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)
  • Liquid Carbonaceous Fuels (AREA)
  • Lubricants (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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