EP0700985B1 - Fuels, for spark-ignition engines, containing polyether amines - Google Patents

Fuels, for spark-ignition engines, containing polyether amines Download PDF

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Publication number
EP0700985B1
EP0700985B1 EP95113660A EP95113660A EP0700985B1 EP 0700985 B1 EP0700985 B1 EP 0700985B1 EP 95113660 A EP95113660 A EP 95113660A EP 95113660 A EP95113660 A EP 95113660A EP 0700985 B1 EP0700985 B1 EP 0700985B1
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Prior art keywords
polyetheramine
fuels
alkyl
fuel
hydrogen
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EP95113660A
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German (de)
French (fr)
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EP0700985A1 (en
Inventor
Knut Dr. Oppenländer
Wolfgang Dr. Günther
Andreas Dr. Henne
Volkmar Dr. Menger
Rainer Dr. Becker
Wolfgang Dr. Reif
Jürgen Dr. Thomas
Harald Dr. Schwahn
Erhard Dr. Henkes
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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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular compounds
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/04—Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/06—Use of additives to fuels or fires for particular purposes for facilitating soot removal
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/16—Hydrocarbons
    • C10L1/1616—Hydrocarbons fractions, e.g. lubricants, solvents, naphta, bitumen, tars, terpentine
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/16—Hydrocarbons
    • C10L1/1625—Hydrocarbons macromolecular compounds
    • C10L1/1633—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds
    • C10L1/1641—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds from compounds containing aliphatic monomers
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
    • C10L1/183—Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom
    • C10L1/1832—Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom mono-hydroxy
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/188—Carboxylic acids; metal salts thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/188—Carboxylic acids; metal salts thereof
    • C10L1/1881—Carboxylic acids; metal salts thereof carboxylic group attached to an aliphatic carbon atom
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
    • C10L1/1905—Esters ester radical containing compounds; ester ethers; carbonic acid esters of di- or polycarboxylic acids
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
    • C10L1/1985—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid polyethers, e.g. di- polygylcols and derivatives; ethers - esters
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • 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
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • 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
    • C10L1/223—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond having at least one amino group bound to an aromatic carbon atom
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/232—Organic compounds containing nitrogen containing nitrogen in a heterocyclic ring
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/232—Organic compounds containing nitrogen containing nitrogen in a heterocyclic ring
    • C10L1/233—Organic compounds containing nitrogen containing nitrogen in a heterocyclic ring containing nitrogen and oxygen in the ring, e.g. oxazoles
    • C10L1/2335—Organic compounds containing nitrogen containing nitrogen in a heterocyclic ring containing nitrogen and oxygen in the ring, e.g. oxazoles morpholino, and derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)

Definitions

  • EP-A 310 875 includes polyetheramines of the above type alkylene radicals derived from propylene oxide or butylene oxide as valve cleaning additives known for petrol. Of the Degree of alkoxylation there is 5 to 100, preferably 5 to 30 specified.
  • Example B is a reaction with butylene oxide and then iso-tridecanol of the molecular weight aminated with ammonia 730, from which a degree of butoxylation of approx. 7.5 can be calculated.
  • the radical R 1 preferably denotes C 8 -C 20 -alkyl, in particular C 9 -C 15 -alkyl, especially C 11 -C 14 -alkyl; C 13 alkyl is very particularly preferred.
  • the mostly long-chain radical R 1 can be linear or preferably branched.
  • radicals R 2 and R 3 or one of the radicals R 2 or R 3 do not represent the (poly) aminoalkylene radicals II or III, they mean or preferably mean C 1 -C 4 -alkyl, for example methyl or ethyl, or especially hydrogen.
  • the bridge member R 4 preferably represents linear or branched C 2 -C 4 -alkylene, in particular 1,2-ethylene or 1,3-propylene.
  • the number m is an integer and preferably denotes one Number from 2 to 6, especially from 2 to 4.
  • the radicals R 5 and R 6 are preferably C 1 -C 4 -alkyl, for example methyl or ethyl, or in particular hydrogen.
  • both radicals R 2 and R 3 are hydrogen or one of the radicals is hydrogen and the other is 2-aminoethyl, 3-aminopropyl or 3- (N, N-dimethylamino) propyl.
  • the latter radicals are derived from the diamines 1,2-ethylenediamine, 1,3-propylenediamine and 3- (N, N-dimethylamino) propylamine.
  • the degree of butoxylation n is preferably 18 to 25, in particular 20 to 23, especially 22.
  • n represents an average value for a statistical distribution of butoxylation products represents.
  • polyetheramines I are expediently - as described in EP-A 310 875 - by reacting alcohols of the formula R 1 ⁇ OH with butylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, isobutylene oxide or mixtures thereof being used here can, and subsequent amination with ammonia or amines of the formula NHR 2 R 3 .
  • the fuels are lead and unleaded normal and Super gasoline into consideration.
  • the petrol can do other Components as hydrocarbons, e.g. Alcohols like methanol, Ethanol or tert-butanol as well as ether, e.g. Methyl tert-butyl ether, contain.
  • ether e.g. Methyl tert-butyl ether
  • Additives such as corrosion inhibitors, stabilizers, antioxidants or other detergents.
  • Corrosion inhibitors are mostly organic ammonium salts Carboxylic acids by appropriate structure of the starting compounds tend to form films. Also amines to increase the pH values are often found in corrosion inhibitors. As non-ferrous metal corrosion protection heterocyclic aromatics are mostly used.
  • Amines in particular are antioxidants or stabilizers such as para-phenylenediamine, dicyclohexylamine, morpholine or To name derivatives of these amines. Also phenolic antioxidants such as 2,4-di-tert-butylphenol or 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid and their derivatives are added to fuels.
  • injector and valve detergents are also optionally amides and imides of polyisobutylene succinic anhydride, Poly (iso) butenamines, poly (iso) butenepolyamines and long chain carboxylic acid amides and imides in fuels contain.
  • Polyetheramines I can mineral oils of the viscosity range SN 500-900, but also Brightstock and synthetic oils such as polyalphaolefin, Trimellitic acid esters or polyethers are used.
  • the esters should be long-chain, branched alcohols With more than 8 carbon atoms, the polyethers are preferably long-chain Starter and high propylene oxide or butylene oxide contents in the Contain molecule.
  • the fuels usually contain the polyetheramines I in Amounts from 10 to 2000 ppm, based on the pure polyetheramine. Usually, however, are already 20 to 1000 ppm, preferably 40 to 400 ppm, sufficient.
  • the polyetheramines I to be used according to the invention are used in fuels mainly as valve cleaning additives, i.e. as detergents. But you can also partially Perform the function of carrier oils for other detergents.
  • the fuels described can be a specific polyetheramine I or a mixture of several polyether amines I.
  • the engine test was on an Opel Kadett 1.2-1 engine using the cyclic test program CEC-F-04-A-87 carried out.
  • the total test duration was 40 hours.
  • the used Gasoline was standard unleaded gasoline and the engine oil used is the reference oil RL-139.
  • the intake valves were evaluated gravimetrically. For this purpose, the inlet valves on the underside were carefully mechanically cleaned of deposits from the combustion chamber. Thereafter, surface-adhering, easily soluble parts on the valves were removed by immersion in cyclohexane and the valves were dried by swirling in air. This treatment was done twice in total. The intake valves were then weighed. From the weight difference between the valve weight before and after the experiment, the amount of deposits per intake valve was obtained. The results of these tests are shown in the following tables. Testing the intake valve load with an Opel Kadett 1.2-1 engine on the test bench with 100 mg polyetheramine per kg unleaded super fuel in accordance with DIN EN 228, 150 l, engine oil RL-139, test duration 40 hours Example No. Polyetheramine Valve deposit mg / inlet valve 1 without (basic value) 491 2nd A 294 3rd B 19th 4th C. 283

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)
  • Output Control And Ontrol Of Special Type Engine (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Polyethers (AREA)

Description

Die vorliegende Erfindung betrifft Kraftstoffe für Ottomotoren, welche geringe Mengen von Polyetheraminen der allgemeinen Formel I R1―(OBu)n― NR2R3 in der

R1
einen C2- bis C30-Alkylrest bezeichnet,
R2 und R3
unabhängig voneinander Wasserstoff, C1- bis C8-Alkyl, einen Aminoalkylenrest der allgemeinen Formel II ―R4―NR5R6 oder einen Polyaminoalkylenrest der allgemeinen Formel III (R4―NR5)m―R6 in denen R4 für einen C2- bis C10-Alkylenrest steht, R5 und R6 unabhängig voneinander Wasserstoff oder C1- bis C8-Alkyl bedeuten und m eine Zahl von 2 bis 8 bezeichnet, bedeuten,
Bu
einen aus Butylenoxid stammenden Butylenrest bezeichnet und
n
für eine Zahl von 12 bis 28 steht,
enthalten.The present invention relates to fuels for gasoline engines which contain small amounts of polyetheramines of the general formula I. R 1 - (OBu) n - NR 2 R 3 in the
R 1
denotes a C 2 to C 30 alkyl radical,
R 2 and R 3
independently of one another hydrogen, C 1 - to C 8 -alkyl, an aminoalkylene radical of the general formula II ―R 4 ―NR 5 R 6 or a polyaminoalkylene radical of the general formula III (R 4 ―NR 5 ) m ―R 6 in which R 4 represents a C 2 to C 10 alkylene radical, R 5 and R 6 independently of one another are hydrogen or C 1 to C 8 alkyl and m denotes a number from 2 to 8,
Bu
denotes a butylene radical derived from butylene oxide and
n
represents a number from 12 to 28,
contain.

Aus der EP-A 310 875 sind Polyetheramine des obigen Typs mit aus Propylenoxid oder Butylenoxid stammenden Alkylenresten als ventilreinigende Additive für Ottokraftstoffe bekannt. Der Alkoxylierungsgrad ist dort mit 5 bis 100, vorzugsweise 5 bis 30 angegeben. Als Beispiel B wird ein mit Butylenoxid umgesetztes und anschließend mit Ammoniak aminiertes iso-Tridecanol des Molgewichtes 730 beschrieben, woraus ein Butoxylierungsgrad von ca. 7,5 errechnet werden kann.EP-A 310 875 includes polyetheramines of the above type alkylene radicals derived from propylene oxide or butylene oxide as valve cleaning additives known for petrol. Of the Degree of alkoxylation there is 5 to 100, preferably 5 to 30 specified. Example B is a reaction with butylene oxide and then iso-tridecanol of the molecular weight aminated with ammonia 730, from which a degree of butoxylation of approx. 7.5 can be calculated.

Derartige Polyetheramine haben zwar schon im Prinzip eine gute ventilreinigende Wirkung, jedoch ist eine weitere Verbesserung noch wünschenswert. Aufgabe der vorliegenden Erfindung war es daher, Kraftstoffadditive bereitzustellen, die eine solche weitere Verbesserung bewirken.In principle, such polyetheramines already have a good one valve cleaning effect, however, is a further improvement still desirable. The object of the present invention was therefore, to provide fuel additives that do bring about further improvement.

Demgemäß wurden die oben definierten Polyetheramine I enthaltenden Kraftstoffe gefunden.Accordingly, the above defined polyetheramines I containing Found fuels.

Der Rest R1 bezeichnet vorzugsweise C8- bis C20-Alkyl, insbesondere C9- bis C15-Alkyl, vor allem C11- bis C14-Alkyl; ganz besonders bevorzugt wird C13-Alkyl. Der meist langkettige Rest R1 kann linear oder vorzugsweise verzweigt sein.The radical R 1 preferably denotes C 8 -C 20 -alkyl, in particular C 9 -C 15 -alkyl, especially C 11 -C 14 -alkyl; C 13 alkyl is very particularly preferred. The mostly long-chain radical R 1 can be linear or preferably branched.

Stehen die Reste R2 und R3 oder einer der Reste R2 oder R3 nicht für die (Poly)Aminoalkylenreste II bzw. III, bedeuten sie bzw. bedeutet er vorzugsweise C1- bis C4-Alkyl, z.B. Methyl oder Ethyl, oder insbesondere Wasserstoff.If the radicals R 2 and R 3 or one of the radicals R 2 or R 3 do not represent the (poly) aminoalkylene radicals II or III, they mean or preferably mean C 1 -C 4 -alkyl, for example methyl or ethyl, or especially hydrogen.

Das Brückenglied R4 steht vorzugsweise für lineares oder verzweigtes C2- bis C4-Alkylen, insbesondere für 1,2-Ethylen oder 1,3-Propylen.The bridge member R 4 preferably represents linear or branched C 2 -C 4 -alkylene, in particular 1,2-ethylene or 1,3-propylene.

Die Zahl m ist eine ganze Zahl und bezeichnet vorzugsweise eine Zahl von 2 bis 6, vor allem von 2 bis 4.The number m is an integer and preferably denotes one Number from 2 to 6, especially from 2 to 4.

Die Reste R5 und R6 bedeuten vorzugsweise C1- bis C4-Alkyl, z.B. Methyl oder Ethyl, oder insbesondere Wasserstoff.The radicals R 5 and R 6 are preferably C 1 -C 4 -alkyl, for example methyl or ethyl, or in particular hydrogen.

In einer bevorzugten Ausführungsform der Erfindung bedeuten beide Reste R2 und R3 Wasserstoff oder einer der Reste bedeutet Wasserstoff und der andere 2-Aminoethyl, 3-Aminopropyl oder 3-(N,N-Dimethylamino)propyl. Die letztgenannten Reste leiten sich von den Diaminen 1,2-Ethylendiamin, 1,3-Propylendiamin bzw. 3-(N,N-Dimethylamino)propylamin ab.In a preferred embodiment of the invention, both radicals R 2 and R 3 are hydrogen or one of the radicals is hydrogen and the other is 2-aminoethyl, 3-aminopropyl or 3- (N, N-dimethylamino) propyl. The latter radicals are derived from the diamines 1,2-ethylenediamine, 1,3-propylenediamine and 3- (N, N-dimethylamino) propylamine.

Der Butoxylierungsgrad n beträgt vorzugsweise 18 bis 25, insbesondere 20 bis 23, vor allem 22. Dabei stellt n einen Durchschnittswert für eine statistische Verteilung von Butoxylierungsprodukten dar.The degree of butoxylation n is preferably 18 to 25, in particular 20 to 23, especially 22. Here n represents an average value for a statistical distribution of butoxylation products represents.

Die Polyetheramine I werden zweckmäßigerweise - wie in der EP-A 310 875 beschrieben - durch Umsetzung von Alkoholen der Formel R1―OH mit Butylenoxid, wobei hier 1,2-Butylenoxid, 2,3-Butylenoxid, Isobutylenoxid oder Gemische hieraus zum Einsatz kommen können, und anschließende Aminierung mit Ammoniak oder Aminen der Formel NHR2R3 hergestellt. The polyetheramines I are expediently - as described in EP-A 310 875 - by reacting alcohols of the formula R 1 ―OH with butylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, isobutylene oxide or mixtures thereof being used here can, and subsequent amination with ammonia or amines of the formula NHR 2 R 3 .

Als Kraftstoffe kommen verbleite und unverbleite Normal- und Superbenzine in Betracht. Die Benzine können auch andere Komponenten als Kohlenwasserstoffe, z.B. Alkohole wie Methanol, Ethanol oder tert.-Butanol sowie Ether, z.B. Methyl-tert.-butyl-ether, enthalten. Neben den erfindungsgemäß zu verwendenden Polyetheraminen I enthalten die Kraftstoffe in der Regel noch weiter Zusätze wie Korrosionsinhibitoren, Stabilisatoren, Antioxidantien oder weitere Detergentien.The fuels are lead and unleaded normal and Super gasoline into consideration. The petrol can do other Components as hydrocarbons, e.g. Alcohols like methanol, Ethanol or tert-butanol as well as ether, e.g. Methyl tert-butyl ether, contain. In addition to the polyetheramines to be used according to the invention I usually still contain the fuels Additives such as corrosion inhibitors, stabilizers, antioxidants or other detergents.

Korrosionsinhibitoren sind meist Ammoniumsalze organischer 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 organic ammonium salts Carboxylic acids by appropriate structure of the starting compounds tend to form films. Also amines to increase the pH values are often found in corrosion inhibitors. As non-ferrous metal corrosion protection heterocyclic aromatics are mostly used.

Als Antioxidantien oder Stabilisatoren sind insbesondere Amine wie para-Phenylendiamin, Dicyclohexylamin, Morpholin oder Derivate dieser Amine zu nennen. Auch phenolische Antioxidantien wie 2,4-Di-tert.-butylphenol oder 3,5-Di-tert.-butyl-4-hydroxyphenylpropionsäure und deren Derivate werden Kraftstoffe zugesetzt.Amines in particular are antioxidants or stabilizers such as para-phenylenediamine, dicyclohexylamine, morpholine or To name derivatives of these amines. Also phenolic antioxidants such as 2,4-di-tert-butylphenol or 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid and their derivatives are added to fuels.

Als Vergaser-, Injektor- und Ventildetergentien sind ferner gegebenenfalls Amide und Imide des Polyisobutylenbernsteinsäureanhydrids, Poly(iso)butenamine, Poly(iso)butenpolyamine sowie langkettige Carbonsäureamide und -imide in den Kraftstoffen enthalten.As carburetor, injector and valve detergents are also optionally amides and imides of polyisobutylene succinic anhydride, Poly (iso) butenamines, poly (iso) butenepolyamines and long chain carboxylic acid amides and imides in fuels contain.

Als Trägeröle für Konzentrate der erfindungsgemäß zu verwendenden Polyetheramine I 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 mit mehr als 8 C-Atomen, die Polyether vorzugsweise langkettige Starter und hohe Propylenoxid- oder Butylenoxid-Gehalte im Molekül enthalten.As carrier oils for concentrates of those to be used according to the invention Polyetheramines I can mineral oils of the viscosity range SN 500-900, but also Brightstock and synthetic oils such as polyalphaolefin, Trimellitic acid esters or polyethers are used. The esters should be long-chain, branched alcohols With more than 8 carbon atoms, the polyethers are preferably long-chain Starter and high propylene oxide or butylene oxide contents in the Contain molecule.

Die Kraftstoffe enthalten die Polyetheramine 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 usually contain the polyetheramines I in Amounts from 10 to 2000 ppm, based on the pure polyetheramine. Usually, however, are already 20 to 1000 ppm, preferably 40 to 400 ppm, sufficient.

Die erfindungsgemäß zu verwendenden Polyetheramine I dienen in den Kraftstoffen hauptsächlich als ventilreinigende Additive, d.h. als Detergentien. Sie können aber auch teilweise die Funktion von Trägerölen für weitere Detergentien ausüben.The polyetheramines I to be used according to the invention are used in fuels mainly as valve cleaning additives, i.e. as detergents. But you can also partially Perform the function of carrier oils for other detergents.

Die beschriebenen Kraftstoffe können ein bestimmtes Polyetheramin I oder eine Mischung aus mehreren Polyetheraminen I enthalten.The fuels described can be a specific polyetheramine I or a mixture of several polyether amines I.

Im folgenden wird die Wirkung der Polyetheramine I im Motor erläutert.The following is the effect of Polyetheramine I in the engine explained.

HerstellungsbeispieleManufacturing examples

Gemäß den allgemeinen Herstellungsvorschriften der EP-A 310 875 für Polyether durch alkalikatalysierte Oxalkylierung und für Polyetheramine durch Umsetzung dieser Polyether mit Ammoniak unter reduzierenden Bedingungen wurden durch Umsetzung von 1 mol iso-Tridecanol (aus Tetramerpropylen) mit

  • Beispiel A: 8 mol 1,2-Butylenoxid (zum Vergleich)
  • Beispiel B: 22 mol 1,2-Butylenoxid (erfindungsgemäß)
  • Beispiel C: 35 mol 1,2-Butylenoxid (zum Vergleich)
    • und durch anschließende Aminierung mit NH3/H2/Raney-Nickel die drei Polyetheramine A, B und C erhalten.In accordance with the general preparation instructions of EP-A 310 875 for polyethers by alkali-catalyzed oxalkylation and for polyetheramines by reacting these polyethers with ammonia under reducing conditions, 1 mol of iso-tridecanol (from tetramer propylene) was reacted with
  • Example A: 8 mol of 1,2-butylene oxide (for comparison)
  • Example B: 22 mol of 1,2-butylene oxide (according to the invention)
  • Example C: 35 mol of 1,2-butylene oxide (for comparison)
    • and by subsequent amination with NH 3 / H 2 / Raney nickel, the three polyether amines A, B and C are obtained.

    Motorische PrüfungMotor test

    Die motorische Prüfung wurde auf einem Opel Kadett 1,2-1-Motor unter Verwendung des cyclischen Testprogramms CEC-F-04-A-87 durchgeführt. Die Gesamttestdauer betrug 40 Stunden. Das verwendete Benzin war marktübliches unverbleites Superbenzin und das verwendete Motorenöl das Referenzöl RL-139.The engine test was on an Opel Kadett 1.2-1 engine using the cyclic test program CEC-F-04-A-87 carried out. The total test duration was 40 hours. The used Gasoline was standard unleaded gasoline and the engine oil used is the reference oil RL-139.

    Die Auswertung der Einlaßventile erfolgte gravimetrisch. Dazu wurden die Einlaßventile nach dem Ausbau an ihrer Unterseite sorgfältig mechanisch von Ablagerungen aus dem Verbrennungsraum befreit. Danach wurden oberflächlich haftende, leicht-lösliche Anteile auf den Ventilen durch Eintauchen in Cyclohexan entfernt und die Ventile durch Schwenken an der Luft getrocknet. Diese Behandlung wurde insgesamt zweimal vorgenommen. Anschließend wurden die Einlaßventile gewogen. Aus der Gewichtsdifferenz zwischen dem Ventilgewicht vor und nach dem Versuch ergab sich die Menge an Ablagerungen pro Einlaßventil. Die Ergebnisse dieser Versuche sind in der folgenden Tabellen wiedergegeben. Prüfung der Einlaßventilbelastung mit einem Opel Kadett 1,2-1-Motor auf dem Prüfstand mit jeweils 100 mg Polyetheramin pro kg unverbleitem Superkraftstoff gemäß DIN EN 228, 150 l, Motorenöl RL-139, Testdauer 40 Stunden Beispiel Nr. Polyetheramin Ventilablagerung mg/Einlaßventil 1 ohne (Grundwert) 491 2 A 294 3 B 19 4 C 283 The intake valves were evaluated gravimetrically. For this purpose, the inlet valves on the underside were carefully mechanically cleaned of deposits from the combustion chamber. Thereafter, surface-adhering, easily soluble parts on the valves were removed by immersion in cyclohexane and the valves were dried by swirling in air. This treatment was done twice in total. The intake valves were then weighed. From the weight difference between the valve weight before and after the experiment, the amount of deposits per intake valve was obtained. The results of these tests are shown in the following tables. Testing the intake valve load with an Opel Kadett 1.2-1 engine on the test bench with 100 mg polyetheramine per kg unleaded super fuel in accordance with DIN EN 228, 150 l, engine oil RL-139, test duration 40 hours Example No. Polyetheramine Valve deposit mg / inlet valve 1 without (basic value) 491 2nd A 294 3rd B 19th 4th C. 283

    Claims (6)

    1. A fuel for gasolene engines, containing a small amount of a polyetheramine of the formula I R1-(OBu)n-NR2R3 where
      R1
      is C2C30-alkyl,
      R2 and R3,
      independently of one another, are each hydrogen, C1-C8-alkyl, aminoalkylene of the formula II -R4-NR5R6 or polyaminoalkylene of the formula III -(R4-NR5)m-R6 where R4 is C2-C10-alkylene, R5 and R6, independently of one another, are each hydrogen or C1-C8-alkyl and m is from 2 to 8,
      Bu
      is a butylene radical derived from butylene oxide and
      n
      is from 12 to 28.
    2. A fuel as claimed in claim 1, containing a polyetheramine I in which R1 is a branched C9-C15-alkyl radical.
    3. A fuel as claimed in claim 1 or 2, containing a polyetheramine I in which both radicals R2 and R3 are hydrogen or one of the radicals R2 and R3 is hydrogen and the other is 2-aminoethyl, 3-aminopropyl or 3-(N,N-dimethylamino)propyl.
    4. A fuel as claimed in any of claims 1 to 3, containing a polyetheramine I in which the degree of butoxylation n is from 20 to 23.
    5. A fuel as claimed in any of claims 1 to 4, containing from 10 to 2000 mg of a polyetheramine I per kg of fuel.
    6. Use of a polyetheramine I as claimed in any of claims 1 to 5 as a valve-cleaning additive in fuels for gasolene engines.
    EP95113660A 1994-09-09 1995-08-31 Fuels, for spark-ignition engines, containing polyether amines Expired - Lifetime EP0700985B1 (en)

    Applications Claiming Priority (2)

    Application Number Priority Date Filing Date Title
    DE4432038 1994-09-09
    DE4432038A DE4432038A1 (en) 1994-09-09 1994-09-09 Fuels containing polyetheramines for gasoline engines

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    EP0700985A1 EP0700985A1 (en) 1996-03-13
    EP0700985B1 true EP0700985B1 (en) 1999-03-03

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    Also Published As

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    US5660601A (en) 1997-08-26
    JP3725588B2 (en) 2005-12-14
    ES2127976T3 (en) 1999-05-01
    DE59505179D1 (en) 1999-04-08
    EP0700985A1 (en) 1996-03-13
    JPH0892574A (en) 1996-04-09
    DE4432038A1 (en) 1996-03-14

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