EP0310875A1 - Fuels containing a polyether amine for spark ignition engines - Google Patents

Fuels containing a polyether amine for spark ignition engines Download PDF

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Publication number
EP0310875A1
EP0310875A1 EP88115566A EP88115566A EP0310875A1 EP 0310875 A1 EP0310875 A1 EP 0310875A1 EP 88115566 A EP88115566 A EP 88115566A EP 88115566 A EP88115566 A EP 88115566A EP 0310875 A1 EP0310875 A1 EP 0310875A1
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radical
formula
carbon atoms
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fuels
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German (de)
French (fr)
Inventor
Dieter Dr. Franz
Charalampos Dr. Gousetis
Claus Peter Jakob
Helmut Dr. Mach
Hans-Peter Dr. Rath
Klaus Starke
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BASF SE
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BASF SE
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    • 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
    • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
    • C10L1/2225—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates hydroxy containing

Definitions

  • the invention relates to fuels for gasoline engines which contain small amounts of a polyetheramine, the polyetheramine being produced by amination of polyethers.
  • Polyetheramines are known as fuel additives for the cleaning and cleaning of carburetors, injectors and valves and e.g. Subject of the PCT application WO 85/01956 or EP-B1 0 100 665.
  • the object was therefore to provide chlorine-free polyetheramines suitable as fuel additives. There was also the task of improving the action of the known polyetheramines or of achieving the same effect with little application.
  • polyetheramines to be used according to the invention are generally synthesized in two stages.
  • compounds of the formula II are prepared in a manner known per se by propoxylation and / or butoxylation of alcohols or amines.
  • the preferred monoalcohols are, in particular, branched alkanols having 3 to 30 carbon atoms, preferably 4 to 15 carbon atoms.
  • oxo alcohols based on ⁇ -olefins with 5 to 30 carbon atoms in particular diisobutene codimer, tri- to decamer-propylene and di- to octamer butene, should be mentioned.
  • suitable diols are hexanediol and dodecanediol, but larger amounts of butylene oxide must be used here in the alkoxylation, so that diols are less preferred.
  • hydroformylation product of a low molecular weight polyisobutene d.i. to alkoxylate a polyisobutylene alcohol having 33 to 61 carbon atoms.
  • the amines to be used as starters are generally primary and secondary monoamines, in particular branched alkylamines having 3 to 30, preferably 4 to 15, carbon atoms.
  • branched alkylamines having 3 to 30, preferably 4 to 15, carbon atoms.
  • the amines corresponding to the abovementioned alcohols are generally primary and secondary monoamines, in particular branched alkylamines having 3 to 30, preferably 4 to 15, carbon atoms.
  • amines are less suitable as starters than the alcohols.
  • the alkoxylation with propylene oxide and / or butylene oxide takes place in a manner known per se.
  • a general manufacturing specification is given below.
  • the amount of propylene oxide or butylene oxide can vary in other areas. As a rule, 3 to 100, preferably 5 to 30, moles of alkylene oxide are used per mole of starter. However, the amount used and the choice of propylene oxide or butylene oxide depends on which starter molecule was used. If the starter molecule contains a long-chain hydrophobic residue such as polyisobutylene alcohol, larger amounts of propylene oxide can be used, and even small amounts of ethylene oxide can be tolerated, although ethylene oxide is normally not used.
  • the polyalkoxides and their amount are selected so that a minimum solubility of 50% by weight in a hydrocarbon, e.g. Toluene or mineral oil SN 200 for the production of a masterbatch is guaranteed.
  • a hydrocarbon e.g. Toluene or mineral oil SN 200 for the production of a masterbatch is guaranteed.
  • the polyethers are generally subjected to amination according to methods known per se without further pretreatment.
  • Amination is understood to mean the introduction of an -NHR 3 group into the polyether with a terminal OH group with elimination of water. The methodology is described in detail in Houben-Weyl 11/1, Chapter llb, pages 108-134, to which reference is hereby made.
  • the free hydrogen atoms on the nitrogen can be replaced by other residues are replaced and a mixture of primary, secondary and tertiary amines is formed.
  • the amination reaction is expediently carried out at temperatures between 160 and 250 ° C. and pressures up to 600 bar, preferably 80-300 bar.
  • Preferred catalysts are cobalt- and nickel-containing catalysts on supports such as Si0 2 or A1 2 0 3 , but Raney nickel or Raney cobalt are also suitable.
  • a quantitative conversion of the OH groups is not necessary for the intended use, especially if the polyether used as the starting compound of the formula is also used as a carrier oil for the gasoline additive formulation. The partial conversion can even be advantageous because you get higher space-time yields.
  • the ammonia or the amine is used in excess in the amination, for example in a 10- to 60-fold, preferably 15- to 40-fold, molar excess. The use of ammonia is preferred.
  • the primary amines for the amination are methyl, ethyl or butylamine.
  • Leaded and unleaded regular and premium gasoline can be used as fuel.
  • the gasolines can also contain components other than hydrocarbons, e.g. Alcohols such as methanol, ethanol, tert. Butanol and ether, e.g. Contain methyl tertiary butyl ether.
  • the fuels generally also contain additives such as corrosion inhibitors, stabilizers, antioxidants, detergents, etc.
  • Corrosion inhibitors are mostly ammonium salts org. Carboxylic acids which tend to form films due to the structure of the starting compounds. Amines to increase the pH are also often found in corrosion inhibitors. Heterocyclic aromatics are mostly used as non-ferrous metal corrosion protection.
  • Antioxidants or stabilizers include, in particular, amines such as para-phenylenediamine, dicyclohexylamine, morpholine or derivatives of these amines.
  • Phenolic antioxidants such as 2,4-di-tert-butylphenol or 3,5-di-tert-butyl-4-hydroxiphenylpropionic acid and their derivatives are also added to fuels and lubricants.
  • the carburetor, injector and valve detergents may also contain amides and imides of polyisobutylene succinic anhydride, polybutenamines, polybutene polyamines and long-chain carbonamides and imides in the fuels.
  • Mineral oils of the viscosity range SN 500-900, but also Brightstock and synthetic oils such as polyalphaolefin, trimellitic acid ester or polyether can be used as carrier oils for concentrates of the polyetheramines to be used according to the invention.
  • the esters should contain long-chain, branched alcohols greater than Ca, the polyethers preferably long-chain starters and high PO or BuO contents, based on the amount of alkylene oxide, in the molecule.
  • the fuels generally contain the polyetheramines of the formula I in amounts of 10 to 2000 ppm based on the pure polyetheramine. In most cases, however, 20 to 1000 ppm, preferably 40 to 400 ppm, are sufficient.
  • the polyethers are prepared by known methods of alkoxylation with alkali.
  • a preliminary reaction is necessary for the reaction with amines.
  • the polyethers prepared according to a) and b) are generally subjected to the subsequent amination without further pretreatment. In the case of higher polyether viscosities, however, dilution with solvent, preferably branched aliphatics such as isododecane, is recommended, so that a viscosity of 50-200 mm 2 / s at 20 .
  • C receives. 800 g of polyether or polyether solution are treated with 1 l of ammonia and 100 g of Raney nickel in a 5 l roll autoclave with 200 bar of hydrogen at 180 ° C. for 5 hours. After cooling, the catalyst is separated off by filtration, excess ammonia is evaporated off and the water of reaction is distilled off azeotropically or under a gentle stream of nitrogen.
  • the running time was 60 hours, the number of cycles was 800. Unleaded, alcohol-containing super gasoline (3% methanol, 2% tert. Butanol) was used as fuel, and the engine oil was the reference oil of the Opel Kadett test CEC-F-0 2 -C-79 , RL 51 used.
  • the intake valves are evaluated gravimetrically.
  • the intake valves on the underside are carefully mechanically freed of deposits from the combustion chamber after removal. Thereafter, surface-adhering, easily soluble parts on the valves are removed by immersion in cyclohexane and the valves are dried by swirling in air. This treatment is done twice in total.
  • the inlet valves are then weighed. The amount of deposits per inlet valve results from the weight difference between the valve weight before and after the test. The results of these tests are shown in Table 1.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Polyethers (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)

Abstract

Fuels for spark-ignition engines, containing small quantities of a polyether-amine of the formula I <IMAGE> in which R<1> is the radical of a monohydric or polyhydric alcohol or of an amine, each having 2 to 30 carbon atoms, X is an oxygen atom or an <IMAGE> group, in which R<4> is a second radical R<1> or a second radical <IMAGE> R<2> is the alkylene radical derived from propylene oxide or butylene oxide, m is one of the numbers 5 to 100 and R<3> is hydrogen or an alkyl radical having 1 to 20 carbon atoms, R<5> is hydrogen, and R<5> and R<3> can also each be the radical <IMAGE> the molecular weight Mn is 500 to 5000, the polyether-amines having been prepared by amination of polyethers of the formula II <IMAGE> in which R<1>, X, R<2> and m are as defined above, with ammonia or primary aliphatic amines, are novel ether-amine additives having an improved valve-cleaning action.

Description

Die Erfindung betrifft Kraftstoffe für Ottomotoren, die geringe Mengen eines Polyetheramins enthalten, wobei das Polyetheramin durch Aminierung von Polyethern hergestellt ist.The invention relates to fuels for gasoline engines which contain small amounts of a polyetheramine, the polyetheramine being produced by amination of polyethers.

Polyetheramine sind als Kraftstoffadditive zur Reinhaltung und Reinigung von Vergasern, Einspritzdüsen und Ventilen bekannt und z.B. Gegenstand der PCT-Anmeldung WO 85/01956 oder der EP-B1 0 100 665.Polyetheramines are known as fuel additives for the cleaning and cleaning of carburetors, injectors and valves and e.g. Subject of the PCT application WO 85/01956 or EP-B1 0 100 665.

Dort sind Verbindungen beschrieben, die ausgehend von Ethylenchlorhydrin, Alkoxylierung, Verätherung der Endhydroxylgruppe und Ersatz des Chloratoms durch eine Aminogruppe hergestellt werden.There compounds are described which are prepared starting from ethylene chlorohydrin, alkoxylation, etherification of the end hydroxyl group and replacement of the chlorine atom by an amino group.

Obgleich diese Polyetheramine ausgezeichnete Ventilreiniger mit ausgeprägtem Reinigungseffekt im Einlaßsystem des Motors sind, haben Sie den Nachteil eines von der Herstellung verbleibenden Chlorgehalts. Kraftstoff- oder Ölzusätze, die Chlor enthalten, sind jedoch aus Gründen der Korrosion und des Umweltschutzes unerwünscht.Although these polyetheramines are excellent valve cleaners with a pronounced cleaning effect in the intake system of the engine, they have the disadvantage of a chlorine content remaining from the manufacture. Fuel or oil additives that contain chlorine are undesirable for reasons of corrosion and environmental protection.

Es bestand daher die Aufgabe chlorfreie, als Kraftstoffadditive geeignete Polyetheramine bereitzustellen. Es bestand weiterhin die Aufgabe, die bekannten Polyetheramine in ihrer Wirkung zu verbessern, bzw. mit geringer Aufwandmenge die gleiche Wirkung zu erzielen.The object was therefore to provide chlorine-free polyetheramines suitable as fuel additives. There was also the task of improving the action of the known polyetheramines or of achieving the same effect with little application.

Es wurde nun überraschenderweise gefunden, daß Kraftstoffe für Ottomotoren, die geringe Mengen Polyetheramine enthalten, eine sehr gute Ventil- und Vergaserreinigungswirkung haben und kein Chlor aufweisen, wenn die Polyetheramine solche der Formel I

Figure imgb0001
sind, in der R1 den Rest eines ein- oder mehrwertigen Alkohols, oder eines Amins jeweils mit 2 bis 30 Kohlenstoffatomen, X ein Sauerstoffatom oder eine
Figure imgb0002
in der R4- für einen zweiten Rest R1 oder einen zweiten Rest
Figure imgb0003
steht, R2 den aus Propylen- oder Butylenoxid stammenden Alkylenrest, m die Zahlen 5 bis 100 und R3 Wasserstoff oder einen Alkylrest mit 1 bis 20 Kohlenstoffatomen, R5 Wasserstoff und R5 und R3 jeweils ferner den Rest
Figure imgb0004
bedeuten können, das Molekulargewicht MN 500 bis 5000 beträgt und wobei die Polyetheramine durch Aminierung von Polyethern der Formel II
Figure imgb0005
in der R1, X, R2 und m die genannten Bedeutungen haben, mit Ammoniak oder primären aliphatischen Aminen hergestellt sind.It has now surprisingly been found that fuels for gasoline engines which contain small amounts of polyether amines have a very good valve and carburetor cleaning action and have no chlorine if the polyether amines are those of the formula I.
Figure imgb0001
 are in which R 1 is the residue of a mono- or polyhydric alcohol, or an amine each having 2 to 30 carbon atoms, X is an oxygen atom or a
Figure imgb0002
 in the R4- for a second residue R 1 or a second residue
Figure imgb0003
 R 2 is the alkylene radical derived from propylene or butylene oxide, m is the numbers 5 to 100 and R 3 is hydrogen or an alkyl radical having 1 to 20 carbon atoms, R 5 is hydrogen and R 5 and R 3 are in each case the radical
Figure imgb0004
 can mean, the molecular weight M N is 500 to 5000 and the polyetheramines by amination of polyethers of the formula II
Figure imgb0005
 in which R 1 , X, R 2 and m have the meanings mentioned, are prepared with ammonia or primary aliphatic amines.

Die erfindungsgemäß zu verwendenden Polyetheramine werden im allgemeinen in zwei Stufen synthetisiert. In einem ersten Schritt stellt man durch Propoxylierung und/oder Butoxylierung von Alkoholen oder Aminen in an sich bekannter Weise Verbindungen der Formel II her.The polyetheramines to be used according to the invention are generally synthesized in two stages. In a first step, compounds of the formula II are prepared in a manner known per se by propoxylation and / or butoxylation of alcohols or amines.

Als Alkanol kommen dabei ein- oder mehrwertige Alkohole in Betracht, wobei jedoch bei mehrwertigen Alkoholen das Verhältnis von OH- zu CH=2-Gruppen nicht größer als 1:3 sein soll. Die bevorzugten Monoalkohole sind insbesondere verzweigte Alkanole mit 3 bis 30 Kohlenstoffatomen, vorzugsweise 4 bis 15 Kohlenstoffatomen. Im einzelnen kommen als Starter neben Ethanol, den n- und Isoalkoholen des Propanols, Butanols, Pentanols, Hexanols, Oktanols wie 2-Ethyl-hexanol, Nonanol und Dekanol, Stearylalkohol, Cetylalkohol sowie Alfole der allgemeinen Formel

Figure imgb0006
in der n 1 bis 11 bedeuten in Betracht. Schließlich sind Oxoalkohole auf Basis von a-Olefinen mit 5 bis 30 C-Atomen insbesondere Diisobuten-Codimer, Tri- bis Dekamer-propylen und Di- bis Octamerbuten zu nennen. Als Diole kommen z.B. Hexandiol und Dodekandiol in Betracht, doch müssen hier bei der Alkoxilierung größere Butylenoxid-Mengen verwendet werden, so daß Diole weniger bevorzugt sind.Monohydric or polyhydric alcohols are suitable as alkanol, but the ratio of OH to CH = 2 groups in polyhydric alcohols should not be greater than 1: 3. The preferred monoalcohols are, in particular, branched alkanols having 3 to 30 carbon atoms, preferably 4 to 15 carbon atoms. In addition to ethanol, the n- and isoalcohols of propanol, butanol, pentanols, hexanols, octanols such as 2-ethylhexanol, nonanol and decanol, stearyl alcohol, cetyl alcohol and alfoles of the general formula
Figure imgb0006
 in which n is 1 to 11 into consideration. Finally, oxo alcohols based on α-olefins with 5 to 30 carbon atoms, in particular diisobutene codimer, tri- to decamer-propylene and di- to octamer butene, should be mentioned. Examples of suitable diols are hexanediol and dodecanediol, but larger amounts of butylene oxide must be used here in the alkoxylation, so that diols are less preferred.

Es ist aber auch möglich, das Hydroformylierungsprodukt eines niedrigmolekularen Polyisobutens d.i. ein Polyisobutylenalkohol mit 33 bis 61 Kohlenstoffatomen zu alkoxylieren.However, it is also possible to use the hydroformylation product of a low molecular weight polyisobutene d.i. to alkoxylate a polyisobutylene alcohol having 33 to 61 carbon atoms.

Die als Starter zu verwendenden Amine sind in der Regel primäre und sekundäre Monoamine insbesondere verzweigte Alkylamine mit 3 bis 30, vorzugsweise 4 bis 15, C-Atomen. Im einzelnen kommen z.B. die den oben genannten Alkoholen entsprechende Amine in Betracht.The amines to be used as starters are generally primary and secondary monoamines, in particular branched alkylamines having 3 to 30, preferably 4 to 15, carbon atoms. In particular, e.g. the amines corresponding to the abovementioned alcohols.

Aus Kostengründen und weil weniger einheitliche Produkte entstehen, sind Amine jedoch weniger als Starter geeignet als die Alkohole.For cost reasons and because less uniform products are formed, amines are less suitable as starters than the alcohols.

Die Alkoxylierung mit Propylenoxid und/oder Butylenoxid erfolgt in an sich bekannter Weise. Eine allgemeine Herstellvorschrift wird weiter unten angegeben. Die Menge an Propylenoxid bzw. Butylenoxid kann in weiteren Bereichen schwanken. In der Regel verwendet man 3 bis 100, vorzugsweise 5 bis 30 Mol Alkylenoxid pro Mol Starter. Die angewandte Menge und die Wahl von Propylenoxid oder Butylenoxid hängt jedoch davon ab, welches Startermolekül verwendet wurde. Enthält das Startermolekül einen langkettigen hydrophoben Rest wie Polyisobutylenalkohol, können größere Mengen Propylenoxid zur Anwendung kommen, ja, es können sogar geringe Mengen Ethylenoxid toleriert werden, obgleich Ethylenoxid normalerweise nicht verwendet wird.The alkoxylation with propylene oxide and / or butylene oxide takes place in a manner known per se. A general manufacturing specification is given below. The amount of propylene oxide or butylene oxide can vary in other areas. As a rule, 3 to 100, preferably 5 to 30, moles of alkylene oxide are used per mole of starter. However, the amount used and the choice of propylene oxide or butylene oxide depends on which starter molecule was used. If the starter molecule contains a long-chain hydrophobic residue such as polyisobutylene alcohol, larger amounts of propylene oxide can be used, and even small amounts of ethylene oxide can be tolerated, although ethylene oxide is normally not used.

Insgesamt gilt, daß die Polyalkoxide und deren Menge so gewählt werden, daß eine Mindestlöslichkeit von 50 Gew.% in einem Kohlenwasserstoff z.B. Toluol oder Mineralöl SN 200 zur Herstellung eines Masterbatch gewährleistet ist.All in all, the polyalkoxides and their amount are selected so that a minimum solubility of 50% by weight in a hydrocarbon, e.g. Toluene or mineral oil SN 200 for the production of a masterbatch is guaranteed.

In einer zweiten Stufe werden dann die Polyether im allgemeinen ohne weitere Vorbehandlung einer Aminierung nach an sich bekannten Methoden unterworfen. Unter Aminierung wird dabei die Einführung einer -NHR3-Gruppe in den Polyether mit endständiger OH-Gruppe unter Wasserabspaltung verstanden. Die Methodik ist im einzelnen in Houben-Weyl 11/1, Kapitel llb, Seiten 108 - 134 beschrieben, worauf hiermit Bezug genommen wird.In a second stage, the polyethers are generally subjected to amination according to methods known per se without further pretreatment. Amination is understood to mean the introduction of an -NHR 3 group into the polyether with a terminal OH group with elimination of water. The methodology is described in detail in Houben-Weyl 11/1, Chapter llb, pages 108-134, to which reference is hereby made.

Wie bei allen aminierenden Hydrierungen können die noch freien Wasserstoffatome am Stickstoff durch weitere Reste

Figure imgb0007
ersetzt werden und es entsteht ein Gemisch von primären, sekundären und tertiären Aminen.As with all aminating hydrogenations, the free hydrogen atoms on the nitrogen can be replaced by other residues
Figure imgb0007
 are replaced and a mixture of primary, secondary and tertiary amines is formed.

Die Aminierungsreaktion wird zweckmäßig bei Temperaturen zwischen 160 und 250 ° C und Drücken bis zu 600 bar, vorzugsweise 80 - 300 bar durchgeführt. Als Katalysatoren kommen vorzugsweise kobalt- und nickelhaltige Katalysatoren auf Trägern wie Si02 oder A1203, aber auch Raney Nickel oder Raney Kobalt kommen in Frage. Ein quantitativer Umsatz der OH Gruppen ist für den Anwendungszweck nicht erforderlich, besonders dann, wenn der als Ausgangsverbindung der Formel benutzte Polyether auch als Trägeröl für die Benzinadditivformulierung verwendet wird. Der Teilumsatz kann sogar vorteilhaft sein, da man höhere Raum-Zeit-Ausbeuten erhält. Im allgemeinen wendet man bei der Aminierung das Ammoniak bzw. das Amin im Überschuß z.B. im 10- bis 60fachen, vorzugsweise 15- bis 40fachen molaren Überschuß an. Dabei ist die Verwendung von Ammoniak bevorzugt. Als primäre Amine für die Aminierung sind vor allem Methyl-, Ethyl- oder Butylamin zu nennen.The amination reaction is expediently carried out at temperatures between 160 and 250 ° C. and pressures up to 600 bar, preferably 80-300 bar. Preferred catalysts are cobalt- and nickel-containing catalysts on supports such as Si0 2 or A1 2 0 3 , but Raney nickel or Raney cobalt are also suitable. A quantitative conversion of the OH groups is not necessary for the intended use, especially if the polyether used as the starting compound of the formula is also used as a carrier oil for the gasoline additive formulation. The partial conversion can even be advantageous because you get higher space-time yields. In general, the ammonia or the amine is used in excess in the amination, for example in a 10- to 60-fold, preferably 15- to 40-fold, molar excess. The use of ammonia is preferred. The primary amines for the amination are methyl, ethyl or butylamine.

Als Kraftstoff kommen verbleites und unverbleites Normal- und Superbenzin in Betracht. Die Benzine können auch andere Komponenten als Kohlenwasserstoffe, z.B. Alkohole wie Methanol, Ethanol, tert. Butanol sowie Ether, z.B. Methyltertiärbutylether enthalten. Neben den erfindungsgemäß zu verwendenden Polyetheraminen enthalten die Kraftstoffe in der Regel noch weiter Zusätze wie Korrosionsinhibitoren, Stabilisatoren, Antioxydantien, Detergents etc.Leaded and unleaded regular and premium gasoline can be used as fuel. The gasolines can also contain components other than hydrocarbons, e.g. Alcohols such as methanol, ethanol, tert. Butanol and ether, e.g. Contain methyl tertiary butyl ether. In addition to the polyetheramines to be used according to the invention, the fuels generally also contain additives such as corrosion inhibitors, stabilizers, antioxidants, detergents, etc.

Korrosionsinhibitoren sind meist Ammoniumsalze org. Carbonsäuren, die durch entsprechende Struktur der Ausgangsverbindungen zur Filmbildung neigen. Auch Amine zur Erhöhung des pH-Wertes finden sich häufig in Korrosionsinhibitoren. Als Buntmetallkorrosionsschutz werden meist heterocyclische Aromaten eingesetzt.Corrosion inhibitors are mostly ammonium salts org. Carboxylic acids which tend to form films due to the structure of the starting compounds. Amines to increase the pH are also often found in corrosion inhibitors. Heterocyclic aromatics are mostly used as non-ferrous metal corrosion protection.

Als Antioxidantien oder Stabilisatoren sind insbesondere Amine wie paraPhenylendiamin, Dicyclohexylamin, Morpholin oder Derivate dieser Amine zu nennen. Auch phenolische Antioxidantien wie 2,4-di-tert-Butylphenol oder 3,5-Di-tert.-butyl-4-hydroxiphenylpropionsäure und deren Derivate werden Kraft- und Schmierstoffen zugesetzt.Antioxidants or stabilizers include, in particular, amines such as para-phenylenediamine, dicyclohexylamine, morpholine or derivatives of these amines. Phenolic antioxidants such as 2,4-di-tert-butylphenol or 3,5-di-tert-butyl-4-hydroxiphenylpropionic acid and their derivatives are also added to fuels and lubricants.

Als Vergaser-, Injector- und Ventildetergents sind ferner gegebenenfalls Amide und Imide des Polyisobutylenbernsteinsäureanhydrids, Polybutenamine, Polybutenpolyamine sowie langkettige Carbonamide und -imide in den Kraftstoffen enthalten.The carburetor, injector and valve detergents may also contain amides and imides of polyisobutylene succinic anhydride, polybutenamines, polybutene polyamines and long-chain carbonamides and imides in the fuels.

Als Trägeröle für Konzentrate der erfindungsgemäß zu verwendenden Polyetheramine können Mineralöle des Viskositätsbereiches SN 500-900, aber auch Brightstock und Syntheseöle wie Polyalphaolefin, Trimellithsäureester oder Polyether eingesetzt werden. Die Ester sollten möglichst langkettige, verzweigte Alkohole größer Ca, die Polyether vorzugsweise langkettige Starter und hohe PO- oder BuO-Gehalte, bezogen auf die Alkylenoxidmenge, im Molekühl enthalten.Mineral oils of the viscosity range SN 500-900, but also Brightstock and synthetic oils such as polyalphaolefin, trimellitic acid ester or polyether can be used as carrier oils for concentrates of the polyetheramines to be used according to the invention. The esters should contain long-chain, branched alcohols greater than Ca, the polyethers preferably long-chain starters and high PO or BuO contents, based on the amount of alkylene oxide, in the molecule.

Die Kraftstoffe enthalten die Polyetheramine der Formel I in der Regel in Mengen von 10 bis 2000 ppm bezogen auf das reine Polyetheramin. Meist sind aber bereits 20 bis 1000 ppm, vorzugsweise 40 bis 400 ppm, ausreichend.The fuels generally contain the polyetheramines of the formula I in amounts of 10 to 2000 ppm based on the pure polyetheramine. In most cases, however, 20 to 1000 ppm, preferably 40 to 400 ppm, are sufficient.

Im folgenden wird die Herstellung der Polyetheramine und ihre Wirkung im Motor im einzelnen erläutert.The production of the polyetheramines and their effect in the engine are explained in detail below.

HerstellungsbeispielManufacturing example

1. Die Herstellung der Polyether erfolgt nach bekannten Verfahren der Oxalkylierung mit Alkali.1. The polyethers are prepared by known methods of alkoxylation with alkali.

a) Starter Alkohola) Starter alcohol

Im einen Autoklaven mit Rührer werden bezogen auf den gesamten Ansatz 0,1 Gew.% KOH fein pulverisiert im Alkohol unter Rühren verteilt und bei 200 mbar auf 130°C erhitzt. Dabei werden restliche Wasserspuren abgezogen. Dann wird der Autoklav geschlossen und Alkylenoxid so zudosiert, daß ein Druck von 6 bar nicht überschritten wird. Die Dosierung verschiedener Alkylenoxide kann gleichzeitig oder nacheinander erfolgen, so daß statistische Polyether oder Blöcke entstehen .mit mehr oder minder scharfen Übergängen. Nach Zulaufende der Alkylenoxide fällt der Druck im Verlauf von 3 bis 10 h auf 2 bis 3 bar. Ist dieser Druck erreicht, kühlt man auf 80 °C und entspannt über ein Membranventil und evakuiert bis auf 20 bis 30 mbar. Nach Aufrechterhalten des verminderten Drucks für ca. 1 h, setzt man dann äquivalente Mengen sauren lonenaustauschers zur Entfernung von Kalium zu und filtiert.In an autoclave with a stirrer, 0.1% by weight of KOH, finely pulverized in alcohol, is distributed with stirring, based on the entire batch, and heated to 130 ° C. at 200 mbar. Any remaining traces of water are removed. The autoclave is then closed and alkylene oxide is metered in so that a pressure of 6 bar is not exceeded. Different alkylene oxides can be metered in simultaneously or in succession, so that statistical polyethers or blocks are formed. With more or less sharp transitions. After the end of the alkylene oxides, the pressure drops to 2 to 3 bar in the course of 3 to 10 h. When this pressure is reached, the mixture is cooled to 80 ° C and relaxed via a membrane valve and evacuated to 20 to 30 mbar. After maintaining the reduced pressure for about 1 h, equivalent amounts of acidic ion exchanger are then added to remove potassium and filtered.

b) Starter Amineb) starter amines

Für die Umsetzung mit Aminen ist eine Vorreaktion notwendig. Dazu werden im Autoklaven unter Rühren die Amine mit 1 bis 4 moläquivalenten Alkylenoxid, je nach Zahl der N-H Bindungen des Amins (NH2 = 2 N-H) und 5 Gew.% Wasser versetzt und man rührt bei 130°C ca. 10 h. Danach wird auf 80 C abgekühlt, entspannt und bis auf 30 bis 40 mbar evakuiert. Dabei wird Wasser quantitativ entfernt. Danach setzt man wie unter a) beschrieben mit Zugabe von pulverisierter KOH die Alkoxylierung fort.A preliminary reaction is necessary for the reaction with amines. For this purpose, the amines are mixed with 1 to 4 molar equivalents of alkylene oxide in the autoclave, with stirring, depending on the number of NH bonds in the amine (NH 2 = 2 NH) and 5% by weight of water, and the mixture is stirred at 130 ° C. for about 10 hours. It is then cooled to 80 ° C., decompressed and evacuated to 30 to 40 mbar. Water is removed quantitatively. The alkoxylation is then continued as described under a) with the addition of powdered KOH.

2. Die gemäß a) und b) hergestellten Polyether werden im allgemeinen ohne weitere Vorbehandlung der nachfolgenden Aminierung unterworfen. Bei höheren Polyetherviskositäten empfiehlt sich jedoch eine Verdünnung mit Lösemittel, vorzugsweise verzweigte Aliphaten wie Isododekan, so daß man eine Viskosität von 50 - 200 mm2/s bei 20. C erhält. 800 g Polyether oder Polyetherlösung werden mit 1 I Ammoniak und 100 g Raney-Nickel in einem 5 I-Rollautoklaven mit 200 bar Wasserstoff bei 180°C 5 Stunden lang behandelt. Nach dem Abkühlen trennt man den Katalysator durch Filtrieren ab, verdampft überschüssiges Ammoniak und destilliert das Reaktionswasser azeotrop oder unter leichtem Stickstoffstrom ab.2. The polyethers prepared according to a) and b) are generally subjected to the subsequent amination without further pretreatment. In the case of higher polyether viscosities, however, dilution with solvent, preferably branched aliphatics such as isododecane, is recommended, so that a viscosity of 50-200 mm 2 / s at 20 . C receives. 800 g of polyether or polyether solution are treated with 1 l of ammonia and 100 g of Raney nickel in a 5 l roll autoclave with 200 bar of hydrogen at 180 ° C. for 5 hours. After cooling, the catalyst is separated off by filtration, excess ammonia is evaporated off and the water of reaction is distilled off azeotropically or under a gentle stream of nitrogen.

BeispieleExamples

Nach den unter 1 a) b) und 2 angegebenen Methoden wurden folgende Produkte hergestellt:

  • A: Starter: iso-Tridekanol (aus Tetramerpropylen)
    • Alkylenoxid: PO/BuO Gewichtsverhältnis 1:1
    • Molgewicht MN: 1950
    • Aminzahl: 31
  • B: Starter: iso-Tridekanol (aus Trimerbuten)
    • Alkylenoxid: BuO
    • Molgewicht MN des Polyethers: 730
    • Aminzahl: 92
  • C: Starter: Polyisobutylalkohol MN 455
    • Alkylenoxid: PO
    • Molgewicht MN des Polyethers: 890
    • Aminzahl: 73
  • D: Starter: Diisotridecylamin
    • Alkylenoxid: PO/BuO Gewichtsverhältnis 70/30
    • Molgewicht MN des Polyethers: 1650
    • Aminzahl: 41
  • E: Wie A, jedoch mit dem Ausgangsprodukt der Aminierung und Mineralöl SN 800 im Gewichtsverhältnis 1:2:1 (Aminoether:Polyether:Mineralöl) verdünnt
  • F: Mischung des Ausgangs-Polyethers gemäß B, Polyetheramin gemäß B und Schmieröldispersant aus Polyisobutenylbernsteinsäureanhydrid und Triethylentetramin (MV 2:1) im Gewichtsverhältnis 6:2:1, wobei das eingesetzte Polyisobutenderivat nur 60 % Wirksubstanz enthält
The following products were produced by the methods given under 1 a) b) and 2:
  • A: Starter: iso-tridekanol (from tetramer propylene)
    • Alkylene oxide: PO / BuO weight ratio 1: 1
    • Molecular weight M N : 1950
    • Amine number: 31
  • B: Starter: iso-tridekanol (from trimerbutene)
    • Alkylene oxide: BuO
    • Molecular weight M N of the polyether: 730
    • Amine number: 92
  • C: Starter: polyisobutyl alcohol M N 455
    • Alkylene oxide: PO
    • Molecular weight M N of the polyether: 890
    • Amine number: 73
  • D: Starter: diisotridecylamine
    • Alkylene oxide: PO / BuO weight ratio 70/30
    • Molecular weight M N of the polyether: 1650
    • Amine number: 41
  • E: As A, but diluted with the starting product of the amination and mineral oil SN 800 in a weight ratio of 1: 2: 1 (amino ether: polyether: mineral oil)
  • F: Mixture of the starting polyether according to B, polyetheramine according to B and lubricating oil dispersant made of polyisobutenylsuccinic anhydride and triethylenetetramine (MV 2: 1) in a weight ratio of 6: 2: 1, the polyisobutene derivative used containing only 60% of active substance

Durchführung der motorischen PrüfungenCarrying out the motor tests

Die motorischen Prüfungen mit den Additiven bzw. Additivpaketen wurden auf einem Daimler Benz M 102.980 Motor mit nachfolgendem Wechsellastprogramm durchgeführt.

Figure imgb0008
The engine tests with the additives or additive packages were carried out on a Daimler Benz M 102.980 engine with the following alternating load program.
Figure imgb0008

Die Laufzeit betrug 60 Stunden, die Zahl der Zyklen 800. Als Kraftstoff wurde unverbleites, alkoholhaltiges Superbenzin (3 % Methanol, 2 % tert. Butanol), als Motorenöl, das Referenzöl des Opel Kadett Tests CEC-F-02-C-79, RL 51 verwendet.The running time was 60 hours, the number of cycles was 800. Unleaded, alcohol-containing super gasoline (3% methanol, 2% tert. Butanol) was used as fuel, and the engine oil was the reference oil of the Opel Kadett test CEC-F-0 2 -C-79 , RL 51 used.

Die Auswertung der Einlaßventile erfolgt gravimetrisch. Dazu werden die Einlaßventile nach dem Ausbau an ihrer Unterseite sorgfältig mechanisch von Ablagerungen aus dem Verbrennungsraum befreit. Danach werden oberflächlich haftende, leicht lösliche Anteile auf den Ventilen durch Eintauchen in Cyclohexan entfernt und die Ventile durch Schwenken an der Luft getrocknet. Diese Behandlung wird insgesamt zweimal vorgenommen. Anschließend werden die Einlaßventile gewogen. Aus der Gewichtsdifferenz zwischen dem Ventilgewicht vor und nach dem Versuch ergibt sich die Menge an Ablagerungen pro Einlaßventil. Die Ergebnisse dieser Versuche sind in Tabelle 1 wiedergegeben.

Figure imgb0009
The intake valves are evaluated gravimetrically. For this purpose, the intake valves on the underside are carefully mechanically freed of deposits from the combustion chamber after removal. Thereafter, surface-adhering, easily soluble parts on the valves are removed by immersion in cyclohexane and the valves are dried by swirling in air. This treatment is done twice in total. The inlet valves are then weighed. The amount of deposits per inlet valve results from the weight difference between the valve weight before and after the test. The results of these tests are shown in Table 1.
Figure imgb0009

Claims (4)

1. Kraftstoffe für Ottomotoren, enthaltend geringe Mengen eines Polyetheramins, dadurch gekennzeichnet, daß das Polyetheramin ein solches der Formel I
Figure imgb0010
ist, in der R1 den Rest eines ein- oder mehrwertigen Alkohols, oder eines Amins jeweils mit 2 bis 30 Kohlenstoffatomen, X ein Sauerstoffatom oder eine
Figure imgb0011
in der R4 für einen zweiten Rest R1 oder einen zweiten Rest
Figure imgb0012
steht, R2 den aus Propylen- oder Butylenoxid stammenden Alkylenrest, m die Zahlen 5 bis 100 und R3 Wasserstoff oder einen Alkylrest mit 1 bis 20 Kohlenstoffatomen, R5 Wasserstoff und R5 und R3 jeweils ferner den Rest
Figure imgb0013
bedeuten können, das Molekulargewicht MN 500 bis 5000 beträgt und wobei die Polyetheramine durch Aminierung von Polyethern der Formel II
Figure imgb0014
in der R1, X, R2 und m die genannten Bedeutungen haben, mit Ammoniak oder primären aliphatischen Aminen hergestellt sind.1. Fuels for gasoline engines containing small amounts of a polyetheramine, characterized in that the polyetheramine is one of formula I.
Figure imgb0010
 is in which R 1 is the residue of a mono- or polyhydric alcohol, or an amine each having 2 to 30 carbon atoms, X is an oxygen atom or a
Figure imgb0011
 in R 4 for a second residue R 1 or a second residue
Figure imgb0012
 R 2 is the alkylene radical derived from propylene or butylene oxide, m is the numbers 5 to 100 and R 3 is hydrogen or an alkyl radical having 1 to 20 carbon atoms, R 5 is hydrogen and R 5 and R 3 are in each case the radical
Figure imgb0013
 can mean, the molecular weight M N is 500 to 5000 and the polyetheramines by amination of polyethers of the formula II
Figure imgb0014
 in which R 1 , X, R 2 and m have the meanings mentioned, are prepared with ammonia or primary aliphatic amines. 2. Kraftstoffe gemäß Anspruch 1, enthaltend ein Polyetheramin der Formel I, in der R3 und RS Wasserstoff bedeuten.2. Fuels according to claim 1, containing a polyetheramine of the formula I in which R 3 and R S are hydrogen. 3. Kraftstoffe gemäß Anspruch 1 und 2, enthaltend ein Polyetheramin der Formel I, in der R1 einen Alkylrest mit 5 bis 15 Kohlenstoffatomen und X Sauerstoff bedeutet.3. Fuels according to Claims 1 and 2, containing a polyetheramine of the formula I in which R 1 is an alkyl radical having 5 to 15 carbon atoms and X is oxygen. 4. Kraftstoffe für Ottomotoren gemäß Ansprüchen 1 bis 3, enthaltend 10 bis 2000 mg eines Polyetheramins der Formel I pro kg Kraftstoff.4. Fuels for gasoline engines according to claims 1 to 3, containing 10 to 2000 mg of a polyetheramine of formula I per kg of fuel.
EP88115566A 1987-09-30 1988-09-22 Fuels containing a polyether amine for spark ignition engines Withdrawn EP0310875A1 (en)

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Cited By (126)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0407950A1 (en) * 1989-07-10 1991-01-16 Nippon Oil And Fats Company, Limited Formal compounds, fuel oil additives, and fuel oil compositions
EP0440248A1 (en) * 1990-02-02 1991-08-07 Kao Corporation Gasoline composition
EP0448365A1 (en) * 1990-03-20 1991-09-25 Exxon Research And Engineering Company Alkyl ether mono amines
EP0489322A2 (en) * 1990-12-06 1992-06-10 BASF Aktiengesellschaft Alkoxylated polyetherdiamines, process for their preparation and fuels for spark ignition engines containing them
US5306315A (en) * 1993-04-01 1994-04-26 Chevron Research And Technology Company Poly(alkylene ether) amines and fuel compositions containing the same
WO1994021754A1 (en) * 1993-03-20 1994-09-29 Basf Aktiengesellschaft Mixtures suitable for use as fuel additives
EP0630959A1 (en) * 1993-06-22 1994-12-28 Texaco Development Corporation Fuel composition
EP0700985A1 (en) 1994-09-09 1996-03-13 BASF Aktiengesellschaft Fuels, for spark-ignition engines, containing polyether amines
US5669939A (en) * 1996-05-14 1997-09-23 Chevron Chemical Company Polyalkylphenoxyaminoalkanes and fuel compositions containing the same
WO2000061708A1 (en) * 1999-04-13 2000-10-19 Basf Aktiengesellschaft Polyalkene alcohol polyetheramines and use thereof in fuels and lubricants
US6221116B1 (en) 1996-09-27 2001-04-24 Chevron Chemical Company Aminocarbamates of polyalkylphenoxyalkanols and fuel compositions containing the same
EP1122295A1 (en) * 1998-10-06 2001-08-08 Nippon Mitsubishi Oil Corporation Gasoline additive for direct-injection gasoline engine
WO2001085874A2 (en) * 2000-05-05 2001-11-15 Basf Aktiengesellschaft Fuel additive compositions for fuels for internal combustion engines with improved viscosity properties and good ivd performance
EP1244763A1 (en) * 1999-11-23 2002-10-02 The Lubrizol Corporation Additive composition
WO2006044892A1 (en) 2004-10-19 2006-04-27 The Lubrizol Corporation Additive and fuel compositions containing detergent and fluidizer and method thereof
US7204863B2 (en) 2001-12-11 2007-04-17 Exxonmobil Research And Engineering Company Gasoline additives for reducing the amount of internal combustion engine intake valve deposits and combustion chamber deposits
US7226489B2 (en) 2001-12-12 2007-06-05 Exxonmobil Research And Engineering Company Gasoline additives for reducing the amount of internal combustion engine intake valve deposits and combustion chamber deposits
WO2009050287A1 (en) 2007-10-19 2009-04-23 Shell Internationale Research Maatschappij B.V. Functional fluids for internal combustion engines
DE102008037662A1 (en) 2007-08-17 2009-04-23 Basf Se Oil soluble detergent, useful e.g. as additive for fuels, comprises reaction products of conversion of polyalkene epoxide with dicarboxylic acid anhydride and conversion of the obtained reaction product with nucleophile
WO2009095443A1 (en) 2008-02-01 2009-08-06 Basf Se Special polyisobutene amines, and use thereof as detergents in fuels
US7601185B2 (en) 2002-03-06 2009-10-13 Basf Aktiengesellschaft Fuel additive mixtures for gasolines with synergistic IVD performance
US7753970B2 (en) 2003-04-01 2010-07-13 Basf Aktiengesellschaft Polyalkene amines with improved applicational properties
DE102010001408A1 (en) 2009-02-06 2010-08-12 Basf Se Use of ketone compounds as a fuel additive to reduce the fuel consumption of diesel engines, preferably direct injection diesel engines, and diesel engines with common rail injection systems
US7850744B2 (en) 2004-08-05 2010-12-14 Basf Aktiengesellschaft Heterocyclic compounds containing nitrogen as a fuel additive in order to reduce abrasion
EP2267104A2 (en) 2006-02-27 2010-12-29 Basf Se Use of polynuclear phenolic compounds as dispersants
EP2270119A1 (en) 2003-04-11 2011-01-05 Basf Se Fuel composition
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WO2012072723A2 (en) 2010-12-02 2012-06-07 Basf Se Use of the reaction product of a hydrocarbyl-substituted dicarboxylic acid and a nitrogen compound for reducing fuel consumption
WO2012072643A2 (en) 2010-11-30 2012-06-07 Basf Se Production of isobutylene homopolymer or copolymer derivatives
WO2012076428A1 (en) 2010-12-09 2012-06-14 Basf Se Polytetrahydrobenzoxazines and bistetrahydrobenzoxazines and use thereof as additive to fuel or lubricant
WO2012097026A1 (en) 2011-01-12 2012-07-19 The Lubrizol Corporation Engine lubricants containing a polyether
WO2012162020A1 (en) 2011-05-26 2012-11-29 The Lubrizol Corporation Stabilized blends containing antioxidants
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WO2012163935A2 (en) 2011-05-30 2012-12-06 Shell Internationale Research Maatschappij B.V. Liquid fuel compositions
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WO2013174619A1 (en) 2012-05-25 2013-11-28 Basf Se Tertiary amines for reducing injector nozzle fouling in direct injection spark ignition engines
WO2014019911A1 (en) 2012-08-01 2014-02-06 Basf Se Process for improving thermostability of lubricant oils in internal combustion engines
WO2014023853A2 (en) 2012-11-06 2014-02-13 Basf Se Tertiary amines for reducing injector nozzle fouling and modifying friction in direct injection spark ignition engines
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WO2014158435A1 (en) 2013-03-13 2014-10-02 The Lubrizol Corporation Engine lubricants containing a polyether
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EP2883944A1 (en) 2013-12-13 2015-06-17 Shell Internationale Research Maatschappij B.V. New uses
US9062266B2 (en) 2012-02-10 2015-06-23 Basf Se Imidazolium salts as additives for fuels
WO2015091458A1 (en) 2013-12-16 2015-06-25 Shell Internationale Research Maatschappij B.V. Liquid fuel compositions
EP2891699A1 (en) 2013-12-31 2015-07-08 Shell Internationale Research Maatschappij B.V. Unleaded fuel compositions
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EP2949733A1 (en) 2014-05-28 2015-12-02 Shell Internationale Research Maatschappij B.V. Gasoline compositions comprising oxanilide uv filter compounds
US9296841B2 (en) 2010-11-30 2016-03-29 Basf Se Preparation of isobutene homo- or copolymer derivatives
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WO2016122911A1 (en) 2015-01-30 2016-08-04 The Lubrizol Corporation Composition for cleaning gasoline engine fuel delivery systems, air intake systems, and combustion chambers
WO2016135036A1 (en) 2015-02-27 2016-09-01 Shell Internationale Research Maatschappij B.V. Use of a lubricating composition
US9434900B2 (en) 2012-12-21 2016-09-06 Shell Oil Company Liquid fuel compositions
WO2017050777A1 (en) 2015-09-22 2017-03-30 Shell Internationale Research Maatschappij B.V. Fuel compositions
WO2017093203A1 (en) 2015-11-30 2017-06-08 Shell Internationale Research Maatschappij B.V. Fuel composition
EP3205705A1 (en) 2013-06-07 2017-08-16 Basf Se Alkylene oxide and hydrocarbyl-substituted polycarboxylic acid quaternised alkylamine as additives in fuels and lubricants and their use
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DE212015000271U1 (en) 2014-11-25 2017-09-06 Basf Se Corrosion inhibitors for fuels and lubricants
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WO2018136541A1 (en) 2017-01-17 2018-07-26 The Lubrizol Corporation Engine lubricant containing polyether compounds
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WO2018188982A1 (en) 2017-04-11 2018-10-18 Basf Se Alkoxylated amines as fuel additives
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US10294436B2 (en) 2014-11-12 2019-05-21 Shell Oil Company Fuel composition
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EP3945126A1 (en) 2020-07-31 2022-02-02 Basf Se Dehazing compositions for fuels
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WO2022128569A2 (en) 2020-12-16 2022-06-23 Basf Se New mixtures for improving the stability of additive packages
WO2022161803A1 (en) 2021-01-27 2022-08-04 Basf Se Branched primary alkyl amines as additives for gasoline fuels
WO2022228989A1 (en) 2021-04-26 2022-11-03 Shell Internationale Research Maatschappij B.V. Fuel compositions
WO2022228990A1 (en) 2021-04-26 2022-11-03 Shell Internationale Research Maatschappij B.V. Fuel compositions
EP4105301A1 (en) 2021-06-15 2022-12-21 Basf Se New gasoline additive packages
WO2022263244A1 (en) 2021-06-16 2022-12-22 Basf Se Quaternized betaines as additives in fuels
WO2023052286A1 (en) 2021-09-29 2023-04-06 Shell Internationale Research Maatschappij B.V. Fuel compositions
EP4163353A1 (en) 2021-10-06 2023-04-12 Basf Se Method for reducing deposits on intake valves
WO2023111550A1 (en) 2021-12-14 2023-06-22 Innospec Limited Methods and uses relating to fuel compositions
EP4269541A1 (en) 2022-04-29 2023-11-01 Basf Se New mixtures for improving or boosting the separation of water from fuels
WO2024017743A1 (en) 2022-07-20 2024-01-25 Shell Internationale Research Maatschappij B.V. Fuel compositions
WO2024083782A1 (en) 2022-10-21 2024-04-25 Shell Internationale Research Maatschappij B.V. Fuel compositions
EP4382588A1 (en) 2022-12-06 2024-06-12 Basf Se Additives for improving thermal stability of fuels
WO2024149635A1 (en) 2023-01-12 2024-07-18 Basf Se Branched amines as additives for gasoline fuels

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102016116348A1 (en) 2016-09-01 2018-03-01 Tunap Gmbh & Co. Kg FUEL ADDITIVES FOR CLEANING A COMBUSTION ENGINE

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3309182A (en) * 1962-09-17 1967-03-14 Exxon Research Engineering Co Polyether diamine as stabilizer for petroleum distillate fuels
US3440029A (en) * 1964-05-20 1969-04-22 Dow Chemical Co Gasoline containing anti-icing additive
US3448154A (en) * 1966-04-04 1969-06-03 Richardson Co Polyamines containing ether oxygen linkages
US3654370A (en) * 1970-08-28 1972-04-04 Jefferson Chem Co Inc Process for preparing polyoxyalkylene polyamines
US4323709A (en) * 1979-11-08 1982-04-06 Uop Inc. Preparation of polymeric reaction products of poly(alkoxyalkylene)amines and epihalohydrins
US4392867A (en) * 1981-12-14 1983-07-12 Texaco Inc. Amino corrosion inhibitor for alcohols
EP0100665A2 (en) * 1982-07-30 1984-02-15 Chevron Research Company Deposit control additives for hydrocarbon fuels and lubricants for use in internal combustion engines
WO1984004754A1 (en) * 1983-05-31 1984-12-06 Chevron Res Methylol polyether amino ethanes in fuel and lubricant compositions
EP0181140A2 (en) * 1984-10-29 1986-05-14 Atlantic Richfield Company Alkoxylated tertiary amine compounds

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3309182A (en) * 1962-09-17 1967-03-14 Exxon Research Engineering Co Polyether diamine as stabilizer for petroleum distillate fuels
US3440029A (en) * 1964-05-20 1969-04-22 Dow Chemical Co Gasoline containing anti-icing additive
US3448154A (en) * 1966-04-04 1969-06-03 Richardson Co Polyamines containing ether oxygen linkages
US3654370A (en) * 1970-08-28 1972-04-04 Jefferson Chem Co Inc Process for preparing polyoxyalkylene polyamines
US4323709A (en) * 1979-11-08 1982-04-06 Uop Inc. Preparation of polymeric reaction products of poly(alkoxyalkylene)amines and epihalohydrins
US4392867A (en) * 1981-12-14 1983-07-12 Texaco Inc. Amino corrosion inhibitor for alcohols
EP0100665A2 (en) * 1982-07-30 1984-02-15 Chevron Research Company Deposit control additives for hydrocarbon fuels and lubricants for use in internal combustion engines
WO1984004754A1 (en) * 1983-05-31 1984-12-06 Chevron Res Methylol polyether amino ethanes in fuel and lubricant compositions
EP0181140A2 (en) * 1984-10-29 1986-05-14 Atlantic Richfield Company Alkoxylated tertiary amine compounds

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
E. MÜLLER: "METHODEN DER ORGANISCHEN CHEMIE", Houben-Weyl, 4. Auflage, Band XI, Teil 1: "Stickstoffverbindungen II", 1957, Georg Thieme Verlag, Stuttgart, DE; Seiten 108-134, Kapitel IIb: "Ersatz der Hydroxylgruppe durch die Aminogruppe" *

Cited By (201)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5213584A (en) * 1989-07-10 1993-05-25 Nippon Oil And Fats Co., Ltd. Formal compounds, fuel oil additives, and fuel oil compositions
EP0407950A1 (en) * 1989-07-10 1991-01-16 Nippon Oil And Fats Company, Limited Formal compounds, fuel oil additives, and fuel oil compositions
EP0440248A1 (en) * 1990-02-02 1991-08-07 Kao Corporation Gasoline composition
US5089029A (en) * 1990-02-02 1992-02-18 Kao Corporation Fuel oil additive and fuel oil additive composition
EP0448365A1 (en) * 1990-03-20 1991-09-25 Exxon Research And Engineering Company Alkyl ether mono amines
US5094667A (en) * 1990-03-20 1992-03-10 Exxon Research And Engineering Company Guerbet alkyl ether mono amines
EP0489322A2 (en) * 1990-12-06 1992-06-10 BASF Aktiengesellschaft Alkoxylated polyetherdiamines, process for their preparation and fuels for spark ignition engines containing them
EP0489322A3 (en) * 1990-12-06 1993-06-16 Basf Aktiengesellschaft Alkoxylated polyetherdiamines, process for their preparation and fuels for spark ignition engines containing them
US6267791B1 (en) 1993-03-20 2001-07-31 Basf Aktiengesellschaft Mixtures suitable as fuel additives
WO1994021754A1 (en) * 1993-03-20 1994-09-29 Basf Aktiengesellschaft Mixtures suitable for use as fuel additives
US5306315A (en) * 1993-04-01 1994-04-26 Chevron Research And Technology Company Poly(alkylene ether) amines and fuel compositions containing the same
EP0630959A1 (en) * 1993-06-22 1994-12-28 Texaco Development Corporation Fuel composition
US5660601A (en) * 1994-09-09 1997-08-26 Basf Aktiengesellschaft Polyetheramine-containing fuels for gasoline engines
EP0700985A1 (en) 1994-09-09 1996-03-13 BASF Aktiengesellschaft Fuels, for spark-ignition engines, containing polyether amines
US5669939A (en) * 1996-05-14 1997-09-23 Chevron Chemical Company Polyalkylphenoxyaminoalkanes and fuel compositions containing the same
US5851242A (en) * 1996-05-14 1998-12-22 Chevron Chemical Company Fuel additive compositions containing polyalkylphenoxy-aminoalkanes and poly (oxyalkylene) amines
US6221116B1 (en) 1996-09-27 2001-04-24 Chevron Chemical Company Aminocarbamates of polyalkylphenoxyalkanols and fuel compositions containing the same
EP1122295A1 (en) * 1998-10-06 2001-08-08 Nippon Mitsubishi Oil Corporation Gasoline additive for direct-injection gasoline engine
EP1122295A4 (en) * 1998-10-06 2002-02-06 Nippon Mitsubishi Oil Corp Gasoline additive for direct-injection gasoline engine
WO2000061708A1 (en) * 1999-04-13 2000-10-19 Basf Aktiengesellschaft Polyalkene alcohol polyetheramines and use thereof in fuels and lubricants
US6548461B1 (en) 1999-04-13 2003-04-15 Basf Aktiengesellschaft Polyalkene alcohol polyetheramines and their use in fuels and lubricants
EP1244763A1 (en) * 1999-11-23 2002-10-02 The Lubrizol Corporation Additive composition
EP1244763A4 (en) * 1999-11-23 2004-05-06 Lubrizol Corp Additive composition
WO2001085874A3 (en) * 2000-05-05 2002-04-04 Basf Ag Fuel additive compositions for fuels for internal combustion engines with improved viscosity properties and good ivd performance
WO2001085874A2 (en) * 2000-05-05 2001-11-15 Basf Aktiengesellschaft Fuel additive compositions for fuels for internal combustion engines with improved viscosity properties and good ivd performance
US6840970B2 (en) 2000-05-05 2005-01-11 Basf Aktiengesellschaft Fuel additive compositions for fuels for internal combustion engines with improved viscosity properties and good IVD performance
KR100727363B1 (en) * 2000-05-05 2007-06-13 바스프 악티엔게젤샤프트 Fuel additive compositions for fuels for internal combustion engines with improved viscosity properties and good ivd performance
US7204863B2 (en) 2001-12-11 2007-04-17 Exxonmobil Research And Engineering Company Gasoline additives for reducing the amount of internal combustion engine intake valve deposits and combustion chamber deposits
US7226489B2 (en) 2001-12-12 2007-06-05 Exxonmobil Research And Engineering Company Gasoline additives for reducing the amount of internal combustion engine intake valve deposits and combustion chamber deposits
US7601185B2 (en) 2002-03-06 2009-10-13 Basf Aktiengesellschaft Fuel additive mixtures for gasolines with synergistic IVD performance
EP2292722A1 (en) 2002-03-28 2011-03-09 The Lubrizol Corporation Method of operating internal combustion engine by introducing detergent into combustion chamber
US7753970B2 (en) 2003-04-01 2010-07-13 Basf Aktiengesellschaft Polyalkene amines with improved applicational properties
EP3736317A1 (en) 2003-04-11 2020-11-11 Basf Se Fuel composition
EP2270119B1 (en) 2003-04-11 2020-07-15 Basf Se Fuel composition
EP2270119A1 (en) 2003-04-11 2011-01-05 Basf Se Fuel composition
US8814957B2 (en) 2004-08-05 2014-08-26 Basf Aktiengesellschaft Heterocyclic compounds containing nitrogen as a fuel additive in order to reduce abrasion
US7850744B2 (en) 2004-08-05 2010-12-14 Basf Aktiengesellschaft Heterocyclic compounds containing nitrogen as a fuel additive in order to reduce abrasion
WO2006044892A1 (en) 2004-10-19 2006-04-27 The Lubrizol Corporation Additive and fuel compositions containing detergent and fluidizer and method thereof
EP3133141A1 (en) 2004-10-19 2017-02-22 The Lubrizol Corporation Additive and fuel compositions containing detergent and fluidizer and method thereof
EP2267104A2 (en) 2006-02-27 2010-12-29 Basf Se Use of polynuclear phenolic compounds as dispersants
EP2272821A2 (en) 2006-02-27 2011-01-12 Basf Se Trinuclear phenolic compounds
EP2457981A1 (en) 2006-09-01 2012-05-30 The Lubrizol Corporation Quaternary ammonium salt of a mannich compound
EP2455406A1 (en) 2006-11-09 2012-05-23 The Lubrizol Corporation Quaternary Ammonium Salt of a Polyalkene-Substituted Amine Compound
US10062471B2 (en) 2007-03-02 2018-08-28 Basf Se Additive formulation suitable for antistatic modification and improving the electrical conductivity of inanimate organic material
US8858838B2 (en) 2007-03-02 2014-10-14 Basf Se Additive formulation suitable for antistatic modification and improving the electrical conductivity of inanimate organic material
US8551365B2 (en) 2007-03-02 2013-10-08 Basf Se Additive formulation suitable for antistatic modification and improving the electrical conductivity of inanimate organic material
US9670430B2 (en) 2007-07-16 2017-06-06 Basf Se Synergistic mixture
US9562202B2 (en) 2007-07-16 2017-02-07 Basf Se Synergistic mixture
US9315759B2 (en) 2007-07-16 2016-04-19 Basf Se Synergistic mixture
DE102008037662A1 (en) 2007-08-17 2009-04-23 Basf Se Oil soluble detergent, useful e.g. as additive for fuels, comprises reaction products of conversion of polyalkene epoxide with dicarboxylic acid anhydride and conversion of the obtained reaction product with nucleophile
WO2009050287A1 (en) 2007-10-19 2009-04-23 Shell Internationale Research Maatschappij B.V. Functional fluids for internal combustion engines
US8486876B2 (en) 2007-10-19 2013-07-16 Shell Oil Company Functional fluids for internal combustion engines
WO2009095443A1 (en) 2008-02-01 2009-08-06 Basf Se Special polyisobutene amines, and use thereof as detergents in fuels
DE102010001408A1 (en) 2009-02-06 2010-08-12 Basf Se Use of ketone compounds as a fuel additive to reduce the fuel consumption of diesel engines, preferably direct injection diesel engines, and diesel engines with common rail injection systems
DE102010039039A1 (en) 2009-08-24 2011-03-03 Basf Se Use of an organic compound as a fuel additive to reduce the fuel consumption of diesel engines, preferably direct-injection diesel engines, with common rail injection systems
US8790426B2 (en) 2010-04-27 2014-07-29 Basf Se Quaternized terpolymer
WO2011134923A1 (en) 2010-04-27 2011-11-03 Basf Se Quaternized terpolymer
WO2011151207A1 (en) 2010-06-01 2011-12-08 Basf Se Low-molecular weight polyisobutyl-substituted amines as detergent boosters
US8911516B2 (en) 2010-06-25 2014-12-16 Basf Se Quaternized copolymer
WO2011161149A1 (en) 2010-06-25 2011-12-29 Basf Se Quaternized copolymer
EP3747915A1 (en) 2010-07-06 2020-12-09 Basf Se Use of quaternised nitrogen compounds as gasoline additives
EP2808350A1 (en) 2010-07-06 2014-12-03 Basf Se Non-acidic quaternised nitrogen compounds and their use as additives in fuels and lubricants
EP3327044A1 (en) 2010-07-06 2018-05-30 Basf Se Composés azotés quaternisés exempts d'acide et leur utilisation comme additifs pour carburants et lubrifiants
WO2012004300A1 (en) 2010-07-06 2012-01-12 Basf Se Acid-free quaternised nitrogen compounds and use thereof as additives in fuels and lubricants
US9296841B2 (en) 2010-11-30 2016-03-29 Basf Se Preparation of isobutene homo- or copolymer derivatives
EP4406982A2 (en) 2010-11-30 2024-07-31 Basf Se Production of isobutylene homo- or copolymer derivatives
US11306161B2 (en) 2010-11-30 2022-04-19 Basf Se Preparation of isobutene homo- or copolymer derivatives
WO2012072643A2 (en) 2010-11-30 2012-06-07 Basf Se Production of isobutylene homopolymer or copolymer derivatives
US10745496B2 (en) 2010-11-30 2020-08-18 Basf Se Preparation of isobutene homo- or copolymer derivatives
WO2012072723A2 (en) 2010-12-02 2012-06-07 Basf Se Use of the reaction product of a hydrocarbyl-substituted dicarboxylic acid and a nitrogen compound for reducing fuel consumption
US9006158B2 (en) 2010-12-09 2015-04-14 Basf Se Polytetrahydrobenzoxazines and bistetrahydrobenzoxazines and use thereof as a fuel additive or lubricant additive
WO2012076428A1 (en) 2010-12-09 2012-06-14 Basf Se Polytetrahydrobenzoxazines and bistetrahydrobenzoxazines and use thereof as additive to fuel or lubricant
EP3263563A1 (en) 2010-12-09 2018-01-03 Basf Se Polytetrahydrobenzoxazines and bistetrahydrobenzoxazines and use thereof as fuel additive or lubricant additive
US9359570B2 (en) 2010-12-09 2016-06-07 Basf Se Polytetrahydrobenzoxazines and bistetrahydrobenzoxazines and use thereof as a fuel additive or lubricant additive
WO2012097026A1 (en) 2011-01-12 2012-07-19 The Lubrizol Corporation Engine lubricants containing a polyether
WO2012162282A1 (en) 2011-05-26 2012-11-29 The Lubrizol Corporation Stabilized blends containing friction modifiers
WO2012162020A1 (en) 2011-05-26 2012-11-29 The Lubrizol Corporation Stabilized blends containing antioxidants
WO2012162027A1 (en) 2011-05-26 2012-11-29 The Lubrizol Corporation Stabilized blends containing friction modifiers
WO2012162219A1 (en) 2011-05-26 2012-11-29 The Lubrizol Corporation Stabilized blends containing friction modifiers
WO2012163935A2 (en) 2011-05-30 2012-12-06 Shell Internationale Research Maatschappij B.V. Liquid fuel compositions
US10550346B2 (en) 2011-06-28 2020-02-04 Basf Se Quaternized nitrogen compounds and use thereof as additives in fuels and lubricants
US10119085B2 (en) 2011-06-28 2018-11-06 Basf Se Quaternized nitrogen compounds and use thereof as additives in fuels and lubricants
EP2540808A1 (en) 2011-06-28 2013-01-02 Basf Se Quaternised nitrogen compounds and their use as additives in fuels and lubricants
WO2013000997A1 (en) 2011-06-28 2013-01-03 Basf Se Quaternized nitrogen compounds and use thereof as additives in fuels and lubricants
US9951285B2 (en) 2011-06-28 2018-04-24 Basf Se Quaternized nitrogen compounds and use thereof as additives in fuels and lubricants
EP2589647A1 (en) 2011-11-04 2013-05-08 Basf Se Quaternised polyether amines and their use as additives in fuels and lubricants
WO2013064689A1 (en) 2011-11-04 2013-05-10 Basf Se Quaternized polyetheramines and use thereof as additives in fuels and lubricants
EP4219667A2 (en) 2011-12-12 2023-08-02 Basf Se Use of quaternised alkylamine as additives in fuels and lubricants
EP2604674A1 (en) 2011-12-12 2013-06-19 Basf Se Use of quaternised alkylamine as additive in fuels and lubricants
WO2013087701A1 (en) 2011-12-12 2013-06-20 Basf Se Use of quaternised alkyl amines as additives in fuels and lubricants
WO2013117616A1 (en) 2012-02-10 2013-08-15 Basf Se Imidazolium salts as additives for fuels and combustibles
US9062266B2 (en) 2012-02-10 2015-06-23 Basf Se Imidazolium salts as additives for fuels
WO2013174619A1 (en) 2012-05-25 2013-11-28 Basf Se Tertiary amines for reducing injector nozzle fouling in direct injection spark ignition engines
WO2014019911A1 (en) 2012-08-01 2014-02-06 Basf Se Process for improving thermostability of lubricant oils in internal combustion engines
US10689326B2 (en) 2012-10-23 2020-06-23 Basf Se Quaternized ammonium salts of hydrocarbyl epoxides and use thereof as additives in fuels and lubricants
WO2014064151A1 (en) 2012-10-23 2014-05-01 Basf Se Quaternized ammonium salts of hydrocarbyl epoxides and use thereof as additives in fuels and lubricants
US10173963B2 (en) 2012-10-23 2019-01-08 Basf Se Quaternized ammonium salts of hydrocarbyl epoxides and use thereof as additives in fuels and lubricants
US9388354B2 (en) 2012-11-06 2016-07-12 Basf Se Tertiary amines for reducing injector nozzle fouling and modifying friction in direct injection spark ignition engines
WO2014023853A2 (en) 2012-11-06 2014-02-13 Basf Se Tertiary amines for reducing injector nozzle fouling and modifying friction in direct injection spark ignition engines
US9434900B2 (en) 2012-12-21 2016-09-06 Shell Oil Company Liquid fuel compositions
WO2014158435A1 (en) 2013-03-13 2014-10-02 The Lubrizol Corporation Engine lubricants containing a polyether
WO2014184066A1 (en) 2013-05-14 2014-11-20 Basf Se Polyalkenylsuccinimides for reducing injector nozzle fouling in direct injection spark ignition engines
US11912950B2 (en) 2013-06-07 2024-02-27 Basf Se Use of nitrogen compounds quaternised with alkylene oxide and hydrocarbyl-substituted polycarboxylic acid as additives in fuels and lubricants
US11111449B2 (en) 2013-06-07 2021-09-07 Basf Se Use of nitrogen compounds quaternised with alkylene oxide and hydrocarbyl-substituted polycarboxylic acid as additives in fuels and lubricants
EP4190882A1 (en) 2013-06-07 2023-06-07 Basf Se Use with alkylene oxide and hydrocarbyl-substituted polycarboxylic acid of quaternised nitrogen compounds as additives in fuels and lubricants
US10407634B2 (en) 2013-06-07 2019-09-10 Basf Se Use of nitrogen compounds quaternised with alkylene oxide and hydrocarbyl-substituted polycarboxylic acid as additives in fuels and lubricants
EP2811007A1 (en) 2013-06-07 2014-12-10 Basf Se Alkylene oxide and hydrocarbyl-substituted polycarboxylic acid quaternised alkylamine as additives in fuels and lubricants and their use
EP3205705A1 (en) 2013-06-07 2017-08-16 Basf Se Alkylene oxide and hydrocarbyl-substituted polycarboxylic acid quaternised alkylamine as additives in fuels and lubricants and their use
EP3653689A1 (en) 2013-06-07 2020-05-20 Basf Se Use with alkylene oxide and hydrocarbyl-substituted polycarboxylic acid of quaternised nitrogen compounds as additives in fuels and lubricants
US10676685B2 (en) 2013-06-07 2020-06-09 Basf Se Use of nitrogen compounds quaternised with alkylene oxide and hydrocarbyl-substituted polycarboxylic acid as additives in fuels and lubricants
EP4442792A2 (en) 2013-06-07 2024-10-09 Basf Se Use with alkylene oxide and hydrocarbyl-substituted polycarboxylic acid of quaternised nitrogen compounds as additives in fuels and lubricants
WO2015003961A1 (en) 2013-07-12 2015-01-15 Basf Se Use of a hydrocarbyl-substituted dicarboxylic acid for improving or boosting the separation of water from fuel oils and gasoline fuels
US10858608B2 (en) 2013-07-12 2020-12-08 Basf Se Use of a hydrocarbyl-substituted dicarboxylic acid for improving or boosting the separation of water from fuel oils and gasoline fuels
US10174269B2 (en) 2013-07-12 2019-01-08 Basf Se Use of a hydrocarbyl-substituted dicarboxylic acid for improving or boosting the separation of water from fuel oils and gasoline fuels
WO2015007553A1 (en) 2013-07-17 2015-01-22 Basf Se Highly reactive polyisobutylene having a high percentage of vinylidene double bonds in the side chains
US9688791B2 (en) 2013-07-17 2017-06-27 Basf Se High-reactivity polyisobutylene having a high content of vinylidene double bonds in the side chains
US10370610B2 (en) 2013-09-20 2019-08-06 Basf Se Use of specific derivatives of quaternized nitrogen compounds as additives in fuels and lubricants
EP3483234A1 (en) 2013-09-20 2019-05-15 Basf Se Use of specialised derivatives of quaternised nitrogen compounds as additives in fuels and lubricants
US10815444B2 (en) 2013-09-20 2020-10-27 Basf Se Use of specific derivatives of quaternized nitrogen compounds as additives in fuels and lubricants
US9957455B2 (en) 2013-10-24 2018-05-01 Basf Se Use of a polyalkylene glycol to reduce fuel consumption
EP3241882A1 (en) 2013-10-24 2017-11-08 Basf Se Fuel composition
US10465138B2 (en) 2013-10-24 2019-11-05 Basf Se Use of a complex ester to reduce fuel consumption
US9951288B2 (en) 2013-10-24 2018-04-24 Basf Se Use of an alkoxylated polytetrahydrofuran to reduce fuel consumption
WO2015058992A1 (en) 2013-10-24 2015-04-30 Basf Se Use of an alkoxylated polytetrahydrofuran as an additive in a fuel
US10030206B2 (en) 2013-10-24 2018-07-24 Basf Se Use of a complex ester to reduce fuel consumption
WO2015058993A2 (en) 2013-10-24 2015-04-30 Basf Se Use of a polyalkylene glycol to reduce fuel consumption
EP2883944A1 (en) 2013-12-13 2015-06-17 Shell Internationale Research Maatschappij B.V. New uses
WO2015091458A1 (en) 2013-12-16 2015-06-25 Shell Internationale Research Maatschappij B.V. Liquid fuel compositions
US9587195B2 (en) 2013-12-16 2017-03-07 Shell Oil Company Liquid composition
US9862904B2 (en) 2013-12-31 2018-01-09 Shell Oil Company Unleaded fuel compositions
EP2891699A1 (en) 2013-12-31 2015-07-08 Shell Internationale Research Maatschappij B.V. Unleaded fuel compositions
US11634654B2 (en) 2014-01-29 2023-04-25 Basf Se Polycarboxylic acid-based additives for fuels and lubricants
EP3363879A2 (en) 2014-01-29 2018-08-22 Basf Se Diesel fuels, containing polycarboxylic acid-based additives
WO2015113681A1 (en) 2014-01-29 2015-08-06 Basf Se Polycarboxylic-acid-based additives for fuels and lubricants
US10240100B2 (en) 2014-01-29 2019-03-26 Basf Se Corrosion inhibitors for fuels and lubricants
US11168273B2 (en) 2014-01-29 2021-11-09 Basf Se Polycarboxylic acid-based additives for fuels and lubricants
US10377958B2 (en) 2014-01-29 2019-08-13 Basf Se Corrosion inhibitors for fuels and lubricants
EP2949733A1 (en) 2014-05-28 2015-12-02 Shell Internationale Research Maatschappij B.V. Gasoline compositions comprising oxanilide uv filter compounds
US10294436B2 (en) 2014-11-12 2019-05-21 Shell Oil Company Fuel composition
DE212015000271U1 (en) 2014-11-25 2017-09-06 Basf Se Corrosion inhibitors for fuels and lubricants
US10781411B2 (en) 2015-01-30 2020-09-22 The Lubrizol Corporation Composition for cleaning gasoline engine fuel delivery systems, air intake systems, and combustion chambers
WO2016122911A1 (en) 2015-01-30 2016-08-04 The Lubrizol Corporation Composition for cleaning gasoline engine fuel delivery systems, air intake systems, and combustion chambers
WO2016135036A1 (en) 2015-02-27 2016-09-01 Shell Internationale Research Maatschappij B.V. Use of a lubricating composition
US11085001B2 (en) 2015-07-16 2021-08-10 Basf Se Copolymers as additives for fuels and lubricants
DE212016000150U1 (en) 2015-07-24 2018-03-16 Basf Se Corrosion inhibitors for fuels and lubricants
US10808195B2 (en) 2015-09-22 2020-10-20 Shell Oil Company Fuel compositions
WO2017050777A1 (en) 2015-09-22 2017-03-30 Shell Internationale Research Maatschappij B.V. Fuel compositions
US11959033B2 (en) 2015-11-30 2024-04-16 Shell Usa, Inc. Fuel composition
WO2017093203A1 (en) 2015-11-30 2017-06-08 Shell Internationale Research Maatschappij B.V. Fuel composition
US10968313B2 (en) 2015-12-03 2021-04-06 China Petroleum & Chemical Corporation Amine polymer and preparation method and use thereof
WO2017144378A1 (en) 2016-02-23 2017-08-31 Basf Se Hydrophobic polycarboxylic acids as friction-reducing additive for fuels
WO2017184688A1 (en) 2016-04-20 2017-10-26 The Lubrizol Corporation Lubricant for two-stroke cycle engines
WO2017218657A2 (en) 2016-06-17 2017-12-21 The Lubrizol Corporation Polyisobutylene-substituted phenol, derivatives thereof, and lubricating compositions containing the polyisobutylene-substituted phenol and its derivatives
US10844308B2 (en) 2016-07-05 2020-11-24 Basf Se Corrosion inhibitors for fuels and lubricants
WO2018007192A1 (en) 2016-07-05 2018-01-11 Basf Se Corrosion inhibitors for fuels and lubricants
WO2018007191A1 (en) 2016-07-05 2018-01-11 Basf Se Use of corrosion inhibitors for fuels and lubricants
US11078418B2 (en) 2016-07-05 2021-08-03 Basf Se Corrosion inhibitors for fuels and lubricants
WO2018007375A1 (en) 2016-07-07 2018-01-11 Basf Se Copolymers as additives for fuels and lubricants
WO2018007445A1 (en) 2016-07-07 2018-01-11 Basf Se Corrosion inhibitors for fuels and lubricants
WO2018007486A1 (en) 2016-07-07 2018-01-11 Basf Se Polymers as additives for fuels and lubricants
US11566196B2 (en) 2016-12-15 2023-01-31 Basf Se Polymers as additives for fuels
US10947467B2 (en) 2016-12-15 2021-03-16 Basf Se Polymers as additives for fuels
WO2018108534A1 (en) 2016-12-15 2018-06-21 Basf Se Polymers as additives for fuels
WO2018114348A1 (en) 2016-12-19 2018-06-28 Basf Se Additives for improving the thermal stability of fuels
WO2018114350A1 (en) 2016-12-20 2018-06-28 Basf Se Use of a mixture of a complex ester with a monocarboxylic acid to reduce friction
US10927319B2 (en) 2016-12-20 2021-02-23 Basf Se Use of a mixture of a complex ester with a monocarboxylic acid to reduce friction
WO2018136541A1 (en) 2017-01-17 2018-07-26 The Lubrizol Corporation Engine lubricant containing polyether compounds
WO2018164979A1 (en) 2017-03-06 2018-09-13 The Lubrizol Corporation Fuel additives
WO2018164986A1 (en) 2017-03-06 2018-09-13 The Lubrizol Corporation Amine salts for use in gasoline engines
EP4108743A1 (en) 2017-03-06 2022-12-28 The Lubrizol Corporation Amine salts for use in gasoline engines
US11130923B2 (en) 2017-04-11 2021-09-28 Basf Se Alkoxylated amines as fuel additives
WO2018188982A1 (en) 2017-04-11 2018-10-18 Basf Se Alkoxylated amines as fuel additives
CN110494534A (en) * 2017-04-11 2019-11-22 巴斯夫欧洲公司 Alkoxylated amines as fuel additive
WO2018188986A1 (en) 2017-04-13 2018-10-18 Basf Se Polymers as additives for fuels and lubricants
US11499107B2 (en) 2018-07-02 2022-11-15 Shell Usa, Inc. Liquid fuel compositions
WO2020007790A1 (en) 2018-07-02 2020-01-09 Shell Internationale Research Maatschappij B.V. Liquid fuel compositions
WO2020260062A1 (en) 2019-06-26 2020-12-30 Basf Se New additive packages for gasoline fuels
WO2021063733A1 (en) 2019-09-30 2021-04-08 Basf Se Use of nitrogen compounds quaternised with alkylene oxide and hydrocarbyl-substituted polycarboxylic acid as additives in fuels and lubricants
US11912949B2 (en) 2019-10-22 2024-02-27 Shell Usa, Inc. Method for reducing intake valve deposits
WO2021078753A1 (en) 2019-10-22 2021-04-29 Shell Internationale Research Maatschappij B.V. Method for reducing intake valve deposits
WO2021101496A1 (en) 2019-11-22 2021-05-27 The Lubrizol Corporation Fuel additive compositions for gasoline direct injection engines
EP3933014A1 (en) 2020-06-30 2022-01-05 Basf Se Addition of additives to fuel for reducing uncontrolled ignition in combustion engines
EP3940043A1 (en) 2020-07-14 2022-01-19 Basf Se Corrosion inhibitors for fuels and lubricants
WO2022017912A1 (en) 2020-07-20 2022-01-27 Shell Internationale Research Maatschappij B.V. Fuel composition
EP3945126A1 (en) 2020-07-31 2022-02-02 Basf Se Dehazing compositions for fuels
WO2022106301A1 (en) 2020-11-20 2022-05-27 Basf Se Mixtures for improving or boosting the separation of water from fuels
WO2022128569A2 (en) 2020-12-16 2022-06-23 Basf Se New mixtures for improving the stability of additive packages
WO2022161803A1 (en) 2021-01-27 2022-08-04 Basf Se Branched primary alkyl amines as additives for gasoline fuels
WO2022228989A1 (en) 2021-04-26 2022-11-03 Shell Internationale Research Maatschappij B.V. Fuel compositions
WO2022228990A1 (en) 2021-04-26 2022-11-03 Shell Internationale Research Maatschappij B.V. Fuel compositions
WO2022263254A1 (en) 2021-06-15 2022-12-22 Basf Se New gasoline additive packages
EP4105301A1 (en) 2021-06-15 2022-12-21 Basf Se New gasoline additive packages
WO2022263244A1 (en) 2021-06-16 2022-12-22 Basf Se Quaternized betaines as additives in fuels
WO2023052286A1 (en) 2021-09-29 2023-04-06 Shell Internationale Research Maatschappij B.V. Fuel compositions
EP4163353A1 (en) 2021-10-06 2023-04-12 Basf Se Method for reducing deposits on intake valves
WO2023111550A1 (en) 2021-12-14 2023-06-22 Innospec Limited Methods and uses relating to fuel compositions
EP4269541A1 (en) 2022-04-29 2023-11-01 Basf Se New mixtures for improving or boosting the separation of water from fuels
WO2024017743A1 (en) 2022-07-20 2024-01-25 Shell Internationale Research Maatschappij B.V. Fuel compositions
WO2024083782A1 (en) 2022-10-21 2024-04-25 Shell Internationale Research Maatschappij B.V. Fuel compositions
EP4382588A1 (en) 2022-12-06 2024-06-12 Basf Se Additives for improving thermal stability of fuels
WO2024149635A1 (en) 2023-01-12 2024-07-18 Basf Se Branched amines as additives for gasoline fuels

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