WO2017144376A1 - Acide polycarboxylique, substitué par l'oxyde d'alkylène et par un groupe hydrocarbyle, de composés azotés quaternisés utilisé comme additif réducteur d'usure par frottement dans des carburants - Google Patents

Acide polycarboxylique, substitué par l'oxyde d'alkylène et par un groupe hydrocarbyle, de composés azotés quaternisés utilisé comme additif réducteur d'usure par frottement dans des carburants Download PDF

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Publication number
WO2017144376A1
WO2017144376A1 PCT/EP2017/053691 EP2017053691W WO2017144376A1 WO 2017144376 A1 WO2017144376 A1 WO 2017144376A1 EP 2017053691 W EP2017053691 W EP 2017053691W WO 2017144376 A1 WO2017144376 A1 WO 2017144376A1
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acid
hydrocarbyl
substituted
quaternizable
alkyl
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PCT/EP2017/053691
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German (de)
English (en)
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Jochen Mezger
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Basf Se
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Priority to EP17706219.7A priority Critical patent/EP3420053A1/fr
Publication of WO2017144376A1 publication Critical patent/WO2017144376A1/fr

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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
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    • C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
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    • 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
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    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
    • C10L1/2225—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates hydroxy containing
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    • 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
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    • 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)
    • C10L1/2387—Polyoxyalkyleneamines (poly)oxyalkylene amines and derivatives thereof (substituted by a macromolecular group containing 30C)
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    • 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
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Definitions

  • alkylene oxide and hydrocarbyl-substituted polycarboxylic acid quaternized nitrogen compounds as Reibverschl admiration-reducing additive to fuels
  • the present invention relates to the use of at least one alkylene oxide and hydrocarbyl-substituted polycarboxylic acid quaternized nitrogen compounds as friction wear-reducing additive in fuel compositions; correspondingly additized fuel compositions and their preparation; and additive concentrates comprising such compounds.
  • Carburettors and intake systems of gasoline engines are heavily loaded by impurities caused by dust particles from the air, unburned hydrocarbon residues from the combustion chamber and the crankcase ventilation gases fed into the gasifier. These residues shift the air-fuel ratio at idle and in the lower part-load range, so that the mixture becomes leaner, the combustion becomes more incomplete and thus the proportion of unburned or partially combusted hydrocarbons in the exhaust gas increases. Increasing gasoline consumption is the result.
  • detergents are often used as surface-active additives, some of which are also suitable for use as detergents in fuel compositions.
  • Such detergents which can originate from a large number of chemical substance classes, such as, for example, polyalkeneamines, polyetheramines, polybutene-Mannich bases or polybutene-succinimides, are generally obtained in combination with carrier oils and, if appropriate, further additive components, such as e.g. Corrosion inhibitors and demulsifiers, for use.
  • Gasoline fuels with and without such gasoline additives show a different behavior with regard to their lubricating properties in gasoline engines, which however is unsatisfactory and should therefore be improved.
  • fuel additives are known as components for improving the lubricity of fuels.
  • fatty acids and derivatives thereof EP-A-780 460, EP-A-829 527
  • alkenyl succinic acid ester WO 97/45507
  • bis (hydroxyalkyl) fatty amine EP-A-869 163
  • Hydroxyacetamides WO 98/30658, US Pat. No. 5,756,435
  • castor oil It is also known with castor oil that its addition to diesel fuels (EP-A-605 857) and / or gasoline fuels (US Pat. No. 5,505,867) can increase the lubricity.
  • Quadraturear nitrogen groups or amino groups include in particular primary, secondary and, above all, tertiary amino groups.
  • Hydrocarbyl is to be construed broadly and includes both long-chain and short-chain, straight or branched hydrocarbon radicals having 1 to 50 carbon atoms, which may additionally contain heteroatoms, such as. O, N, NH, S, may be included in their chain.
  • preferred hydrocarbyl radicals are hydrocarbon radicals.
  • a particular group of hydrocarbyl radicals includes both long and short chain, straight chain or branched alkyl radicals having 1 to 1000, 3 to 500, 4 to 400 carbon atoms.
  • “Long-chain” or “high molecular weight” hydrocarbyl radicals are straight-chain or branched hydrocarbon radicals and have 7 to 50 or 8 to 50 or 8 to 40 or 10 to 20 carbon atoms, which may additionally contain heteroatoms, such as O, N, NH, S, in can contain their chain.
  • the radicals may be mono- or polyunsaturated and one or more non-cumulated, such as 1 to 5, such as 1, 2 or 3 CC double bonds or C-C triple bonds, in particular 1, 2 or 3 double bonds, have. They can be natural or synthetic.
  • M n number-average molecular weight
  • M n number-average molecular weight
  • they are composed essentially of C 2-6, in particular C 2-4, monomer units such as ethylene, propylene, n- or isobutylene or mixtures thereof, it being possible for the various monomers to be randomly distributed or incorporated in polymerized form as blocks.
  • Such long-chain hydrocarbyl radicals are also referred to as polyalkylene radicals or poly-C2-6 or poly-C2-4-alkylene radicals.
  • Suitable long-chain hydrocarbyl radicals and their preparation are also described, for example, in WO2006 / 135881 and the literature cited therein.
  • particularly useful polyalkylene radicals are polyisobutenyl radicals derived from so-called "highly reactive" polyisobutenes, which are distinguished by a high content of terminal double bonds. Terminal arranged double bonds are alpha-olefinic double bonds of the type
  • Suitable highly reactive polyisobutenes are, for example, polyisobutenes which have a proportion of vinylidene double bonds of greater than 70 mol%, in particular greater than 80 mol% or greater than 85 mol%. Particular preference is given to polyisobutenes which have uniform polymer skeletons. Uniform polymer skeletons have, in particular, those polyisobutenes which are composed of at least 85% by weight, preferably at least 90% by weight and more preferably at least 95% by weight, of isobutene units. Such highly reactive polyisobutenes preferably have a number-average molecular weight in the abovementioned range.
  • the highly reactive polyisobutenes can have a polydispersity in the range from 1:05 to 7, in particular from about 1, 1 to 2.5, for example of less than 1, 9 or less than 1.5.
  • polydispersity is meant the quotient of weight average molecular weight Mw divided by the number average molecular weight Mn.
  • number-average molecular weights can be adjusted in a manner known in principle by mixing polyisobutenes of different number-average molecular weights or by extractive enrichment of polyisobutenes of defined molecular weight ranges.
  • a specific group of long-chain hydrocarbyl radicals includes straight-chain or branched alkyl radicals ("long-chain" alkyl radicals) having 8 to 50, such as 8 to 40 or 8 to 30 or 10 to 20 carbon atoms.
  • Another group of special long-chain hydrocarbyl radicals comprises polyalkylene radicals which are in particular composed essentially of C 2 - 6, in particular C 2-4 monomer units, such as ethylene, propylene, n- or isobutylene or mixtures thereof and have a degree of polymerization of from 2 to 100, or "3 to 50 or 4 to 25.”
  • Short-chainhydrocarbyl or “low-molecular hydrocarbyl” in particular represents straight-chain or branched alkyl or alkenyl, optionally interrupted by one or more, such as, for example, 2, 3 or 4 heteroatom groups, such as -O- or -NH-, or optionally mono- or polysubstituted, for example 2, 3 or 4-times.
  • Hydrocarbon represents straight-chain or mono- or polysubstituted bridging groups having 1 to 10 carbon atoms, optionally interrupted by one or more, such as 2, 3 or 4 heteroatom groups, such as -O- or -NH-. or optionally mono- or polysubstituted, such as 2, 3 or 4-times substituted.
  • Alkyl or “lower alkyl” in particular represents saturated, straight-chain or branched hydrocarbon radicals having 1 to 4, 1 to 5, 1 to 6, or 1 to 7, carbon atoms, such as.
  • Alkenyl is mono- or polysubstituted, especially monounsaturated, straight-chain or branched hydrocarbon radicals having 2 to 4, 2 to 6, or 2 to 7 carbon atoms and a double bond in any position, for.
  • C2-C6 alkenyl such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3 Methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl 3-
  • Haldroxyalkenyl stands in particular for the mono- or polysubstituted, in particular simply hydroxylated, analogs of the above alkenyl radicals
  • Aryl is mononuclear or polynuclear, preferably mono- or binuclear, optionally substituted aromatic radicals having 6 to 20, such as 6 to 10 ring carbon atoms, such as phenyl, biphenyl, naphthyl, such as 1- or 2-naphthyl, tetrahydronaphthyl, Fluorenyl, indenyl and phenanthrenyl. These aryl radicals may optionally carry 1, 2, 3, 4, 5 or 6 identical or different substituents.
  • the quaternized nitrogen compounds to be used in the present invention are at least one reaction product comprising a quaternized nitrogen compound or a partial fraction thereof containing a quaternized nitrogen compound purified by the reaction product, the reaction product being obtainable by reacting a quaternizable nitrogen compound, such as e.g. a quaternizable alkylamine containing at least one quaternizable, in particular tertiary, amino group with a quaternizing agent which converts the at least one quaternizable, especially tertiary, amino group into a quaternary ammonium group, the quaternizing agent being a hydrocarbyl epoxide in combination with a free hydrocarbyl substituted polycarboxylic acid ,
  • a quaternizable nitrogen compound such as e.g. a quaternizable alkylamine containing at least one quaternizable, in particular tertiary, amino group
  • a quaternizing agent which converts the
  • the quaternizable tertiary amine is a compound of formula (3) wherein at least two of R a , R b and R c are the same or different and are straight or branched C 10 -C 20 alkyl and the rest of the radical is C 1 -C 4 -alkyl.
  • the quaternizing agent comprises an epoxide of the general formula (4) in which
  • radicals Rd contained therein are identical or different and stand for H or for a Hydrocarbylrest, wherein the hydrocarbyl radical is an aliphatic or aromatic radical having at least 1 to 10 carbon atoms.
  • the hydrocarbyl substituent of this carboxylic acid is a polyalkylene radical having a degree of polymerization of 2 to 100, or 3 to 50 or 4 to 25.
  • Tertiary amines are especially compounds of the above formula (3) and are compounds known per se, such as e.g. described in EP-A-2 033 945.
  • the segment NR a Rb is derived from a secondary amine, such as dioctadecylamine, di-cocoamine, dihydrogenated tallowamine and methylbehenylamine.
  • Amine compounds such as those available from natural materials, are also suitable.
  • mention may be made of a secondary hydrogenated tallow amine wherein the alkyl groups are derived from hydrogenated tallow fat and about 4 wt .-% of Ci 4 , 31 wt .-% Ci6 and 59 wt .-% cis-alkyl groups have.
  • the tertiary amine starting material (3) can also be formed such that the radicals R a , Rb and R c are identical or different short-chain alkyl radicals, in particular straight-chain or branched alkyl groups having 1 to 7 or in particular 1 to 4 carbon atoms.
  • the polyether-substituted amine may have a number average molecular weight in the range of 500 to 5000, in particular 800 to 3000 or 900 to 1500.
  • the quaternizable, polyether-substituted amines are in particular nitrogen compound of the general formula Ia-1 or Ib-2
  • R 1 and R 2 are the same or different and are alkyl, alkenyl, hydroxyalkyl, hydroxyalkenyl, aminoalkyl or aminoalkenyl, or R 1 and R 2 together represent alkylene, oxyalkylene or aminoalkylene;
  • Rs and R 4 are identical or different and are H, alkyl, alkylaryl, or aryl;
  • R 6 is alkyl, alkenyl, optionally mono- or polyunsaturated cycloalkyl, aryl, each optionally substituted, e.g. with at least one hydroxyl radical or alkyl radical, or interrupted by at least one heteroatom;
  • A is a straight-chain or branched alkylene radical which is optionally interrupted by one or more heteroatoms, such as N, O and S;
  • n is an integer value of 1 to 50;
  • R1 and R2 are identical or different and are C 1 -C 6 -alkyl, hydroxy-C 1 -C 6 -alkyl, hydroxy-C 1 -C 6 -alkenyl, or amino Ci-C6-alkyl, or R1 and R2 together form a C2-C6-alkylene, C2-C6-oxyalkylene or C2-C6-aminoalkylene radical;
  • R 6 is C 1 -C 20 alkyl, e.g. C10-C20, Cn-C2o or Ci2-C2o-alkyl or aryl or alkylaryl, wherein alkyl is in particular C1-C20- stands;
  • A is a straight-chain or branched C 2 -C 6 -alkylene radical which is optionally interrupted by one or more heteroatoms, such as N, O and S;
  • n is an integer value of 1 to 30.
  • reaction products of ⁇ , ⁇ -dimethylethanolamine and propylene oxide as described in Synthesis Example 1 of WO 2013/064689.
  • This reaction may also be carried out uncatalyzed or with an amine (for example imidazole) as a catalyst, e.g. in M. Lonescu, Chemistry and Technology of Polyols for Polyurethanes, 2005, ISBN 978-85957-501-7.
  • Nitrogen compounds of general formula Ia-1 can be prepared wherein an aminoalkanol of the general formula II
  • R 1, R 2 and A have the meanings given above,
  • R 3 and R 4 have the meanings given above,
  • Nitrogen compounds of the general formula Ia-2 can be prepared wherein
  • R6 has the meanings given above, with an epoxide of the general formula III
  • R 6 -OH (V) where R 6 is alkyl, alkenyl, optionally mono- or polyunsaturated cycloalkyl, aryl, in each case optionally substituted, for example with at least one hydroxyl radical or alkyl radical, or interrupted by at least one heteroatom; and
  • R 1 and R 2 are the same or different and are alkyl, alkenyl, hydroxyalkyl, hydroxyalkenyl, aminoalkyl or aminoalkenyl, or R 1 and R 2 together represent alkylene, oxyalkylene or aminoalkylene;
  • A is a straight-chain or branched alkylene or alkenylene radical which is optionally interrupted by one or more heteroatoms, such as N, O and S;
  • quaternizable aminoalcohols are compounds selected from hydroxyalkyl-substituted mono- or polyamines having at least one quaternizable, primary, secondary or tertiary amino group and at least one hydroxyl group which is attachable to a polyether radical.
  • the quaternizable nitrogen compound is selected from hydroxyalkyl-substituted primary, secondary, and especially tertiary monoamines and hydroxyalkyl-substituted primary, secondary and especially tertiary diamines.
  • suitable "hydroxyalkyl-substituted mono- or polyamines" are those endowed with at least one, such as 1, 2, 3, 4, 5 or 6, hydroxyalkyl substituents.
  • hydroxyalkyl-substituted monoamines may be mentioned: N-hydroxyalkyl-monoamines, ⁇ , ⁇ -dihydroxyalkyl-monoamines and ⁇ , ⁇ , ⁇ -trihydroxyalkyl-monoamines, wherein the hydroxyalkyl groups are the same or different and are also as defined above , Hydroxyalkyl stands in particular for 2-hydroxyethyl, 3-hydroxypropyl or 4-hydroxybutyl.
  • hydroxyalkyl-substituted polyamines and especially “hydroxyalkyl-substituted diamines” may be mentioned: (N-hydroxyalkyl) -alkylenediamines, N, N-dihydroxyalkylalkylenediamines wherein the hydroxyalkyl groups are the same or different and are also as defined above.
  • Hydroxyalkyl stands in particular for 2-hydroxyethyl, 3-hydroxypropyl or 4-hydroxybutyl
  • Alkylene stands in particular for ethylene len, propylene or butylene.
  • the amino alcohols of the general formula II can be alkoxylated in a manner known in principle to give alkoxylated amines of the general formula Ia-1.
  • alkoxylations The carrying out of alkoxylations is known in principle to the person skilled in the art. It is also known to the person skilled in the art that the reaction conditions, in particular the choice of catalyst, can influence the molecular weight distribution of the alkoxylates.
  • C 2 -C 6 -alkylene oxides are used, for example ethylene oxide, propylene oxide or butylene oxide. Preference is given in each case to the 1, 2-alkylene oxides.
  • the alkoxylation may be a base-catalyzed alkoxylation.
  • the amino alcohols (II) can be mixed in a pressure reactor with alkali metal hydroxides, preferably potassium hydroxide or with alkali metal such as sodium methylate.
  • the catalyst can be neutralized by addition of acid (eg acetic acid or phosphoric acid) and can be filtered off if necessary.
  • acid eg acetic acid or phosphoric acid
  • the basic catalyst can also be neutralized by adding commercial Mg silicates, which are then filtered off.
  • the alkoxylation can also be carried out in the presence of a solvent.
  • This may be, for example, toluene, xylene, dimethylformamide or ethylene carbonate.
  • the alkoxylation of the amino alcohols can also be carried out by other methods, for example by acid-catalyzed alkoxylation.
  • Doppelhydroxidtone as described in DE 43 25 237 A1 can be used, or it can double metal cyanide catalysts (DMC catalysts) can be used.
  • DMC catalysts are disclosed, for example, in DE 102 43 361 A1, in particular in sections [0029] to [0041], and in the literature cited therein.
  • Zn-Co type catalysts can be used.
  • the aminoalcohol can be admixed with the catalyst, the mixture can be dehydrated as described above and reacted with the alkylene oxides as described. It is usually not more than 1000 ppm catalyst used with respect to the mixture, and the catalyst can remain in the product due to this small amount.
  • the amount of catalyst can typically be less than 1000 ppm, for example 250 ppm and less.
  • the alkoxylation can alternatively also be carried out by reaction of the compounds (IV) and (V) with cyclic carbonates such as, for example, ethylene carbonate. a2) starting from alkanols of the formula V:
  • polyethers (Ib-1)
  • the polyethers obtained in this way can subsequently be prepared by reductive amination with ammonia, primary amines or secondary amines (VII) by conventional methods in continuous or batch processes using customary hydrogenation or amination catalysts, for example those which contain catalytically active constituents based on Elements Ni, Co, Cu, Fe, Pd, Pt, Ru, Rh, Re, Al, Si, Ti, Zr, Nb, Mg, Zn, Ag, Au, Os, Ir, Cr, Mo "W or combinations of these elements contained among themselves, in conventional amounts to the corresponding polyetheramines (lb-2) are reacted.
  • the reaction can be carried out without solvent or at high polyether viscosities in the presence of a solvent, preferably in the presence of presently branched aliphatics such as isododecane be performed.
  • the amine component (VII) is generally used in excess, for example in 2 to 100 times the excess, preferably 10 to 80 times the excess.
  • the reaction is carried out at pressures of 10 to 600 bar over a period of 10 minutes to 10 hours. After cooling, the catalyst is separated by filtration, excess amine component (VII) is evaporated off and the reaction water is distilled off azeotropically or under a gentle stream of nitrogen.
  • the resulting polyetheramine (Ib-2) has primary or secondary amine functionalities (R 1 and / or R 2 is H), this can subsequently be converted into a polyether amine having a tertiary amine function (R 1 and R 2 not equal to H).
  • the alkylation can be carried out in a manner known in principle by reaction with alkylating agents.
  • alkylating agents such as, for example, alkyl halides, alkylaryl halides, dialkyl sulfates, alkylene oxides, if appropriate in combination with acid, are suitable; aliphatic or aromatic carboxylic acid esters, in particular dialkylcarboxylates; alkanoates; cyclic non-aromatic or aromatic carboxylic esters; dialkyl; and mixtures thereof.
  • the reactions to the tertiary polyetheramine can also take place by reductive amination by reaction with a carbonyl compound such as formaldehyde in the presence of a reducing agent.
  • Suitable reducing agents are formic acid or hydrogen in the presence of a suitable heterogeneous or homogeneous hydrogenation catalyst.
  • the reactions can be carried out without solvent or in the presence of solvents.
  • suitable solvents are, for example, H 2 O, alkanols, such as methanol or ethanol, or 2-ethylhexanol, aromatic solvents, such as toluene, xylene or solvent mixtures of the Solvesso series, or aliphatic solvents, in particular mixtures of branched aliphatic solvents.
  • the reactions are carried out at temperatures of 10 ° C to 300 ° C at pressures of 1 to 600 bar over a period of 10 minutes to 10 hours.
  • the reducing agent is used at least stoichiometrically, preferably in excess, in particular in a 2- to 10-fold excess.
  • reaction product thus formed (polyetheramine Ib-1 or Ib-2) can theoretically be further purified or the solvent removed. Usually, however, this is not absolutely necessary, so that the reaction product can be converted into the next synthesis step, the quaternization, without further purification.
  • polyalkene-substituted amines having at least one tertiary nitrogen group are also suitable as quaternizable nitrogen compounds.
  • This linking group is likewise known and described, for example, in WO 2008/060888 or US 2008/01 13890 and the further prior art cited therein, to which reference is hereby expressly made.
  • Such polyalkene-substituted amines having at least one tertiary amino group are derivable from an olefin polymer and an amine such as ammonia, monoamines, polyamines or mixtures thereof. They can be prepared by a variety of methods, such as the following exemplified methods:
  • One method of making a polyalkene-substituted amine involves reacting a halogenated olefin polymer with an amine as described in U.S. Patents 3,275,554, 3,438,757, 3,454,555, 3,565,804, 3,755,433, and 3,822,289.
  • Another method of preparing a polyalkene-substituted amine involves reacting a hydroformylated olefin with a polyamine and hydrogenating the reaction product as described in US 5,567,845 and 5,496,383.
  • Another method of making a polyalkene-substituted amine involves converting a polyalkene using a conventional one Epoxidation reagent with or without catalyst, into the corresponding epoxide and the reaction of the epoxide to the polyalkene-substituted amine by reaction with ammonia or an amine under the conditions of the reductive animation, as described in US 5,350,429.
  • Another method of preparing polyalkene-substituted amine involves the hydrogenation of a ⁇ -aminonitrile prepared by reacting an amine with a nitrile, as described in US 5,492,641.
  • Another method for preparing a polyalkene-substituted amine involves hydroformylating a polybutene or polyisobutylene with a catalyst such as rhodium or cobalt in the presence of CO and hydrogen at elevated pressures and temperatures, as described in US 4,832,702.
  • the polyalkenes used for the preparation are derived from olefin polymers.
  • the olefin polymers may include homopolymers and copolymers of polymerizable olefin monomers having 2 to about 16 carbon atoms, 2 to about 6 carbon atoms, or 2 to about 4 carbon atoms.
  • Interpolymers are those in which two or more olefin monomers are interpolymerized by known conventional techniques to give polyalkenes with units within their structure derived from each of the two or more olefin monomers.
  • interpolymers include copolymers, terpolymers and tetrapolymers.
  • Polyalkenes from which the polyalkene-substituted amines are derived are also commonly referred to as "polyolefins".
  • terminal and internal olefin monomers that can be used to prepare the polyalkenes by conventional methods are: ethylene, propylene, the butenes (butylene), especially 1-butene, 2-butene and isobutylene, 1-pentene, 1 - Hexene, 1-hexene, 1-octene, 1-nonene, 1-decene, 2-pentene, propylene tetramer, diisobutylene, isobutylene trimer, 1, 2-butadiene, 1, 3-butadiene, 1, 2-pentadiene, 1, 3-pentadiene, 1, 4-pentadiene, isoprene, 1, 5-hexadiene, 2-methyl-5-propyl-1-hexene, 3-pentene, 4-octene and 3, 3-dimethyl-1-pentene.
  • the olefin polymer is preparable by polymerization of a C 4 refinery stream having a butene content of about 35 to about 75 weight percent and an isobutene content of about 30 to about 60 weight percent in the presence of a Lewis acid catalyst such as aluminum trichloride or boron trifluoride.
  • a Lewis acid catalyst such as aluminum trichloride or boron trifluoride.
  • These polybutenes usually contain predominantly (more than about 80% of the total repeat units) isobutene repeat units of the type (-CH 2 -C (CH 3 ) 2-)
  • the polyalkene substituent of the polyalkene-substituted amine is derived from a polyisobutylene.
  • the amines that can be used to form the polyalkene-substituted amine include ammonia, monoamines, polyamines, or mixtures thereof, including mixtures of various monoamines, mixtures of various polyamines, and mixtures of monomines and polyamines (the diamines).
  • the amines include aliphatic, aromatic, heterocyclic and carbocyclic amines.
  • Monoamines and polyamines are characterized by the presence in their structure of at least one> NH group.
  • the amines can be aliphatic, cycloaliphatic, aromatic or heterocyclic.
  • the monoamines are generally substituted by a hydrocarbon group of 1 to 50 carbon atoms.
  • these hydrocarbon groups may be aliphatic and free of acetylenically unsaturated groups and may have 1 to about 30 carbon atoms.
  • the monoamines may have the formula HNR 1 R 2 wherein R 1 is a hydrocarbon group of up to 30 carbon atoms and R 2 is hydrogen or a hydrocarbyl group of up to about 30 carbon atoms.
  • Suitable monoamines are methylamine, ethylamine, diethylamine, 2-ethylhexylamine, di (2-ethylhexyl) amine, n-butylamine, di-n-butylamine, allylamine, isobutylamine, cocoamine, stearylamine, laurylamine, methyl laurylamines and oleylamine ,
  • Aromatic monoamines are those monoamines in which a carbon atom of the aromatic ring structure is bonded directly to the amine nitrogen atom.
  • the aromatic ring will usually be a mononuclear aromatic ring (i.e., derived from benzene) but may have fused aromatic rings, and especially those derived from naphthalene.
  • Examples of aromatic monoamines are aniline, di (para-methylphenyl) amine, naphthylamine, N- (n-butyl) aniline.
  • aliphatic-substituted, cycloaliphatic-substituted and heterocyclic-substituted aromatic monoamines are: para-dodecylaniline, cyclohexyl-substituted naphthylamine and thienyl-substituted aniline.
  • Hydroxyamines are also suitable monoamines. Such compounds are the hydroxyhydrocarbyl-substituted analogs of the aforementioned monoamines.
  • Examples of hydroxy-substituted monoamines include: ethanolamine, di-3-propanolamine, 4-hydroxybutylamine, diethanolamine and N-methyl-2-hydroxypropylamine.
  • the amine of the polyalkene-substituted amines may be a polyamine.
  • the polyamine may be aliphatic, cycloaliphatic, heterocyclic or aromatic.
  • Examples of the polyamines include: alkylene polyamines, hydroxy group-containing polyamines, aryl polyamines and heterocyclic polyamines.
  • the alkylene polyamines include those of the following formula: HN (R 5 ) - (alkylene-N (R 5 )) n- (R 5 ) wherein n is in the range of 1 to about 10 and eg in the range of 2 to about 7, or of 2 is about 5, and the " alkylene " group has 1 to about 10 carbon atoms, such as 2 to about 6, or 2 to about 4 carbon atoms;
  • each R 5 is independently hydrogen, an aliphatic group, a hydroxyl or amine substituted aliphatic group of up to about 30 carbon atoms each.
  • R 5 is H or lower alkyl (an alkyl group having from 1 to about 5 carbon atoms).
  • alkylene polyamines include: methylenepolyamines, ethylenepolyamines, butylenepolyamines, propylenepolyamines, pentylenepolyamines, hexylenepolyamines and heptylenepolyamines. The higher homologs of such amines and related aminoalkyl substituted piperazines are also included.
  • alkylenepolyamines for preparing the polyalkene-substituted amines are the following: ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, propylenediamine, 3-dimethylaminopropylamine, trimethylenediamine, hexamethylenediamine, decamethylenediamine, octamethylenediamine, di (heptamethylene) triamine, tripropylenetetramine, pentaethylenehexamine , Di (trimethylene triamine), N- (2-aminoethyl) piperazine and 1,4-bis (2-aminoethyl) piperazine.
  • Ethylene polyamines such as those mentioned above, are particularly suitable for reasons of cost and effectiveness. Such polyamines are described in detail in the chapter entitled “Diamines and Higher Amines” in Encyclopedia of Chemical Technology, Second Edition, Kirk-Othemer, Vol. 7, pp. 27-39, Interscience Publishers, Division of John Wiley & Sons, 1965. Such compounds are most conveniently prepared by reacting an alkylene chloride with ammonia or by reacting an ethyleneimine with a ring-opening reagent such as ammonia. These reactions lead to the preparation of complex mixtures of alkylene polyamines, including cyclic condensation products such as piperazines.
  • alkylene polyamine bottoms include those containing less than two, usually less than 1, weight percent of material below about 200 ° C.
  • a typical example of such ethylene-polyamine bottoms are "E-100" products from Dow Chemical Company of Freeport, Texas
  • alkylenepolyamine bottoms include cyclic condensation products such as piperazine and higher analogs of diethylenetriamine, triethylenetetriamines, and the like.
  • Hydroxyl-containing polyamines include: hydroxyalkylalkylenepolyamines having one or more hydroxyalkyl substituents on the nitrogen atoms.
  • Such polyamines can be prepared by reacting the above-described alkylene polyamines with one or more alkylene oxides (e.g., ethylene oxide, propylene oxide, and butylene oxide).
  • alkylene oxides e.g., ethylene oxide, propylene oxide, and butylene oxide
  • Similar alkylene oxide-alkanolamine reaction products can also be, for example, the products of the reaction of primary, secondary or tertiary alkanolamines with ethylene, propylene or higher epoxides in a molar ratio of 1: 1 to 1: 2. Reactant ratios and temperatures for carrying out such reactions are known to those skilled in the art.
  • the hydroxyalkyl-substituted alkylene polyamine may be a compound in which the hydroxyalkyl group is a hydroxy-lower alkyl group, ie, has fewer than eight carbon atoms.
  • hydroxyalkyl-substituted poly amines include N- (2-hydroxyethyl) ethylenediamine (also known as 2- (2-aminoethylamino) ethanol), N, N-bis (2-hydroxyethyl) ethylenediamine, 1- (2-hydroxyethyl) piperazine, monohydroxypropyl substituted diethylenetriamine , Dihydroxypropyl-substituted tetraethylenepentamine and N- (3-hydroxybutyl) tetramethylenediamine.
  • Arylpolyamines are analogs to the above-mentioned aromatic monoamines.
  • aryl polyamines include: N, N'-di-n-butyl-para-phenylenediamine and bis (para-aminophenyl) methane.
  • Heterocyclic mono- and polyamines may include: aziridines, azetidines, azolidines, pyridines, pyrroles, indoles, piperidines, imidazoles, piperazines, isoindoles, purines, morpholines, thiomorpholines, N-aminoalkylmorpholines, N-aminoalkylthiomorpholines, N-aminoalkylpiperazines , N, N'-diamino-alkylpiperazines, azepines, azocines, azonines, anovanes and tetra-, di- and perhydro derivatives of each of the above compounds and mixtures of two or more of these heterocyclic amines.
  • the number average molecular weight of such polyalkene-substituted amines is about 500 to about 5000, such as 1000 to about 1500 or about 500 to about 3000.
  • Any of the above polyalkene-substituted amines, which are secondary or primary amines, can become tertiary amines with alkylating agents alkylated, which are also known as quaternizing, such as dialkyl sulfates, alkyl halides, hydrocarbyl-substituted carbonates; Hydrocarbylepoxiden in combination with an acid and mixtures thereof.
  • the alkylation of a primary amine will occur in one step, for example, using two moles of alkyl halide in the presence of an excess of heterogeneous base, such as sodium carbonate.
  • the polyamine can be exhaustively or partially alkylated in a manner known per se.
  • the hydrophobic "long chain” or “high molecular weight” hydrocarbyl radical which provides sufficient solubility of the quaternized product in the fuel has a number average molecular weight (M ") of from 85 to 20,000, such as 1 to 10,000, or 200 to 10,000 or 350 to 5,000, such as 350 to 3,000, 500 to 2,500, 700 to 2,500, or 800 to 1,500.
  • Typical hydrophobic hydrocarbyl radicals include polypropenyl, polybutenyl and polyisobutenyl radicals, for example having a number average molecular weight M n of 3,500 to 5,000, 350 to 3,000, 500 to 2,500, 700 to 2,500 and 800 to 1,500.
  • the quaternizable nitrogen compounds are selected from
  • Suitable "hydroxyalkyl-substituted mono- or polyamines" are those endowed with at least one, such as 1, 2, 3, 4, 5 or 6, hydroxyalkyl substituents.
  • Examples are, in particular, ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, 1,4-butylenediamine and isomers thereof, pentanediamine and isomers thereof, hexanediamine and isomers thereof, heptanediamine and isomers thereof, and one or more times, e.g. one or two C 1 -C 4 alkylated, e.g. methylated, derivatives of the aforementioned diamine compounds, such as 3-dimethylamino-1 - propylamine (DMAPA), ⁇ , ⁇ -diethylaminopropylamine, and N, N-dimethylaminoethylamine.
  • DMAPA 3-dimethylamino-1 - propylamine
  • DMAPA 3-dimethylamino-1 - propylamine
  • DMAPA 3-dimethylamino-1 - propylamine
  • DMAPA 3-dimethylamino-1 - propy
  • Aromatic carbocyclic diamines having two primary amino groups are the diamino substituted derivatives of benzene, biphenyl, naphthalene, tetrahydronaphthalene, fluorene, indene, and phenanthrene.
  • the reaction can also be carried out under elevated, condensation-promoting temperatures, for. B. in the range of or 90 to 100 ° C or 100 to 170 ° C.
  • the reaction time may be in the range of a few minutes or a few hours, e.g. about 1 minute to about 10 hours.
  • the reaction can be carried out at about 0.1 to 2 atm pressure, but especially at about atmospheric pressure.
  • the reactants are presented in particular in approximately equimolar amounts, optionally a lower, z. 0.05 to 0.5 times, e.g. 0.1 to 0.3 times the molar excess of the polycarboxylic acid compound is desirable.
  • the reactants may be presented in a suitable inert organic aliphatic or aromatic solvent or a mixture thereof. Typical examples are e.g. Solvesso series solvent, toluene or xylene.
  • the solvent can also serve, for example, azeotropically remove condensation water from the reaction mixture. In particular, however, the reactions are carried out without solvent.
  • reaction product thus formed can theoretically be further purified or the solvent removed. Usually, however, this is not absolutely necessary, so that the reaction product can be converted into the next synthesis step, the quaternization, without further purification.
  • the quaternization of the at least one quaternizable tertiary nitrogen atom takes place with at least one quaternizing agent selected from epoxides, in particular hydrocarbyl epoxides.
  • Rd radicals contained therein are the same or different and represent H or a hydrocarbyl radical, wherein the hydrocarbyl radical has at least 1 to 10 carbon atoms.
  • these are aliphatic or aromatic radicals, such as linear or branched C 1-10 -alkyl radicals or aromatic radicals, such as phenyl or C 1-4 -alkylphenyl.
  • Suitable hydrocarbyl epoxides are, for example, aliphatic and aromatic alkylene oxides, in particular C 2-12 -alkylene oxides, such as ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 2-methyl-1,2-propene oxide (isobutene oxide), 1, 2-pentenoxide, 2,3-pentenoxide, 2-methyl-1, 2-butene oxide, 3-methyl-1, 2-butene oxide, 1, 2-hexene oxide, 2,3-hexene oxide, 3,4-hexene oxide, 2-methyl-1,2-pentene oxide, 2-ethyl-1,2-butene oxide, 3-methyl-1,2-pentene oxide, 1,2-decene oxide, 1,2-dodecene oxide or 4-methyl-1,2-diene pentene; and also aromatic-substituted ethylene oxides, such as optionally substituted styrene oxide, in particular styrene oxide or 4-methyl-styrene
  • epoxides as quaternizing these are in the presence of free acids, especially in the presence of free hydrocarbyl-substituted unsaturated, especially saturated, optionally substituted, especially unsubstituted protic acids, such as especially with hydrocarbyl-substituted dicarboxylic acids, especially hydrocarbyl Substituted C3-C2s or C3-C12-dicarboxylic acids, in particular unsubstituted, saturated C3-C6 dicarboxylic acid are used.
  • Suitable dicarboxylic acids are saturated acids, such as malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic -, sebacic acid, undecanedioic acid and dodecanedioic acid or higher molecular weight acids, such as tert-, hexa- or octadecanedioic acid-substituted acids, such as malic acid, ⁇ -ketoglutaric acid, oxaloacetic acid; glutamic acid; aspartic acid; and unsaturated acids such as maleic acid and fumaric acid; such as in particular malonic, succinic, glutaric, adipic and pimelic acid.
  • aromatic dicarboxylic acid such as phthalic acid.
  • hydrocarbyl-substituted dicarboxylic acids can also be used in their anhydride form.
  • the ring opening of the anhydride is then effected by the addition of water.
  • hydrocarbyl-substituted dicarboxylic acid anhydrides are hydrocarbyl-substituted succinic anhydrides, such as those marketed by the company Pentagon: n-dodecenylsuccinic anhydride CAS 19780-1 1-1, n-Octadecenylbernsteinklanchanhydrid CAS. 28777-98-2, i-Octadecenyl succinic anhydride CAS.
  • polyisobutene succinic anhydride PIBSA
  • PIBSA polyisobutene succinic anhydride
  • MSA maleic anhydride
  • BM PIBSA bismaleinated PIBSA
  • BMG degree of bismaralination
  • PIB MSA PIBSA BM PIBSA Particularly preferred is PIBSA having a degree of bis-maleination up to 30, preferably up to 25 and more preferably up to 20%. As a rule, the degree of bismaleination is at least 2, preferably at least 5 and particularly preferably at least 10%.
  • the targeted preparation is described for example in US 5,883,196.
  • the same alcohol is preferably used for such a reaction of the hydrocarbyl-substituted dicarboxylic anhydrides, such as 2-ethylhexanol or 2-propylheptanol, preferably 2-ethylhexanol or 2-propylheptanol, or butyldiglycol, butylglycol, methoxypropoxypropanol or Butoxy dipropanol.
  • the hydrocarbyl-substituted dicarboxylic anhydrides such as 2-ethylhexanol or 2-propylheptanol, preferably 2-ethylhexanol or 2-propylheptanol, or butyldiglycol, butylglycol, methoxypropoxypropanol or Butoxy dipropanol.
  • Such alcoholysis is preferably carried out with stoichiometric amounts of alcohol or amine at temperatures of 50 to 150 ° C, but it can also be an excess of alcohol or amine, preferably alcohol are used. This then expediently remains in the reaction mixture and serves as a solvent in the subsequent quaternization.
  • Per equivalent of quaternizable tertiary Nitrogen atom can be used, for example, 0.1 to 2.0, 0.2 to 1, 5, or 0.5 to 1, 25 equivalents of dicarboxylic acid. In particular, however, approximately approximately molar proportions of the dicarboxylic acid are used.
  • the mixture is then sufficiently purged with N 2, and adjusted to a suitable form and the epoxide (eg propylene oxide) is metered in the required stoichiometric amounts at a temperature between 20 ° C and 180 ° C.
  • epoxide eg propylene oxide
  • 0.1 to 4.0, 0.2 to 3, or 0.5 to 2 equivalents of epoxide can be used per equivalent of quaternizable tertiary nitrogen atom.
  • epoxide in relation to the tertiary amine to fully quaternize the tertiary amine group.
  • a molar excess of alkylene oxide can be set, whereby the free carboxyl group of the dicarboxylic acid is partially or completely esterified.
  • the mixture is then over a suitably long period of a few minutes to about 24 hours, such as stirred for about 10 h at a temperature between 20 ° C and 180 ° C (eg 50 ° C), cooled, such as to about 20 to 50 ° C. , purged with N2 and the reactor emptied.
  • the reaction can be carried out at about 0.1 to 20 bar, such as 1 to 10 or 1, 5 to 5 bar pressure.
  • the reaction can also be carried out at atmospheric pressure.
  • an inert gas atmosphere such as nitrogen, is useful.
  • the reactants may be presented in a suitable inert organic aliphatic or aromatic solvent or mixture thereof for quaternization.
  • suitable inert organic aliphatic or aromatic solvent or mixture thereof for quaternization.
  • Typical examples are e.g. Solvesso series solvents, toluene or xylene or 2-ethylhexanol, or 2-propylheptanol, and also butyldiglycol, butylglycol, methoxypropoxypropanol, butoxydipropanol or straight-chain and branched saturated hydrocarbons, such as paraffins or naphthenes.
  • the quaternization can also be carried out in the absence of a solvent.
  • the quaternization may be carried out in the presence of a protic solvent, optionally also in combination with an aliphatic or aromatic solvent.
  • suitable protic solvents have a dielectric constant (at 20 ° C.) of greater than 7.
  • the protic solvent may contain one or more OH groups and may also be water.
  • Suitable solvents may also be alcohols, glycols and glycol ether.
  • suitable protic solvents may be those mentioned in WO 2010132259.
  • Particularly suitable solvents are methanol, ethanol, n-propanol, isopropanol, all isomers of butanol, all isomers of pentanol, all isomers of hexanol, 2-ethylhexanol, 2-propylheptanol, as well as mixtures of various alcohols.
  • the presence of a protic solvent can positively influence the conversion and reaction rate of quaternization. b) work-up of the reaction mixture
  • the final reaction product thus formed can theoretically be further purified or the solvent removed.
  • excess reagent such as excess epoxide, to be removed. This can be done for example by introducing nitrogen at atmospheric pressure or under reduced pressure.
  • solvents after the reaction for example solvents of the Solvesso series, 2-ethylhexanol, or substantially aliphatic solvents. Usually, however, this is not absolutely necessary, so that the reaction product can be used without further purification as an additive, if appropriate after mixing with further additive components (see below).
  • Components (X) are those which, at the dosage used in fuels, reduce the frictional wear value (R, in ⁇ ) according to the HFRR test (corresponding to CEC F-06-A-96) compared with the same fuel without component (X ), preferably those which show a reduction of the fretting value by at least 5%, more preferably by at least 10% and most preferably by at least 15%.
  • the component (X) is selected from the group consisting of from the group consisting of
  • components (Xa) are preferably at least one saturated or unsaturated, aliphatic monocarboxylic acid having 8 to 30, preferably 10 to 28 and particularly preferably 12 to 24 carbon atoms.
  • components (Xa) are octanoic acid (caprylic acid), pelargonic acid
  • Nonanoic acid decanoic acid (capric acid), undecanoic acid, dodecanoic acid (lauric acid), tridecanic acid, tetradecanoic acid (myristic acid), pentadecanoic acid, palmitic acid (hexadecanoic acid), margaric acid (heptadecanoic acid), stearic acid (octadecanoic acid), nonadecanoic acid, arachic acid ( Eicosanoic acid), behenic acid (docosanoic acid), tetracosanoic acid (lignoceric acid), cerotic acid (hexacosanoic acid), triacontanoic acid (melissic acid), palmitoleic acid [(9Z) -hexadec-9-enoic acid], oleic acid [(9Z) -octadec-9-enoic acid], elaidic acid [(9E) -o
  • polycyclic hydrocarbon compound selected from the group consisting of natural resin acids obtained from distillation residues of natural oils extracted from tree resins, especially conifer resins.
  • the resin acids are preferably selected from the group consisting of abietic acid, dihydroabietic acid, tetrahydroabietic acid, dehydroabietic acids, neoabietic acid, pimaric acid, levopimaric acid, palustric acid and their derivatives.
  • components (Xb) are esters of the fatty acid esters listed above under component (Xa) with mono-, di- or polyhydric alcohols.
  • Monohydric alcohols are alcohols containing from 1 to 4 carbon atoms, such as methanol, ethanol, / so-propanol, n-propanol, n-butanol, / so-butanol, seA "butanol, fe-butanol, alcohols having from 6 to 12 carbon atoms, such as n-hexanol, n-heptanol, n-octanol, n-decanol, n-dodecanol (lauryl alcohol), 2-ethylhexanol, and fatty alcohols, for example lauryl alcohol (1-dodecanol), myristyl alcohol (1-tetradecanol), cetyl alcohol (1 Hexadecanol), stearyl alcohol (1-octadecanol), 9-cis-octadecen-1-ol (oleyl alcohol), 9-trans-octadecene
  • Di- and polyhydric alcohols aliphatic, cycloaliphatic and araliphatic alcohols which carry two or more hydroxyl groups and have from 2 to 20 carbon atoms.
  • these are ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 1-dimethylethane-1, 2-diol, 2-butyl-2-ethyl-1, 3-propanediol, 2-ethyl-1, 3 Propanediol, 2-methyl-1,3-propanediol, neopentyl glycol, hydroxypivalic acid neopentyl glycol ester, 1, 2, 1, 3 or 1, 4-butanediol, 1, 6-hexanediol, 1, 10-decanediol, bis ( 4-hydroxycyclohexane) isopropylidene, tetramethylcyclobutanediol, 1, 2-, 1, 3- or 1, 4-cyclohexan
  • the alcohol may be alkoxylates of the formula (I), wherein
  • R 10 is an alkyl or alkenyl radical having 1 to 30 carbon atoms, preferably 4 to 24 and particularly preferably 6 to 20 carbon atoms,
  • n is a positive integer from 3 to 50, preferably from 5 to 40 and more preferably from 10 to 30 and
  • the alkyl group R 10 is preferably methyl, ethyl, / so-propyl, n-propyl, n-butyl, / so-butyl, sea “butyl, fe-butyl, n-hexyl, n-heptyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, n-eicosyl, 2-ethylhexyl or 2-propylheptyl.
  • Further components (Xb) may be alkoxylated diols and polyols of the formula (Ia) to (Id),
  • aryl, alkyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles C1-cis-alkyl for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl , Heptyl, octyl, 2-ethylhexyl, 2,4,4-trimethylpentyl, decyl, Dodecyl, tetradecyl, hetadecyl, octadecyl, 1, 1-dimethylpropyl, 1, 1-dimethylbutyl, 1, 1, 3,3-tetramethylbutyl, preferably methyl, ethyl or n-propyl, most preferably methyl or ethyl.
  • components (Xc) are complex esters of fatty acids, in particular the fatty acids listed above under (Xa), with dihydric and polyhydric alcohols, in particular the dihydric and polyhydric alcohols listed above under (Xb), and with di- and polybasic carboxylic acids.
  • particularly preferred dihydric and polyhydric alcohols are the at least trihydric, very particularly preferably the trihydric to hexahydric alcohols listed above under (Xb).
  • Preferred dibasic carboxylic acids are aliphatic dicarboxylic acids, such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecane-a, ü) -dicarboxylic acid, dodecane- ⁇ , ⁇ -dicarboxylic acid, cis- and trans Cyclohexane-1,2-dicarboxylic acid, cis- and trans -cyclohexane-1,3-dicarboxylic acid, cis- and trans-cyclohexane-1,4-dicarboxylic acid, cis- and trans-cyclopentane-1,2-dicarboxylic acid, cis- and trans-cyclopentane-1,3-dicarboxylic acid.
  • aromatic dicarboxylic acids for example phthalic acid
  • the dicarboxylic acids mentioned can also be substituted by one or more radicals selected from
  • C 1 -C 10 -alkyl groups for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neo -Pentyl, 1, 2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, iso-heptyl, n-octyl, 2-ethylhexyl, trimethylpentyl, n-nonyl or n- decyl,
  • C3-C12 cycloalkyl groups for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; preferred are cyclopentyl, cyclohexyl and cycloheptyl;
  • Alkylene groups such as methylene or ethylidene or C 6 -C 14 aryl groups such as phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9-phenanthryl Phenyl, 1-naphthyl and 2-naphthyl, more preferably phenyl.
  • substituted dicarboxylic acids which may be mentioned are: 2-methylmalonic acid, 2-ethylmalonic acid, 2-phenylmalonic acid, 2-methylsuccinic acid,
  • mixtures of two or more of the aforementioned dicarboxylic acids can be used.
  • Preferred dicarboxylic acids are aliphatic dicarboxylic acids which may be substituted or unsubstituted, preferably substituted.
  • the dicarboxylic acids can be used either as such or in the form of derivatives in the preparation of complex esters.
  • Mono- or dialkyl esters preferably mono- or di-C 1 -C 4 -alkyl esters, particularly preferably mono- or dimethyl esters or the corresponding mono- or diethyl esters,
  • mixed esters preferably mixed esters with different C1-C4 alkyl components, more preferably mixed methyl ethyl esters.
  • C 1 -C 4 -alkyl in this document means methyl, ethyl, / so-propyl, n-propyl,
  • Malonic acid, succinic acid, glutaric acid, adipic acid, 1, 2, 1, 3 or 1, 4-cyclohexanedicarboxylic acid (hexahydrophthalic acids), phthalic acid, isophthalic acid, terephthalic acid or their mono- or dialkyl esters are particularly preferably used.
  • polybasic carboxylic acids are tricarboxylic acids and polycarboxylic acids, preferably aconitic acid, 1,3,5-cyclohexanetricarboxylic acid, 1, 2,4-benzenetricarboxylic acid, 1,3,5-benzene tricarboxylic acid, 1, 2,4,5-Benzoltetracarbonklare (pyromellitic acid) and mellitic acid and low molecular weight polyacrylic acids.
  • Tricarboxylic acids or polycarboxylic acids can be used in the preparation of the complex ester reaction either as such or in the form of derivatives.
  • Mono-di- or trialkyl preferably mono-, di- or tri-d-C4-alkyl, particularly preferably mono-, di- or trimethyl esters or the corresponding mono-, di- or
  • mixed esters preferably mixed esters with different
  • C 1 -C 4 -alkyl components more preferably mixed methyl ethyl esters.
  • a mixture of a tri- or polycarboxylic acid and one or more of its derivatives for example a mixture of pyromellitic acid and pyromellitic dianhydride.
  • a mixture of several different derivatives of one or more tri- or polycarboxylic acids for example a mixture of 1,3,5-cyclohexanetricarboxylic acid and pyromellitic dianhydride.
  • the complex esters (Xb) are those as described in WO 15/059063 A2 [this is our PF 75573, FM 238/255], there in particular page 3, line 37 to page 5, line 42, which is hereby incorporated by reference into the present disclosure.
  • components (Xd) are fatty acid amides of mono-, di- or polyamines or polyetheramines, in particular the fatty acids listed above under (Xa) with di- and polyamines or polyetheramines, particularly preferably di- and polyamines in which the amino groups in the majority of which are connected by 1, 2-ethylene and / or 1, 3-propylene groups or polyetheramines, as listed below under (Xh).
  • the underlying polyamines can either be structurally clearly defined low molecular weight oligoamines or polymers with up to 1000, in particular up to 500, especially up to 100 nitrogen atoms in the macromolecule.
  • the latter are then usually polyalkyleneimines, for example polyethyleneimines, or polyvinylamines.
  • the said polyamines are reacted with Cs to C3o-fatty acids, in particular C 16- to C 20 -fatty acids, or fatty acid-analogous compounds containing free carboxyl groups, to give the acid amides (Xd).
  • Cs to C3o-fatty acids in particular C 16- to C 20 -fatty acids, or fatty acid-analogous compounds containing free carboxyl groups
  • Xd acid amides
  • the reaction of the polyamines with the fatty acid to give the oil-soluble acid amides of the component (Xd) takes place completely or partially. In the latter case, subordinate fractions of the product are usually present in the form of corresponding ammonium salts. However, the completeness of the conversion to the acid amides can generally be controlled by the reaction parameters.
  • Suitable polyamines suitable for the conversion to the acid amides of component (Xd) are, for example: ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, dipropylenetriamine, tripropylenetetramine, tetrapropylenepentamine, pentapropylenhexamine, polyethyleneimines of an average degree of polymerization (corresponding to the number of Nitrogen atoms) of z. B. 10, 35, 50 or 100 and polyamines, which were obtained by reaction of oligoamines (with chain extension) with acrylonitrile and subsequent hydrogenation, for. N, N'-bis (3-aminopropyl) ethylenediamine.
  • Suitable fatty acids for the conversion to the acid amides of component (Xd) are pure fatty acids and technically customary fatty acid mixtures containing, for example, stearic acid, palmitic acid, lauric acid, oleic acid, linoleic acid and / or linolenic acid.
  • Naturally occurring fatty acid mixtures for example tallow fatty acid, coconut oil fatty acid, trans fatty acid, coconut oil fatty acid, soybean oil fatty acid, rapeseed oil fatty acid, peanut oil fatty acid or palm oil fatty acid, which contain oleic acid and palmitic acid as main components.
  • fatty acid analogues containing free carboxyl groups which are likewise suitable for reaction with the stated polyamines to the acid amides of component (Xd) are monoesters of long-chain alcohols of dicarboxylic acids such as tallow fatty alcohol maleate or tallow fatty alcohol succinic acid or corresponding glutaric or adipic acid monoesters.
  • the oil-soluble aliphatic compound (Xd) is an acid amide of aliphatic polyamines having 2 to 6 nitrogen atoms and C 16 to C 20 fatty acids, all primary and secondary amino functions of the polyamines being converted into acid amide functions.
  • a typical example of an oil-soluble acid amide of component (Xd) is the reaction product of 3 moles of oleic acid with 1 mole of diethylenetriamine.
  • the component (Xe) is alkanolamines, preferably those of the formula
  • R 14 is an alkyl or alkenyl radical having 1 to 30 carbon atoms, preferably 4 to 24 and particularly preferably 6 to 20 carbon atoms,
  • k, m and n are each independently a positive integer from 0 to 50, preferably 1 to 40 and more preferably 2 to 30 and
  • each Xi for i 1 to k, 1 to m and 1 to n independently selected from the group
  • these are alkanolamides as described in WO 2009/050256 A1 [this is our PF 60246, FM100], there especially from page 3, line 24 to page 6, line 12 and page 11, line 4 to Page 12, line 22, which is hereby incorporated by reference into the present disclosure.
  • such alkanolamides are those described in WO 2010/005720 A1 [this is our PF 61053, FM38], there in particular paragraph
  • the components (Xg) are alkoxylated monohydric or polyhydric alcohols.
  • Alkoxylated monohydric or polyhydric alcohols are, for example, those described by the formulas (I) or (Ia) to (Id) above under (Xb).
  • Polyetheramines (Xi) are those of the formula (IV), R 5 -O - [- Xi-] n -YH (IV) where
  • R 15 is an alkyl or alkenyl radical having 1 to 30 carbon atoms, preferably 4 to 24 and particularly preferably 6 to 20 carbon atoms,
  • n is a positive integer from 3 to 50, preferably from 5 to 40 and more preferably from 10 to 30 and
  • -CH (C 2 H 5 ) -CH 2 -O- and most preferably selected from the group consisting of -CH 2 -CH (CH 3 ) -O- and -CH (CH 3 ) -CH 2 -O-, and
  • at least one further conventional fuel additive such as, for example, selected from detergent additives, carrier oils, corrosion inhibitors and mixtures containing one or more of these additives
  • a reduction of the fretting value (R i in ⁇ ), determined as described in the following experimental part, is observed to be around 5 to 70, e.g. 5 to 60, 5 to 50, 10 to 60, 10 to 50, 15 to 60 or 15 to 50% compared with the detected value before adding the lubricity improver (X).
  • the determination method is based on an HFRR test commonly used in the diesel fuel sector (according to CEC F-06-A-96), but measuring at room temperature (25 ° C) and under a load of 720g (about 7.06 N). he follows.
  • the fuels to be investigated are ground by distillation to 50% by volume before the measurement.
  • Another object of the invention are fuel compositions comprising, in a major amount of a common base fuel, an attrition-reducing amount of at least one lubricity enhancer (X) in combination with at least one quaternized nitrogen compound.
  • the invention also relates to additive concentrates comprising an amount of at least one lubricity improver (X) which reduces the coefficient of fretting in combination with at least one quaternized nitrogen compound in combination with at least one further customary fuel additive. Particular preference is given to using the above-described friction modifiers in gasoline fuels.
  • a final object of the invention is a process for producing a fuel composition having improved fretting performance, which comprises adding to a commercial fuel composition an effective amount of the described quaternized nitrogen compounds in combination with at least one lubricity enhancer (X) as defined above or an additive concentrate as defined above.
  • Lubricity improvers (X) and quaternized nitrogen compounds are each added in amounts of, for example, 5 to 2000 ppm by weight, preferably 10 to 1500, more preferably 25 to 1000, very preferably 40 to 800 and in particular 50 to 500 ppm by weight.
  • the weight ratio of lubricity improver (X) and quaternized nitrogen compound can be varied, for example, in a ratio of from 25: 1 to 1:25, preferably from 15: 1 to 1:15, particularly preferably from 10: 1 to 1:10, completely particularly preferably from 5: 1 to 1: 5 and in particular 2: 1 to 1: 2.
  • the weight ratio of lubricity improver (X) and quaternized nitrogen compound 1 1.
  • the friction modifier formulations according to the invention can be added to the fuels to be added individually or in admixture with other effective additive components (coadditives).
  • detergent additives As examples, detergency additives and / or valve seat wear-inhibiting effect (hereinafter referred to as detergent additives) may be cited.
  • This detergent additive has at least one hydrophobic hydrocarbon radical having a number-average molecular weight (Mn) 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 (Mn) of from 85 to 20,000, especially from 13 to 10,000, especially from 300 to 5000.
  • Mn number average molecular weight
  • amines such as e.g. Ammonia, monoamines or polyamines, such as dimethylaminopropylamine, ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine.
  • amines such as e.g. Ammonia, monoamines or polyamines, such as dimethylaminopropylamine, ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine.
  • Corresponding additives based on polypropene are described in particular in WO-A-94/24231.
  • monoamino groups (a) containing additives are the compounds obtainable from polyisobutene epoxides by reaction with amines and subsequent dehydration and reduction of the amino alcohols, as described in particular in DE-A-196 20 262.
  • Carboxyl groups or their alkali metal or alkaline earth metal salts (d) containing additives are preferably copolymers of C2-C4o-olefins with maleic anhydride having a total molecular weight of 500 to 20,000 whose carboxyl groups wholly or partially to the alkali metal or alkaline earth metal salts and a remaining group of the carboxyl groups with Alcohols or amines are implemented.
  • Such additives are known in particular from EP-A-307 815.
  • Such additives are mainly used to prevent valve seat wear and, as described in WO-A-87/01 126, can be advantageously used in combination with conventional fuel detergents such as poly (iso) butenamines or polyetheramines.
  • Sulfonic acid groups or their alkali metal or alkaline earth metal salts (e) containing additives are preferably alkali metal or alkaline earth metal salts of a Sulfobernsteinklakylesters, as described in particular in EP-A-639 632.
  • Such additives are primarily used to prevent valve seat wear and can be used to advantage in combination with conventional fuel detergents such as poly (iso) butenamines or polyetheramines.
  • Polyoxy-C2-C4-alkylene (f) containing additives are preferably polyether or polyetheramines, which by reaction of C2-C6o-alkanols, C6-C3o-alkanediols, mono- or di-C2-C3o-alkylamines, Ci-C3o-Alkylcyclohexanolen or C 1 -C 30 -alkylphenols having from 1 to 30 mol of ethylene oxide and / or propylene oxide and / or butylene oxide per hydroxyl group or amino group and, in the case of polyetheramines, 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 meet carrier oil properties. Typical examples of these are tridecanol or Isotridecanolbutoxylate, Isononylphenolbutoxylate and polyisobutenol butoxylates and propoxylates and the corresponding reaction products with ammonia.
  • Carboxylic ester groups (g) containing additives are preferably esters of mono-, di- or tricarboxylic acids with long-chain alkanols or polyols, especially those having a minimum viscosity of 2 mm 2 / s at 100 ° C, as described in particular in DE-A-38 38 918 .
  • mono-, di- or tricarboxylic acids it is possible to use aliphatic or aromatic acids, especially suitable long-chain representatives having, for example, 6 to 24 carbon atoms as ester alcohols or polyols.
  • esters are adipates, phthalates, isophthalates, terephthalates and trimellitates of iso-octanol, iso-nonanol, iso-decanol and of isotridecanol. Such products also meet carrier oil properties.
  • Succinic anhydride-derived groupings containing hydroxyl and / or amino and / or amido and / or imido groups (h) are preferably correspondingly preferred.
  • derivatives with aliphatic polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine.
  • Such gasoline additives are described in particular in US Pat. No. 4,849,572.
  • Mannich reaction of substituted phenols with aldehydes and mono- or polyamines generated groupings (i) containing additives are preferably reaction products of polyisobutene-substituted phenols with formaldehyde and mono- or polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine or dimethylaminopropylamine.
  • Such "polyisobutene-Mannich bases" are described in particular in EP-A-831 141.
  • additive formulations according to the invention can moreover be combined with still further customary components and additives.
  • Here are primarily carrier oils without pronounced detergent action to call.
  • Suitable mineral carrier oils are fractions obtained in petroleum processing, such as bright stock or base oils with viscosities such as from class SN 500-2000; but also aromatic hydrocarbons, paraffinic hydrocarbons and alkoxyalkanols. Also useful is a fraction known as "hydrocrack oil” and obtained from the refining of mineral oil (vacuum distillate cut having a boiling range of about 360 to 500 ° C, available from high pressure, catalytically hydrogenated and isomerized and deproteinized natural mineral oil). Also suitable are mixtures of the abovementioned mineral carrier oils.
  • suitable polyethers or polyetheramines are preferably compounds containing polyoxy-C 2 -C 4 -alkylene groups which are prepared by reacting C 2 -C 60 -alkanols, C 6 -C 30 -alkanediols, mono- or di-C 2 -C 30 -alkylamines, C 1 -C 30 -alkylcyclohexanols or C 1 -C 30 -alkylphenols with 1 to 30 mol of ethylene oxide and / or propylene oxide and / or butylene oxide per hydroxyl group or amino group and, in the case of polyetheramines, by subsequent reductive amination with ammonia, monoamines or polyamines.
  • polyetheramines poly-C 2 -C 6 -alkylene oxide amines or functional derivatives thereof can be used. Typical examples of these are tridecanol or Isotridecanolbutoxylate, Isononylphenolbutoxylate and polyisobutene butoxylates and propoxylates and the corresponding reaction products with ammonia.
  • suitable synthetic carrier oils are alcohol-started polyethers of about 5 to 35, e.g. about 5 to 30, C3-C6 alkylene oxide units, e.g. selected from propylene oxide, n-butylene oxide and i-butylene oxide units, or mixtures thereof.
  • suitable starter alcohols 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 -C 18 -alkyl radical.
  • Preferred examples are tridecanol and nonylphenol.
  • corrosion inhibitors for example based on film-forming ammonium salts of organic carboxylic acids or heterocyclic acrylates 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 phenols such as 2,4-di-tert-butylphenol or 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid
  • demulsifiers demulsifiers
  • Antistatic agents Metallocenes such as ferrocene; Methylcyclopentadienyl manganese tricarbonyl; Lubricity improvers (other than the triazoles of the invention) such as certain fatty acids, alkenyl succinic acid esters,
  • amines are added to lower the pH of the fuel.
  • additive compositions according to the invention can be used in all conventional gasoline fuels, as described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 5th Ed. 1990, Vol. A16, p. 719 et seq.
  • the aromatics content of the gasoline is, for example, from 0 to 50, e.g. 30 to 42 vol.%, In particular 32 to 40 vol.%, Or at most 35 vol.%.
  • the sulfur content of the gasoline is, for example, 2 to 500, e.g. 5 to 100 ppm by weight, or maximally 0 ppm by weight.
  • the gasoline may, for example, have an olefin content of up to 50% by volume, e.g. from 6 to 21% by volume, especially 7 to 18% by volume; a benzene content of up to 5% by volume, e.g. 0.5 to 1.0% by volume, in particular 0.6 to 0.9% by volume and / or an oxygen content of up to 25% by volume, such as e.g. up to 10 wt .-% or 1, 0 to 2.7 wt .-%, in particular from 1, 2 to 2.0 wt .-%, have.
  • an olefin content of up to 50% by volume, e.g. from 6 to 21% by volume, especially 7 to 18% by volume
  • a benzene content of up to 5% by volume e.g. 0.5 to 1.0% by volume, in particular 0.6 to 0.9% by volume
  • an oxygen content of up to 25% by volume such as e.g. up to 10 wt .-% or 1, 0 to 2.7 w
  • gasoline fuels may be mentioned by way of example, which at the same time have an aromatic content of not more than 38 or 35% by volume, 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 vol .-% and an oxygen content of 1, 0 to 2.7 wt .-% have.
  • the content of alcohols and ethers in gasoline can vary over a wide range.
  • Examples of typical maximum contents for methanol are 15% by volume, for ethanol 65% by volume, for isopropanol 20% by volume, for tert-butanol 15% by volume, for isobutanol 20% by volume and for ethers with 5 or more C atoms in the molecule 30 vol .-%.
  • the summer vapor pressure of the gasoline is usually not more than 70 kPa, in particular 60 kPa (each at 37 ° C).
  • the ROZ of the gasoline is usually 75 to 105.
  • a common range for the corresponding MOZ is 65 to 95.
  • the specified specifications are determined by conventional methods (DIN EN 228).
  • Isopar® M is an isoparaffinic hydrocarbon blend from Exxon Mobil with a typical boiling range to ASTM D86 of 170 ° C to 290 ° C.
  • the resulting fretting values (R) are given in microns ( ⁇ ); the lower the value, the lower the wear that occurs.

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Abstract

La présente invention concerne l'utilisation d'au moins un acide polycarboxylique, substitué par l'oxyde d'alkylène et par un groupe hydrocarbyle, de composés azotés quaternisés comme additif réducteur d'usure par frottement dans des compositions de carburants. L'invention concerne également des compositions de carburants correspondantes comprenant un tel additif et la production de ces compositions, ainsi que des concentrés d'additifs comprenant des composés de ce type.
PCT/EP2017/053691 2016-02-23 2017-02-17 Acide polycarboxylique, substitué par l'oxyde d'alkylène et par un groupe hydrocarbyle, de composés azotés quaternisés utilisé comme additif réducteur d'usure par frottement dans des carburants WO2017144376A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100006049A1 (en) * 2008-07-11 2010-01-14 Basf Corporation Composition and Method to Improve the Fuel Economy of Hydrocarbon Fueled Internal Combustion Engines
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WO2015059063A2 (fr) * 2013-10-24 2015-04-30 Basf Se Utilisation d'un ester complexe pour réduire la consommation de carburant
EP2960319A2 (fr) * 2014-06-25 2015-12-30 Afton Chemical Corporation Carboxylates d'ammonium quaternaire soluble hydrocarbyle et compositions de carburant contenant ces derniers

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WO2015059063A2 (fr) * 2013-10-24 2015-04-30 Basf Se Utilisation d'un ester complexe pour réduire la consommation de carburant
EP2960319A2 (fr) * 2014-06-25 2015-12-30 Afton Chemical Corporation Carboxylates d'ammonium quaternaire soluble hydrocarbyle et compositions de carburant contenant ces derniers

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