Polybutene and polyisobutene amine, process for their preparation and fuel or lubricating compositions containing them
11 claims: 11 independent, 0 dependent
- 1A fuel or lubricant composition which contains one or more polybutene- or polyisobuteneamines of the general formula I where R1 is a polybutene or polyisobutene radical derived from isobutene and up to 20% by weight of n-butene and R2 and Rs may be identical or different and are each hydrogen, an aliphatic or aromatic hydrocarbon, a primary or secondary, aromatic or aliphatic aminoalkylene radical or polyaminoalkylene radical, a polyoxyalkylene radical or a hetaryl or heterocyclyl radical, or, together with the nitrogen atom to which they are bonded, form a ring in which further hetero atoms may be present, and which has been obtained by hydroformylation of a polybutene or polyisobutene and subsequent reductive amination. 1. A process for the preparation of a polybutene- or polyisobuteneamine, wherein the polybutene- or polyisobuteneamine of the general formula I where R1 is a polybutene or polyisobutene radical derived from isobutene and up to 20% by weight of n-butene and R2 and Rs may be identical or different and are each hydrogen, an aliphatic or aromatic hydrocarbon radical, a primary or secondary, aromatic or aliphatic aminoalkylene radical or polyaminoalkylene radical, a polyoxyalkylene radical or a hetaryl or heterocyclyl radical, or, together with the nitrogen atom to which they are bonded, form a ring in which further hetero atoms may be present, is obtained by hydroformylating a polybutene or polyisobutene with a rhodium or cobalt catalyst in the presence of CO and H2 at from 80 to 200°C and CO/H2 pressures of up to 600 bar and subsequently subjecting the oxo product to amination under hydrogenating conditions. 1. Composition de combustible ou de lubrifiant, caractérisée en ce qu'elle contient une polybutène- ou polyisobutène-amine qui répond à la formule générale I dans laquelle R1 représente un reste polybutène ou polyisobutène dérivé d'isobutène et, pour une proportion allant jusqu'à 20% en poids, de n-butène, etR2 et R3, qui peuvent être identiques ou différents, peuvent être mis pour des atomes d'hydrogène, des restes hydrocarbonés aliphatiques ou aromatiques, des restes aminoalkylène ou des restes polyaminoalkylène, primaires ou secondaires, aromatiques ou aliphatiques, des restes polyoxyalkylène, des restes hétéroaryle ou hétérocycliques, ou forment ensemble, avec l'atome d'azote auquel ils sont fixés, un noyau dans lequel d'autres hétéroatomes encore peuvent être présents,et qui a été obtenue par hydroformylation d'un polybutène ou d'un polyisobutène, suivie d'amination réductrice. 1. Kraft- oder Schmierstoffzusammensetzung, dadurch gekennzeichnet, daß sie mindestens ein Polybuten- oder Polyisobutenamin enthält, daß der allgemeinen Formel 1 entspricht:worin Ri einen von Isobuten und bis zu 20 Gew.-% n-Buten abgeleiteten Polybuten- oder Polyisobutenrest darstellt undR2 und Rs, die gleich oder verschieden sein können, für Wasserstoff, aliphatische oder aromatische Kohlenwasserstoffreste, primäre oder sekundäre, aromatische oder aliphatische Aminoalkylenreste oder Polyaminoalkylenreste, Polyoxyalkylenreste, Heteroaryl- oder Heterocyclylreste stehen können, oder gemeinsam mit dem Stickstoffatom, an das sie gebunden sind, einen Ring bilden, in dem noch weitere Heteroatome vorhanden sein können, und das durch Hydroformylierung eines Polybutens oder Polyisobutens und anschließende hydrierende Aminierung erhalten worden ist. 1. Procédé de préparation de polybutène- ou polyisobutène-amines, caractérisé en ce que, pour l'obtention de polybutène- ou polyisobutène-amines de formule générale 1 dans laquelle Ri représente un reste polybutène ou polyisobutène dérivé d'isobutène et, pour une proportion allant jusqu'à 20% en poids, de n-butène, etR2 et R3, qui peuvent être identiques ou différents, peuvent être mis pour des atomes d'hydrogène, des restes hydrocarbonés aliphatiques ou aromatiques, des restes aminoalkylène ou des restes polyaminoalkylène primaires ou secondaires, aromatiques ou aliphatiques, des restes polyoxyalkylène, des restes hétéroaryle ou hétérocycliques, ou forment ensemble, avec l'atome d'azote auquel ils sont fixés, un noyau dans lequel d'autres hétéroatomes encore peuvent être présents,on hydroformyle un polybutène ou un polyisobutène avec un catalyseur au rhodium ou au cobalt en présence de CO et de H2 à des températures comprises entre 80 et 200°C et sous des pressions de CO/H2 allant jusqu'à 600 bars, puis on soumet le produit oxo à une amination hydrogénante. 1. Verfahren zur Herstellung von Polybuten- oder Polyisobutenaminen, dadurch gekennzeichnet, daß man zur Gewinnung von Polybutyl- oder Polyisobutenaminen der allgemeinen Formel worin Ri einen von Isobuten und bis zu 20 Gew.-% n-Buten abgeleiteten Polybuten- oder Polyisobutenrest darstellt undR2 und R3, die gleich oder verschieden sein können, für Wasserstoff, aliphatische oder aromatische Kohlenwasserstoffreste, primäre und sekundäre, aromatische oder aliphatische Aminoalkylenreste oder Polyaminoalkylenreste, Polyoxyalkylenreste, Heteroaryl- oder Heterocyclylreste stehen können, oder gemeinsam mit dem Stickstoffatom, an das sie gebunden sind, einen Ring bilden, in dem noch weitere Heteroatome vorhanden sein können, .ein Polybuten oder Polyisobuten mit einem Rhodium- oder Kobaltkatalysator in Gegenwart von CO und H2 bei Temperaturen zwischen 80 und 200°C und CO/H2-Drucken von bis zu 600 bar hydroformyliert und anschließend eine hydrierende Aminierung des Oxoprodukts durchführt.
- 2A fuel or lubricant composition as claimed in claim 1, wherein R1 has the meanings given in claim 1 and R2 and Rs are identical or different and are each hydrogen, alkyl, aryl, hydroxyalkyl, an aminoalkylene radical of the general formula II where R4 is alkylene and R5 and Rs are identical or different and are each hydrogen, alkyl, aryl, hydroxyalkyl or polybutyl or polyisobutyl,a polyaminoalkylene radical of the general formula III where the radicals R4 are identical or different and R4, Rs and R6 have the above meanings and m is an integer from 2 to 8, or a polyoxyalkylene radical of the general formula IV where the radicals R4 may be identical or different and have the above meanings, X is alkyl or H, and n is an integer from 1 to 30,or where R2 and R3, together with the nitrogen atom to which they are bonded, form a morpholinyl, pyridyl, piperidyl, pyrrolyl, pyrimidinyl, pyrrolinyl, pyrrolidinyl, pyrazinyl or pyridazinyl radical. 2. A process for the preparation of a polybutene- or polyisobuteneamine of the formula (I) as claimed in claim 1, wherein in the formula (1) R1 has the meanings given and R2 and R2 are identical or different and are each hydrogen, alkyl, aryl, hydroxyalkyl, an aminoalkylene radical of the general formula II where R4 is alkylene and R5 and Rs are identical or different and are each hydrogen, alkyl, aryl, hydroxyalkyl or polybutyl or polyisobutyl,a polyaminoalkylene radical of the general formula III where the radicals R4 are identical or different and the radicals R5 are identical or different and R4, R5 and R6 have the above meanings and m is an integer from 2 to 8, or a polyoxyalkylene radical of the general formula IV where the radicals R4 may be identical or different and have the above meanings, X is alkyl or H, and n is an integer from 1 to 30,or where Rz and R3, together with the nitrogen atom to which they are bonded, form a morpholinyl, pyridyl, piperidyl, pyrrolyl, pyrimidinyl, pyrrolinyl, pyrrolidinyl, pyrazinyl or pyridazinyl radical. 2. Composition de combustible ou de lubrifiant selon la revendication 1, dans laquelle Ri a la signification donnée dans la revendication 1 et R2 et R3 sont identiques ou différents et représentent chacun un atome d'hydrogène, un reste alkyle, aryle, hydroxyalkyle, un reste aminoalkylène de formule générale Il dans laquelle R4 est mis pour un reste alkylène etR5 et R6, qui sont identiques ou différents, sont mis chacun pour un atome d'hydrogène ou pour un reste alkyle, aryle, hydroxyalkyle, polybutyle ou polyisobutyle,un reste polyaminoalkylène de formule générale III dans laquelleles restes R4 sont chaque fois identiques ou différents,les restes Rs sont chaque fois identiques ou différents,les restes R4, Rs et R6 ont les significations données précédemment etm est mis pour un nombre entier de 2 à 8, ouun reste polyoxyalkylène de formule générale IV dans laquelleles restes R4 peuvent être chaque fois identiques ou différents et ont les significations précédentes,X est mis pour un radical alkyle ou H etn est un nombre entier entre 1 et 30,ou dans laquelle R2 et R3 forment ensemble, avec l'atome d'azote auquel ils sont fixés, un reste morpholinyle, un reste pyridyle, un reste pipéridyle, un reste pyrrolyle, un reste pyrimidinyle, un reste pyrro- linyle, un reste pyrrolidinyle, un reste pyrazinyle ou un reste pyridazinyle. 2. Kraft- oder Schmierstoffzusammensetzung nach Anspruch 1, worin Ri die in Anspruch 1 angegebene Bedeutung besitzt und R2 und Rs gleich oder verschieden sind und jeweils Wasserstoff, Alkyl, Aryl, Hydroxyalkyl, einen Aminoalkylenrest der allgemeinen Formel II worin R4 für einen Alkylenrest-steht undRs und Rs, die gleich oder verschieden sind, für Wasserstoff, Alkyl, Aryl, Hydroxyalkyl oder Polybuten oder Polyisobutenrest stehen, einen Polyaminoalkylenrest der allgemeinen Formel III worin die Reste R4 jeweils gleich oder verschieden sind und die ResteRs jeweils gleich oder verschieden sind und die Reste R4, Rs und R6 die zuvor genannten Bedeutungen besitzen, und m für eine ganze Zahl von 2 bis 8 steht, oder einen Polyoxyalkylenrest der allgemeinen Formel IV worin die Reste R4 jeweils gleich oder verschieden sein können und die vorstehende Bedeutung besitzen, X für Alkyl oder H steht und n eine ganze Zahl zwischen 1 und 30 darstellt,bedeuten, oder worin R2 und R3 zusammen mit dem Stickstoffatom, an das sie gebunden sind, einen Morpholinylrest, Pyridylrest, Piperidylrest, Pyrrolylrest, Pyrimidinylrest, Pyrrolinylrest, Pyrrolidinylrest, Pyrazinylrest oder Pyridazinylrest, darstellen. 2. Procédé de préparation de polybutène- ou polyisobutène-amines de formule (I) selon la revendication 1, caractérisé en ce que dans la formule (1), Ri a la signification donnée précédemment et R2 et Rs sont identiques ou différents et représentent chacun un atome d'hydrogène, un reste alkyle, aryle, hydroxyalkyle, un reste aminoalkylène de formule générale Il dans laquelle R4 est mis pour un reste alkylène etR5 et Rs, qui sont identiques ou différents, sont mis chacun pour un atome d'hydrogène ou pour un reste alkyle, aryle, hydroxyalkyle, polybutyle ou polyisobutyle,un reste polyaminoalkylène de formule générale III dans laquelleles restes R4 sont chaque fois identiques ou différents,les restes Rs sont chaque fois identiques ou différents,les restes R4, R5 et R6 ont les significations données précédemment etm est mis pour un nombre entier de 2 à 8, ouun reste polyoxyalkylène de formule générale IV dans laquelleles restes R4 peuvent être chaque fois identiques ou différents et ont les significations précédentes,X est mis pour un radical alkyle ou H etn est un nombre entier entre 1 et 30,ou dans laquelle R2 et Rs forment ensemble, avec l'atome d'azote auquel ils sont fixés, un reste morpholinyle, un reste pyridyle, un reste pipéridyle, un reste pyrrolyle, un reste pyrimidinyle, un reste pyrroliny- le, un reste pyrrolidinyle, un reste pyrazinyle ou un reste pyridazinyle. 2. Verfahren zur Herstellung von Polybuten- oder Polyisobutenaminen der Formel (I) gemäß Anspruch 1, dadurch gekennzeichnet, daß in der Formel (I) R1 die angegebene Bedeutung besitzt und R2 und R3 gleich oder verschieden sind und jeweils Wasserstoff, Alkyl, Aryl, Hydroxyalkyl, einen Aminoalkylenrest der allgemeinen Formel II worin R4 für einen Alkylenrest steht undRs und R6, die gleich oder verschieden sind, für Wasserstoff, Alkyl, Aryl, Hydroxyalkyl oder einen Polybuten oder Polyisobutenrest stehen, einen Polyaminoalkylenrest der allgemeinen Formel III worin die Reste R4 jeweils gleich oder verschieden sind und die Reste R5 jeweils gleich oder verschieden sind und die Reste R4, Rs und Rs die zuvor genannten Bedeutungen besitzen, und m für eine ganze Zahl von 2 bis 8 steht, odereinen Polyoxyalkylenrest der allgemeinen Formel IV worin die Reste R4 jeweils gleich oder verschieden sein können und die vorstehende Bedeutung besitzen, X für Alkyl oder H steht und n eine ganze Zahl zwischen 1 und 30 darstellt,bedeuten, oder worin R2 und R3 zusammen mit dem Stickstoffatom, an das sie gebunden sind, einen Morpholinylrest, Pyridylrest, Piperidylrest, Pyrrolylrest, Pyrimidinylrest, Pyrrolinylrest, Pyrrolidinylrest, Pyrazinylrest oder Pyridazinylrest, darstellen.
- 3A fuel or lubricant composition as claimed in claim 1 of the general formula I where Ri is a polybutene or polyisobutene radical of 20 to 400 carbon atoms which is derived from isobutene and up to 20% by weight of n-butene, and R2 and R3 are identical or different and are each hydrogen, C1-C10-Alkyl, phenyl, naphthyl, C2-C10-hydroxyalkyl, an aminoalkylene radical of the general formula II where R4 is C1-C10-alkylene and R5 and R6 are identical or different and are each hydrogen, C1-C10- alkyl, phenyl, naphthyl, C2-C10-hydroxyalkyl or polybutene or polyisobutene, each of 20 to 400 carbon atoms, a polyaminoalkylene radical of the general formula III where the radicals R4 are identical or different, the radicals Rs are identical or different and R4, Rs and Rs have the above meanings and m is an integer from 2 to 8, ora polyoxyalkylene radical of the general formula IV' where the radicals R4 are identical or different and have the above meanings and n is an integer from 1 to 30, or where R2 and R3, together with the nitrogen atom to which they are bonded, form a morpholinyl radical. 3. A process for the preparation of a polybutene- or polyisobuteneamine of the formula (I) as claimed in claim 1, wherein, in the formula (I), Ri is a polybutyl or polyisobutyl radical of 20 to 400 carbon atoms which is derived from isobutene and up to 20% by weight of n-butene, R2 and R3 are identical or different and are each hydrogen, C1-C10-alkyl, phenyl, naphthyl, C2-C10-hydroxyalkyl, an aminoalkylene radical of the general formula II where R4 is C1-C10-alkylene and R5 and R6 are identical or different and are each hydrogen, C1-C10- alkyl, phenyl, naphthyl, C2-C10-hydroxyalkyl or polybutyl or polyisobutyl, each of 20 to 400 carbon atoms,a polyaminoalkylene radical of the general formula III where the radicals R4 are identical or different, the radicals R5 are identical or different and R4, R5 and R6 have the above meanings and m is an integer from 2 to 8, ora polyoxyalkylene radical of the general formula IV' where the radicals R4 are identical or different and have the above meanings and n is an integer from 1 to 30, or where R2 and R3, together with the nitrogen atom to which they are bonded, form a morpholinyl radical. 3. Composition de combustible ou de lubrifiant selon la revendication 1 de formule générale dans laquelle R1 représente un reste polybutène ou polyisobutène à 20-400 atomes de carbone, dérivé d'isobutène et, pour une proportion allant jusqu'à 20% en poids, de n-butène etR2 et R3, qui sont identiques ou différents, représentent chacun un atome d'hydrogène, un reste alkyle en Ci à Cio, phényle, naphtyle, hydroxyalkyle en C2 à C10, un reste aminoalkylène de formule générale Il dans laquelleR4 est mis pour un radical alkylène en C1 à C10 etR5 et R6, qui sont identiques ou différents, sont mis chacun pour des atomes d'hydrogène, des restes alkyle en C1-C10, phényle, naphtyle, hydroxyalkyle en C2-C10 ou des restes polybutène ou polyisobutène contenant dans chaque cas 20 à 400 atomes de carbone,un reste polyaminoalkylène de formule générale III dans laquelleles restes R4 sont chaque fois identiques ou différents,les restes Rs sont chaque fois identiques ou différents,les restes R4, R5 et R6 ont les significations données précédemment etm est mis pour un nombre entier de 2 à 8, ouun reste polyoxyalkylène de formule générale IV' dans laquelleles restes R4 sont chaque fois identiques ou différents et ont les significations précédentes etn est un nombre entier entre 1 et 30, ou dans laquelle R2 et Rs forment ensemble, avec l'atome d'azote auquel ils sont fixés, un reste morpholinyle. 3. Kraft- oder Schmierstoffzusammensetzung nach Anspruch 1 der allgemeinen Formel worin R1 einen von Isobuten und bis zu 20 Gew.-% n-Buten abgeleiteten Polybuten- oder Polyisobutenrest mit 20 bis 400 Kohlenstoffatomen darstellt, und R2 und Rs, die gleich oder verschieden sind, Wasserstoff, C1-C10-Alkyl, Phenyl, Naphthyl, C2-C10-Hydroxyalkyl, einen Amionalkylenrest der allgemeinen Formel II worinR4 für einen C1-C10-Alkylenrest und R5 und R6, die gleich oder verschieden sind, für Wasserstoff, C1-C10-Alkyl, Phenyl, Naphthyl, C2-C10-Hydroxyalkyl oder einen Polybuten oder Polyisobutenrest mit jeweils 20 bis 400 Kohlenstoffatomen stehen, einen Polyaminoalkylenrest der allgemeinen Formel III worindie Reste R4 jeweils gleich oder verschieden sind, die Reste Rs jeweils gleich oder verschieden sind, die Reste R4, Rs und Rs die vorstehenden Bedeutungen besitzen und m eine ganze Zahl von 2 bis 8 darstellt, oder einen Polyoxyalkylenrest der allgemeinen Formel IV' worindie Reste R4 jeweils gleich oder verschieden sind und die vorstehende Bedeutung besitzen und n eine ganze Zahl zwischen 1 und 30 darstellt,bedeuten, oder worin R2 und R3 zusammen mit dem Stickstoffatom, an das sie gebunden sind, einen Morpholinylrest darstellen. 3. Procédé de préparation de polybutène- ou polyisobutène-amines de formule (I) selon la revendication 1, caractérisé en ce que dans la formule (I), Ri représente un reste polybutyle ou polyisobutyle à 20-400 atomes de carbone, dérivé d'isobutène et, pour une proportion allant jusqu'à 20% en poids, de n-butène etR2 et R3, qui sont identiques ou différents, représentent chacun un atome d'hydrogène, un reste alkyle en C1 à C10, phényle, naphtyle, hydroxyalkyle en C2 à C10, un reste aminoalkylène de formule générale II dans laquelleR4 est mis pour un radical alkylène en C1 à C10 etR5 et Rs, qui sont identiques ou différents, sont mis pour des atomes d'hydrogène, des restes alkyle en C1-C10, phényle, naphtyle, hydroxyalkyle en C2-C10 ou des restes polybutyle ou polyisobutyle contenant dans chaque cas de 20 à 400 atomes de carbone,un reste polyaminoalkyle de formule générale III dans laquelleles restes R4 sont chaque fois identiques ou différents,les restes R5 sont chaque fois identiques ou différents,les restes R4, R5 et R6 ont les significations donées précédemment etm est mis pour un nombre entier de 2 à 8, ouun reste polyoxyalkylène de formule générale IV' dans laquelleles restes R4 sont chaque fois identiques ou différents et ont les significations précédentes etn est un nombre entier entre 1 et 30,ou dans laquelle R2 et R3 forment ensemble, avec l'atome d'azote auquel ils sont fixés, un reste morpholinyle. 3. Verfahren zur Herstellung von Polybuten- oder Polyisobutenaminen der Formel (I) gemäß Anspruch 1, dadurch gekennzeichnet, daß in der Formel (I) R1 einen von Isobuten und bis zu 20 Gew.-% n-Buten abgeleiteten Polybutyl- oder Polyisobutylrest mit 20 bis 400 Kohlenstoffatomen darstellt, und R2 und R3, die gleich oder verschieden sind, Wasserstoff, C1-C10-Alkyl, Phenyl, Naphthyl, C2-C10-Hydroxyalkyl, einen Aminoalkylenrest der allgemeinen Formel II worinR4 für einen C1-C10-A)kyienrest und R5 und R6, die gleich oder verschieden sind, für Wasserstoff, C1-C10-Alkyl, Phenyl, Naphthyl, C2-C10-Hydroxyalkyl oder einen Polybuten- oder Polyisobutenrest mit jeweils 20 bis 400 Kohlenstoffatomen stehen,einen Polyaminoalkylenrest der allgemeinen Formel III worindie Reste R4 jeweils gleich oder verschieden sind, die Reste R5 jeweils gleich oder verschieden sind, die Reste R4, Rs und R6 die vorstehenden Bedeutungen besitzen und m eine ganze Zahl von 2 bis 8 darstellt, odereinen Polyoxyalkylenrest der allgemeinen Formel IV' worindie Reste R4 jeweils gleich oder verschieden sind und die vorstehende Bedeutung besitzen und n eine ganze Zahl zwischen 1 und 30 darstellt,bedeuten, oder worin R2 und Rs zusammen mit dem Stickstoffatom, an das sie gebunden sind, einen Morpholinylrest darstellen.
- 4A fuel or lubricant composition of the general formulae I to IV' as claimed in claim 3 wherein R1 is a polybutene or polyisobutene radical of 35 to 200 carbon atoms which is derived from isobutene and up to 20% by weight of n-butene, and R2 and R3 are identical or different and are each hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, phenyl, -CH2-CH2-NH2, where p is an integer from 1 to 7, in particular from 1 to 3, -CH2-CH2-OH, where q is an integer from 1 to 30, or, together with the nitrogen atom to which they are bonded, form a morpholinyl radical. 4. A process for the preparation of a polybutene- or polyisobuteneamine of the formula (I) as claimed in claim 1, wherein, in the formula (I), R1 is a polybutene or polyisobutene radical of 35 to 200 carbon atoms which is derived from isobutene and up to 20% by weight of n-butene, and R2 and Rs are identical or different and are each hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, phenyl, -CH2-CH2-NH2, where p is an integer from 1 to 7, in particular from 1 to 3, where q is an integer from 1 to 30, or, together with the nitrogen atom to which they are bonded, form a morpholinyl radical. 4. Composition de combustible ou de lubrifiant de formules générales 1 à IV' selon la revendication 3, dans laquelle le reste Ri représente un reste polybutène ou polyisobutène à 35-200 atomes de carbone, dérivé d'isobutène et, pour une proportion allant jusqu'à 20% en poids, de n-butène, et R2 et R3 sont identiques ou différents et représentent chacun un atome d'hydrogène, un reste méthyle, éthyle, n-propyle, i-propyle, n-butyle, butyle secondaire, i-butyle, butyle tertiaire, pentyle, hexyle, phényle,-[-CH2-CH2-NH]p-CH2-CH2-NH2 (p étant mis pour un nombre entier de 1 à 7, en particulier de 1 à 3), CH2-CH2-OH, -[-CH2-CH2-O-]q-CH2-OH (q étant mis pour un nombre entier de 1 à 30), ou représentent ensemble, avec l'atome d'azote auquel ils sont fixés, un reste morpholinyle. 4. Kraft- oder Schmierstoffzusammensetzung der allgemeinen Formeln I bis IV' nach Anspruch 3, worin der Rest R1 einen von Isobuten und bis zu 20 Gew.-% n-Buten abgeleiteten Polybuten- oder Polyisobutenrest mit 35 bis 200 Kohlenstoffatomen darstellt, und R2 und R3 gleich oder verschieden sind und Wasserstoff, Methyl, Ethyl, n-Propyl, i-Propyl, n-Butyl, sec.-Butyl, i-Butyl, tert-.Butyl, Pentyl, Hexyl, Phenyl, worin p für eine ganze Zahl von 1 bis 7, insbesondere 1 bis 3, steht, -CH2-CH2-OH, worin q für eine ganze Zahl zwischen 1 und 30 steht, bedeuten, oder gemeinsam mit dem Stickstoffatom, an das sie gebunden sind, einen Morpholinylrest darstellen. 4. Procédé de préparation de polybutène- ou polyisobutène-amines de formule (I) selon la revendication 1, caractérisé en ce que dans la formule (1), le reste R1 représente un reste polybutène ou polyisobutène à 35-200 atomes de carbone, dérivé d'isobutène et, pour une proportion allant jusqu'à 20% en poids, de n-butène, et R2 et R3 sont identiques ou différents et représentent chacun un atome d'hydrogène, un reste méthyle, éthyle, n-propyle, i-propyle, n-butyle, butyle secondaire, i-butyle, butyle tertiaire, pentyle, hexyle, phényle, (p étant mis pour un nombre entier de 1 à 7, en particulier de 1 à 3), CH2-CH2-OH, (q étant mis pur un nombre entier de 1 à 30), ou représentent ensemble, avec l'atome d'azote auquel ils sont fixés, un reste morpholinyle. 4. Verfahren zur Herstellung von Polybuten- oder Polyisobutenaminen der Formel (I) gemäß Anspruch 1, dadurch gekennzeichnet, daß in der Formel (I) der Rest R1 einen von Isobuten und bis zu 20 Gew.-% n-Buten abgeleiteten Polybuten- oder Polyisobutenrest mit 35 bis 200 Kohlenstoffatomen darstellt, und R2 und R3 gleich oder verschieden sind und Wasserstoff, Methyl, Ethyl, n-Propyl, i-Propyl, n-Butyl, sec.-Butyl, i-Butyl, tert.-Butyl, Pentyl, Hexyl, Phenyl, worin p für eine ganze Zahl von 1 bis 7, insbesondere 1 bis 3, steht, -CH2-CH2-OH, worin q für eine ganze Zahl zwischen 1 und 30 steht, bedeuten, oder gemeinsam mit dem Stickstoffatom, an das sie gebunden sind, einen Morpholinylrest darstellen.
- 5A fuel composition as claimed in any of claims 1 to 4, which contains the polybutene or polyisobuteneamine in an amount of from 10 to 2,000 ppm, in particular from 100 to 400 ppm, based on the total weight of the composition. 5. Composition de combustible selon l'une quelconque des revendications 1 à 4, caractérisée en ce qu'elle contient la polybutène- ou polyisobutèneamine dans une proportion de 10 à 2000 ppm, en particulier de 100 à 400 ppm, par rapport au poids total de la composition. 5. Kraftstoffzusammensetzung nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß sie das Polybuten- oder Polyisobutenamin in einer Menge von 10 bis 2000 ppm, insbesondere 100 bis 400 ppm, bezogen auf das Gesamtgewicht der Zusammensetzung, enthält.
- 6A lubricant composition as claimed in any of claims 1 to 4, which contains the polybutene or polyisobutene in an amount of from 0.5 to 5, in particular from 1 to 3, % by weight, based on the total weight of composition. 6. Composition de lubrifiant selon l'une quelconque des revendications 1 à 4, caractérisée en ce qu'elle contient la polybutène- ou polyisobutèneamine dans une proportion de 0,5 à 5% en poids, en particulier de 1 à 3% en poids, par rapport au poids total de la composition. 6. Schmierstoffzusammensetzung nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß sie das Polybuten- oder Polyisobutenamin in einer Menge von 0,5 bis 5 Gew.-%, insbesondere 1 bis 3 Gew.-%, bezogen auf das Gesamtgewicht der Zusammensetzung, enthält.
- 7A polybutene or polyisobutene of the general formula I where R1 is a polybutene or polyisobutene radical of 20 to 400 carbon atoms which is derived from isobutene and up to 20% by weight of n-butene, and R2 and Rs are identical or different and are each hydrogen, C1-C10-alkyl, phenyl, naphthyl, C1-C10-hydroxyalkyl, an aminoalkylene radical of the general formula II where R4 is C1-C10-alkylene and R5 and R6 are identical or different and are each hydrogen, C1-C10- alkyl, phenyl, naphthyl, C1-C10-hydroxyalkyl or polybutene or polyisobutene, each of 20 to 400 carbon atoms,a polyaminoalkylene radical of the general formula III where the radicals R4 are identical or different, the radicals Rs are identical or different and R4, Rs and Rs have the above meanings and m is an integer from 1 to 7, ora polyoxyalkylene radical of the general formula IV' where the radicals R4 are identical or different and have the above meanings and n is an integer from 1 to 30, or where R2 and Rs, together with the nitrogen atom to which they are bonded, form a morpholinyl radical, individually or as a mixture with one another. 7. Polybuten- oder Polyisobutenamine der allgemeinen Formel 1 worin Ri einen von Isobuten und bis zu 20 Gew.-% n-Buten abgeleiteten Polybuten- oder Polyisobutenrest mit 20 bis 400 Kohlenstoffatomen darstellt, undR2 und R3, die gleich oder verschieden sind, Wasserstoff, C1-C10-Alkyl, Phenyl, Naphthyl, C1-C10-Hydroxyalkyl, einen Aminoalkylenrest der allgemeinen Formel II worinR4 für einen C1-C10-Alkylenrest und R5 und R6, die gleich oder verschieden sind, für Wasserstoff, C1-C10-Alkyl, Phenyl, Naphthyl, C1-C10-Hydroxyalkyl oder einen Polybuten oder Polyisobutenrest mit jeweils 20 bis 400 Kohlenstoffatomen stehen, einen Polyaminoalkylenrest der allgemeinen Formel III worindie Reste R4 jeweils gleich oder verschieden sind, die Reste R5 jeweils gleich oder verschieden sind, die Reste R4, R5 und R6 die vorstehenden Bedeutungen besitzen und m eine ganze Zahl von 1 bis 7 darstellt, oder einen Polyoxyalkylenrest der allgemeinen Formel IV' worindie Reste R4 jeweils gleich oder verschieden sind und die vorstehende Bedeutung besitzen und n eine ganze Zahl zwischen 1 und 30 darstellt,bedeuten, oder worin R2 und R3 zusammen mit dem Stickstoffatom, an das sie gebunden sind, einen Morpholinylrest darstellen, einzeln oder in Mischung untereinander. 7. Polybutène- ou polyisobutène-amines de formule générale 1 dans laquelle R1 représente un reste polybutène ou polyisobutène à 20-400 atomes de carbone, dérivé d'isobutène et, pour une proportion allant jusqu'à 20% en poids, de n-butène, etR2 et R3, qui sont identiques ou différents, représentent chacun un atome d'hydrogène, un reste alkyle en C1-C10, phényle, naphtyle, hydroxyalkyle en C1-C10, un reste aminoalkylène de formule générale II dans laquelleR4 est mis pour un reste alkylène en C1-C10 etR5 et R6, qui sont identiques ou différents, sont mis chacun pour un atome d'hydrogène, un reste en C1-C10, phényle, naphtyle, hydroxyalkyle en C1-C10 ou polybutène ou polyisobutène contenant chaque fois de 20 à 400 atomes de carbone,un reste polyaminoalkylène de formule générale III dans laquelleles restes R4 sont chaque fois identiques ou différents,les restes R5 sont chaque fois identiques ou différents,les restes R4, R5 et R6 ont les significations données précédemment etm est mis pour un nombre entier de 1 à 7, ouun reste polyoxyalkylène de formule générale IV' dans laquelleles restes R4 sont chaque fois identiques ou différents et ont les significations précédentes etn est un nombre entier entre 1 et 30,ou dans laquelle R2 et R3 forment ensemble, avec l'atome d'azote auquel ils sont fixés, un reste morpholinyle, ces polybutène- ou polyisobutène-amines étant utilisées individuellement ou en mélanges entre elles.
- 8Use of a polybutene- or polyisobuteneamine of the general formula I as claimed in claim 7 in fuel or lubricant compositions for internal combustion engines. 8. Utilisation des polybutène- ou polyisobutène-amines de formule générale I selon la revendication 7 dans des compositions de carburant ou de lubrifiant pour des moteurs à combustion interne. 8. Verwendung der Polybuten- oder Polyisobutenamine nach der allgemeinen Formel I gemäß Anspruch 7 in Kraft- oder Schmierstoffzusammensetzungen für Verbrennungsmotoren.
- 9A process for the preparation of a polybutene- or polyisobuteneamine of the general formula I as claimed in claim 7, wherein the polybutene or polyisobutene is hydroformylated with a rhodium or cobalt catalyst in the presence of CO and H2 at from 80 to 200°C and under a CO/H2 pressure of up to 600 bar and the oxo product is then subjected to a Mannich reaction or amination under hydrogenating conditions. 9. Procédé de préparation des polybutène- ou polyisobutène-amines de formule générale 1 selon la revendication 7, caractérisé en ce qu'on hydroformyle un polybutène ou un polyisobutène avec un catalyseur au rhodium ou au cobalt en présence de CO et de H2 à des températures comprises entre 80 et 200°C et sous des pressions de CO/H2 allant jusqu'à 600 bars, puis on soumet le produit oxo à une réaction de Mannich ou à une amination hydrogénante. 9. Verfahren zur Herstellung der Polybuten- oder Polyisobutenamine der allgemeinen Formel I gemäß Anspruch 7, dadurch gekennzeichnet, daß man ein Polybuten oder Polyisobuten mit einem Rhodium- oder Kobaltkatalysator in Gegenwart von CO und H2 bei Temperaturen zwischen 80 und 200°C und CO/H2-Drucken von bis zu 600 bar hydroformyliert und anschließend eine Mannichreaktion oder hydrierende Aminierung des Oxoprodukts durchführt.
- 10A polybutene or polyisobutene alcohol of the general formula V where R1 is a polybutene or polyisobutene radical derived from isobutene and up to 20% by weight of n-butene. 10. Polybuten- oder Polyisobutenalkohole der allgemeinen Formel V:worin Ri einen von Isobuten und bis zu 20 Gew.-% n-Buten abgeleiteten Polybuten- oder Polyisobutenrest darstellt. 10. Polybutène- ou polyisobutène-alcools de formule générale V dans laquelle Ri représente un reste polybutène ou polyisobutène dérivé d'isobutène et, pour une proportion allant jusqu'à 20% en poids, de n-butène.
- 11A polybutene or polyisobutene alcohol of the general formula V as claimed in claim 10, wherein the radical Ri is of 20 to 400 carbon atoms. 11. Polybuten- oder Polyisobutenalkohole der allgemeinen Formel V nach Anspruch 10, worin der Rest R1 20 bis 400 Kohlenstoffatome aufweist. 11. Polybutène- ou polyisobutène-alcools de formule générale V selon la revendication 10, dans lesquels le reste R1 comporte de 20 à 400 atomes de carbone.
Independent claims11
45 paragraphs, as filed
The invention relates to fuel and lubricant compositions which contain polybutene or polyisobutene amines. The invention further relates to certain polybutene or polyisobutene amines and a process for their preparation.
Polybutenamines and their use as fuel and lubricant additives have been known for a long time and are described, for example, in US Pat. No. 3,275,554 and DE-A 2 125 039.
The prior art polybutenamines are prepared by halogenating polybutenes and reacting the halides with amines. In the manufacture of these products, ionic halogen is formed, which must be removed as far as possible.
There has therefore been no lack of attempts in the prior art to improve the known products, especially since the removal of the ionogenic halogen not only requires complex measures, but also considerable amounts of halogen always remain in the reaction products, cf. DE-A 2 245 918.
DE-A 2 702 604 describes so-called reactive polyisobutenes which can be reacted with maleic anhydride (MA) and oligo- or polyamines to form mineral oil auxiliaries. The mineral oil auxiliaries obtainable in this way have the great advantage that they are virtually halogen-free. A disadvantage is the difficult accumulation of MSA (en reaction) combined with tar formation, ie undesirable by-products.
The invention has for its object to provide fuel or lubricant compositions that prevent the deposits in the intake system of gasoline engines or have a particularly good dispersant effect.
This object is achieved with a fuel or lubricant composition which is characterized in that it contains at least one polybutene or polyisobutenamine; that corresponds to the general formula 1:<chemistry id="chem0001" num="0001"><img file="EP0244616B1_D0001.tif" /></chemistry>wherein<ul id="ul0001" list-style="none"><li>R<sub>1</sub> represents a polybutene or polyisobutene radical derived from isobutene and up to 20% by weight of n-butene and</li><li>R<sub>2</sub> and R<sub>3</sub>which may be the same or different, represent hydrogen, aliphatic or aromatic hydrocarbons, primary or secondary, aromatic or aliphatic aminoalkylene radicals or polyaminoalkylene radicals, polyoxyalkylene radicals, heteroaryl or heterocyclyl radicals, or together with the nitrogen atom to which they are bonded, form a ring , in which further heteroatoms may be present, and which has been obtained by hydroformylation of a polybutene or polyisobutene and subsequent hydrogenating amination.</li></ul>
According to a preferred embodiment of the invention, a fuel or lubricant composition containing compounds of the general formula is provided in which R<sub>1</sub> represents a polybutene or polyisobutene radical derived from isobutene and up to 20% by weight of n-butene, and in which R<sub>2</sub> and Rs are identical or different and are each hydrogen, alkyl, aryl, hydroxyalkyl, an aminoalkylene radical of the general formula il<chemistry id="chem0002" num="0002"><img file="EP0244616B1_D0002.tif" /></chemistry>wherein<ul id="ul0002" list-style="none"><li>R<sub>4</sub> represents an alkylene radical and</li><li>Rs and R<sub>6</sub>, which are the same or different, represent hydrogen, alkyl, aryl, hydroxyalkyl or a polybutene or polyisobutene radical, a polyaminoalkylene radical of the general formula III<chemistry id="chem0003" num="0003"><img file="EP0244616B1_D0003.tif" /></chemistry>where the radicals R<sub>4</sub> are each the same or different and the residues</li><li>Rs are the same or different and the radicals R<sub>4</sub>, Rs and Rs have the meanings given above, and m represents an integer from 2 to 8, or</li><li>a polyoxyalkylene radical of the general formula IV<chemistry id="chem0004" num="0004"><img file="EP0244616B1_D0004.tif" /></chemistry>where the radicals R<sub>4</sub> can each be the same or different and have the above meaning, X represents alkyl or H and n represents an integer between 1 and 30,</li><li>mean, or in which R<sub>2</sub> and R<sub>3</sub> together with the nitrogen atom to which they are attached represent a morpholinyl radical, pyridyl radical, piperidyl radical, pyrrolyl radical, pyrimidinyl radical, pyrrolinyl radical, pyrrolidinyl radical, pyrazinyl radical or pyridazinyl radical.</li></ul>
According to a particularly preferred embodiment, a fuel or lubricant composition containing compounds of the general formula is provided:<chemistry id="chem0005" num="0005"><img file="EP0244616B1_D0005.tif" /></chemistry>wherein<ul id="ul0003" list-style="none"><li>R<sub>1</sub> represents a polybutene or polyisobutene radical with 20 to 400 carbon atoms derived from isobutene and up to 20% by weight of n-butene, and</li><li>R<sub>2</sub> and R<sub>3</sub>that are the same or different, hydrogen, C<sub>1</sub>-C<sub>10</sub>-Alkyl, phenyl, naphthyl, C<sub>1</sub>-C<sub>10</sub>-Hydroxyalkyl, an aminoalkylene radical of the general formula II<chemistry id="chem0006" num="0006"><img file="EP0244616B1_D0006.tif" /></chemistry>wherein</li><li>R<sub>4</sub> for a C<sub>2</sub>-C<sub>10</sub>-Alkylene radical and</li><li>R<sub>5</sub> and R<sub>6</sub>, which are the same or different, for hydrogen, C<sub>1</sub>-C<sub>10</sub>-Alkyl, phenyl, naphthyl, C<sub>1</sub>-C<sub>10</sub>-Hydroxyalkyl or a polybutene or polyisobutene radical each having 20 to 400 carbon atoms, a polyaminoalkylene radical of the general formula III<chemistry id="chem0007" num="0007"><img file="EP0244616B1_D0007.tif" /></chemistry>wherein</li><li>the residues R<sub>4</sub> are each the same or different,</li><li>the radicals Rs are in each case the same or different,</li><li>the residues R<sub>4</sub>, Rs and Rs have the above meanings and</li><li>m represents an integer from 2 to 8, or</li><li>a polyoxyalkylene radical of the general formula IV '<chemistry id="chem0008" num="0008"><img file="EP0244616B1_D0008.tif" /></chemistry>where the radicals R<sub>4</sub> are each the same or different and have the above meaning and n represents an integer between 1 and 30,</li><li>mean, or in which R<sub>2</sub> and R<sub>3</sub> together with the nitrogen atom to which they are attached represent a morpholinyl radical.</li></ul>
According to a further preferred embodiment, a fuel or lubricant composition is provided with a content of compounds of the general formula I to IV ', in which the radical Ri is a polybutene or polyisobutene radical derived from isobutene and up to 20% by weight of n-butene with 32 to 200 carbon atoms, and<ul id="ul0004" list-style="none"><li>R<sub>2</sub> and R<sub>3</sub> are identical or different and are hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, sec.-butyl, i-butyl, tert.-butyl, pentyl, hexyl, phenyl,<chemistry id="chem0009" num="0009"><img file="EP0244616B1_D0009.tif" /></chemistry><chemistry id="chem0010" num="0010"><img file="EP0244616B1_D0010.tif" /></chemistry>where p is an integer from 1 to 7, in particular 1 to 3, -CH2CH2-OH,<chemistry id="chem0011" num="0011"><img file="EP0244616B1_D0011.tif" /></chemistry>where q is an integer between 1 and 30, or together with the nitrogen atom to which they are attached represent a morpholinyl radical.</li></ul>
Since approximately 50% by weight of the active substance in fuel additives can be replaced by polyisobutene (PiB) without loss of effectiveness, the addition of PIB is particularly advantageous for reasons of cost. The polyisobutene can be one with a molecular weight M<sub>N</sub> from 300 to 2000, preferably 500 to 1500.
If the invention is a fuel composition, that is to say a fuel for internal combustion engines, the polybutene or polyisobutenamine of the general formula 1 can be present, for example, in an amount of 10-2000 mg / kg, in particular 100-400 mg / kg of fuel .
In the lubricant composition according to the invention, the polybutene or polyisobutenamine can be present, for example, in an amount of 0.5-5% by weight, in particular 1-3% by weight, based on the total weight of the composition.
The invention also relates to polybutene or polyisobutene amines of the general formula 1<chemistry id="chem0012" num="0012"><img file="EP0244616B1_D0012.tif" /></chemistry>wherein<ul id="ul0005" list-style="none"><li>R<sub>1</sub> represents a polybutene or polyisobutene radical with 20 to 400 carbon atoms derived from isobutene and up to 20% by weight of n-butene, and</li><li>R<sub>2</sub> and R<sub>3</sub>that are the same or different, hydrogen, C<sub>1</sub>-C<sub>10</sub>-Alkyl, phenyl, naphthyl, C<sub>2</sub>-C<sub>10</sub>-Hydroxyalkyl, an aminoalkylene radical of the general formula II<chemistry id="chem0013" num="0013"><img file="EP0244616B1_D0013.tif" /></chemistry>wherein</li><li>R<sub>4</sub> for a C<sub>1</sub>-C<sub>10</sub>Alkylene radical and R<sub>5</sub> and R<sub>6</sub>, which are the same or different, for hydrogen, C<sub>1</sub>-C<sub>10</sub>-Alkyl, phenyl, naphthyl, C<sub>2</sub>-C<sub>10</sub>Hydroxyalkyl or a polybutene or polyisobutene radical each having 20 to 400 carbon atoms,</li><li>a polyaminoalkylene radical of the general formula III<chemistry id="chem0014" num="0014"><img file="EP0244616B1_D0014.tif" /></chemistry>wherein</li><li>the residues R<sub>4</sub> are each the same or different, the radicals R<sub>5</sub> are each the same or different, the radicals R<sub>4</sub>, Rs and R<sub>6</sub> have the above meanings and m represents an integer from 2 to 8, or</li><li>a polyoxyalkylene radical of the general formula IV '<chemistry id="chem0015" num="0015"><img file="EP0244616B1_D0015.tif" /></chemistry>where the radicals R<sub>4</sub> are each the same or different and have the above meaning and n represents an integer between 1 and 30,</li><li>mean, or wherein Rz and R<sub>3</sub> together with the nitrogen atom to which they are attached represent a morpholinyl radical, individually or as a mixture with one another.</li></ul>
The compounds of the general formula I can be prepared via the step of the compounds of the general formula V by reacting a corresponding polybutene or polyisobutene with a rhodium or cobalt catalyst in the presence of CO and H.<sub>2</sub> at temperatures between 80 and 200 ° C and CO / H<sub>2</sub>-Hydroformylated pressure up to 600 bar and then carries out a hydrogenating amination of the oxo product. The amination reaction is expediently carried out at temperatures of 80-200 ° C. and hydrogen pressures up to 600 bar, preferably 80-300 bar.
The products obtained in this way are distinguished from the products according to DE 1 545 487 obtained by halogenation of polybutenes and amination by the absence of chlorine compounds and improved effectiveness.
A suitable, inert solvent is expediently used in the production process in order to reduce the viscosity of the reaction mixture. Low-sulfur aliphatic, cycloaliphatic and aromatic hydrocarbons are particularly suitable as solvents. Aliphatic solvents which are free from sulfur compounds and contain less than 1% aromatics are particularly preferred. They have the advantage that no heat of hydrogenation is released and no hydrogen is consumed at high amination temperatures. In the amination and hydroformylation reaction, the solvent content is between 0 and 70% by weight, depending on the viscosity of the polymer and the solvent. Higher dilutions are just as uneconomical as a solvent exchange between the oxination and amination.
In the process according to the invention, polybutene conversions of 80-90% can easily be achieved. The polybutenes, which are predominantly composed of isobutene units (the isobutene content is usually more than 80% by weight) have, for example, a molecular weight M.<sub>N</sub> from 300-5000, preferably from 500-2500. According to the invention, so-called reactive polybutenes, in particular polybutene A, B or C, can be used. A reactive polybutene is an unsaturated polymer with high chemical uniformity, with more than 10% of the double bonds being a-permanent. DE 2 702 604 describes a way of producing such polybutenes. A polymer prepared in this way contains approximately 60% α-olefin and 30% β-olefin, trisubstituted.
Medium-reactive polybutenes are usually obtained by polymerizing isobutene or isobutene-containing C.<sub>4</sub>-Cuts obtained with aluminum-containing catalysts are chemically less uniform and contain only small amounts of α-olefin, usually less than 10%. The signals in the C<sub>13</sub>-NMR show the difference. The β-permanent, trisubstituted, chemically uniform proportion in polybutene B is approximately 40%, the α-olefin proportion approximately 10%.
Finally, the polybutene A can be described as not very reactive and no longer has any notable chemically uniform proportions.
Particularly suitable polybutenes and polyisobutenes for the preparation of the polyamines of the general formula and the alcohols of the general formula V according to the invention are those which have an average degree of polymerization P of 10 to 100 and in which the proportion E of double bonds which are capable of reacting with maleic anhydride Is 60 to 90%. A value E = 100% corresponds to the calculated theoretical value in the event that each molecule of the butene or isobutene polymer contains such a reactive double bond. The value E is calculated for a reaction of the polyisobutene with maleic anhydride in a weight ratio of 5: 1 and heating the mixture to 200 with stirring for 4 hours<sub>°</sub>C. Further details can be found in GB-A 1 592 016, the disclosure of which is expressly incorporated herein by reference.
The polybutenes are commercial products.
The oxo product formed in the hydroformylation is normally in the form of an aldehyde / alcohol mixture. It can be further processed as a mixture or can be hydrated beforehand for reasons of storage stability. Hydrated products are less reactive.
The invention also relates to the polybutene or polyisobutene alcohols of the general formula V formed in the hydroformylation described<chemistry id="chem0016" num="0016"><img file="EP0244616B1_D0016.tif" /></chemistry>where R<sub>1</sub> represents a polybutene or polyisobutene radical derived from isobutene and up to 20% by weight of n-butene. These compounds are useful, for example, as intermediates for the preparation of the compounds of the general formula 1. As described above, they are formed by hydroformylation of the polybutenes explained above. Polybutene or polyisobutene alcohols of the formula V in which the radical R 1 has 20 to 400 carbon atoms are particularly preferred.
For economic reasons, polybutene or polyisobutenamines of the general formula I in which the radicals R<sub>2</sub> and R<sub>3</sub> are each hydrogen, suitable for the fuel sector, ie in the fuel compositions according to the invention, particularly as a valve-cleaning or valve-cleaning additive. The dosage of the polybutene or polyisobutene amines of the general formula I as a fuel additive expediently asks 10-2000 mg / kg, a range of 50-800 mg / kg being preferred. An optimal effect can be achieved in the range of 100-400 ppm as an additive to petrol for internal combustion engines. Smaller amounts can be metered with the same good effect if the nitrogen content is higher and the usual carrier substances are higher, especially by using polyamines, for example dimethylaminopropylamine or by using polybutene or polyisobutenamines of the general formula with a lower molecular weight polybutene or polyisobutene content, For example, polybutene, polybutene alcohol, bright stock or other mineral oils can be dosed. When using polyamines, such as diethylene triamine to pentaethylene hexamine, one rather obtains gasifier detergent or so-called ashless dispersants for lubricating oils.
The halogen content of the polybutene or polyisobutene amines according to the invention corresponds to that of the starting materials. It is usually below 30 mg / kg.
Insofar as there are hydroxyl groups in the compounds of the general formula I, these compounds are particularly interesting as a fuel additive.
The fuel or lubricant composition according to the invention has a number of advantages over the prior art, such as, for example, the fact that it is saturated compounds, that there are no corrosion problems, that the synthesis is less expensive and more environmentally friendly and that there is no chlorine or product contamination Bromine occurs.
The invention is further illustrated by the examples below.
example 1
500 g Polybutene with a molecular weight M<sub>N</sub> = 950, 300 g of dodecane and 2.8 g of cobalt octacarbonyl are in a 2.5 I stirred autoclave at 280 bar CO / H<sub>e.g.</sub> 1: 1 with stirring for 5 hours to 185<sub>°</sub>C. heated. Then it is cooled to room temperature and the catalyst is removed with 400 ml of 10% aqueous acetic acid. Then it is washed neutral. The oxo product obtained in this way is treated with 1 l of ammonia and 300 g of ethanol and 100 g of Raney cobalt in a 5 l roll autoclave with 200 bar of hydrogen at 180 ° C. for 5 hours. After cooling, the catalyst is separated off by filtration, the excess ammonia is evaporated off and the solvent is separated off by distillation.
The polybutene used in this example is a highly reactive polybutene C which was produced in accordance with DE-A 2 702 604.
The polybutene conversion is shown in the table below.
Example 2
The procedure is as in Example 1, except that the hydroformylation is carried out at a temperature of only 120<sub>°</sub>C with 0.5 g of rhodium dicarbonylacetylacetonate as a catalyst. Instead of ammonia, dimethylaminopropylamine is used. The reaction temperature of the amination stage is only 80 ° C. Since the hydroformylation reaction proceeds predominantly in the direction of the aldehyde, the reaction with dimethylaminopropylamine is facilitated. The excess amine is removed by distillation together with the solvent.
Examples 3, 4 and 5
The general procedure of Example 1 is followed, using dimethylaminopropylamine as the amine component. The polybutene used in Example 3 is a slightly reactive polybutene (referred to as polybutene A), in Example 4 a medium-reactive polybutene B is used and in Example 5 a highly reactive polybutene C is used. These polybutenes have a molecular weight M.<sub>N</sub> from 900-1000. As in Example 1, the conversion is determined by preparative column chromatography on silica gel by gravimetry of the evaporated hexane fraction, which contains only unreacted polybutene. The purity of this fraction is ensured by base number and nitrogen determination.
Example 6
The procedure is as described in Example 1, with the exception that 2.8 g of cobalt octacarbonyl is used as the catalyst. The amine component is tetraethylene pentamine.
Comparative Examples A and B
The prior art products were prepared by chlorination of polybutene C and dehydrohalogenation in accordance with US-A-3,275,554, Example 1. In the case of comparative example B, a lower conversion than that according to the invention was achieved in the synthetic route via polybutylene chloride, which is in accordance with DE-A-2 245 918.
The utility of the substances prepared as described above has been investigated in fuel compositions and lubricant compositions. Examples 1 to 5 and Comparative Example A are studies on the additive fuel, Example 6 and Comparative Example B relate to lubricant compositions.
The valve cleaning effect of the additive fuels was assessed after 40 hours via valve deposits in the Opel Kadett 1.2 I engine after standardized testing in accordance with the CEC meth or F-02-C79.
The dispersant effect for lubricating oils was determined using the spot method described by A. Schilling in "Les Huiles Pour Moteurs et le Graissage des Moteurs", Volume 1, 1962, pages 89-90.
From the data compiled in the table below, it can be seen that the fuel or lubricant composition according to the invention is superior to the prior art in terms of valve-cleaning action or dispersant action.<tables id="tabl0001" num="0001"><img file="EP0244616B1_D0017.tif" /></tables>
91 sheets
Sheet 1 Sheet 2 Sheet 3 Sheet 4 Sheet 5 Sheet 6 Sheet 7 Sheet 8 Sheet 9 Sheet 10 Sheet 11 Sheet 12 Sheet 13 Sheet 14 Sheet 15 Sheet 16 Sheet 17 Sheet 18 Sheet 19 Sheet 20 Sheet 21 Sheet 22 Sheet 23 Sheet 24 Sheet 25 Sheet 26 Sheet 27 Sheet 28 Sheet 29 Sheet 30 Sheet 31 Sheet 32 Sheet 33 Sheet 34 Sheet 35 Sheet 36 Sheet 37 Sheet 38 Sheet 39 Sheet 40 Sheet 41 Sheet 42 Sheet 43 Sheet 44 Sheet 45 Sheet 46 Sheet 47 Sheet 48 Sheet 49 Sheet 50 Sheet 51 Sheet 52 Sheet 53 Sheet 54 Sheet 55 Sheet 56 Sheet 57 Sheet 58 Sheet 59 Sheet 60 Sheet 61 Sheet 62 Sheet 63 Sheet 64 Sheet 65 Sheet 66 Sheet 67 Sheet 68 Sheet 69 Sheet 70 Sheet 71 Sheet 72 Sheet 73 Sheet 74 Sheet 75 Sheet 76 Sheet 77 Sheet 78 Sheet 79 Sheet 80 Sheet 81 Sheet 82 Sheet 83 Sheet 84 Sheet 85 Sheet 86 Sheet 87 Sheet 88 Sheet 89 Sheet 90 Sheet 91
Every citation, both ways
| Document | Relation | Office | Cited during |
|---|---|---|---|
| WO2011045309A1 | Cited by | World Intellectual Property Organization (WIPO) | Applicant |
| DE1545487A | Cites | Germany | – |
| DE2702604A | Cites | Germany | – |
| FR2424956A | Cites | France | – |
| FR2476655A | Cites | France | – |
| GB2136438A | Cites | United Kingdom | – |
| US4134844A | Cites | United States of America | – |
| US4202784A | Cites | United States of America | – |
18 members in 7 offices
Priority claims4
| Document | Office | Kind | Date |
|---|---|---|---|
| 3611230 | Germany | A | |
| 3611230 | Germany | – | |
| 3611230 | – | – | – |
| DE19863611230 | – | – | – |
Members18
| Document | Office | Kind | |
|---|---|---|---|
| DK170087D0 | Denmark | D0 | |
| NO871393D0 | Norway | D0 | |
| DK170087A | Denmark | A | |
| NO871393L | Norway | L | |
| DE3611230A1 | Germany | A1 | |
| JPS62241992A | Japan | A | |
| EP0244616A2 | European Patent Office (EPO) | A2 | |
| EP0244616A3 | European Patent Office (EPO) | A3 | |
| US4832702A | United States of America | A | |
| EP0244616B1This record | European Patent Office (EPO) | B1 | |
| DE3763421D1 | Germany | D1 | |
| ES2016585B3 | Spain | B3 | |
| NO168828B | Norway | B | |
| NO168828C | Norway | C | |
| DK169584B1 | Denmark | B1 | |
| JPH07103385B2 | Japan | B2 | |
| JPH08100188A | Japan | A | |
| JP2696076B2 | Japan | B2 |
37 legal events, as 4 offices reported them to INPADOC
Over the term
Point at a mark for the eventEvents
| Event | Code | Office | |
|---|---|---|---|
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Be: patent expiredExpiredBE20 | BE20 | EP | |
| Announcement of lapse in spainLapsedFD2A | FD2A | ES | |
| Nl: ceased due to reaching the maximum lifetime of a patentCeasedNLV7 | NLV7 | EP | |
| Se: european patent has lapsedLapsedEUG | EUG | EP | |
| Patent ceasedCeasedPL | PL | CH | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| European patent in force as of 2002-01-01IF02 | IF02 | GB | |
| Se: european patent in force in swedenEAL | EAL | EP | |
| No opposition filedOpposition26N | 26N | EP | |
| No opposition filed within time limitOppositionORIGINAL CODE: 0009261PLBE | PLBE | EP | |
| Information on the status of an ep patent application or granted ep patentGrantedSTATUS: NO OPPOSITION FILED WITHIN TIME LIMITSTAA | STAA | EP | |
| It: last paid annual feeITTA | ITTA | EP | |
| Gb: translation filed (gb section 80(3)/1977)GBT8 | GBT8 | EP | |
| Fr: translation filedET | ET | EP | |
| Gb: translation of ep patent filed (gb section 77(6)(a)/1977)GBT | GBT | EP | |
| Corresponds to:REF | REF | EP | |
| It: translation for a ep patent filedITF | ITF | EP | |
| It: translation for a ep patent filedITF | ITF | EP | |
| Designated contracting statesAK | AK | EP | |
| (expected) grantORIGINAL CODE: 0009210GRAA | GRAA | EP | |
| First examination report despatched17Q | 17Q | EP | |
| Request for examination filed17P | 17P | EP | |
| Designated contracting statesAK | AK | EP | |
| Designated contracting statesAK | AK | EP | |
| Search report despatchedORIGINAL CODE: 0009013PUAL | PUAL | EP | |
| Public reference made under article 153(3) epc to a published international application that has entered the european phaseORIGINAL CODE: 0009012PUAI | PUAI | EP |
Numbers
- Publication
- 0244616
- Publication, DOCDB
- 0244616
- Publication, EPODOC
- EP0244616
- Application
- 87104371
- Application, DOCDB
- 87104371
- Application, EPODOC
- EP19870104371
Titles3
- German
- Polybuten- und Polyisobutenamine, Verfahren zu deren Herstellung und diese enthaltende Kraft- und Schmierstoffzusammensetzungen
- English
- Polybutene and polyisobutene amine, process for their preparation and fuel or lubricating compositions containing them
- French
- Polybutène et polyisobutèneamine, leur procédé de préparation et compositions de combustibles et de lubrifiants qui les contiennent
Classification
- CPC, 16
- C10M133/58
- C08F8/32
- C10L1/2383
- C10L1/2387
- C10M133/54
- C10M2215/04
- C10M2215/042
- C10M2215/06
- C10M2215/22
- C10M2215/221
- C10M2215/225
- C10M2215/226
- C10M2215/26
- C10M2215/30
- C10M2217/046
- C10M2217/06
- IPC, 20
- C10L1 22
- C08F8 00
- C08F8 30
- C08F8 32
- C10L1 222
- C10L1 234
- C10L1 2383
- C10L1 2387
- C10L10 08
- C10M133 00
- C10M133 04
- C10M133 38
- C10M133 52
- C10M133 54
- C10M133 58
- C10M149 12
- C10N30 04
- C10N40 00
- C10N40 25
- C10N70 00
Designated states10
- Contracting states, 10
- Belgium
- Switzerland
- Germany
- Spain
- France
- United Kingdom
- Italy
- Liechtenstein
- Netherlands (Kingdom of the)
- Sweden
