WO2007039488A1 - Aminoalkylamides d'acides gras a substitution hydroxyalkyle utilises en tant que modificateurs de friction - Google Patents

Aminoalkylamides d'acides gras a substitution hydroxyalkyle utilises en tant que modificateurs de friction Download PDF

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Publication number
WO2007039488A1
WO2007039488A1 PCT/EP2006/066623 EP2006066623W WO2007039488A1 WO 2007039488 A1 WO2007039488 A1 WO 2007039488A1 EP 2006066623 W EP2006066623 W EP 2006066623W WO 2007039488 A1 WO2007039488 A1 WO 2007039488A1
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formula
group
additive composition
fuel
compound
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PCT/EP2006/066623
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English (en)
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Ludwig Völkel
Arno Lange
Christian Lockemann
Dietmar Posselt
Joseph T. Joseph
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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
    • C10L1/224—Amides; Imides carboxylic acid amides, imides
    • 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
    • C10L1/221—Organic compounds containing nitrogen compounds of uncertain formula; reaction products where mixtures of compounds are obtained
    • 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
    • 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
    • C10L10/08—Use of additives to fuels or fires for particular purposes for improving lubricity; for reducing wear

Definitions

  • the present invention relates to hydroxyalkyl-substituted aminoalkylamides of fatty acids as friction modifiers for fuels.
  • Carburettors and inlet systems of Otto engines, and also injection systems for fuel proportioning, are subjected to increasing load due to contamination caused by dust parti- cles from the air, unburned hydrocarbon residues from the combustion chamber and crankcase breather gases passed to the carburettor.
  • valve seat wear occurs in the case of Otto engines of less recent design when fuelled with unleaded gasolines.
  • anti-valve seat recession additives based on alkali metal or alkaline earth metal compounds have been developed.
  • gasolines For trouble-free running, modern Otto engines require automotive fuels having a complex set of properties which can only be guaranteed when use is made of appropriate gasoline additives.
  • Such gasolines usually consist of a complex mixture of chemical compounds and are characterized by physical parameters.
  • the interrelationship between gasolines and appropriate additives in known fuel compositions is still unsatisfactory as regards their detergent action or their pollution-abating properties and their anti-valve seat recession action.
  • EP-A-0798364 describes a diesel fuel additive comprising an amide obtained by dehydration-condensation between a carboxylic acid and an aliphatic amine.
  • the additive reducesthe amount of deposit in the injection nozzle of comression-ignition diesel en- gines, improves the lubricity of the fuel and reduces the wear of the fuel injection pump.
  • Preferred amines are monoamines or propylene diamines substituted by C 8 -C 20 - hydrocarbyl groups.
  • EP-A-0301448 refers to a gasoline composition containing alkali metal salts or alkaline earth metal salts of monoamides of dicarboxylic acids or of the amides of tri- or tetra- carboxylic acids as additives for reducing wear at the valves of Otto engines and also for reducing corrosion.
  • R 1 is an aliphatic C 8 -C 30 -hydrocarbyl group
  • R 2 is hydrogen, CrC 8 -alkyl or C 2 -C 8 -hydroxyalkyl
  • R 3 and R 4 are, independently of each other, hydrogen, C 2 -C 8 -hydroxyalkyl or a group of the formula 4A-OJ x A-OH;
  • A is a linear or branched C 2 -C 4 -alkylene group
  • B is a linear or branched C 2 -C 8 -alkylene group, a group of the formula 4E-OJ v E- or a group of the formula 4E-NR 5 JvE-;
  • E is a linear or branched C 2 -C 8 -alkylene group
  • R 5 is hydrogen, Ci-C 8 -alkyl, C 2 -C 8 -hydroxyalkyl or a group of the formula 4A- w and x are, independently of each other, 0 or an integer from 1 to 10; and
  • v is an integer from 1 to 10; and wherein the molar ratio of the amine and each carboxylic group contained in the carboxylic acid or derivative thereof is 1.5:1 to 10:1 ;
  • step (1 ) (2) in case at least one of the radicals R 3 and R 4 is hydrogen, reacting the product obtained in step (1 ) with an alkylene oxide of the formula P , wherein R 6 is H, methyl or ethyl, and where the molar R 6 ratio of alkylene oxide per each hydrogen atom bound to a nitrogen atom contained in the group B or NR 3 R 4 of the amine R 2 HN-B-NR 3 R 4 introduced in step (1 ) is 4: 1 to 1 : 1.
  • the invention is also related to a method for producing the above additive composition.
  • the invention is further related to a fuel composition containing a fuel as major component and at least one compound of the formula (I) as defined below or the additive composition as defined above and optionally at least one further additive.
  • the invention is related to an additive concentrate, comprising at least one compound of the formula (I) as defined below or the additive composition as defined above and at least one diluent and/or at least one further additive.
  • the invention is related to a method for producing a fuel composition with improved friction properties, where a fuel or a commercial fuel composition is additized with at least one compound of the formula (I) as defined below or with the additive composition as defined above or with the additive concentrate as defined above.
  • the organic moieties mentioned in the above definitions of the variables are - like the term halogen - collective terms for individual listings of the individual group members.
  • the prefix C n -C m indicates in each case the possible number of carbon atoms in the group.
  • aliphatic C 8 -C 30 -hydrocarbyl group denotes an acyclic radical essentially composed of carbon atoms and hydrogen atoms and containing 8 to 30 carbon atoms.
  • the hydrocarbyl group is an alkyl, alkenyl, alkadienyl, alkatrienyl or an aliphatic polyenyl radical containing more than 3 olefinic double bonds.
  • C 8 -C 30 -Alkenyl is a singly unsaturated straight-chain or branched aliphatic hydrocarbon radical having from 8 to 30 carbon atoms.
  • Examples include octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptade- cenyl, octadecenyl, nonadecenyl, eicosenyl, hencosenyl, docosenyl, tricosenyl, tetra- cosenyl, pentacosenyl, hexacosenyl, heptacosenyl, octacosenyl, nonacosenyl, squalenyl, constitutional isomers thereof, the higher homologs and
  • C 4 -C 7 -Alkenyl is a singly unsaturated straight-chain or branched aliphatic hydrocarbon radical having from 4 to 7 carbon atoms.
  • Examples include 1-, 2- and 3-butenyl, 2- methylpropen-3-yl, 2-methylpropen-1-yl, 1-, 2-, 3- and 4-pentenyl, 1-, 2-, 3-, 4- or 5- hexenyl, 1-, 2-, 3-, 4-, 5- or 6-heptenyl and their constitutional isomers.
  • C 8 -C 30 -Alkadienyl is an unsaturated straight-chain or branched aliphatic hydrocarbon radical having 2 olefinic, non-vicinal double bonds and from 8 to 30 carbon atoms.
  • the double bonds may be conjugated or isolated double bonds.
  • Examples include octadi- enyl, nonadienyl, decadienyl, undecadienyl, dodecadienyl, tridecadienyl, tetradecadi- enyl, pentadecadienyl, hexadecadienyl, heptadecadienyl, octadecadienyl, nonadecadi- enyl, eicosadienyl, hencosadienyl, docosadienyl, tricosadienyl, tetracosadienyl, penta- cosadienyl, hexacosadienyl, heptacosadienyl, octacosadienyl, nonacosadienyl, squaladienyl, constitutional isomers thereof, the higher homologs and their constitu
  • C 4 -C 7 -Alkadienyl is an unsaturated straight-chain or branched aliphatic hydrocarbon radical having 2 olefinic, non-vicinal double bonds and from 4 to 7 carbon atoms.
  • the double bonds may be conjugated or isolated double bonds.
  • Examples include 1 ,3- butadienyl, 1 ,3-, 1 ,4- and 2,4-pentadienyl, 1 ,3-, 1 ,4-, 1 ,5-, 2,4-, 2,5- and 3,5-hexadienyl, 1 ,3-, 1 A-, 1 ,5-, 1 ,6-, 2,4-, 2,5-, 2,6-, 3,5-, 3,6- and 4,6-heptadienyl and their constitutional isomers.
  • Ce-C 3 o-Alkatrienyl is an unsaturated straight-chain or branched aliphatic hydrocarbon radical having 3 olefinic, non-vicinal double bonds and from 8 to 30 carbon atoms.
  • the double bonds may be conjugated or isolated double bonds.
  • Examples include octa- trienyl, nonatrienyl, decatrienyl, undecatrienyl, dodecatrienyl, tridecatrienyl, tetradeca- trienyl, pentadecatrienyl, hexadecatrienyl, heptadecatrienyl, octadecatrienyl, nonadeca- trienyl, eicosatrienyl, hencosatrienyl, docosatrienyl, tricosatrienyl, tetracosatrienyl, pen- tacosatrienyl, hexacosatrienyl, heptacosatrienyl, octacosatrienyl, nonacosatrienyl, squalatrienyl, constitutional isomers thereof, the higher homologs and their constitutional isomers.
  • C 6 -C 7 -Alkatrienyl is an unsaturated straight-chain or branched aliphatic hydrocarbon radical having 3 olefinic, non-vicinal double bonds and 6 or 7 carbon atoms.
  • the double bonds may be conjugated or isolated double bonds. Examples include 1 ,3,5- hexatrienyl, 1 ,3,5-, 1 ,3,6-, 1 ,4,6- and 2,4,6-heptatrienyl and constitutional isomers thereof.
  • C ⁇ -Cso-Polyenyl is generally an unsaturated straight-chain or branched aliphatic hydrocarbon radical having at least two olefinic, non-vicinal double bonds and from 8 to 30 carbon atoms.
  • the double bonds may be conjugated or isolated double bonds. Examples include the above-listed C ⁇ -C3o-alkadienyl and Ce-C3o-alkatrienyl radicals and fur- ther straight-chain or branched aliphatic hydrocarbon radicals having four, five, six or more olefinic, non-vicinal double bonds.
  • C 8 -C 30 -AIkVl is a straight-chain or branched alkyl group having from 8 to 30 carbon at- oms.
  • Examples include octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pen- tadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, hencosyl, docosyl, trico- syl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, squalyl, constitutional isomers thereof, the higher homologs and their constitutional isomers.
  • Ci-C 4 -Alkyl is a straight-chain or branched alkyl group having from 1 to 4 carbon atoms. Examples of an alkyl group are methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl, iso-butyl or tert-butyl.
  • C 1 -C 2 Alkyl is methyl or ethyl
  • C 1 -C3 alkyl is additionally n-propyl or isopropyl.
  • C-i-C ⁇ -Alkyl is a straight-chain or branched alkyl group having from 1 to 8 carbon atoms.
  • Examples include CrC 4 -alkyl as mentioned above and also pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1 ,1- dimethylpropyl, 1 ,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1 ,1-dimethylbutyl, 1 ,2-dimethylbutyl, 1 ,3-dimethylbutyl, 2,2- dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1 ,1 ,2- trimethylpropyl, 1 ,2,2-trimethylpropyl,
  • C 4 -C 7 -Alkyl is a straight-chain or branched alkyl group having from 4 to 7 carbon at- oms.
  • Examples include n-butyl, 2-butyl, iso-butyl, tert-butyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1 ,1- dimethylpropyl, 1 ,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1 ,1-dimethylbutyl, 1 ,2-dimethylbutyl, 1 ,3-dimethylbutyl, 2,2- dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1 ,1 ,
  • C 2 -C 8 -Hydroxyalkyl is a straight-chain or branched alkyl group having from 2 to 8 carbon atoms, in particular 2 to 4 carbon atoms, wherein at least one, e.g. 1 , 2, 3, or 4 of the hydrogen atoms are replaced by a hydroxy group such as in 2-hydroxy-1 -ethyl, 2- and 3-hydroxy-1 -propyl, 2-, 3- and 4-hydroxy-1 -butyl, 2-, 3-, 4- and 5-hydroxy-1 -pentyl, 2-, 3-, 4-, 5- and 6-hydroxy-1 -hexyl, 2-, 3-, 4-, 5-, 6- and 7-hydroxy-1 -heptyl, 2-, 3-, 4-, 5-, 6-, 7- and 8-hydroxy-1 -octyl, 2, 3-d ihydroxy-1 -propyl and constitutional isomers thereof.
  • C 5 -C 8 -Hydroxyalkyl is a straight-chain or branched alkyl group having from 5 to 8 carbon atoms, wherein at least one, e.g. 1 , 2, 3, or 4 of the hydrogen atoms are replaced by a hydroxy group such as in 2-, 3-, 4- and 5-hydroxy-1 -pentyl, 2-, 3-, 4-, 5- and 6- hydroxy-1-hexyl, 2-,3-, 4-, 5-, 6- and 7-hydroxy-1-heptyl, 2-,3-, 4-, 5-, 6-, 7- and 8- hydroxy-1-octyl and constitutional isomers thereof.
  • C 2 -C 8 -Al ky I en e is a linear or branched hydrocarbon bridging group having 2, 3, 4, 5, 6, 7 or 8 carbon atoms, like 1 ,2- ethylene, 1 ,2- and 1 ,3-propylene, 1 ,2-, 1 ,3-, 2,3- and 1 ,4- butylene, 2,2-dimethyl-1 ,2-ethylene, 1 ,1-dimethyl-1 ,2-ethylene, 1 ,5-pentylene, 1 ,6- hexylene, 1 ,7-heptylene, 1 ,8-octylene and constitutional isomers thereof.
  • C 2 -C 4 -Alkylene is a linear or branched hydrocarbon bridging group having 2, 3 or 4 carbon atoms, like 1 ,2- ethylene, 1 ,2- and 1 ,3-propylene, 1 ,2-, 1 ,3-, 2,3- and 1 ,4- butylene, 2,2-dimethyl-1 ,2-ethylene, 1 ,1-dimethyl-1 ,2-ethylene and the like.
  • Groups of the formula 4A-OJ 3 A-OH, wherein a represents w, x, y or z, are, in case a is 0, C 2 -C 4 hydroxyalkyl groups, such as 2-hydroxyethyl, 2-hydroxypropyl, 3- hydroxypropyl, 2-, 3- or 4-hydroxybutyl, 3-hydroxy-3-butyl or 2,2-dimethyl-2- hydroxyethyl.
  • the groups comprise a (poly)ether moiety -A-O-A-.
  • Examples therefor include groups of the formula 4CaH 4 -OJ a C 2 H 4 -OH, 4(CH 2 ) S -OJ 3 (CH 2 ) S -OH, 4CH 2 -CH(CH 3 )-OJ a CH 2 -CH(CH 3 )-OH, 4CH(CH 3 )-CH 2 -OJ a CH(CH 3 )-CH 2 -OH, 4(CH 2 ) 4 -OJ a (CH 2 ) 4 -OH and the like.
  • Groups of the formula 4E-OJ v E- are (poly)ether bridging groups containing at least one ether moiety -E-O-E-.
  • Examples include groups of the formula 4C 2 H 4 -OJvC 2 H 4 -, 4(CH 2 )3-OJv(CH 2 ) 3 -, 4CH 2 -CH(CHa)-OJvCH 2 -CH(CH 3 )-, 4CH(CH 3 )-CH 2 -OJ v CH(CH 3 )-CH 2 -, 4(CH 2 ) 4 -OJ v (CH 2 ) 4 - and the like, wherein v is an integer from 1 to 10.
  • Groups of the formula 4E-NR 5 JvE- are (poly)amine bridging groups. Examples include groups of the formula 4C 2 H 4 -NHJ v C 2 H 4 -, 4C 2 H 4 -N(CH 3 )J v C 2 H 4 -, 4C 2 H 4 -N(C 2 H 5 )J v C 2 H 4 -, 4C 2 H 4 -N(C 2 H 4 OH)J v C 2 H 4 -, 4tCH 2 ) 3 -NHJ v (CH 2 ) 3 -, 4(CH 2 ) 3 -N(CH 3 )J v (CH 2 ) 3 -, 4tCH 2 ) 3 -N(C 2 H 5 )Jv(CH 2 ) 3 -, 4(CH 2 ) 3 -N(C 2 H 4 OH)Jv(CH 2 ) 3 -,
  • CrC 4 -alkanols are saturated alcohols containing 1 to 4 carbon atoms and one hydroxyl group. Examples are methanol, ethanol, propanol, isopropanol, n-butanol, butan-2-ol, isobutanol and tert-butanol.
  • C 2 -C6-polyols are saturated alcohols containing 2 to 6 carbon atoms and at least two, e.g. 2, 3, 4, 5 or 6, hydroxyl groups which are bound to different carbon atoms.
  • Exam- pies include glycol, glycerol, trimethylolpropane, erythritol, pentaerythritol, sorbitol and the like.
  • the additive composition of the invention comprises at least one compound of formula (I)
  • R 1 , R 2 , A, B and x are as defined above;
  • y is O or an integer from 1 to 10.
  • the additive composition of the invention optionally further comprises at least one compound of the formula (II)
  • R 1 , R 2 , A, B and x are as defined above;
  • R 7 is hydrogen, CrC 8 -alkyl or C 2 -C 8 -hydroxyalkyl
  • z is O or an integer from 1 to 10.
  • the radical R 1 in the carboxylic acid R 1 COOH or in carboxylic acid derivative thereof or in the compounds of formulae (I) and (II) is C 8 -C 30 - alkyl, preferably Ci 4 -C 24 -alkyl, C 8 -C 30 -alkenyl, preferably Ci 4 -C 24 -alkenyl, or an aliphatic C 8 -C 30 -polyenyl radical, e.g. a C 8 -C 30 -alkadienyl radical or a C 8 -C 30 -alkatrienyl radical, preferably a Ci 4 -C 24 -polyenyl radical, e.g.
  • the additive composition of the invention may also contain minor amounts of compounds derived from a carboxylic acid R 1 COOH or from a carboxylic acid derivative thereof, such as compounds of formulae (I) and (II), wherein R 1 is a lower hydrocarbyl radical, such as C 4 -C 7 -alkyl, C 4 -C 7 -alkenyl, C 4 -C 7 -alkadienyl or C 6 -C 7 -alkatrienyl.
  • Minor amounts means up to 5% by weight, e.g. up to 3% by weight, preferably up to 2% by weight, based on the total weight of the compounds derived from the carboxylic acid R 1 COOH or from the carboxylic acid derivative thereof, such as compounds of formulae (I) and (II).
  • the additive composition of the invention is derived from at least two different carboxylic acids R 1 COOH or from at least two different carboxylic acid derivatives thereof, the mixture containing at least two of the following components:
  • the components (b), (c) and/or (d) are contained in a total amount of at least 5% by weight, more preferably at least 10% by weight, even more preferably at least 20% by weight, in particular at least 30% by weight, especially at least 40% by weight, e.g. at least 50% by weight, based on the total weight of the compounds obtained by the above-described method.
  • the additive composition of the invention comprises at least two different compounds of formula (I), the mixture containing at least two of the following components:
  • (c1 ) at least one compound of formula (I), wherein R 1 is C 8 -C 30 -alkadienyl, preferably Ci 4 -C 24 -alkadienyl;
  • (d1 ) at least one compound of formula (I), wherein R 1 is C 8 -C 3 o-alkatrienyl, preferably Ci 4 -C 24 -alkatrienyl.
  • R 1 is C 8 -C 3 o-alkatrienyl, preferably Ci 4 -C 24 -alkatrienyl.
  • the components (t>1 ), (c1 ) and/or ( ⁇ "l ) are contained in a total amount of at least 5% by weight, more preferably at least 10% by weight, even more preferably at least 20% by weight, in particular at least 30% by weight, especially at least 40% by weight, e.g. at least 50% by weight, based on the total weight of the compounds of formula (I).
  • the carboxylic acid R 1 COOH or the carboxylic acid derivative thereof are synthetic or natural fatty acids or fatty acid derivatives thereof. Accordingly, the compounds of formulae (I) and (II) or more precisely the moiety R 1 CO in compounds (I) and (II) are preferably derived from synthetic or natural fatty acids or fatty acid derivatives.
  • Sources for natural fatty acids and fatty acid derivatives are, for example, vegetable and animal oils and fats.
  • Natural fats and oils are solid, semi-solid or liquid products obtained from plants and animals and consisting essentially of mixed glycerol esters of fatty acids. In fats and oils of vegetable origin, the contained fatty acids are essentially even-numbered, whereas animal fats and oils also contain odd-numbered fatty acids.
  • suitable fats and oils are soy bean oil, rapeseed oil, sunflower oil, arachis oil, cottonseed oil, coconut oil, palm oil, palm kernel oil, linseed oil, castor oil, olive oil, grape-seed oil, tall oil, cacao butter, tallow oil, fish oil and the like.
  • Preferred natural fats and oils are rapeseed oil, castor oil and tall oil.
  • fatty acids of natural or synthetic origin are saturated, linear fatty acids, such as butyric acid, valeric acid, caproic acid, oenantic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, penta- decanoic acid, palmitic acid, margaric acid, stearic acid, nonadecanoic acid, arachic acid, behenic acid, lignoceric acid, cerotinic acid and melissic acid; saturated, branched fatty acids, such as isobutyric acid, isovaleric acid and tuberculostearic acid; unsaturated fatty acids containing one olefinic double bond, such as palmitoleic acid, oleic acid, eicosenoic acid and erucic acid; unsaturated fatty acids containing two olefinic double bonds, such as linoleic acid and docos
  • the carboxylic starting material is a mixture of fatty acids or fatty acid derivatives, especially mixtures as they occur in their natural sources.
  • the moiety R 1 CO in compounds (I) and (II) is derived from mixed fatty acids or fatty acid derivatives, especially from mixtures as they are present in their natural sources.
  • pure fatty acids and pure fatty acid derivatives of natural or synthetic origin are also suitable sources.
  • Suitable derivatives of the carboxylic acid R 1 COOH are all derivatives which can react with an amine to give an amide, such as esters R 1 COOR 3 , acid halides R 1 COX, wherein X is a halogen atom, or acid anhydrides R 1 C0-0-0C-R b .
  • Suitable esters R 1 COOR 3 are derived from C r C 4 -alkanols R 3 OH, wherein R 3 is C r C 4 - alkyl, such as methanol, ethanol, propanol, isopropanol, n-butanol, butan-2-ol, isobu- tanol and tert-butanol, or from C 2 -C6-polyols, such as glycol, glycerol, trimethylolpro- pane, erythritol, pentaerythritol and sorbitol.
  • the ester R 1 COOR 3 is an active ester obtained by the reaction of the acid with an active esters forming alcohol, such as p-nitrophenol, N-hydroxysuccinimide or OPfp (pentafluorophenol).
  • a preferred acid halide is the acid chloride, which can be obtained e.g. by reacting the acid with a chlorinating agent, such as thionyl chloride.
  • Suitable acid derivatives forming mixed anhydrides with the carboxylic acid R 1 COOH are the esters of chloro- formic acid, e.g. isopropylchloroformiate and isobutylchloroformiate.
  • the reaction is preferably carried out in the presence of a coupling reagent.
  • Suitable coupling reagent activators
  • carbodiimides such as DCC (dicyclohexylcarbodiimide) and DCI (diisopropylcarbodiimide)
  • benzotria- zol derivatives such as HBTU ((O-benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate) and HCTU (1 H-benzotriazolium-1-
  • phosphonium-derived activators such as BOP ((benzotriazol-1-yloxy)-tris(dimethylamino)phosphonium hexafluorophosphate), Py-BOP ((benzotriazol-i-yloxy)-tripyrrolidinphosphonium hexafluorophosphate) and Py-BrOP (bromotripyrrolidinphosphonium hexafluorophosphate).
  • BOP (benzotriazol-1-yloxy)-tris(dimethylamino)phosphonium hexafluorophosphate)
  • Py-BOP (benzotriazol-i-yloxy)-tripyrrolidinphosphonium hexafluorophosphate)
  • Py-BrOP bromotripyrrolidinphosphonium hexafluorophosphate
  • the activator is used in excess.
  • the benzotriazol and phosphonium coupling reagents are generally used in a
  • esters R 1 COOR 3 are used as starting materials in step (1 ).
  • Preferred esters are those with Ci-C 4 -alkanols, especially the methyl or ethyl ester, or esters with poly- ols, especially the glycerol esters. If esters with polyols are used, mixed esters, i.e. esters with different radicals R 1 , can be used. However it is more preferred to use esters with Ci-C 4 -alkanols, especially the methyl or ethyl ester.
  • step (1 ) as starting material in step (1 ) is used the above-named esters of the natural and synthetic fatty acids listed above.
  • the natural oils or fats like those exemplified above as such, where the fatty acids contained therein are mainly present as (mixed) glycerol esters.
  • the reesterified natural oils and fats may be obtained by first hydrolyzing the fat or oil, e.g. by reacting it with a base, such as KOH or NaOH, and then, usually after a neutralization step, esterifying the resulting acid with an alcohol, preferably with a CrC 4 -alkanol, especially with methanol or ethanol. Espe- daily, the methyl or ethyl esters of reesterified natural oils or fats are used.
  • the radical R 2 in the amine reacted in step (1 ) and in compounds of formulae (I) or (II) is hydrogen or Ci-C 4 -alkyl. More preferably, R 2 is hydrogen.
  • the group A is a linear or branched C 2 -C 4 -alkylene group, such as 1 ,2-ethylene, 1 ,2- propylene, 1 ,3-propylene, 1 ,2-, 1 ,3-, 2,3- and 1 ,4-butylene, 2, 2-dimethyl-1 ,2-ethylene, and 1 ,1-dimethyl-1 ,2-ethylene.
  • A is C 2 -C3-alkylene, such as 1 ,2-ethylene, 1 ,2- propylene and 1 ,3-propylene, and in particular, A is 1 ,2-ethylene (-CH 2 -CH 2 -) or 1 ,2-propylene (-CH 2 -CH(CH 3 )- or -CH(CH 3 )-CH 2 -). Especially, A is 1 ,2-ethylene.
  • the group E is a linear or branched C 2 -C 8 -alkylene group, such as 1 ,2-ethylene, 1 ,2- and 1 ,3-propylene, 1 ,2-, 1 ,3-, 2,3- and 1 ,4-butylene, 2,2-dimethyl-1 ,2-ethylene, 1 ,1- dimethyl-1 ,2-ethylene, 1 ,5-pentylene, 1 ,6-hexylene, 1 ,7-heptylene, 1 ,8-octylene and constitutional isomers thereof.
  • E is a linear C 2 -C 8 -alkylene group, such as 1 ,2- ethylene, 1 ,3-propylene, 1 ,4-butylene, 1 ,5-pentylene, 1 ,6-hexylene, 1 ,7-heptylene, and 1 ,8-octylene.
  • E is a linear C 2 -C 4 -alkylene group, such as 1 ,2- ethylene, 1 ,3-propylene and 1 ,4-butylene.
  • the bridging group B is a linear or branched C 2 -C 8 -alkylene group, a group of the formula 4E-OJvE- or a group of the formula 4E-NR 5 JvE-.
  • Groups 4E-OJvE- are derived from (poly)ethers, whereas groups 4E-NR 5 JvE- are (poly)amine bridging groups.
  • Preferred groups E are as mentioned above.
  • R 5 is hydrogen or a group of the formula 4A-OJwA-OH.
  • w is preferably O or 1 and preferred bridging groups A are as mentioned above.
  • w is O and A is 1 ,2-ethylene or 1 ,2-propylene, especially 1 ,2-ethylene.
  • v is preferably 1 , 2, 3, 4 or 5, more preferably 1 , 2 or 3.
  • B is a linear or branched C 2 -C 8 -alkylene group or a group of the formula 4E-NR 5 JvE-, wherein preferred embodiments of E and R 5 are as defined above.
  • B is a linear or branched C 2 -C 8 -alkylene group.
  • B is a linear C 2 -C 8 -alkylene group, such as 1 ,2- ethylene, 1 ,3-propylene, 1 ,4-butylene, 1 ,5-pentylene, 1 ,6-hexylene, 1 ,7-heptylene, and 1 ,8- octylene, and in particular a linear C 2 -C 6 -alkylene group, such as 1 ,2- ethylene, 1 ,3- propylene, 1 ,4-butylene, 1 ,5-pentylene and 1 ,6-hexylene.
  • B is 1 ,3- propylene.
  • R 3 and R 4 are, independently from each other, hydrogen, C 5 -C 8 - hydroxyalkyl or a group of the formula -[A-OJ x A-OH, wherein A and xand their preferred embodiments are as defined above. Particularly, both R 3 and R 4 are hydrogen.
  • R 2 HN-B-NR 3 R 4 are either diamines (in case B is not a group 4E-NR 5 JvE) or polyamines with 3 or more amino functions.
  • R 2 is H or d-C 4 -alkyl and in particular H.
  • B is a linear or branched C 2 -C 8 -alkylene group or a group of the formula 4E-NR 5 JvE-, wherein preferred embodiments of E and R 5 are as defined above.
  • B is a linear or bridged C 2 -C ⁇ -alkylene group.
  • B is a linear C 2 -C ⁇ -alkylene group, such as 1 ,2- ethylene, 1 ,3-propylene, 1 ,4-butylene, 1 ,5-pentylene, 1 ,6-hexylene, 1 ,7- heptylene, and 1 ,8-octylene, and in particular a linear C 2 -C6-alkylene group, such as 1 ,2- ethylene, 1 ,3-propylene, 1 ,4-butylene, 1 ,5-pentylene and 1 ,6-hexylene.
  • B is 1 ,3-propylene.
  • R 3 and R 4 are, independently from each other, hydrogen, Cs-C ⁇ -hydroxyalkyl or a group of the formula 4A-OJ x A-OH, wherein A and x a ⁇ nre as defined above. Particularly, both R 3 and R 4 are hydrogen. Especially, R 2 , R 3 and R 4 are hydrogen.
  • Useful amines R 2 HN-B-NR 3 R 4 are e.g. 1 ,2-ethylenediamine, diethylentriamine, triethyl- enetetramine, tetraethylenepentamine, pentaethylenehexamine, 1 ,3-propylenediamine, dipropylentriamin, tripropylenetetramine, tetrapropylenepentamine, pentapropylene- hexamine, 1 ,4-butylenediamine, dibutylenetriamine, tributylenetetramine, tetrabutyle- nepentamine, pentabutylenehexamine, 1 ,5-pentylenediamine, 1 ,6-hexylenediamine, 1 ,7-heptylenediamine, 1 ,8-octylenediamine, N-methylethylene-1 ,2-diamine, N- ethylethylene-1 ,2-d
  • Preferred amines are N-unsubstituted di- and polyamines, such as 1 ,2- ethylenediamine, diethylentriamine, triethylenetetramine, tetraethylenepentamine, pen- taethylenehexamine, 1 ,3-propylenediamine, dipropylentriamin, tripropylenetetramine, tetrapropylenepentamine, pentapropylenehexamine, 1 ,4-butylenediamine, dibuty- lenetriamine, tributylenetetramine, tetrabutylenepentamine, pentabutylenehexamine, 1 ,5-pentylenediamine, 1 ,6-hexylenediamine, 1 ,7-heptylenediamine and 1 ,8- octylenediamine.
  • More preferred amines are N-unsubstituted diamines, such as 1 ,2- ethylenediamine, 1 ,3-propylenediamine, 1 ,4-butylenediamine, 1 ,5-pentylenediamine, 1 ,6-hexylenediamine, 1 ,7-heptylenediamine and 1 ,8-octylenediamine.
  • 1 ,3- propylenediamine is used.
  • the radical R 7 is preferably hydrogen, d-C ⁇ -alkyl or C 5 -Ce- hydroxyalkyl, more preferably hydrogen or CrC 4 -alkyl and in particular CrC 4 -alkyl.
  • x, y and z are preferably 0, 1 or 2, more preferably 0 or 1 and in particular 0.
  • R 2 is H
  • B is a linear C 2 -C 6 -alkylene group, preferably a linear C 2 -C 4 -alkylene group and in particular 1 ,3-propylene
  • A is 1 ,2-ethylene or 1 ,2- propylene, especially 1 ,2-ethylene
  • x and y are 0, 1 or 2, preferably 0 or 1 and in particular 0.
  • Particularly preferred compounds (I) are compounds of formulae (l-a) and (l-b)
  • A is 1 ,2-ethylene (-(CH 2 ) 2 -) or 1 ,2-propylene (-CH 2 -CH(CH 3 )- Or -CH(CH 3 )- CH 2 -), especially 1 ,2-ethylene, and a is 2, 3, 4, 5 or 6, preferably 2, 3 or 4, more pref- erably 2 or 3 and especially 3.
  • R 2 is H
  • B is a linear C 2 -C6-alkylene group, preferably a linear C 2 -C 4 -alkylene group and in particular 1 ,3-propylene
  • R 7 is CrC 4 -alkyl
  • A is 1 ,2- ethylene or 1 ,2-propylene, especially 1 ,2-ethylene
  • z is 0, 1 or 2, preferably 0 or 1 and in particular 0.
  • compound (I) is contained in the additive composition of the invention in an amount of at least 50% by weight, more preferably at least 60% by weight, in particular at least 70% by weight, based on the total weight of compounds obtained in the method comprising steps (1 ) and (2).
  • the additive composition of the invention does essentially not contain any compounds of formula (II).
  • the term "does essentially not contain” means that the composition contains not more than 1 % by weight, preferably not more than 0.5% by weight, more preferably not more than 0.1 % by weight of compounds of formula (II), based on the total weight of compounds obtained by the method comprising reaction steps (1 ) and (2).
  • the additive composition of the invention may further contain at least one customary carrier.
  • Customary carriers comprise conventional solvents, diluents and carrier oils. Conventional solvents, diluents and carrier oils are described below.
  • the additive composition of the invention may also contain at least one conventional fuel additive. Conventional fuel additives are described below.
  • step (1 ) is generally carried out under reaction conditions well known in the art for the formation of carboxylic amides which are described, e.g., in Jerry March, Advanced Organic Chemistry, John Wiley, 3 rd edition, pages 370 ff.
  • the reaction can be carried out in the presence of a suitable solvent.
  • suitable solvents are those which do not adversely interfere with the reactants or the reaction product, e.g., aromatics, such as benzene and toluene, ethers, such as diethylether, dipro- pylether, methylbutylether, tetrahydrofurane and dioxane, and chlorinated aliphatics, such as methylene chloride, chloroform, dichloroethane and the like.
  • the amine used in step (1 ) is a liquid, the reaction is generally carried out in excess amine as solvent and without any further solvent.
  • the molar ratio of the amine NHR 2 -B-NR 3 R 4 and each carboxylic group contained in the carboxylic acid R 1 COOH or the carboxylic acid derivative thereof is 1.5:1 to 10:1 , preferably 1 :1.5 to 1 :8, more preferably 1 :2 to 1 :6 and in particular 1 :2 to 1 :5.
  • the molar ratio of the reactants shall make sure that amides are obtained as main product wherein at least one amino group derived from the amine, preferably the group NR 3 R 4 , is not bound to a carbon atom derived from the carboxylic group of the acid or acid derivative.
  • Step (1 ) is generally carried out at moderate or elevated temperatures, e.g. of from 25 to 170°C, preferably from 25 to 150°C, more preferably from 80 to 150°C.
  • moderate or elevated temperatures e.g. of from 25 to 170°C, preferably from 25 to 150°C, more preferably from 80 to 150°C.
  • both radicals R 3 and R 4 in the amine R 2 HN-B-NR 3 R 4 are C 2 -C 8 -hydroxyalkyl or a group of the formula 4A-OJ x A-OH, or at least one of the radicals R 3 and R 4 , preferably both, are hydrogen.
  • step (2) of the method of the invention is not necessary because step (1 ) already yields an N-hydroxyalkyl-substituted aminoalkyl amide, thus making step (2) superfluous.
  • the thus obtained reaction mixture is then usually freed of excess amine, for instance by distillation, preferably under reduced pressure. If any solvent (different from excess amine) is present, this may be removed, too, e.g. by dis- tillation, preferably under reduced pressure. However it is preferred not to remove the solvent, but to use the reaction mixture as obtained.
  • the reaction mixture contains as main product one or more compounds of formula (I) and may further contain smaller amounts of secondary products such as (II).
  • the reaction mixture may be purified, e.g. in order to obtain pure compound (I) or compound (I) with minor amounts of secondary products and/or impurities, or the reaction product may be used as such. Preferably, the reaction product is used as such.
  • step (2) is carried out.
  • step (2) Preferably, excess amine is removed before the reaction product of step (1 ) is introduced in step (2).
  • the reaction product may be purified further; however usually it is introduced without further purification or isolation into step (2).
  • Preferred alkylene oxides are ethylene oxide and propylene oxide, i.e. R 6 is preferably H or methyl. In particular, ethylene oxide is used.
  • the amount of alkylene oxide used in step (2) is dependent from the number "n" of hydrogen atoms bound to basic nitrogen atoms in the amide formed in step (1 ) (i.e. the hydrogen atom bound to the amide-N is not counted).
  • the amount of alkylene oxide used in step (2) is further based on the hypothesis that each carboxylic group contained in the carboxylic acid (derivative) introduced in step (1 ) has reacted with one amine to give an amide.
  • the molar ratio of alkylene oxide per each hydrogen atom bound to nitrogen atoms contained in the moieties B and NR 3 R 4 of the amine NHR 2 -B-NR 3 R 4 is 1 :1 to 4:1 , preferably 1 :1 to 2:1 , in particular 1 :1 to 1.5:1 and especially approximately 1 :1.
  • the alkylene oxide is introduced in an amount of (1 x n) to (4 x n) moles, preferably (1 x n) to (2 x n) moles, more preferably (1 x n) to (1.5 x n) moles and in particular about (1 x n) moles per mole of carboxylic groups contained in the carboxylic acid (derivative) introduced in step (1 ).
  • the amount of alkylene oxide shall make sure that all groups NR 3 R 4 contained in the reaction product of step (1 ) are converted into bis(hydroxyalkylamino) groups.
  • the reaction of step (2) is carried out at elevated temperatures, preferably of from 40°C to 200°C, more preferably from 60°C to 170°C and in particular from 100°C to 170°C.
  • the solvent if any present, may be removed, e.g. by distillation, preferably under reduced pressure. However it is preferred not to remove the solvent, but to use the reaction mixture as obtained. Excess amine is preferably removed after the completion of step (1 ), as already mentioned. In case there is still some excess amine present, this is prefarbly removed after the completion of step (2).
  • the obtained reaction mixture generally contains as main product one or more compounds of formula (I) and may also contain smaller amounts of secondary products such as compounds of formula (II). Further possible secondary products are compounds of formulae (III) and (IV):
  • R , R and B are as defined above;
  • R 8 is hydrogen, d-C ⁇ -alkyl, Ca-C ⁇ -hydroxyalkyl or a group of the formula -[A-0]wA-0H, wherein A and w are as defined above.
  • R 1 , R 2 and B are as defined above.
  • R 8 is a group of the formula 4A-OJwA-OH. More preferably, R 8 is a group of the formula 4A-OJwA-OH, wherein A is C 2 -C 4 -alkylene, in particular C 2 -C 3 -alkylene and especially 12-ethylene. In an even more preferred embodiment, w is O.
  • the reaction product can be used as such or may be purified, e.g. in order to obtain pure compound (I) or compound (I) with minor amounts of secondary products and/or impurities.
  • the reaction product is used as such.
  • compound (I) is contained in the additive composition of the invention in an amount of at least 50% by weight, more preferably at least 60% by weight, in particular at least 70% by weight, based on the total weight of compounds obtained in the method comprising steps (1 ) and (2) (however freed of excess amine and solvent, if any present).
  • compound (I) is contained in the additive composition of the invention in an amount of preferably at least 50% by weight, more preferably at least 60% by weight, in particular at least 70% by weight, based on the total weight of compounds (I), (II), (III) and (IV).
  • the additive composition of the invention does essentially not contain any compounds of formula (II).
  • the term "does essentially not contain” means that the composition contains not more than 1 % by weight, preferably not more than 0.5% by weight, more preferably not more than 0.1 % by weight of compounds of formula (II), based on the total weight of compounds obtained by the method comprising reaction steps (1 ) and (2) (however freed of excess amine and solvent, if any present) or alternatively based on the total weight of compounds (I), (II), (III) and (IV).
  • the compound of formula (III) is contained in the additive composition of the invention in an amount of not more than 5% by weight, more preferably not more than 2% by weight, in particular not more than 1 % by weight, based on the total weight of the reaction product obtained in steps (1 ) and (2) of the above method (however freed of excess amine and solvent, if any present).
  • the compound of formula (III) is contained in the additive composition of the invention in an amount of not more than 5% by weight, more preferably not more than 2% by weight, in particular not more than 1 % by weight, based on the total weight of the reaction product obtained in steps (1 ) and (2) of the above method (however freed of excess amine and solvent, if any present).
  • the compound of formula (III) is contained in the additive composition of the invention in an amount of not more than 5% by weight, more preferably not more than 2% by weight, in particular not more than 1 % by weight, based on the total weight of the reaction product obtained in steps (1 ) and (2) of the above method
  • (III) is contained in the additive composition of the invention in an amount of not more than 5% by weight, more preferably not more than 2% by weight, in particular not more than 1 % by weight, based on the total weight of compounds (I), (II), (III) and (IV).
  • the compound of formula (IV) is contained in the additive composition of the invention in an amount of not more than 5% by weight, more preferably not more than 2% by weight, in particular not more than 1 % by weight, based on the total weight of the reaction product obtained in steps (1 ) and (2) of the above method (however freed of excess amine and solvent, if any present).
  • the compound of formula (IV) is contained in the additive composition of the invention in an amount of not more than 5% by weight, more preferably not more than 2% by weight, in particular not more than 1 % by weight, based on the total weight of the reaction product obtained in steps (1 ) and (2) of the above method (however freed of excess amine and solvent, if any present).
  • the compound of formula (IV) is contained in the additive composition of the invention in an amount of not more than 5% by weight, more preferably not more than 2% by weight, in particular not more than 1 % by weight, based on the total weight of the reaction product obtained in steps (1 ) and (2) of the above method
  • (IV) is contained in the additive composition of the invention in an amount of not more than 5% by weight, more preferably not more than 2% by weight, in particular not more than 1 % by weight, based on the total weight of compounds (I), (II), (III) and (IV).
  • the reaction product obtained by said method can be one or more compounds of formula (I) or can be a complex mixture which may contain, besides compound (I), compounds (II), (III) and/or (IV), and also further components such as unreacted acid or acid derivative, unreacted amine, hydroxyalkylated amine and more.
  • the additive composition obtainable by the above method may further contain customary carriers and/or at least one further conventional fuel additive. Customary carriers and additional additives are described below.
  • the invention is further related to a method for producing the additive composition of the invention, which method comprises the steps of
  • R 6 is H, methyl or ethyl.
  • the invention is related to the use of the compound of the formula (I) alone or of the additive composition of the invention as friction modifying agent in a fuel.
  • the fuel is additized with the compound of formula (I) or with the additive composition in an amount of from 10 to 300, more preferably from 20 to 200, in particular from 25 to 150 mg per kg of the fuel.
  • the compound of formula (I) or the additive composition can be used in the fuel in combination with at least one further conventional fuel additive.
  • Conventional fuel addtives are, e.g., detergent additives, carrier oils, corrosion inhibitors, antioxidants, antistatics, markers, etc., and mixtures thereof.
  • Additives having a detergent action or an anti-valve-seat-wear action are e.g. compounds which contain at least one hydrophobic hydrocarbon group 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 group in the additives which provides sufficient solubility in the fuel, has a number-average molecular weight (M n ) of from 85 to 20,000, preferably from 113 to 10,000 and more preferably from 300 to 5000.
  • Typical hydrophobic hydrocarbon groups, particularly in conjunction with the polar groups (a), (c), (h) and (i), are polypropenyl, polybutenyl and polyisobutenyl radicals having molecular weights M n of from 300 to 5000, preferably from 500 to 2500 and more preferably from 750 to 2250.
  • Additives containing monoamino or polyamino groups are preferably polyalkene monoamines or polyalkene polyamines based on polypropylene or highly reactive (ie containing predominantly terminal double bonds - mostly in the ⁇ -and ⁇ -positions) or conventional (ie containing predominantly centered double bonds) polybutylene or polyisobutylene having a molecular weight M n of from 300 to 5000.
  • Such additives based on highly reactive polyisobutylene which can be prepared from the polyisobutylene containing up to 20 wt% of n-butylene units, by hydroformylation and reductive amination with ammonia, monoamines or polyamines such as dimethylaminopro- pylamine, ethylenediamine, diethylenetriamine, triethylenetetramine or tetrethylenepen- tamine, are disclosed, in particular, in EP-A 244,616.
  • the synthesis of the additives is based on polybutylene or polyisobutylene having predominantly centered double bonds (mostly in the ⁇ and y positions) as starting materials, an obvious choice is the synthesis method involving chlorination and subsequent amination, or oxidation of the double bond with air or ozone to form the carbonyl or carboxyl compound, with subsequent amination under reductive (hydrogenating) conditions.
  • This amination may be carried out using the same amines as mentioned above for the reductive amination of hydro- formylated, highly reactive polyisobutylene.
  • Corresponding additives based on polypropylene are described, in particular, in WO-A 94/24231.
  • additives containing monoamino groups (a) are the hydrogenation products of the reaction products of polyisobutylenes having an average degree of polymerization P of from 5 to 100 with nitrogen oxides or mixtures of nitrogen oxides and oxygen, as described, in particular, in WO-A 97/03946.
  • additives containing monoamino groups (a) are the compounds produced from polyisobutylene epoxides by reaction with amines followed by dehydration and reduction of the amino alcohols, as described, in particular, in DE-A 196 20 262.
  • Additives containing nitro groups, optionally combined with hydroxyl groups (b), are preferably reaction products of polyisobutylenes having an average degree of polymerization P of from 5 to 100 or from 10 to 100 with nitrogen oxides or mixtures of nitrogen oxides and oxygen, as described, in particular, in WO-A 96/03367 and WO-A 96/03479. These reaction products are usually mixtures of pure nitropolyisobutanes (eg ⁇ , ⁇ -dinitropolyisobutane) and mixed hydroxynitropolyisobutanes (eg ⁇ -nitro- ⁇ - hydroxypolyisobutane).
  • Additives containing hydroxyl groups combined with monoamino or polyamino groups (c) are in particular reaction products of polyisobutylene epoxides, obtainable from polyisobutylene preferably containing predominantly terminal double bonds and having a molecular weight M n of from 300 to 5000, with ammonia or mono- or polyamines, as described, in particular, in EP-A 476,485.
  • Additives containing carboxylic acid groups or the alkali metal or alkaline earth metal salts thereof (d) are preferably copolymers of C 2 -C 4 0 olefins with maleic anhydride having a total molecular weight of from 500 to 20,000 whose carboxylic acid groups have been converted entirely or partially to the alkali metal or alkaline earth metal salts and the remainder of the carboxylic acid groups has been caused to react with alcohols or amines.
  • Such additives are disclosed, in particular, in EP-A 307,815. Said additives mainly serve to prevent valve seat wear and can be used, as described in WO-A 87/01 126, with advantage combined with conventional fuel detergents such as poly(iso)butylene amines or polyether amines.
  • Additives containing sulfo groups or the alkali metal or alkaline earth metal salts thereof are preferably alkali metal or alkaline earth metal salts of an alkyl sulfosuccinate, as described, in particular, in EP-A 639,632.
  • Such additives mainly serve to prevent valve seat wear and can be used with advantage combined with conventional fuel detergents such as poly(iso)butylene amines or polyether amines.
  • Additives containing polyoxy-(C 2 -C 4 alkylene) groups (f) are preferably polyethers or polyether amines, which are obtained by reaction of C 2 -C6o alkanols, C6-C 3 o al- kanediols, mono- or di-(C 2 -C 3 o alkyl)amines, (CrC 3 o alkyl)cyclohexanols or (CrC 30 al- kyl)phenols with from 1 to 30 mol of ethylene oxide and/or propylene oxide and/or buty- lene oxide per hydroxyl group or amino group and, in the case of polyether amines, by subsequent reductive amination with ammonia, monoamines or polyamines.
  • Such products are described, in particular, in EP-A 310,875, EP-A 356,725, EP-A 700,985 and US-A 4,877,416.
  • polyethers such products also have flotation oil characteristics.
  • Typical examples thereof are tridecanol butoxylates or isotridecanol butoxy- lates, isononylphenol butoxylates, polyisobutenol butoxylates and polyisobutenol pro- poxylates and the corresponding reaction products with ammonia.
  • Additives containing carboxylate groups (g) are preferably esters of mono-, di- or tricarboxylic acids with long-chain alkanols or polyols, in particular those having a mini- mum viscosity of 2 mm 2 /s at 100°C, as described, in particular, in DE-A 3,838,918.
  • the mono-, di- or tri-carboxylic acids used can be aliphatic or aromatic acids, and suitable ester alcohols or ester polyols are primarily long-chain representatives containing, for example, from 6 to 24 carbon atoms.
  • esters are adi- pates, phthalates, isophthalates, terephthalates and trimellitates of isooctanol, isonon- anol, isodecanol and isotridecanol. Such products also have flotation oil characteristics.
  • Additives containing groups derived from succinic anhydride and containing hydroxyl and/or amino and/or amido and/or imido groups (h) are preferably corresponding derivatives of polyisobutenyl succinic anhydride, which are obtained by reaction of con- ventional or highly reactive polyisobutylene having a molecular weight M n of from 300 to 5000 with maleic anhydride by thermal treatment or via chlorinated polyisobutylene.
  • derivatives with aliphatic polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine or tetrethylenepentamine.
  • Such fuel additives are described, in particular, in US-A 4,849,572.
  • Additives containing groups (i) produced by Mannich reaction of substituted phenols with aldehydes and mono- or poly-amines are preferably reaction products of polyiso- butylene-substituted phenols with formaldehyde and mono- or polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetrethylenepentamine or dimethylaminopropylamine.
  • the polyisobutenyl-substituted phenols can be derived from conventional or highly reactive polyisobutylene having a molecular weight M n of from 300 to 5000.
  • Such "polyisobutylene Mannich bases” are described, in particular, in EP-A 831 ,141.
  • mineral carrier oils examples include mineral carrier oils (base oils) and synthetic carrier oils.
  • suitable mineral carrier oils are in particular those of viscosity class Solvent Neutral (SN) 500 to 2000, as well as aromatic and paraffinic hydrocarbons and alkoxyalkanols.
  • Another useful mineral carrier oil is a fraction known as "hydrocrack oil” which is obtained from refined mineral oil (boiling point of approximately 360 to 500°C; obtainable from natural mineral oil which is isomerized, freed of paraffin components and catalytically hydrogenated under high pressure).
  • suitable polyethers or polyether amines are compounds containing poly- oxy-C 2 -C 4 -alkylene groups which can be obtained by reacting C 2 -C 6 o-alkanols, C 6 -C 30 - alkandiols, mono- or di-C 2 -C 30 -alkylamines, CrC 30 -alkylcyclohexanols oder CrC 30 - alkylphenols with 1 to 30 mol ethylene oxide and/or propylene oxide and/or butylene oxide per hydroxyl group or amino group and in case of the polyether amine by subsequent reductive amination with ammonia, monoamines or polyamines.
  • polyetheramines can be used, for instance, poly-C 2 -C6- alkylenoxide amines or functional derivatives thereof.
  • suitable polyethers or polyether amines are tridecanol butoxylates and isotridecanol butoxy- lates, isononylphenol butoxylates and polyisobutenol butoxylates and propoxylates as well as the corresponding reaction products with ammonia.
  • carboxylic esters of long-chain alkanols are esters of mono-, di- and tricarboxylic acids with long-chain alkanols or polyhydric alcohols such as described e.g. in DE-A-3838918.
  • Suitable mono-, di- and tricarboxylic acids are aliphatic or aromatic carboxylic acids.
  • Suitable alkanols and polyhydric alcohols contain 6 to 24 carbon atoms.
  • Typical examples of such esters are the adipates, phthalates, iso-phthalates, terephthalates and trimellitates of isooctanol, isononanol, isodecanol and isotridecanol, e.g. di-n-tridecyl phthalate or di-iso-tridecyl phthalate.
  • Examples for particularly useful synthetic carrier oils are alcohol-initiated polyethers containing about 5 to 35, e.g. 5 to 30 C 3 -C6-alkylenoxide units, such as propylenoxide, n-butylenoxide and i-butylenoxide units or mixtures thereof.
  • Non-limiting examples for alcoholic starters are long-chain alkanols or phenols substituted by long-chain alkyl groups, where the alkyl group preferably is linear or branched C 6 -Ci 8 -alkyl.
  • Preferred examples for the alcoholic starters are tridecanol and nonylphenol.
  • suitable synthetic carrier oils are alkoxylated alkylphenols, such as described e.g. in DE-A-10 102 913.6.
  • synthetic carrier oils are used.
  • Preferred synthetic carrier oils are alkanol alkoxylates, in particular alkanol propoxylates and alkanol butoxylates.
  • corrosion inhibitors for example based on ammonium salts of organic carboxylic acids, which salts tend to form films, or on heterocyclic aromatics in the case of corrosion protection of nonferrous metals, antioxidants or stabilizers, for example based on amines, such as p-phenylenediamine, dicyclohexylamine or derivatives thereof and on phenols, such as 2,4-di-tert- butylphenol or 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid, dehazers, demulsifiers, antistatic agents, metallocenes such as ferrocene or methylcyclopentadienyl manga- nese tricarbonyl, lubricity additives (different from compound (I)), such as certain fatty acids, alkenylsuccinic esters, bis(hydroxyalkyl)fatty amines, hydroxyacetamides and castor oil, antiknock additives, anti-icing additives,
  • the invention is also related to a fuel composition containing a fuel as major component and at least one compound of the formula (I) alone or the additive composition of the invention and optionally at least one further additive.
  • Suitable additional additives are those listed above.
  • Suitable fuels are middle distillates and gasolines.
  • Suitable middle distillates are e.g. diesel fuel, kerosene and heating oil.
  • gasoline includes blends of distillate hydrocarbon fuels with oxygenated compounds such as ethanol, as well as the distillate fuels themselves.
  • Suitable gasolines are e.g. those described in Ullmann's Encyclopedia of Industrial Chemistry, 5 th edition, 1990, volume A16, page 719 ff.
  • Suitable gasolines are e.g. those having an aromatics content of not more than 60% by volume, e.g. not more than 42% by volume or not more than 35% by volume and/or a sulfur content of not more than 2000 ppm by weight, e.g. not more than 150 ppm by weight or not more than 10 ppm by weight.
  • the aromatics content of the gasoline is e.g. from 10 to 50% by volume, e.g. from 30 to 42% by volume, in particular from 32 to 40% by volume or not more than 35% by volume.
  • the sulfur content is e.g. of from 2 to 500 ppm by weight, e.g. of from 5 to 100 or not more than 10 ppm by weight.
  • the olefin content of the gasoline can be up to 50% by volume, e.g. from 6 to 21 % by volume, in particular from 7 to 18% by volume.
  • the gasoline has a benzene content of not more than 5% by volume, e.g. from 0.5 to 1.0% by volume, in particular from 0.6 to 0.9% by volume.
  • the gasoline has an oxygen content of not more than 25% by weight, e.g. up to 10% by weight or from 1.0 to 2.7% by weight, and in particu- lar from 1.2 to 2.0% by weight.
  • a gasoline which has an aromatics content of not more than 38% by volume or preferably not more than 35% by volume, and at the same time an olefin content of not more than 21 % by volume, a sulfur content of not more than 50 or 10 ppm by weight, a benzene content of not more than 1.0% by volume and an oxygen content of from 1.0 to 2.7% by weight.
  • the amount of alcohols and ethers contained in the gasoline may vary over wide ranges. Typical maximum contents are e.g. methanol 15% by volume, ethanol 65% by volume, isopropanol 20% by volume, tert-butanol 15% by volume, isobutanol 20% by volume and ethers containing 5 or more carbon atoms in the molecule 30% by volume.
  • the summer vapor pressure of the gasoline (at 37°C) is usually not more than 7OkPa, in particular not more than 6OkPa.
  • the research octane number (RON) of the gasoline is usually from 75 to 105.
  • a usual range for the corresponding motor octane number (MON) is from 65 to 95.
  • the invention is related to an additive concentrate, comprising at least one compound of the formula (I) or the additive composition of the invention and at least one diluent or a solvent and/or at least one further additive.
  • Suitable additional additives are those mentioned above.
  • Suitable diluents and solvents are e.g. aromatic and aliphatic hydrocarbons, such as benzene, toluene, the xylenes, solvent naphtha, alkanols with 3 to 8 carbon atoms, e.g. propanol, isopropanol, n-butanol, sec-butanol, isobutanol and the like, in combination with hydrocarbon solvents, and alkoxyalkanols.
  • the compound(s) of formula (I) or the additive composition of the invention are preferably present in the concentrates in an amount of from 0.1 to 80% by weight, more preferably from 1 to 70% by weight and in particular from 5 to 60% by weight, based on the total weight of the concentrate.
  • the invention is related to a method for producing a fuel composition with improved friction properties, where a fuel or a commercial fuel composition is additized with at least one compound of the formula (I) as defined above or with the additive composition of the invention or with the additive concentrate as defined above.
  • the compound(s) of formula (I) or the additive composition of the invention and optionally said additional additives are metered into the fuel or fuel composition, where they become effective.
  • the compounds (I) or the additive composition of the invention and optionally the additional additives can be added to the fuel or to the fuel composition individually or as a previously prepared concentrate (additive package).
  • the compounds of formula (I) exhibit, in addition to their good friction modifying characteristics, a good compatibility with other additives and solvents in the concentrates and a good solubility in the fuel. Moreover, they do not adversely affect the properties of other additives present in the fuel or in the concentrate. Furthermore, they exhibit an additional corrosion protection for metals, especially for aluminium, magnesium, tin, lead, copper, iron, zinc, chromium, manganese and silver, and for alloys containing at least one of these metals.
  • HFFR-test - a High Frequency Reciprocating Rig (HFFR)-test - a standard procedure for evaluating diesel fuel lubricity - was carried out using a HFFR-apparatus from PCS instruments, London.
  • the test conditions (according to CEC F-06-A-96) were modified to suit the use of gasolines (temperature: 25°C; load: 720 g).
  • the applicability of the HFFR-test to gasolines is proved by D. Margaroni, Industrial Lubrication and Tribology, Vol. 50, No. 3, May/June 1998, pp. 108-1 18, and W. D. Ping, S. Korcek, H. Spikes, SAE Techn. Paper 962010, pp. 51-59 (1996).
  • the gasolines Prior to testing, the gasolines (gasolines according to EN 228) were gently concentrated to 50 vol.-% using the distillation apparatus MP 628 from Herzog, Lauda- Konigshofen, Germany.
  • the lubricity of the unadditized concentrated gasoline was tested according to the above-described HFFR-test and compared with the lubricity observed when the concentrated gasoline was additized as shown in table 1.
  • the resulting wear scar diameters are also listed in table 1. The lower the value of the wear scar diameter, the better the performance of the additive in the fuel composition.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne des aminoalkylamides d'acides gras à substitution hydroxyalkyle qui sont utilisés en tant que modificateurs de friction pour carburants.
PCT/EP2006/066623 2005-09-23 2006-09-22 Aminoalkylamides d'acides gras a substitution hydroxyalkyle utilises en tant que modificateurs de friction WO2007039488A1 (fr)

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US71956905P 2005-09-23 2005-09-23
US60/719,569 2005-09-23

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010091069A1 (fr) 2009-02-05 2010-08-12 Butamax™ Advanced Biofuels LLC Compositions d'additif de régulation du dépôt d'essence

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US2267965A (en) * 1939-07-18 1941-12-30 Carbide & Carbon Chem Corp Hydroxyalkyl glyoxalidines
US2609931A (en) * 1948-04-17 1952-09-09 Fram Corp Method of filtering
US2681354A (en) * 1950-09-02 1954-06-15 Nopco Chem Co Condensation of ethylene oxide with amino substituted amides
US2854324A (en) * 1955-11-09 1958-09-30 Petrolite Corp Fuel oil composition
GB1112754A (en) * 1965-03-22 1968-05-08 Armour & Co Novel amino amides and their use in hydrocarbon fuels
US3449095A (en) * 1967-12-22 1969-06-10 Ethyl Corp Gasoline compositions
US3468639A (en) * 1965-08-06 1969-09-23 Chevron Res Gasolines containing deposit-reducing monoamides of polyamines characterized by improved water tolerance
EP0180910A2 (fr) * 1984-11-02 1986-05-14 Phillips Petroleum Company Produits de réactions d'amidoamines et d'époxydes utilisables comme additifs pour combustibles
JPS6465191A (en) * 1987-09-04 1989-03-10 Dai Ichi Kogyo Seiyaku Co Ltd Additive for long-life, high-concentration coal-water slurry
EP0773278A1 (fr) * 1995-11-13 1997-05-14 Ethyl Petroleum Additives Limited Additif pour combustible
WO2001038463A1 (fr) * 1999-11-19 2001-05-31 Basf Aktiengesellschaft Utilisation de sels d'acide gras d'oligoamines alcoxylees comme agents ameliorants du pouvoir lubrifiant de produits petroliers
US6835217B1 (en) * 2000-09-20 2004-12-28 Texaco, Inc. Fuel composition containing friction modifier

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2267965A (en) * 1939-07-18 1941-12-30 Carbide & Carbon Chem Corp Hydroxyalkyl glyoxalidines
US2609931A (en) * 1948-04-17 1952-09-09 Fram Corp Method of filtering
US2681354A (en) * 1950-09-02 1954-06-15 Nopco Chem Co Condensation of ethylene oxide with amino substituted amides
US2854324A (en) * 1955-11-09 1958-09-30 Petrolite Corp Fuel oil composition
GB1112754A (en) * 1965-03-22 1968-05-08 Armour & Co Novel amino amides and their use in hydrocarbon fuels
US3468639A (en) * 1965-08-06 1969-09-23 Chevron Res Gasolines containing deposit-reducing monoamides of polyamines characterized by improved water tolerance
US3449095A (en) * 1967-12-22 1969-06-10 Ethyl Corp Gasoline compositions
EP0180910A2 (fr) * 1984-11-02 1986-05-14 Phillips Petroleum Company Produits de réactions d'amidoamines et d'époxydes utilisables comme additifs pour combustibles
JPS6465191A (en) * 1987-09-04 1989-03-10 Dai Ichi Kogyo Seiyaku Co Ltd Additive for long-life, high-concentration coal-water slurry
EP0773278A1 (fr) * 1995-11-13 1997-05-14 Ethyl Petroleum Additives Limited Additif pour combustible
WO2001038463A1 (fr) * 1999-11-19 2001-05-31 Basf Aktiengesellschaft Utilisation de sels d'acide gras d'oligoamines alcoxylees comme agents ameliorants du pouvoir lubrifiant de produits petroliers
US6835217B1 (en) * 2000-09-20 2004-12-28 Texaco, Inc. Fuel composition containing friction modifier

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Title
DATABASE WPI Week 198916, Derwent World Patents Index; AN 1989-118957, XP002418646 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010091069A1 (fr) 2009-02-05 2010-08-12 Butamax™ Advanced Biofuels LLC Compositions d'additif de régulation du dépôt d'essence
US8465560B1 (en) 2009-02-05 2013-06-18 Butamax Advanced Biofuels Llc Gasoline deposit control additive composition

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