EP0356726A2 - Fuel compositions containing esters from polycarboxylic acids and long chain alcohols - Google Patents

Fuel compositions containing esters from polycarboxylic acids and long chain alcohols Download PDF

Info

Publication number
EP0356726A2
EP0356726A2 EP89114039A EP89114039A EP0356726A2 EP 0356726 A2 EP0356726 A2 EP 0356726A2 EP 89114039 A EP89114039 A EP 89114039A EP 89114039 A EP89114039 A EP 89114039A EP 0356726 A2 EP0356726 A2 EP 0356726A2
Authority
EP
European Patent Office
Prior art keywords
esters
alcohols
fuels
fuels according
carbon atoms
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP89114039A
Other languages
German (de)
French (fr)
Other versions
EP0356726B1 (en
EP0356726A3 (en
Inventor
Hans Peter Dr. Rath
Helmut Dr. Mach
Joachim Dr. Schulze
Hans Dr. Otterbach
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 EP0356726A2 publication Critical patent/EP0356726A2/en
Publication of EP0356726A3 publication Critical patent/EP0356726A3/en
Application granted granted Critical
Publication of EP0356726B1 publication Critical patent/EP0356726B1/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
    • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters

Definitions

  • the invention relates to fuels for internal combustion engines with improved properties containing esters of aromatic di-, tri- or tetracarboxylic acids and long-chain alcohols.
  • the invention relates to fuel compositions for gasoline engines.
  • additive packages are added to gasoline in amounts of up to 2500 mg / kg. These generally consist of 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 are said to reduce the increase in the octane requirement of engines as the number of operating hours increases.
  • esters as a gasoline additive has long been known. Their use as a gasoline additive is e.g. described in DE-OS 21 29 461. The esters mentioned there are, as expressly mentioned in the patent specification mentioned, thermally unstable.
  • thermally stable esters with a high molecular weight and based on branched alcohols are excellent carrier oils, as a result of which 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 have a low content, e.g. 0.005 to 0.2 wt.%, Based on the composition of esters of aromatic di-, tri- and tetracarboxylic acids with long-chain aliphatic alcohols containing only carbon, hydrogen and oxygen, which have been prepared by hydroformylation of branched olefins, the Total carbon number of the esters is at least 36 carbon atoms and the molecular weight is 550 to 1500, preferably 600 to 1200.
  • esters to be used are prepared in a manner known per se by esterification or transesterification processes, the carboxyl groups being essentially completely esterified.
  • Aromatic di-, tri- or tetracarboxylic acids are o-phthalic acid, isophthalic acid, terephthalic acid, trimesic acid, trimellitic acid and pyromellitic acid. Of these, o-phthalic acid is preferred.
  • Oxo alcohols from higher branched olefins with generally more than 13 carbon atoms for example oligomers of butene such as tetramer to octamer butene, ie C 2 , C 2 s, C 29 and / or C 33 oxo alcohols, serve as alcohol components and oxo oils, the residues of oxo alcohol distillation from the production of higher alcohols such as nonanol to pentadecanol.
  • the oxo reaction or hydroformylation is the well-known reaction of olefins with CO / H 2 over a cobalt or rhodium catalyst to produce the homologous aldehydes and alcohols.
  • the alcohols can be obtained from the aldehydes by hydrogenation. Details are described in Kirk-Othmer, Encyclopedia of Chemical Technology, third edition, vol. 16, pages 637ff, to which reference is hereby made.
  • aliphatic ether alcohols each with an ether and hydroxyl group and with at least 17 carbon atoms, which can be isolated, for example, from the distillation residues of the oxo alcohols Cs, Cs, C10, C 13 and C 13 / C 15 and from which it is assumed that they can be characterized by the following general formula: where n is 7, 8, 9, 12 and 12 to 14.
  • 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 tert-butyl ether are also included
  • ethers such as methyl tert-butyl ether are also included
  • the permissible mixtures are mostly nationally defined worldwide.
  • esters to be used according to the invention are generally combined with detergents, such as amides of oleic acid, ethylenediaminetetraacetic acid according to EP-A-6527 or polyisobutenyl succinic acid, and in particular polybutenamines prepared from polybutene alcohol with NH 3 , aminoethylethanolamine, dimethylaminopropylamine, triethylene tetramine, or tetraethylene pentamine, or tetraethylene pentamine as described in US Pat. No. 3,756,793, DE-A-21 25 039, EP 244 616, to which reference is hereby made, corrosion inhibitors, mostly low molecular weight.
  • detergents such as amides of oleic acid, ethylenediaminetetraacetic acid according to EP-A-6527 or polyisobutenyl succinic acid, and in particular polybutenamines prepared from polybutene alcohol with NH 3 , aminoethylethanolamine, dimethylamino
  • 1150 g oxo oil from the cobalt-catalyzed production of iso-decanol with an OH number of 154, an acid number of 0.76, a saponification number of 36 and a CO number of 1.8 and with a predominant content of alcohols at 20 ° C -Atoms, are heated under reflux with 208 g phthalic anhydride, 0.2 g tetrabutyl orthotitanate and 150 g toluene on a water separator for 36 h. 28 g of water separate out and the acid number drops to 2.
  • 1043 g of an ester mixture are obtained, which is characterized as follows:
  • Example C 360 g of the ether alcohol with 21 carbon atoms (1.1 mol) mentioned in Example C are condensed in a stirred flask with 74 g of phthalic anhydride (0.5 mol) in the presence of 0.1 g of tetrabutyl orthotitanate at 200 ° C. in a stream of nitrogen. After 24 h the acid number is still 1.1.
  • the procedure is as in Example C, but after the pressure distillation, a steam distillation is carried out to deplete the acid with 300 g of water.
  • the following table shows the effect of known carrier oils and the esters to be used according to the invention in combination with known detergents in gasoline for internal combustion engines.
  • the amounts of esters listed in the table were added unleaded premium petrol (RON 95; DIN 51607) and test bench tests were carried out with a 1.2 I Opel Kadett engine in accordance with CEC-F-02-T-79.
  • the reference oil RL 51 was used as engine oil.
  • the table shows an increasing effect on the inlet valves of the 1.2 I Opel Kadett with the molecular weight of the ester.
  • Experiments 2 to 4 of the table show a gradual reduction in the intake valve deposits compared to operating with fuel without additives (experiment 1).
  • a Solvent Neutral 500 with a viscosity of 17 mm 2 / s at 100 ° C was used.
  • a polypropylene glycol with a viscosity of 100 mm 2 / s at 40 ° C was used.
  • Experiments 4 to 8 are esters of high purity, ie OH number less than 1, acid number less than 0.1 and ash less than 1 mg / kg.
  • the C 2 s phthalate was prepared with an alcohol which was obtained by hydroformylation of a hexa-isobutene from the preparation of reactive polyisobutene according to DE-AS 27 02 604.
  • the viscosity of this ester is 31 mm 2 / s at 100 0 C.
  • the recommended dosage of the commercial polybutenamine for formulations with mineral oil is 350 mg / kg.
  • the esters according to the invention enable a saving of about 30% in polymeric detergent. Results with other higher viscosity detergents are comparable.

Abstract

Fuel compositions containing esters made from aromatic di-, tri- or tetracarboxylic acids with branched, long-chain aliphatic alcohols or ether alcohols, the total carbon number of the esters being at least 36 carbon atoms and the molecular weight being 550 to 1500.

Description

Die Erfindung betrifft Kraftstoffe für Verbrennungsmaschinen mit verbesserten Eigenschaften mit einem Gehalt an Estern von aromatischen Di-, Tri- oder Tetracarbonsäuren und langkettigen Alkoholen.The invention relates to fuels for internal combustion engines with improved properties containing esters of aromatic di-, tri- or tetracarboxylic acids and long-chain alcohols.

Insbesondere betrifft die Erfindung Kraftstoffzusammensetzungen für Ottomotoren.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 2500 mg/kg zu. Diese bestehen im allgemeinen aus Detergentien, 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 2500 mg / kg. These generally consist of 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.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 are said to reduce the increase in the octane requirement of engines as the number of operating hours increases.

Die Verwendung von Estern als Benzinzusatz ist seit langem bekannt. Ihre Verwendung als Benzinzusatz ist z.B. in der DE-OS 21 29 461 beschrieben. Die dort genannten Ester sind, wie in der genannten Patentschrift ausdrücklich erwähnt, thermisch instabil.The use of esters as a gasoline additive has long been known. Their use as a gasoline additive is e.g. described in DE-OS 21 29 461. The esters mentioned there are, as expressly mentioned in the patent specification mentioned, thermally unstable.

Ferner sind in DE 23 16 535 Trimellithsäuredodecylester und in GB 1 217 468 Ester von z.B. C,2-Cls-Alkoholen, die durch Oxosynthese hergestellt worden sind, beschrieben. In beiden Fällen sollen überwiegend unverzweigte Alkohole verwendet werden.Furthermore, DE 23 16 535 trimellitic acid dodecyl ester and in GB 1 217 468 esters of, for example, C 2 -C 1 s-alcohols, which have been prepared by oxosynthesis, are described. In both cases predominantly unbranched alcohols should be used.

Es wurde nun überraschenderweise gefunden, daß thermisch stabile Ester mit hohem Molekulargewicht und auf Basis verzweigter Alkohole ausgezeichnete Trägeröle darstellen, 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.It has now surprisingly been found that thermally stable esters with a high molecular weight and based on branched alcohols are excellent carrier oils, as a result of which 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 einen geringen Gehalt, z.B. 0,005 bis 0,2 Gew.%, bezogen auf die Zusammensetzung an Estern aromatischer Di-, Tri- und Tetracarbonsäuren mit langkettigen aliphatischen, nur Kohlenstoff, Wasserstoff und Sauerstoff enthaltenden Alkoholen, die durch Hydroformylierung von verzweigten Olefinen hergestellt worden sind, aufweisen, wobei die Gesamtkohlenstoffzahl der Ester mindestens 36 C-Atome und das Molekulargewicht 550 bis 1500, vorzugsweise 600 bis 1200 beträgt.Accordingly, the invention relates to fuel compositions which have a low content, e.g. 0.005 to 0.2 wt.%, Based on the composition of esters of aromatic di-, tri- and tetracarboxylic acids with long-chain aliphatic alcohols containing only carbon, hydrogen and oxygen, which have been prepared by hydroformylation of branched olefins, the Total carbon number of the esters is at least 36 carbon atoms and the molecular weight is 550 to 1500, preferably 600 to 1200.

Die zu verwendenden Ester werden in an sich bekannter Weise durch Veresterungs- oder Umesterungsverfahren hergestellt, wobei die Carboxylgruppen im wesentlichen vollständig verestert werden. Als aromatische Di-, Tri- oder Tetracarbonsäuren kommen o-Phthalsäure, Isophthalsäure, Terephthalsäure, Trimesinsäure, Trimellithsäure und Pyromellithsäure in Betracht. Davon ist o-Phthalsäure bevorzugt. Als Alkoholkomponenten dienen Oxoalkohole aus höheren verzweigten Olefinen mit in der Regel mehr als 13 C-Atomen, z.B. Oligomeren des Butens wie Tetramer- bis Octamerbuten, d.s. C2,-, C2s-, C29- und/oder C33-Oxoalkohole und Oxoöle, d.s. Rückstände der Oxoalkoholdestillation der Herstellung höherer Alkohole wie Nonanol bis Pentadecanol. Die Oxo-Reaktion oder Hydroformylierung ist dabei die wohlbekannte Umsetzung von Olefinen mit CO/H2 über einem Cobalt- oder Rhodiumkatalysator unter Herstellung der homologen Aldehyde und Alkohole. Aus den Aldehyden kann man durch Hydrierung die Alkohole gewinnen. Einzelheiten sind in Kirk-Othmer, Encyclopedia of Chemical Technology, third edition, Bd. 16, Seiten 637ff beschrieben, worauf hiermit Bezug genommen wird.The esters to be used are prepared in a manner known per se by esterification or transesterification processes, the carboxyl groups being essentially completely esterified. Aromatic di-, tri- or tetracarboxylic acids are o-phthalic acid, isophthalic acid, terephthalic acid, trimesic acid, trimellitic acid and pyromellitic acid. Of these, o-phthalic acid is preferred. Oxo alcohols from higher branched olefins with generally more than 13 carbon atoms, for example oligomers of butene such as tetramer to octamer butene, ie C 2 , C 2 s, C 29 and / or C 33 oxo alcohols, serve as alcohol components and oxo oils, the residues of oxo alcohol distillation from the production of higher alcohols such as nonanol to pentadecanol. The oxo reaction or hydroformylation is the well-known reaction of olefins with CO / H 2 over a cobalt or rhodium catalyst to produce the homologous aldehydes and alcohols. The alcohols can be obtained from the aldehydes by hydrogenation. Details are described in Kirk-Othmer, Encyclopedia of Chemical Technology, third edition, vol. 16, pages 637ff, to which reference is hereby made.

Als Alkoholkomponenten kommen ferner aliphatische Etheralkohole mit je einer Ether- und Hydroxygruppe und mit mindestens 17 Kohlenstoffatomen in Betracht, die z.B. aus den Destillationsrückständen der Oxoalkohole Cs, Cs, C10, C13 und C13/C15 isoliert werden können und von denen angenommen wird, daß sie durch folgende allgemeine Formel charakterisiert werden können:

Figure imgb0001
wobei n 7, 8, 9, 12 und 12 bis 14 bedeutet.Also suitable as alcohol components are aliphatic ether alcohols, each with an ether and hydroxyl group and with at least 17 carbon atoms, which can be isolated, for example, from the distillation residues of the oxo alcohols Cs, Cs, C10, C 13 and C 13 / C 15 and from which it is assumed that they can be characterized by the following general formula:
Figure imgb0001
 where n is 7, 8, 9, 12 and 12 to 14.

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 Kohle hydrierung, 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 tert-butyl ether are also included The permissible mixtures are mostly nationally defined worldwide.

Die erfindungsgemäß zu verwendenden Ester werden den Kraftstoffen in der Regel zusammen mit Detergentien, wie Amiden der Ölsäure, Ethylendiamintetraessigsäure gemäß EP-A-6527 oder der Polyisobutenylbernsteinsäure, sowie insbesondere Polybutenaminen hergestellt aus Polybutenalkohol mit NH3, Aminoethylethanolamin, Dimethylaminopropylamin, Triethylentetramin, oder Tetraethylenpentamin, wie sie in US-A-3 756 793, DE-A-21 25 039, EP 244 616, auf die hiermit Bezug genommen wird, beschrieben sind, Korrosionsinhibitoren, d.s. meist niedermolekulare. Verbindungen mit Amid- und/oder Ammonium- und/oder Amin-und/oder Säuregruppierungen oder Triazol- sowie Imidazolderivate, phenolischen oder aminischen Antioxydantien, wie Di-tert.-butylphenol oder Paraphenylendiamin und Vereisungsverhinderern, wie Alkoholen oder Diolen zugesetzt. Hierbei ist die Kombination der erfindungsgemäß zu verwendenden Ester mit Polybutenaminen bevorzugt, wobei das Mengenverhältnis der Ester 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 Esteranteils im Verhältnis zu den Polybutenaminen oder Amiden.The esters to be used according to the invention are generally combined with detergents, such as amides of oleic acid, ethylenediaminetetraacetic acid according to EP-A-6527 or polyisobutenyl succinic acid, and in particular polybutenamines prepared from polybutene alcohol with NH 3 , aminoethylethanolamine, dimethylaminopropylamine, triethylene tetramine, or tetraethylene pentamine, or tetraethylene pentamine as described in US Pat. No. 3,756,793, DE-A-21 25 039, EP 244 616, to which reference is hereby made, corrosion inhibitors, mostly low molecular weight. Compounds with amide and / or ammonium and / or amine and / or acid groups or triazole and imidazole derivatives, phenolic or aminic antioxidants, such as di-tert-butylphenol or paraphenylenediamine and anti-icing agents, such as alcohols or diols, are added. Here, the combination of the esters to be used according to the invention with polybutenamines is preferred, the quantitative ratio of the esters 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 ester content in relation to the polybutenamines or amides.

Obgleich die Gründe für die Wirkung der zu verwendenden Ester nicht im einzelnen bekannt sind, kann festgestellt werden, daß die Wirksamkeit sich mit zunehmendem Molekulargewicht erhöht. Demzufolge ist die untere Molekulargewichtsgrenze nicht scharf und die obere Grenze allein durch die Viskosität, Handhabbarkeit und die Verfügbarkeit der Alkohole bestimmt.Although the reasons for the action of the esters to be used are not known in detail, it can be seen that the effectiveness increases with increasing molecular weight. As a result, the lower molecular weight limit is not sharp and the upper limit is determined solely by the viscosity, manageability and availability of the alcohols.

In den folgenden Beispielen wird die Herstellung und Verwendung einiger repräsentativer Ester erläutert.The following examples illustrate the preparation and use of some representative esters.

Herstellungsbeispiel AProduction example A

1180 g Oxoöl aus der Cobalt-katalysierten Herstellung von iso-Nonanol, mit einer Säurezahl von 8, einer OH-Zahl von 138, einer Verseifungszahl von 62 und einer CO-Zahl von 1,2 und mit einem überwiegenden Gehalt an Alkoholen mit 18 C-Atomen, werden mit 163 g Phthalsäureanhydrid, 0,25 g Tetrabutylorthotitanat und 150 g Toluol 20 h am Wasserabscheider unter Rückfluß erhitzt. Dabei werden 22 ml Wasser abgeschieden. Die Säurezahl fällt auf 1,1. Die Mischung wird abgekühlt, mit 5 %iger Na2C03-Lösung neutralisiert und bei 130°C und 780 mbar 1 kg Wasser in 3 Stunden zugetropft (Wasserdampdestillation). Man erhält 908 g eines Estergemisches mit folgenden Eigenschaften:

Figure imgb0002
1180 g oxo oil from the cobalt-catalyzed production of iso-nonanol, with an acid number of 8, an OH number of 138, a saponification number of 62 and a CO number of 1.2 and with a predominant alcohol content of 18 ° C -Atoms, with 163 g of phthalic anhydride, 0.25 g of tetrabutyl orthotitanate and 150 g of toluene are heated under reflux for 20 h on a water separator. 22 ml of water are separated. The acid number drops to 1.1. The mixture is cooled, neutralized with 5% Na 2 CO 3 solution and 1 kg of water are added dropwise at 130 ° C. and 780 mbar (steam distillation). 908 g of an ester mixture having the following properties are obtained:
Figure imgb0002

Herstellungsbeispiel BProduction example B

1150 g Oxoöl aus der Cobalt-katalysierten Herstellung von iso-Dekanol mit einer OH-Zahl von 154, einer Säurezahl von 0,76 einer Verseifungszahl von 36 und einer CO-Zahl von 1,8 und mit einem überwiegenden Gehalt an Alkoholen mit 20 C-Atomen, werden mit 208 g Phthalsäureanhydrid, 0,2 g Tetrabutylorthotitanat und 150 g Toluol 36 h am Wasserauskreiser unter Rückfluß erhitzt. Dabei scheiden sich 28 g Wasser ab und die Säurezahl sinkt auf 2. Nach Neutralisation, Wäsche und Wasserdampfdestillation erhält man 1043 g eines Estergemisches, das wie folgt charakterisiert ist:

Figure imgb0003
1150 g oxo oil from the cobalt-catalyzed production of iso-decanol with an OH number of 154, an acid number of 0.76, a saponification number of 36 and a CO number of 1.8 and with a predominant content of alcohols at 20 ° C -Atoms, are heated under reflux with 208 g phthalic anhydride, 0.2 g tetrabutyl orthotitanate and 150 g toluene on a water separator for 36 h. 28 g of water separate out and the acid number drops to 2. After neutralization, washing and steam distillation, 1043 g of an ester mixture are obtained, which is characterized as follows:
Figure imgb0003

In gleicher Weise wurden die Ester für die Versuche 8 und 11 hergestellt.The esters for experiments 8 and 11 were prepared in the same way.

Herstellungsbeispiel CProduction example C

360 g eines Etheralkohols mit 21 Kohlenstoffatomen (Handelsprodukt Exxal 21 der Esso Chemie) (1,1 mol) werden it 64 g Trimellithsäureanhydrid (0,33 mol) bei 240 C mit 0,1 g Tetrabutylorthotitanat verestert, wobei ca. 3 I trockenen Stickstoffs pro Stunde durch den Rührkolben perlen und das gebildete Reaktionswasser abtreiben. Nach 16 h ist die Säurezahl auf 6,2 mg KOH pro g Ester gefallen. Man kühlt ab, setzt 1 g Wasser zu und filtriert in einem Druckfilter über eine 10 cm dicke Schüttung aus 200 g pulverisiertem Na2C03.

Figure imgb0004
360 g of an ether alcohol with 21 carbon atoms (commercial product Exxal 21 from Esso Chemie) (1.1 mol) are esterified with 64 g of trimellitic anhydride (0.33 mol) at 240 ° C. with 0.1 g of tetrabutyl orthotitanate, using about 3 l of dry nitrogen per hour through the stirring flask and drive off the water of reaction formed. After 16 h the acid number has dropped to 6.2 mg KOH per g ester. The mixture is cooled, 1 g of water is added and the mixture is filtered in a pressure filter over a 10 cm bed of 200 g of powdered Na 2 CO 3 .
Figure imgb0004

Herstellungsbeispiel DProduction example D

In einem Rührkolben werden 360 g des in Beispiel C genannten Etheralkohols mit 21 Kohlenstoffatomen (1,1 mol) mit 74 g Phthalsäureanhydrid (0,5 mol) in Gegenwart von 0,1 g Tetrabutylorthotitanat bei 200 C im Stickstoffstrom kondensiert. Nach 24 h beträgt die Säurezahl noch 1,1. Es wird wie in Beispiel C verfahren, jedoch nach der Druckdestillation eine Wasserdampfdestillation zur Abreicherung der Säure mit 300 g Wasser durchgeführt.

Figure imgb0005
360 g of the ether alcohol with 21 carbon atoms (1.1 mol) mentioned in Example C are condensed in a stirred flask with 74 g of phthalic anhydride (0.5 mol) in the presence of 0.1 g of tetrabutyl orthotitanate at 200 ° C. in a stream of nitrogen. After 24 h the acid number is still 1.1. The procedure is as in Example C, but after the pressure distillation, a steam distillation is carried out to deplete the acid with 300 g of water.
Figure imgb0005

Herstellungsbeispiel EProduction example E

In einem Rührkolben werden 195 g eines Etheralkohols mit 27 Kohlenstoffatomen (0,5 mol) (Herkunft Oxoöl der Trimerbuten-Hydroformylierung) mit 33 g Phthalsäureanhydrid und 0,1 g Tetrabutylorthotitanat bei 240 °C im Stickstoffstrom kondensiert. Nach 16 h ist eine Säurezahl von 1,6 erreicht und die Kondensation wird abgebrochen. Nach dem Abkühlen wird, wie in Beispiel C beschrieben, aufgearbeitet.

Figure imgb0006
195 g of an ether alcohol with 27 carbon atoms (0.5 mol) (origin oxo oil from trimerbutene hydroformylation) are condensed in a stirred flask with 33 g phthalic anhydride and 0.1 g tetrabutyl orthotitanate at 240 ° C. in a nitrogen stream. After 16 h an acid number of 1.6 is reached and the condensation is stopped. After cooling, the mixture is worked up as described in Example C.
Figure imgb0006

In der folgenden Tabelle ist die Wirkung bekannter Trägeröle und der erfindungsgemäß zu verwendenden Ester auch in Kombination mit bekannten Detergentien in Benzin für Verbrennungsmaschinen gezeigt. Die in der Tabelle angegebenen Mengen der Ester wurden Superbenzin unverbleit (ROZ 95; DIN 51607) zugesetzt und Prüfstandsversuche mit einem 1,2 I Opel-Kadett-Motor gemäß CEC-F-02-T-79 durchgeführt. Als Motorenöl wurde das Referenzöl RL 51 verwendet.

Figure imgb0007
The following table shows the effect of known carrier oils and the esters to be used according to the invention in combination with known detergents in gasoline for internal combustion engines. The amounts of esters listed in the table were added unleaded premium petrol (RON 95; DIN 51607) and test bench tests were carried out with a 1.2 I Opel Kadett engine in accordance with CEC-F-02-T-79. The reference oil RL 51 was used as engine oil.
Figure imgb0007

Die Tabelle zeigt eine mit dem Molekulargewicht des Esters zunehmende Wirkung auf die Einlaßventile des 1,2 I Opel-Kadett.The table shows an increasing effect on the inlet valves of the 1.2 I Opel Kadett with the molecular weight of the ester.

Die Versuche 2 bis 4 der Tabelle zeigen eine graduelle Verminderung der Einlaßventilablagerungen gegenüber dem Betrieb mit Kraftstoff ohne Zusatz (Versuch 1). Für Versuch 2 wurde ein Solvent Neutral 500 mit einer Viskosität von 17 mm2/s bei 100 °C verwendet. Bei Versuch 3 wurde ein Polypropylenglykol mit einer Viskosität von 100 mm2/s bei 40 °C eingesetzt. Die Ester mit zum Teil deutlich niedrigeren Viskositäten zeigen bereits allein eine weit bessere Wirkung. Bei den Versuchen 4 bis 8 handelt es sich um Ester hoher Reinheit, d.h. OH-Zahl unter 1, Säurezahl unter 0,1 und Asche kleiner 1 mg/kg. Das C2s-Phthalat wurde mit einem Alkohol hergestellt, der durch Hydroformylierung eines Hexa-iso-butens aus der Herstellung von reaktivem Polyisobuten gemäß DE-AS 27 02 604 erhalten wurde. Die Viskosität dieses Esters beträgt 31 mm2/s bei 1000 C.Experiments 2 to 4 of the table show a gradual reduction in the intake valve deposits compared to operating with fuel without additives (experiment 1). For Test 2, a Solvent Neutral 500 with a viscosity of 17 mm 2 / s at 100 ° C was used. In experiment 3, a polypropylene glycol with a viscosity of 100 mm 2 / s at 40 ° C was used. The esters, some with significantly lower viscosities, already have a far better effect. Experiments 4 to 8 are esters of high purity, ie OH number less than 1, acid number less than 0.1 and ash less than 1 mg / kg. The C 2 s phthalate was prepared with an alcohol which was obtained by hydroformylation of a hexa-isobutene from the preparation of reactive polyisobutene according to DE-AS 27 02 604. The viscosity of this ester is 31 mm 2 / s at 100 0 C.

Für die Oxoölester sind keine Molekulargewichte angegeben, da es sich chemisch um keine einheitlichen Substanzen handelt. Vielmehr leigen Substanzgemische vor, die noch Monocarbonsäureester, Ether und Kohlenwasserstoff mit niedrigem Molekulargewicht enthalten. Die Hauptwirkung geht jedoch von den Diestern der höheren Etheralkohole aus, die in den Oxoölen enthalten sind.No molecular weights are given for the oxo oil esters, since they are chemically not uniform substances. Rather, there are mixtures of substances that still contain monocarboxylic acid esters, ethers and hydrocarbons with a low molecular weight. The main effect, however, comes from the diesters of the higher ether alcohols contained in the oxo oils.

Die Kombination der erfindungsgemäß zu verwendenden Trägeröle mit handelsüblichem Polybutenamin, hergestellt aus Polybuten MG 1300 und Aminoethylethanolamin, Wirksubstanzgehalt 50 %, zeigt die synergistische Wirkung der Esterformulierungen im Vergleich zu einer Polyetherformulierung. Die empfohlene Dosierung des handelsüblichen Polybutenamins ist für Formulierungen mit Mineralöl 350 mg/kg. Demgegenüber ermöglichen die erfindungsgemäßen Ester eine Einsparung von etwa 30 % an polymeren Detergens. Ergebnisse mit anderen Detergentien höherer Viskosität sind vergleichbar.The combination of the carrier oils to be used according to the invention with commercially available polybutenamine, produced from polybutene MG 1300 and aminoethylethanolamine, active substance content 50%, shows the synergistic effect of the ester formulations in comparison to a polyether formulation. The recommended dosage of the commercial polybutenamine for formulations with mineral oil is 350 mg / kg. In contrast, the esters according to the invention enable a saving of about 30% in polymeric detergent. Results with other higher viscosity detergents are comparable.

Claims (7)

1. Kraftstoffe für Verbrennungsmotoren enthaltend 0,005 bis 0,2 Gew.%, bezogen auf die Kraftstoffe, an Estern aus aromatischen Di-, Tr- oder Tetracarbonsäuren mit langkettigen aliphatischen Alkoholen, die durch Hydroformylierung von verzweigten Olefinen hergestellt worden sind, wobei die Gesamtkohlenstoffzahl der Ester mindestens 36 C-Atome und das Molekulargewicht 550 bis 1500 beträgt.1. Fuels for internal combustion engines containing 0.005 to 0.2% by weight, based on the fuels, of esters of aromatic di-, tr- or tetracarboxylic acids with long-chain aliphatic alcohols which have been prepared by hydroformylation of branched olefins, the total carbon number being Ester at least 36 carbon atoms and the molecular weight is 550 to 1500. 2. Kraftstoffe gemäß Anspruch 1, dadurch gekennzeichnet, daß die Ester als Alkoholkomponente C21-, C25-, Cε»- und/oder C33-Oxoalkohole aus Oligomerbutenen oder Polyisobutenen mit hohem Vinylidenanteil enthalten.2. Fuels according to claim 1, characterized in that the esters contain as alcohol component C 21 -, C 25 -, Cε »- and / or C 33 -oxo alcohols from oligomer butenes or polyisobutenes with a high vinylidene content. 3. Kraftstoffe gemäß Anspruch 1, dadurch gekennzeichnet, daß die Ester Phthalsäurediester sind.3. Fuels according to claim 1, characterized in that the esters are phthalic diesters. 4. Kraftstoffe gemäß Anspruch 1, dadurch gekennzeichnet, daß die Ester als Alkoholkomponente Destillationsrückstände der Hydroformylierung von Olefinen enthalten.4. Fuels according to claim 1, characterized in that the esters contain distillation residues of the hydroformylation of olefins as the alcohol component. 5. Kraftstoffe gemäß Anspruch 1, dadurch gekennzeichnet, daß die Ester als Alkoholkomponente langkettige aliphatische Etheralkohole enthalten, die je eine Ether- und eine Hydroxygruppe und mindestens 17 Kohlenstoffatome enthalten.5. Fuels according to claim 1, characterized in that the esters contain as the alcohol component long-chain aliphatic ether alcohols, each containing an ether and a hydroxyl group and at least 17 carbon atoms. 6. Kraftstoffe gemäß Anspruch 5, dadurch gekennzeichnet, daß die Alkohole solche der Formel Cn+1H2n+3 - O - Cn+2H2n+4OH sind, in der n 7, 8, 9, 12 und 12 bis 14 bedeutet und die Kohlenwasserstoffreste verzweigt sind.6. Fuels according to claim 5, characterized in that the alcohols are those of the formula C n + 1 H 2n + 3 - O - C n + 2 H 2n + 4 OH, in which n 7, 8, 9, 12 and 12 to 14 means and the hydrocarbon radicals are branched. 7. Kraftstoffe gemäß Anspruch 1, dadurch gekennzeichnet, daß sie neben den Estern Detergentien, Vereisungsverhinderer, Korrosionsinhibitoren und Antioxydantien enthalten.7. Fuels according to claim 1, characterized in that, in addition to the esters, they contain detergents, anti-icing agents, corrosion inhibitors and antioxidants.
EP89114039A 1988-08-06 1989-07-29 Fuel compositions containing esters from polycarboxylic acids and long chain alcohols Expired - Lifetime EP0356726B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3826797 1988-08-06
DE3826797A DE3826797A1 (en) 1988-08-06 1988-08-06 FUEL COMPOSITIONS CONTAINING POLYCARBONIC ACIDIC LOW-CHAIN ALCOHOLS

Publications (3)

Publication Number Publication Date
EP0356726A2 true EP0356726A2 (en) 1990-03-07
EP0356726A3 EP0356726A3 (en) 1990-03-28
EP0356726B1 EP0356726B1 (en) 1992-05-13

Family

ID=6360387

Family Applications (1)

Application Number Title Priority Date Filing Date
EP89114039A Expired - Lifetime EP0356726B1 (en) 1988-08-06 1989-07-29 Fuel compositions containing esters from polycarboxylic acids and long chain alcohols

Country Status (3)

Country Link
EP (1) EP0356726B1 (en)
DE (2) DE3826797A1 (en)
ES (1) ES2030945T3 (en)

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0706552A1 (en) † 1994-05-02 1996-04-17 Chevron Chemical Company Fuel additive compositions containing an aliphatic amine, a polyolefin and an aromatic ester
EP0781786A1 (en) 1995-12-29 1997-07-02 Chevron Chemical Company Substituted aromatic polyalkyl ethers and fuel compositions containing the same
EP0781794A1 (en) 1995-12-19 1997-07-02 Chevron Chemical Company Very long chain alkylphenyl polyoxyalkylene amines and fuel compositions containing the same
EP0781785A2 (en) 1995-12-29 1997-07-02 Chevron Chemical Company Polyalkylphenyl and polyalkyloxycarbonylphenyl amino and nitro benzoates and fuel compositions containing the same
EP0782980A1 (en) 1995-12-29 1997-07-09 Chevron Chemical Company Polyalkylphenyl and polyalkyloxycarbonylphenyl hydrobenzoates and fuel compositions containing the same
US5880219A (en) * 1994-03-07 1999-03-09 Exxon Chemical Patents Inc. Polymers having terminal hydroxyl, aldehyde, or alkylamino substituents and derivatives thereof
EP1627907A1 (en) 2004-08-17 2006-02-22 Chevron Oronite Company LLC A fuel composition for rectifying fuel gauge sending unit problems
WO2009068538A1 (en) * 2007-11-28 2009-06-04 Shell Internationale Research Maatschappij B.V. Gasoline compositions
WO2011032857A2 (en) 2009-09-15 2011-03-24 Basf Se Use of derivatives of aromatic compounds as markers for liquids
US8394898B2 (en) 2009-07-31 2013-03-12 The University Of Southern Mississippi In situ formation of hydroxy chain end functional polyolefins
US8552122B2 (en) 2009-03-31 2013-10-08 The University Of Southern Mississippi Amine-terminated telechelic polymers and precursors thereto and methods for their preparation
WO2019180685A1 (en) 2018-03-23 2019-09-26 Chevron Oronite Company Llc Composition and method for preventing or reducing low speed pre-ignition in spark-ignited internal combustion engines
WO2020070672A1 (en) 2018-10-04 2020-04-09 Chevron Oronite Company Llc Hydride donors as an additive for reducing low speed pre-ignition events
WO2020095189A1 (en) 2018-11-07 2020-05-14 Chevron Usa Inc. Amino alkanediols and carboxylate salts as additives for improving fuel efficiency
WO2020099953A1 (en) 2018-11-15 2020-05-22 Chevron Oronite Company Llc Composition and method for preventing or reducing low speed pre-ignition in spark-ignited internal combustion engines
WO2021048677A1 (en) 2019-09-10 2021-03-18 Chevron Oronite Company Llc Reducing friction in combustion engines through fuel additives
WO2022009105A1 (en) 2020-07-07 2022-01-13 Chevron Oronite Company Llc Fuel additives for mitigating injector nozzle fouling and reducing particulate emissions
WO2022058894A1 (en) 2020-09-17 2022-03-24 Chevron Oronite Company Llc Aryloxy alkylamines as fuel additives for reducing injector fouling in direct injection spark ignition gasoline engines
WO2022208251A1 (en) 2021-03-31 2022-10-06 Chevron Oronite Company Llc Fuel additives for reducing low speed pre-ignition events
WO2022208250A1 (en) 2021-03-31 2022-10-06 Chevron Oronite Company Llc Compositions for mitigating low speed pre-ignition events
WO2023062477A1 (en) 2021-10-14 2023-04-20 Chevron U.S.A. Inc. Polyamide fuel additives

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3916365A1 (en) * 1989-05-19 1990-11-22 Basf Ag FUEL COMPOSITIONS CONTAINING ALKOXYLATION PRODUCTS
DE4309074A1 (en) 1993-03-20 1994-09-22 Basf Ag Mixtures suitable as fuel additives
US5691422A (en) * 1994-03-07 1997-11-25 Exxon Chemical Patents Inc. Saturated polyolefins having terminal aldehyde or hydroxy substituents and derivatives thereof
US5405419A (en) * 1994-05-02 1995-04-11 Chevron Chemical Company Fuel additive compositions containing an aliphatic amine, a polyolefin and a poly(oxyalkylene) monool
DE4434603A1 (en) 1994-09-28 1996-04-04 Basf Ag Mixture of amines, hydrocarbon polymers and carrier oils suitable as a fuel and lubricant additive
US6660050B1 (en) 2002-05-23 2003-12-09 Chevron U.S.A. Inc. Method for controlling deposits in the fuel reformer of a fuel cell system

Citations (5)

* 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
GB1217468A (en) * 1969-04-18 1970-12-31 Shell Int Research Ester mixtures
DE2129461A1 (en) * 1970-06-16 1971-12-23 Shell Int Research Fuels and fuels
GB2081299A (en) * 1980-07-29 1982-02-17 Exxon Research Engineering Co Two-stroke Fuel-lubricant Composition
EP0277345A1 (en) * 1987-01-08 1988-08-10 BASF Aktiengesellschaft Fuel or lubricant composition containing polybutyl or polyisobutyl derivatives

Patent Citations (5)

* 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
GB1217468A (en) * 1969-04-18 1970-12-31 Shell Int Research Ester mixtures
DE2129461A1 (en) * 1970-06-16 1971-12-23 Shell Int Research Fuels and fuels
GB2081299A (en) * 1980-07-29 1982-02-17 Exxon Research Engineering Co Two-stroke Fuel-lubricant Composition
EP0277345A1 (en) * 1987-01-08 1988-08-10 BASF Aktiengesellschaft Fuel or lubricant composition containing polybutyl or polyisobutyl derivatives

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Römpps Chemie-Lexikon; Achte, neubearbeitete und erweiterte Auflage;Franckh'sche Verlagshandlung Stuttgart, Seiten 4507, 4508 u. 2101, 2102 *

Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5880219A (en) * 1994-03-07 1999-03-09 Exxon Chemical Patents Inc. Polymers having terminal hydroxyl, aldehyde, or alkylamino substituents and derivatives thereof
EP0706552B2 (en) † 1994-05-02 2007-01-24 Chevron Oronite Company LLC Fuel additive compositions containing an aliphatic amine, a polyolefin and an aromatic ester
EP0706552A1 (en) † 1994-05-02 1996-04-17 Chevron Chemical Company Fuel additive compositions containing an aliphatic amine, a polyolefin and an aromatic ester
EP0781794A1 (en) 1995-12-19 1997-07-02 Chevron Chemical Company Very long chain alkylphenyl polyoxyalkylene amines and fuel compositions containing the same
EP0781786A1 (en) 1995-12-29 1997-07-02 Chevron Chemical Company Substituted aromatic polyalkyl ethers and fuel compositions containing the same
EP0781785A2 (en) 1995-12-29 1997-07-02 Chevron Chemical Company Polyalkylphenyl and polyalkyloxycarbonylphenyl amino and nitro benzoates and fuel compositions containing the same
EP0782980A1 (en) 1995-12-29 1997-07-09 Chevron Chemical Company Polyalkylphenyl and polyalkyloxycarbonylphenyl hydrobenzoates and fuel compositions containing the same
EP1627907A1 (en) 2004-08-17 2006-02-22 Chevron Oronite Company LLC A fuel composition for rectifying fuel gauge sending unit problems
WO2009068538A1 (en) * 2007-11-28 2009-06-04 Shell Internationale Research Maatschappij B.V. Gasoline compositions
US8552122B2 (en) 2009-03-31 2013-10-08 The University Of Southern Mississippi Amine-terminated telechelic polymers and precursors thereto and methods for their preparation
US9315595B2 (en) 2009-03-31 2016-04-19 Chevron Oronite Company Llc Amine-terminated telechelic polymers and precursors thereto and methods for their preparation
US9150672B2 (en) 2009-07-31 2015-10-06 The University Of Southern Mississippi In situ formation of hydroxy chain end functional polyolefins
US8394898B2 (en) 2009-07-31 2013-03-12 The University Of Southern Mississippi In situ formation of hydroxy chain end functional polyolefins
WO2011032857A2 (en) 2009-09-15 2011-03-24 Basf Se Use of derivatives of aromatic compounds as markers for liquids
WO2020194041A2 (en) 2018-03-23 2020-10-01 Chevron Oronite Company Llc Composition and method for preventing or reducing low speed pre-ignition in spark-ignited internal combustion engines
WO2019180685A1 (en) 2018-03-23 2019-09-26 Chevron Oronite Company Llc Composition and method for preventing or reducing low speed pre-ignition in spark-ignited internal combustion engines
WO2020070672A1 (en) 2018-10-04 2020-04-09 Chevron Oronite Company Llc Hydride donors as an additive for reducing low speed pre-ignition events
WO2020095189A1 (en) 2018-11-07 2020-05-14 Chevron Usa Inc. Amino alkanediols and carboxylate salts as additives for improving fuel efficiency
US11142715B2 (en) 2018-11-07 2021-10-12 Chevron U.S.A. Inc. Amino alkanediols and carboxylate salts as additives for improving fuel efficiency
WO2020099953A1 (en) 2018-11-15 2020-05-22 Chevron Oronite Company Llc Composition and method for preventing or reducing low speed pre-ignition in spark-ignited internal combustion engines
WO2021048677A1 (en) 2019-09-10 2021-03-18 Chevron Oronite Company Llc Reducing friction in combustion engines through fuel additives
WO2022009105A1 (en) 2020-07-07 2022-01-13 Chevron Oronite Company Llc Fuel additives for mitigating injector nozzle fouling and reducing particulate emissions
WO2022058894A1 (en) 2020-09-17 2022-03-24 Chevron Oronite Company Llc Aryloxy alkylamines as fuel additives for reducing injector fouling in direct injection spark ignition gasoline engines
WO2022208251A1 (en) 2021-03-31 2022-10-06 Chevron Oronite Company Llc Fuel additives for reducing low speed pre-ignition events
WO2022208250A1 (en) 2021-03-31 2022-10-06 Chevron Oronite Company Llc Compositions for mitigating low speed pre-ignition events
WO2023062477A1 (en) 2021-10-14 2023-04-20 Chevron U.S.A. Inc. Polyamide fuel additives

Also Published As

Publication number Publication date
ES2030945T3 (en) 1992-11-16
EP0356726B1 (en) 1992-05-13
DE3826797A1 (en) 1990-02-08
EP0356726A3 (en) 1990-03-28
DE58901397D1 (en) 1992-06-17

Similar Documents

Publication Publication Date Title
EP0356726B1 (en) Fuel compositions containing esters from polycarboxylic acids and long chain alcohols
EP0374461B1 (en) Fuels for combustion machines
EP0548617B1 (en) Fuels for spark ignition engines
EP0012345B1 (en) Fuel oils and their application
EP0398100B1 (en) Fuel compositions containing alkoxylation products
EP0464489B1 (en) Ester containing fuels, for spark ignition- and diesel engines
DE69532917T3 (en) FUEL OIL COMPOSITION WITH POLYOXYALKYLENE
EP0289785B1 (en) Process to prevent or reduce scales in mixture preparation devices of engines
DE60214332T2 (en) Alkyl-substituted cresol polyalkoxylates and their use in fuels
DE3826608A1 (en) FUELS CONTAINING POLYETHERAMINE OR POLYETHERAMINE DERIVATIVES FOR OTTO ENGINES
EP0639632A1 (en) Additive for lead-free, spark-ignited internal combustion engine fuels as well as a fuel containing the same
EP0700985A1 (en) Fuels, for spark-ignition engines, containing polyether amines
EP0310875A1 (en) Fuels containing a polyether amine for spark ignition engines
EP3736317A1 (en) Fuel composition
EP1230330B1 (en) Use of fatty acid salts of alkoxylated oligoamines as lubricity improvers for petroleum products
DE3814601A1 (en) DETERGENT FOR HYDROCARBON FUELS
EP0704519B1 (en) Mixture of amines, hydrocarbonpolymers and carrier oils, suitable as fuel and lubricant additive
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
DE60020783T2 (en) Fuel dispersant with increased lubricating property
EP0006527A1 (en) Fuels for Otto-cycle engines containing mixtures of additives
EP1177270B1 (en) Polyalkene alcohol polyetheramines and use thereof in fuels and lubricants
EP0693509A1 (en) Reaction products of polyolefins and vinyl esters and use thereof as lubricating oil and fuel additives
DE964279C (en) Additive for motor fuels
DE3709195A1 (en) Storage-stable emulsifiers

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

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A2

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

AK Designated contracting states

Kind code of ref document: A3

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

17P Request for examination filed

Effective date: 19900308

17Q First examination report despatched

Effective date: 19910114

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE DE ES 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: 58901397

Country of ref document: DE

Date of ref document: 19920617

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)
ET Fr: translation filed
REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2030945

Country of ref document: ES

Kind code of ref document: T3

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
REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

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

Ref country code: NL

Payment date: 20040704

Year of fee payment: 16

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

Ref country code: FR

Payment date: 20040708

Year of fee payment: 16

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

Ref country code: ES

Payment date: 20040719

Year of fee payment: 16

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

Ref country code: GB

Payment date: 20040728

Year of fee payment: 16

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

Ref country code: DE

Payment date: 20040806

Year of fee payment: 16

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

Ref country code: BE

Payment date: 20040909

Year of fee payment: 16

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: 20050729

Ref country code: GB

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

Effective date: 20050729

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

Ref country code: ES

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

Effective date: 20050730

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

Ref country code: BE

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

Effective date: 20050731

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

Ref country code: DE

Free format text: LAPSE BECAUSE OF THE APPLICANT RENOUNCES

Effective date: 20050813

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

Ref country code: NL

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

Effective date: 20060201

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

Effective date: 20050729

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: 20060331

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

Effective date: 20060201

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20060331

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20050730

BERE Be: lapsed

Owner name: *BASF A.G.

Effective date: 20050731