybutenamins ist für Formulierungen mit Mineralöl 350 mg/kg. Demgegenüber ermöglichen die erfindungsgemäßen Trägeröle eine Einsparung von etwa 30 % an polymeren Detergentien. Ergebnisse mit anderen Detergentien höherer Viskosität sind vergleichbar.Here, the carrier oils to be used according to the invention were combined with commercially available polybutenamine, produced from polybutene MG 1300 and aminoethylethanolamine, active substance content 50%. The recommended dosage of the commercial polybutenamine for formulations with mineral oil is 350 mg / kg. In contrast, the carrier oils according to the invention enable a saving of about 30% in polymeric detergents. Results with other higher viscosity detergents are comparable.

Ein weiterer Vorteil der neuen Trägeröle ist ihre Verträglichkeit mit Polyisobuten vom Molekulargewicht 800 bis 2 000, das in den meisten der für Benzinadditive verwendeten Detergentien enthalten ist. Polyether auf Propenoxidbasis sind nur wenig verträglich; d.h. zur Herstellung eines Additivpaketes benötigt man höhere Lösemittelmengen. Auch sind die erfin­dungsgemäßen Trägeröle, deren Komponenten teilweise Abfallprodukte sind bzw. daraus isoliert werden können, deutlich kostengünstiger herzustellen als Polyether, vor allem wenn letzere wegen der Polyisobutenverträglich­keit auf Butenoxidbasis hergestellt werden. Da die stoffgemische insbe­sondere bei Teilveresterung eine Reihe niedermolekularer Verbindungen enthalten, sind sie besser für die Bekämpfung des Ventilsteckens geeignet als reine Polyether mit höheren Molekulargewichten.Another advantage of the new carrier oils is their compatibility with polyisobutene with a molecular weight of 800 to 2,000, which is contained in most of the detergents used for gasoline additives. Propene oxide-based polyethers are not very compatible; i.e. higher amounts of solvent are required to produce an additive package. The carrier oils according to the invention, the components of which are partly waste products or can be isolated therefrom, are significantly cheaper to produce than polyethers, especially if the latter are produced on the basis of butene oxide based on polyisobutene. Since the substance mixtures contain a number of low molecular weight compounds, particularly in the case of partial esterification, they are more suitable for combating valve plugging than pure polyethers with higher molecular weights.

Claims (11)

1. Kraftstoffe für Verbrennungsmotoren, enthaltend geringe Mengen Alko­xylierungsprodukte, erhältlich durch Umsetzung von Alkylenoxiden mit 2 bis 4 C-Atomen mit Oxoölen oder Fraktionen der Oxoöle sowie mit Oxoölen oder Fraktionen der Oxoöle teilveresterten Carbonsäuren, wobei die Oxoöle Destillationsrückstände der Herstellung von Oxoalkoholen mit mehr als 8 Kohlenstoffatomen sind.1.Fuels for internal combustion engines, containing small amounts of alkoxylation products, obtainable by reacting alkylene oxides with 2 to 4 carbon atoms with oxo oils or fractions of oxo oils and with oxo oils or fractions of oxo oils partially esterified carboxylic acids, the oxo oils being distillation residues from the production of oxo alcohols with more than Are 8 carbon atoms. 2. Kraftstoffe für Verbrennungsmotoren, enthaltend geringe Mengen Alkoxylierungsprodukte, gemäß Anspruch 1 erhältlich durch Umsetzung von Propenoxid und/oder Butenoxid und/oder in untergeordneten Mengen Ethenoxid mit Oxoölen oder Fraktionen der Oxoöle sowie mit Oxoölen oder Fraktionen der Oxoöle teilveresterten Carbonsäuren, wobei die Oxoöle Desitllationsrückstände der Herstellung von Oxoalkoholen mit mehr als 8 Kohlenstoffatomen sind.2. Fuels for internal combustion engines, containing small amounts of alkoxylation products, obtainable according to claim 1 by reaction of propene oxide and / or butene oxide and / or in minor amounts of ethene oxide with oxo oils or fractions of oxo oils and with oxo oils or fractions of oxo oils partially esterified carboxylic acids, the oxo oils being desitrification residues the production of oxo alcohols with more than 8 carbon atoms. 3. Kraftstoffe gemäß Anspruch 1, dadurch gekennzeichnet, daß sie 0,002 bis 0,2 Gew.% der Alkoxylierungsprodukte enthalten.3. Fuels according to claim 1, characterized in that they contain 0.002 to 0.2% by weight of the alkoxylation products. 4. Kraftstoffe gemäß Anspruch 1, dadurch gekennzeichnet, daß das Molver­hältnis der Alkylenoxide zu OH-Gruppen und freien Carboxylgruppen im Ester oder Oxoöl bis zu 30, und zu den freien Carboxylgruppen minde­stens 2 beträgt.4. Fuels according to claim 1, characterized in that the molar ratio of the alkylene oxides to OH groups and free carboxyl groups in the ester or oxo oil is up to 30, and to the free carboxyl groups is at least 2. 5. Kraftstoffe gemäß Anspruch 1, dadurch gekennzeichnet, daß die Oxoöle zu mehr als 50 Gew.% aus einem Etheralkohol bestehen, der je eine Ether- und eine Alkoholgruppe und 2 n + 1 Kohlenstoffatome besitzt, wobei n für die Anzahl der Kohlenstoffatome des Oxoalkohols steht und 9 bis 33 bedeutet.5. Fuels according to claim 1, characterized in that the oxo oils consist of more than 50% by weight of an ether alcohol, each having an ether and an alcohol group and 2 n + 1 carbon atoms, where n is the number of carbon atoms of the oxo alcohol stands and means 9 to 33. 6. Kraftstoffe gemäß Anspruch 1, dadurch gekennzeichnet, daß die Oxoöle Destillationsrückstände der Herstellung von Oxoalkoholen aus Oligo­meren des Propens und/oder von Butenen sind.6. Fuels according to claim 1, characterized in that the oxo oils are distillation residues from the production of oxo alcohols from oligomers of propene and / or of butenes. 7. Kraftstoffe gemäß Anspruch 1, dadurch gekennzeichnet, daß die Oxoöle Destillationsrückstände aus Oxoalkoholen von Oligomeren der n-Butene sind.7. Fuels according to claim 1, characterized in that the oxo oils are distillation residues from oxo alcohols of oligomers of n-butenes. 8. Kraftstoffe gemäß Anspruch 1, dadurch gekennzeichnet, daß die Oxoöl­fraktion aus dem Oxoöl isolierte Etheralkohole sind.8. Fuels according to claim 1, characterized in that the oxo oil fraction from the oxo oil are isolated ether alcohols. 9. Kraftstoffe gemäß Anspruch 1, dadurchgekennzeichnet, daß die Alkoxy­lierungsprodukte solche von mit Oxoölen oder daraus gewonnene Etheralkoholen teilveresterten Carbonsäuren sind.9. Fuels according to claim 1, characterized in that the alkoxylation products are those of partially esterified with oxo oils or ether alcohols obtained therefrom carboxylic acids. 10. Kraftstoffe gemäß Anspruch 8, dadurch gekennzeichnet, daß zur Teil­veresterung Carbonsäuregemische eingesetzt werden.10. Fuels according to claim 8, characterized in that carboxylic acid mixtures are used for partial esterification. 11. Kraftstoffe gemäß Anspruch 1, dadurch gekennzeichnet, daß sie neben den Alkoxylierungsprodukten Detergentien, Vereisungsverhinderer, Korrosionsinhibitoren und Antooxydanten enthalten.11. Fuels according to claim 1, characterized in that they contain, in addition to the alkoxylation products, detergents, anti-icing agents, corrosion inhibitors and antioxidants.
EP90108498A 1989-05-19 1990-05-07 Fuel compositions containing alkoxylation products Expired - Lifetime EP0398100B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3916365 1989-05-19
DE3916365A DE3916365A1 (en) 1989-05-19 1989-05-19 FUEL COMPOSITIONS CONTAINING ALKOXYLATION PRODUCTS

Publications (2)

Publication Number Publication Date
EP0398100A1 true EP0398100A1 (en) 1990-11-22
EP0398100B1 EP0398100B1 (en) 1992-08-19

Family

ID=6380993

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90108498A Expired - Lifetime EP0398100B1 (en) 1989-05-19 1990-05-07 Fuel compositions containing alkoxylation products

Country Status (4)

Country Link
US (1) US5123932A (en)
EP (1) EP0398100B1 (en)
CA (1) CA2016885A1 (en)
DE (2) DE3916365A1 (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0452328A1 (en) * 1987-11-18 1991-10-23 Chevron Res & Tech Synergistic fuel compositions.
EP0647700A1 (en) * 1993-10-06 1995-04-12 Ethyl Corporation Fuel compositions and additives therefor
US5702517A (en) * 1994-12-22 1997-12-30 Basf Aktiengesellschaft Additives for plastics, in particular for PVC
EP1118653A1 (en) * 2000-01-18 2001-07-25 Krueger, Andrezej Method for obtaining components of a packet of additives for engine fuels
US6533528B2 (en) 2000-06-16 2003-03-18 Deere & Company Support frame for front attached implements of an operating machine and associated locating pins

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5352251A (en) * 1993-03-30 1994-10-04 Shell Oil Company Fuel compositions
US5458660A (en) * 1994-09-19 1995-10-17 Shell Oil Company Fuel compositions
US5507843A (en) * 1994-09-19 1996-04-16 Shell Oil Company Fuel compositions
US5855630A (en) * 1994-09-19 1999-01-05 Shell Oil Company Fuel compositions
US5489315A (en) * 1994-09-19 1996-02-06 Shell Oil Company Fuel compositions comprising hydantoin-containing polyether alcohol additives
US5458661A (en) * 1994-09-19 1995-10-17 Shell Oil Company Fuel compositions
US6312481B1 (en) 1994-09-22 2001-11-06 Shell Oil Company Fuel compositions
US5709718A (en) * 1995-03-15 1998-01-20 Shell Oil Company Fuel compositions containing a polyether
US5507844A (en) * 1995-06-19 1996-04-16 Shell Oil Company Fuel compositions
US5492546A (en) * 1995-06-19 1996-02-20 Shell Oil Company Fuel compositions
US6261327B1 (en) 1997-05-29 2001-07-17 Shell Oil Company Additive concentrates for rapidly reducing octane requirement
DE10012722A1 (en) * 2000-03-16 2001-09-20 Basf Ag Mixtures of di- or tri-basic carboxylic acid monoesters with OH group free 18-45 C ethers and esters, useful for leather treatment, contain up to 85 wt.% ether groups and up to 16 wt.% ester groups
UA97656C2 (en) * 2006-12-14 2012-03-12 Шелл Інтернаціонале Рісерч Маатшаппідж Б.В. Plumbic-free fuel composition, methods for petrol octane number increasing and for reducing of depositions on primary valve of internal combustion engine
EP2417228B1 (en) * 2009-04-09 2014-12-24 Shell Oil Company Fuel composition and its use

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1317217A (en) * 1961-05-31 1963-02-08 Inst Francais Du Petrole Method of reducing wear in injection engines and fuel compositions for these engines
FR1425263A (en) * 1961-04-12 1966-01-24 Inst Francais Du Petrole Novel esters and polyesters derived from by-products of the manufacture of substituted metadioxanes and conjugated diolefins, and their manufacturing process
GB1217468A (en) * 1969-04-18 1970-12-31 Shell Int Research Ester mixtures
US3859318A (en) * 1969-05-19 1975-01-07 Lubrizol Corp Products produced by post-treating oil-soluble esters of mono- or polycarboxylic acids and polyhydric alcohols with epoxides
US3901665A (en) * 1972-10-06 1975-08-26 Du Pont Multi-functional fuel additive compositions
EP0092256A1 (en) * 1982-04-21 1983-10-26 Union Carbide Corporation Process for preparing nonionic surfactants by an oxyalkylation with calcium and/or strontium catalysts
EP0277345A1 (en) * 1987-01-08 1988-08-10 BASF Aktiengesellschaft Fuel or lubricant composition containing polybutyl or polyisobutyl derivatives
EP0302487A1 (en) * 1987-08-06 1989-02-08 BASF Aktiengesellschaft Etherification of polyoxyalkylene derivatives
EP0356726B1 (en) * 1988-08-06 1992-05-13 BASF Aktiengesellschaft Fuel compositions containing esters from polycarboxylic acids and long chain alcohols

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2843463A (en) * 1955-09-12 1958-07-15 Gulf Research Development Co Non-stalling gasoline fuel compositions
DE1047525B (en) * 1956-04-05 1958-12-24 Exxon Standard Sa Diesel oil and heating oil additive
US2955928A (en) * 1956-09-11 1960-10-11 Exxon Research Engineering Co Gasoline composition
US3054666A (en) * 1960-03-17 1962-09-18 Exxon Research Engineering Co Motor fuel composition
CA920366A (en) * 1968-12-24 1973-02-06 Owen Keith Fuel compositions
GB1346765A (en) * 1970-06-16 1974-02-13 Shell Int Research Fuel compositions
DE2127468A1 (en) * 1971-06-03 1972-12-14 Pohlig-Heckel-Bleichert Vereinigte Maschinenfabriken AG, 5000 Köln Device for the continuous loading of a stationary train comprising several railway wagons by means of endless conveyors
DE2316535A1 (en) * 1973-04-03 1974-10-24 Basf Ag Motor oils contg. polycarboxylic acid derivs. - as thermally stable detergent additives which do not decompose at inlet valve temps.

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1425263A (en) * 1961-04-12 1966-01-24 Inst Francais Du Petrole Novel esters and polyesters derived from by-products of the manufacture of substituted metadioxanes and conjugated diolefins, and their manufacturing process
FR1317217A (en) * 1961-05-31 1963-02-08 Inst Francais Du Petrole Method of reducing wear in injection engines and fuel compositions for these engines
GB1217468A (en) * 1969-04-18 1970-12-31 Shell Int Research Ester mixtures
US3859318A (en) * 1969-05-19 1975-01-07 Lubrizol Corp Products produced by post-treating oil-soluble esters of mono- or polycarboxylic acids and polyhydric alcohols with epoxides
US3901665A (en) * 1972-10-06 1975-08-26 Du Pont Multi-functional fuel additive compositions
EP0092256A1 (en) * 1982-04-21 1983-10-26 Union Carbide Corporation Process for preparing nonionic surfactants by an oxyalkylation with calcium and/or strontium catalysts
EP0277345A1 (en) * 1987-01-08 1988-08-10 BASF Aktiengesellschaft Fuel or lubricant composition containing polybutyl or polyisobutyl derivatives
EP0302487A1 (en) * 1987-08-06 1989-02-08 BASF Aktiengesellschaft Etherification of polyoxyalkylene derivatives
EP0356726B1 (en) * 1988-08-06 1992-05-13 BASF Aktiengesellschaft Fuel compositions containing esters from polycarboxylic acids and long chain alcohols

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0452328A1 (en) * 1987-11-18 1991-10-23 Chevron Res & Tech Synergistic fuel compositions.
EP0452328A4 (en) * 1987-11-18 1993-03-10 Chevron Research And Technology Company Synergistic fuel compositions
EP0647700A1 (en) * 1993-10-06 1995-04-12 Ethyl Corporation Fuel compositions and additives therefor
US5702517A (en) * 1994-12-22 1997-12-30 Basf Aktiengesellschaft Additives for plastics, in particular for PVC
EP1118653A1 (en) * 2000-01-18 2001-07-25 Krueger, Andrezej Method for obtaining components of a packet of additives for engine fuels
US6533528B2 (en) 2000-06-16 2003-03-18 Deere & Company Support frame for front attached implements of an operating machine and associated locating pins

Also Published As

Publication number Publication date
US5123932A (en) 1992-06-23
EP0398100B1 (en) 1992-08-19
DE3916365A1 (en) 1990-11-22
CA2016885A1 (en) 1990-11-19
DE59000262D1 (en) 1992-09-24

Similar Documents

Publication Publication Date Title
EP0398100B1 (en) Fuel compositions containing alkoxylation products
EP0356726B1 (en) Fuel compositions containing esters from polycarboxylic acids and long chain alcohols
EP0356725B2 (en) Fuels for spark ignition engines containing polyether amines or polyether amine derivatives
EP0012345B1 (en) Fuel oils and their application
EP0374461B1 (en) Fuels for combustion machines
EP0277345B1 (en) Fuel or lubricant composition containing polybutyl or polyisobutyl derivatives
US5242469A (en) Gasoline additive composition
DE69532917T3 (en) FUEL OIL COMPOSITION WITH POLYOXYALKYLENE
EP0464489B1 (en) Ester containing fuels, for spark ignition- and diesel engines
EP0310875A1 (en) Fuels containing a polyether amine for spark ignition engines
DE2926225C2 (en)
DE60214332T2 (en) Alkyl-substituted cresol polyalkoxylates and their use in fuels
EP1612257A2 (en) Fuel composition
EP1098953B1 (en) Fuel compositions containing propoxilate
EP2270119A1 (en) Fuel composition
DE3814601A1 (en) DETERGENT FOR HYDROCARBON FUELS
EP1157086A1 (en) Polyalkenealcohol-polyalkoxylates and their use in fuels and lubricants
EP0489322A2 (en) Alkoxylated polyetherdiamines, process for their preparation and fuels for spark ignition engines containing them
EP0704519A1 (en) Mixture of amines, hydrocarbonpolymers and carrier oils, suitable as fuel and lubricant additive
DE60020783T2 (en) Fuel dispersant with increased lubricating property
EP2782985A1 (en) Amine mixture
EP0006527A1 (en) Fuels for Otto-cycle engines containing mixtures of additives
EP1177270B1 (en) Polyalkene alcohol polyetheramines and use thereof in fuels and lubricants
DE3709195A1 (en) Storage-stable emulsifiers
DE69910824T2 (en) FUEL ADDITIVE AND FUEL COMPOSITION CONTAINING THEM

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19900821

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): BE DE FR GB IT NL

17Q First examination report despatched

Effective date: 19910619

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE DE FR GB IT NL

ITF It: translation for a ep patent filed

Owner name: ING. C. GREGORJ S.P.A.

REF Corresponds to:

Ref document number: 59000262

Country of ref document: DE

Date of ref document: 19920924

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)
ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19960424

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19960501

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19960514

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19960515

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19960528

Year of fee payment: 7

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19970507

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19970516

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Effective date: 19970531

BERE Be: lapsed

Owner name: BASF A.G.

Effective date: 19970531

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19971201

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19970507

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19980130

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 19971201

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20050507