WO2013075978A1 - Mélange d'amines - Google Patents

Mélange d'amines Download PDF

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Publication number
WO2013075978A1
WO2013075978A1 PCT/EP2012/072498 EP2012072498W WO2013075978A1 WO 2013075978 A1 WO2013075978 A1 WO 2013075978A1 EP 2012072498 W EP2012072498 W EP 2012072498W WO 2013075978 A1 WO2013075978 A1 WO 2013075978A1
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WO
WIPO (PCT)
Prior art keywords
weight
amine
parts
polyisobutene
variable
Prior art date
Application number
PCT/EP2012/072498
Other languages
German (de)
English (en)
Inventor
Harald Schwahn
Marc Walter
Original Assignee
Basf Se
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Basf Se filed Critical Basf Se
Priority to CA2856684A priority Critical patent/CA2856684A1/fr
Priority to BR112014012561A priority patent/BR112014012561A2/pt
Priority to JP2014542770A priority patent/JP2014533760A/ja
Priority to SG11201402422RA priority patent/SG11201402422RA/en
Priority to AU2012342721A priority patent/AU2012342721A1/en
Priority to CN201280057776.6A priority patent/CN103975046A/zh
Priority to MX2014006055A priority patent/MX2014006055A/es
Priority to EP12783629.4A priority patent/EP2782985A1/fr
Priority to KR1020147017001A priority patent/KR20140103978A/ko
Publication of WO2013075978A1 publication Critical patent/WO2013075978A1/fr
Priority to ZA2014/04493A priority patent/ZA201404493B/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—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)
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • 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, 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
    • 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
    • C10L2270/00—Specifically adapted fuels
    • C10L2270/02—Specifically adapted fuels for internal combustion engines
    • C10L2270/023—Specifically adapted fuels for internal combustion engines for gasoline engines
    • 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
    • C10L2300/00—Mixture of two or more additives covered by the same group of C10L1/00 - C10L1/308
    • C10L2300/20—Mixture of two components

Definitions

  • the present invention relates to an amine mixture which is used as predominant components
  • the variable x is 0 or 1
  • the variable m den Value 0 or 1 and the variable n can assume the value 1, 2 or 3, wherein the polyisobuteneamine (I) has a number-average molecular weight of 300 to 2500, and
  • the present invention relates to a fuel composition containing this amine mixture, as well as the use of this amine mixture for cleaning and keeping intake valves clean in intake manifold gasoline engines and injectors in direct injection gasoline engines.
  • the hydrocarbylamines and the nitrogen-containing fuel detergents are prepared separately and combined together in the additive formulation.
  • WO 2009/074608 (2) describes fuel additive formulations which contain polyisobutenyl monoamines or polyisobutenyl polyamines as nitrogen-containing dispersants, synthetic or mineral carrier oils and amines such as di-n-tridecylamine, hydrogenated tallow fatty amine or cocoamine. Such amines serve as enhancers in valve cleaning and valve maintenance in internal combustion engines.
  • the nitrogen-containing dispersants and the amines are, however, prepared separately and combined only in the additive formulation.
  • the preparation of such relatively long-chain amines is usually carried out from the corresponding alcohols by a complex amination step with ammonia or non-ammonia. dermolekularen amines before they can be incorporated into the fuel additive formulations. If such amines are to be used in fuel additive formulations, the object is to provide a simpler and more cost-effective synthesis of these amines.
  • the present invention thus relates to the amine mixture initially defined by its method of preparation, hereinafter referred to as "amine mixture according to the invention.” Since a part of the described amine mixtures as substance mixtures - regardless of their method of preparation - represents new substances, such amine mixtures are also the subject of the present invention, below also referred to as "amine mixture according to the invention".
  • the amine mixture according to the invention preferably contains 50 to 95 parts by weight, in particular 70 to 90 parts by weight of component (A) and 5 to 50 parts by weight, in particular 10 to 30 parts by weight of component (B), wherein the sum of parts by weight of components (A) and (B) is 100 parts by weight.
  • Such groups PIB occur primarily in embodiments (ii) and (iii).
  • R 1 n-butene
  • This aminomethyl-ene grouping is usually predominantly at the o and ß-carbon atom or preferably predominantly at the ⁇ -carbon atom of the last isobutene unit in the polymer chain.
  • Such polybutyl or Polyisobutylreste R 1 occur mainly in embodiment (i).
  • EP-A 244 616 (3) describes the preparation of polybutyl and polyisobutylamines of the formula R 1 -CH 2 -NR 2 R 3 by hydroformylation of polybutene or polyisobutene and subsequent reductive amination of the resulting oxo product with ammonia or amines in analogy to the embodiment (i) described.
  • the meanings of the variables R 2 and R 3 for the formulas determining the present invention are encompassed by the meanings of the variables R 2 and R 3 as defined in (3).
  • R 2 and R 3 are identical or different for the present invention and are preferably hydrogen or linear or branched C 1 - to C 13 -alkyl radicals such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.
  • Suitable amines HNR 2 R 3 are methylamine, dimethylamine, ethylamine, diethylamine, ethylmethylamine, n-propylamine, di-n-propylamine, iso-propylamine, diisopropylamine, n-butylamine, di-n-butylamine, n Butylmethylamine, iso-butylamine, diisobutylamine, tert-butylamine, di-tert-butylamine, 2-ethylhexylamine, 2-propylheptylamine, 1, 2-ethylenediamine, dimethylaminopropylamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine.
  • both variables R 2 and R 3 are hydrogen, whereby the amine HNR 2 R 3 denotes ammonia.
  • variable R 1 preferably represents a polybutyl or polyisobutyl radical derived from isobutene and 0 to 20% by weight, in particular 0 to 5% by weight, in particular 0 to 1% by weight, of n-butene, which is 20 to 176 , in particular 36 to 104, in particular contains 60 to 88 carbon atoms.
  • the polyisobuteneamine of the general formula (I) preferably has a number-average molecular weight of 500 to 1500, in particular from 900 to 1300.
  • the reductive amination of the mixture of the oxo product formed during the hydroformylation of polybutene or polyisobutene, which is generally an aldehyde / alcohol mixture, and the alcohol of the formula R 4 -OH is usually as described in document (3 ).
  • This reaction with ammonia or amines of the formula NHR 2 R 3 in a hydrogen atmosphere is generally carried out at temperatures of 80 to 200 ° C. and pressures of up to 600 bar, preferably 80 to 300 bar.
  • the oxo product produced in a precursor is usually - according to the teaching of (3) - by hydroformylation of the polybutene or polyisobutene, which preferably has a high content of terminal double bonds (vinylidene double bonds), in particular at least 70%, especially at least 80% vinylidene Double bonds, prepared with carbon monoxide / hydrogen in the presence of a suitable rhodium or cobalt catalyst at temperatures between 80 and 200 ° C and pressures of up to 600 bar.
  • a customary hydrogenation catalyst for example Raney Nickel or Raney cobalt.
  • a preferred embodiment of the present invention is an amine mixture which is considered to be predominant components
  • R is -CH 2 -NR 2 R 3 (Ia) in which the variable R 1 is a polybutyl or polyisobutyl radical derived from isobutene and from 0 to 20% by weight of n-butene and the variables R 2 and R 3 are as defined above have and
  • the reductive amination of the mixture of the epoxide formed in the epoxidation of polybutene or polyisobutene and the alcohol of the formula R 4 -OH is usually carried out as described in EP-A 476 485 (4).
  • This reaction with ammonia or amines of the formula NHR 2 R 3 is generally carried out in bulk or in a solvent which is inert under the reaction conditions, for example dissolved in aliphatic or aromatic hydrocarbons. or in ethers, at elevated temperature, for example at the reflux of the respective solvent or in a pressure vessel.
  • the presence of mostly stoichiometric amounts of water as catalyst has proved to be advantageous.
  • Acid or Lewis acid compounds such as p-toluenesulfonic acid, carboxylic acids, boron trifluoride etherates, titanates or stannates can be used as additional catalysts.
  • the epoxide produced in a precursor is usually - according to the teaching of (4) - by conventional epoxidizing agents such as m-chloroperbenzoic acid, tert-butyl hydroperoxide or peracetic acid, optionally in the presence of Studentsgangsmetallkatalysato- ren such as molybdenum or tungsten salts or complexes, from polybutene or polyisobutene, which preferably has a high content of terminal double bonds (vinylidene double bonds), in particular at least 70%, especially at least 80% vinylidene double bonds.
  • the reductive amination of the mixture of the nitro compound formed in the reaction of polybutene or polyisobutene with nitrogen oxides or mixtures of nitrogen oxides and oxygen and the alcohol of the formula R 4 -OH is usually as described in WO 96/03367 (5). , WO 96/03479 (6) and WO 97/03946 (7).
  • This reaction with ammonia or amines of the formula NHR 2 R 3 is generally carried out as catalytic hydrogenation with hydrogen in the presence of hydrogenation catalysts, for example noble metal catalysts such as platinum, palladium, ruthenium, rhodium, osmium or iridium, Raney catalysts such as nickel, Cobalt, iron or copper, mixed catalysts containing, for example, nickel, zirconium, copper and molybdenum or copper, chromium, zinc and barium, or oxidic or sulfidic hydrogenation catalysts, at elevated temperatures, in particular at 150 to 220 ° C and hydrogen pressures of 1 to 300 bar and usually carried out in solvents such as hydrocarbons or ethers.
  • hydrogenation catalysts for example noble metal catalysts such as platinum, palladium, ruthenium, rhodium, osmium or iridium, Raney catalysts such as nickel, Cobalt, iron or copper, mixed catalysts containing, for example, nickel, zir
  • the nitro compound produced in a precursor is usually - according to the teachings of documents (5) to (7) - by reacting nitrogen oxides, in particular nitrogen monoxide, nitrogen dioxide, dinitrogen trioxide and / or dinitrogen tetroxide, or mixtures of these nitrogen oxides and oxygen with polybutene or Polyisobutene, which preferably has a high content of terminal double bonds (vinylidene double bonds), in particular at least 70%, especially at least 80% of vinylidene the double bonds, having, unpressurized or under pressure, discontinuous or continuous and advantageously produced in inert organic solvents such as hydrocarbons, halogenated hydrocarbons, ethers, amides and / or esters.
  • nitrogen oxides in particular nitrogen monoxide, nitrogen dioxide, dinitrogen trioxide and / or dinitrogen tetroxide, or mixtures of these nitrogen oxides and oxygen
  • polybutene or Polyisobutene which preferably has a high content of terminal double bonds (
  • variable R 4 in the alkanols of the formula R 4 -OH and in the resulting aliphatic amines of component (B) denotes a linear or branched C 7 to C 23 alkyl radical or a polybutyl or polyisobutyl radical having from 24 to 600 carbon atoms , Particular preference is given to a branched C 7 - to C 13 -alkyl radical or a polybutyl or polyisobutyl radical having from 24 to 600, in particular from 28 to 176, especially from 32 to 88 carbon atoms.
  • linear or branched C6 to C600-alkyl radicals in particular C7 to C23 linear or branched alkyl radicals and polybutyl or polyisobutyl radicals having 24 to 600 carbon atoms are n-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, 2-methylhexyl,
  • inert organic solvents may be included under the reaction conditions.
  • inert organic solvents are especially aliphatic, cycloaliphatic and aromatic hydrocarbons such as alkanes, eg.
  • n-pentane n-hexane or n-heptane, or technical alkane mixtures
  • cyclohexane, cycloheptane, cyclooctane toluene, xylenes, naphthalenes or tetrahydronaphthalene ("tetralin")
  • ethers such as diethyl ether, tert-butyl methyl ether or tetrahydrofuran are used.
  • ethers such as diethyl ether, tert-butyl methyl ether or tetrahydrofuran are used.
  • the abovementioned solvents can usually already be added in the precursors-ie in the hydroformylation in embodiment (i), in the epoxidation in embodiment (ii) and in the reaction with nitrogen oxides or nitrogen oxide / oxygen mixtures in embodiment (iii) become.
  • Suitable paraffinic solvents L1 are, for example, the products sold under the name Mihagol® by BP Germany products, eg. B. Mihagol M with a proportion of n-paraffins with a chain length of 1 1 to 13 carbon atoms of at least 99 wt .-%.
  • Suitable naphthenic solvents L2) are, for example, the products marketed under the name LIAV® by Fortum Oil and Gas, eg. B.
  • Nessol LIAV 230 with predominant proportions of saturated cyclic aliphatics having a carbon number of 10 to 14.
  • inert organic solvents under the reaction conditions, especially with the concomitant use of L1), L2) or mixtures of L1) and L2) in the vol .Mixing ratio of 10:90 to 90:10, you put this in usually in the weight ratio amine mixture of (A) and (B) to solvent of 50 to 99: 1 to 50, in particular 55 to 90: 5 to 10, especially 60 to 75: 25 to 40 a
  • the present invention also provides a process for the preparation of an amine mixture, which is used as predominant components
  • PIB (CH 2 ) x (OH) m (NR 2 R 3 ) n (I) in which the group PIB is a skeleton derived from 0 to 20% by weight n-butene-containing polybutene or polyisobutene or one of isobutene and 0 to 20% by weight of n-butene-derived polybutyl or polyisobutyl radical
  • the variables R 2 and R 3 which may be identical or different, represent hydrogen, aliphatic or aromatic hydrocarbon radicals, primary or secondary, aromatic or aliphatic aminoalkylene radicals or polyaminoalkyl radicals
  • Polyoxyalkylenreste, heteroaryl or Heterocyclylreste may stand, or together with the nitrogen atom to which they are attached, form a ring in which further heteroatoms may be present
  • the variable x is the value 0 or 1
  • the variable m the value 0 or 1 and the variable n can take the value 1, 2 or 3, wherein the
  • the present invention is also an amine mixture, which as the predominant components (A) 0.1 to 99.9 parts by weight of a polyisobutenamine of the general formula
  • PIB (CH 2 ) x (OH) m (NR 2 R 3 ) in which the group PIB comprises a skeleton derived from 0 to 20% by weight of n-butene-containing polybutene or polyisobutene or one of isobutene and 0 to 20% by weight.
  • the variables R 2 and R 3 which can be identical or different, represent hydrogen, aliphatic or aromatic hydrocarbon radicals, primary or secondary, aromatic or aliphatic aminoalkylene radicals or polyaminoalkyl radicals, polyoxyalkylene radicals, Heteroaryl or Heterocyclylreste may stand, or together with the nitrogen atom to which they are attached form a ring in which further heteroatoms may be present, and the variable x is the value 0 or 1, the variable m is 0 or 1 and the variable n can assume the value 1, 2 or 3, the polyisobuteneamine (I) having a number-average molecular weight of 300 to 2500, and
  • this amine mixture contains as component ( ⁇ ') an aliphatic amine of the general formula (II) in which the variable R 14 denotes a branched C 6 - to Cg-alkyl radical and the variables R 2 and R 3 in each case denote hydrogen.
  • This amine mixture particularly preferably contains, as component ( ⁇ '), an aliphatic amine of the general formula (II) in which the variable R 14 denotes a 2-ethylhexyl radical and the variables R 2 and R 3 denote hydrogen in each case.
  • this amine mixture contains as component (A) a polyisobuteneamine of the general formula (Ia)
  • R is -CH 2 -NR 2 R 3 (Ia) in which the variable R 1 is a polybutyl or polyisobutyl radical having a number average molecular weight of from 300 to 2,500 and derived from isobutene and from 0 to 20% by weight of n-butene; 2 and R 3 each denote hydrogen, and as component ( ⁇ ') an aliphatic amine of the general formula (II) in which the variable R 14 denotes a 2-ethylhexyl radical and the variables R 2 and R 3 also each denote hydrogen.
  • the amine mixture according to the invention from the predominant components (A) and (B) or (A) and ( ⁇ ') is outstandingly suitable as a fuel additive, in particular for cleaning and keeping intake valves intact in intake manifold injection gasoline engines and of injectors in direct injection gasoline engines. Therefore, a fuel composition, in particular a gasoline fuel composition containing the amine mixture according to the invention, also subject of the present invention.
  • such a fuel composition has an Al koholgehalt, in particular a content of C r to C 4 alkanols such as methanol or especially ethanol, from 0 to 100 vol .-%, more preferably from more than 0 to 90 vol .-%, in particular from 5 to 90 vol .-% , especially from 50 to 85 vol .-%, and is suitable for operating gasoline engines.
  • Al koholgehalt in particular a content of C r to C 4 alkanols such as methanol or especially ethanol, from 0 to 100 vol .-%, more preferably from more than 0 to 90 vol .-%, in particular from 5 to 90 vol .-% , especially from 50 to 85 vol .-%, and is suitable for operating gasoline engines.
  • the amine mixture according to the invention When operating an internal combustion engine with a fuel composition containing it, the amine mixture according to the invention exhibits a very good detergency effect.
  • the injection nozzles and the entire intake system of the engine it also exerts a number of other beneficial effects as fuel additives: they reduce valve sticking and / or improve the compatibility of the detergents with carrier oils.
  • polyether and polyetheramine carrier oils especially at low temperatures, and / or they improve the compatibility in fuel compositions containing a mineral fuel fraction and C r C 4 alkanols.
  • fuel additive concentrates containing the amine mixture according to the invention sufficiently low viscosity (ie they have a sufficiently low viscosity), so that capacity bottlenecks in the production of such fuel additive concentrates due to temporary flow rates through the equipment and lines - even with the concomitant use of inert Solvents or diluents - should be avoided; the comparatively low viscosity also has an unpredictable beneficial effect on the mode of action as fuel additives.
  • fuel composition is to be understood in the context of the present invention preferably a gasoline fuel composition.
  • gasoline fuels all commercially available gasoline fuel compositions are considered.
  • a typical representative here is the market-standard basic fuel of Eurosuper according to EN 228.
  • gasoline compositions of the specification according to WO 00/47698 are also possible fields of use for the amine mixture according to the invention.
  • a gasoline composition having an aromatic content of at most 60% by volume, such as a maximum of 42% by volume, and a sulfur content of at most 2000, such as e.g. maximum 150 ppm by weight, to name.
  • the aromatics content of the gasoline composition is preferably not more than 50% by volume, in particular from 1 to 45% by volume, especially from 5 to 40% by volume.
  • the sulfur content of the gasoline is preferably at most 500 ppm by weight, in particular 0.5 to 150 ppm by weight, especially 1 to 100 ppm by weight.
  • the gasoline composition for example, an olefin content up to 50 vol .-%, preferably from 0.1 to 21 vol .-%, in particular from 2 to 18% by volume, a benzene content of up to 5 vol .-%, preferably 0 to 1, 0 vol .-%, in particular 0.05 to 0.9 vol .-%, and / or an oxygen content of up to 47.5 wt .-%, such as 0.1 to 2.7 wt. % or, for example, from 2.7 to 47.5% by weight (for gasoline compositions containing predominantly lower alcohols).
  • gasoline fuel compositions may also be mentioned by way of example, which at the same time has an aromatics content of not more than 38% by volume, an olefin content of not more than 21% by volume, a sulfur content of not more than 50 ppm by weight, a benzene content of not more than 1.0% by volume. -% and have an oxygen content of 0.1 to 47.5 wt .-%.
  • the summer vapor pressure of the gasoline composition is usually not more than 70 kPa, in particular 60 kPa (each at 37 ° C).
  • the RON of the gasoline composition is typically 75 to 105.
  • a typical range for the corresponding MOZ is 65 to 95.
  • the specified specifications are determined by conventional methods (DIN EN 228).
  • Suitable C r to C 4 -alkanols are methanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol and, in particular, ethanol; Mixtures of said C r C 4 alkanols are possible as low alcohol fuel components.
  • the inventive fuel composition may also contain ethers having 5 or more carbon atoms, for example methyl tert-butyl ether, in the molecule in an amount of up to 30% by volume.
  • the amine mixture according to the invention can be added to the fuel composition to be additive alone or in admixture with other effective additive components (co-additives).
  • co-additives there may be mentioned various additives having detergent action and / or having valve seat wear-inhibiting action (hereinafter collectively referred to as detergent additives) of the component (A) of the amine mixture of the present invention.
  • detergent additives generally has at least one hydrophobic hydrocarbon radical having a number-average molecular weight (M n ) of from 85 to 20 000 and at least one polar group selected from:
  • the hydrophobic hydrocarbon radical in the above detergent additives which provides sufficient solubility in the fuel, has a number average molecular weight (M n ) of 85 to 20,000, especially 1 13 to 10,000, especially 300 to 5,000.
  • M n number average molecular weight
  • amine mixture according to the invention can be combined with even more customary components and additives.
  • carrier oils are present here mineral base or on synthetic basis without pronounced detergent action to call.
  • Suitable mineral carrier oils are fractions obtained in petroleum processing, such as kerosene or naphtha, bright stock or base oils having viscosities, for example from class SN 500 to 2000; but also aromatic hydrocarbons, paraffinic hydrocarbons and alkoxyalkanols. Also useful is a fraction known as "hydrocrack oil” and obtained in the refining of mineral oil (vacuum distillate cut having a boiling range of about 360 ° to 500 ° C., obtainable from high pressure, catalytically hydrogenated and isomerized and deparaffinated natural mineral oil). Also suitable are mixtures of the abovementioned mineral carrier oils.
  • useful synthetic carrier oils can be selected from polyolefins (polyalphaolefins or polyinteralalefins), (poly) esters, (poly) alkoxylates, polyethers, aliphatic polyetheramines, alkylphenol-initiated polyethers, alkylphenol-promoted polyetheramines and carboxylic acid esters of long-chain alkanols.
  • particularly suitable synthetic carrier oils are alcohol-started polyethers containing about 5 to 35 C3 to C6 alkylene oxide units, usually selected from propylene oxide, n-butylene oxide and isobutylene oxide units or mixtures thereof.
  • Nonlimiting examples of starter alcohols suitable for this purpose are long-chain alkanols or long-chain alkyl-substituted phenols, where the long-chain alkyl radical is in particular a straight-chain or branched C 6 - to C 18 -alkyl radical. Preferred examples of this are tridecanol and nonylphenol.
  • Further customary fuel additives are corrosion inhibitors, for example based on film-forming ammonium salts of organic carboxylic acids or of heterocyclic aromatics in the case of non-ferrous metal corrosion protection; Antioxidants or stabilizers, for example based on amines such as p-phenylenediamine, dicyclohexylamine or derivatives thereof or of phenols such as 2,4-di-tert-butylphenol or 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid; demulsifiers; Antistatic agents; Metallocenes such as ferrocene; methylcyclopentadienyl; Lubricity additives such as certain fatty acids, alkenyl succinic esters, bis (hydroxyalkyl) fatty amines, hydroxyacetamides or castor oil; as well as dyes (markers).
  • amines are added to lower the pH of the fuel.
  • the components or additives mentioned can be added to the fuel composition individually or as a previously prepared concentrate (additive package) together with the amine mixture according to the invention.
  • the amine mixture of the invention is the fuel composition - either separately or in the form of a concentrate with other components or additives and optionally conventional solvents and diluents - usually in an amount of 5 to 5000, preferably 10 to 2000, in particular 25 to 1000, before all 50 to 500 ppm by weight, in each case as pure substance indicated (ie without solvents and diluents and other components or additives) and based on the total amount of the fuel composition added.
  • the other components or additives mentioned are, if desired, added in conventional amounts.
  • the resulting oxo product was treated together with 75 g of 2-ethylhexanol, 1.0 liter of ammonia and 100 g of Raney cobalt in a 5 liter roll autoclave under a hydrogen pressure of 200 bar at 180 ° C. After cooling the mixture, the Raney cobalt catalyst was filtered off, excess ammonia evaporated and the solvent was distilled off.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Liquid Carbonaceous Fuels (AREA)

Abstract

Mélange d'amines contenant (A) une polyisobutène-amine PIB(CH2)x(OH)m(NR2R3)n, PIB représentant un squelette dérivé de polybutène ou de polyisobutène ou un groupe polybutyle ou polyisobutyle, R2 et R3 représentant un atome d'hydrogène, des groupes hydrocarbonés aliphatiques ou aromatiques, des groupes aminoalkylène ou polyaminoalkylène aromatiques ou aliphatiques, primaires ou secondaires, des groupes polyoxyalkylène, des groupes hétéroaryle ou hétérocyclyle, et x = 0 ou 1, m = 0 ou 1 et n = 1, 2 ou 3, et (B) une amine aliphatique R4-NR2R3, R4 représentant un groupe alkyle en C6 à C600, ce mélange d'amines pouvant être obtenu par amination réductrice d'un mélange comprenant (i) le produit oxo formé par hydroformylation de polybutène ou de polyisobutène et un alcanol R4-OH, ou (ii) l'époxyde formé par époxydation de polybutène ou de polyisobutène et un alcanol R4-OH, ou (iii) le composé nitré formé par réaction de polybutène ou de polyisobutène avec des oxydes d'azote et un alcanol R4-OH, avec de l'ammoniac ou une amine HNR2R3. Ce mélange d'amines peut être utilisé pour nettoyer ou maintenir propres des soupapes d'admission et des injecteurs de moteurs à étincelles.
PCT/EP2012/072498 2011-11-23 2012-11-13 Mélange d'amines WO2013075978A1 (fr)

Priority Applications (10)

Application Number Priority Date Filing Date Title
CA2856684A CA2856684A1 (fr) 2011-11-23 2012-11-13 Melange d'amines
BR112014012561A BR112014012561A2 (pt) 2011-11-23 2012-11-13 mistura de aminas, processo para preparar uma mistura de aminas, composição de combustível, e, uso de uma mistura de aminas
JP2014542770A JP2014533760A (ja) 2011-11-23 2012-11-13 アミン混合物
SG11201402422RA SG11201402422RA (en) 2011-11-23 2012-11-13 Amine mixture
AU2012342721A AU2012342721A1 (en) 2011-11-23 2012-11-13 Amine mixture
CN201280057776.6A CN103975046A (zh) 2011-11-23 2012-11-13 胺混合物
MX2014006055A MX2014006055A (es) 2011-11-23 2012-11-13 Mezcla de aminas.
EP12783629.4A EP2782985A1 (fr) 2011-11-23 2012-11-13 Mélange d'amines
KR1020147017001A KR20140103978A (ko) 2011-11-23 2012-11-13 아민 혼합물
ZA2014/04493A ZA201404493B (en) 2011-11-23 2014-06-19 Amine mixture

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EP11190333.2 2011-11-23
EP11190333 2011-11-23

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WO2013075978A1 true WO2013075978A1 (fr) 2013-05-30

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JP (1) JP2014533760A (fr)
KR (1) KR20140103978A (fr)
CN (1) CN103975046A (fr)
AU (1) AU2012342721A1 (fr)
BR (1) BR112014012561A2 (fr)
CA (1) CA2856684A1 (fr)
MX (1) MX2014006055A (fr)
SG (1) SG11201402422RA (fr)
WO (1) WO2013075978A1 (fr)
ZA (1) ZA201404493B (fr)

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WO2014184013A1 (fr) * 2013-05-14 2014-11-20 Basf Se Mélange d'amines
WO2015028391A1 (fr) * 2013-08-27 2015-03-05 Bp Oil International Limited Procédés et utilisations pour le contrôle de dépôts sur des soupapes dans des moteurs à allumage commandé et injection directe
WO2015028392A1 (fr) * 2013-08-27 2015-03-05 Bp Oil International Limited Procédés et utilisations pour le nettoyage des dépôts de soupape d'aspiration et d'injecteur direct

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RU2019135830A (ru) * 2017-04-11 2021-05-11 Басф Се Алкоксилированные амины в качестве присадок к топливу
CN114057918B (zh) * 2021-12-03 2024-03-15 新丰博兴聚合材料有限公司 一种胺改性树脂及其制备方法和应用

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Publication number Priority date Publication date Assignee Title
WO2014184013A1 (fr) * 2013-05-14 2014-11-20 Basf Se Mélange d'amines
WO2015028391A1 (fr) * 2013-08-27 2015-03-05 Bp Oil International Limited Procédés et utilisations pour le contrôle de dépôts sur des soupapes dans des moteurs à allumage commandé et injection directe
WO2015028392A1 (fr) * 2013-08-27 2015-03-05 Bp Oil International Limited Procédés et utilisations pour le nettoyage des dépôts de soupape d'aspiration et d'injecteur direct
CN105722958A (zh) * 2013-08-27 2016-06-29 英国石油国际有限公司 用于控制直接喷射式火花点火发动机中的阀上的沉积物的方法和用途
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US11685873B2 (en) 2013-08-27 2023-06-27 Bp Oil International Limited Methods and uses for controlling deposits on valves in direct-injection spark-ignition engines

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BR112014012561A2 (pt) 2017-06-13
CA2856684A1 (fr) 2013-05-30
SG11201402422RA (en) 2014-09-26
KR20140103978A (ko) 2014-08-27
ZA201404493B (en) 2016-01-27
JP2014533760A (ja) 2014-12-15
AU2012342721A1 (en) 2014-07-03
CN103975046A (zh) 2014-08-06
EP2782985A1 (fr) 2014-10-01
MX2014006055A (es) 2014-08-08

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