EP0511982B1 - Saturated, branched fatty acids with 21 to 28 carbon atoms or esters of the same with c1-c36 alkanols, process for producing them and their use - Google Patents
Saturated, branched fatty acids with 21 to 28 carbon atoms or esters of the same with c1-c36 alkanols, process for producing them and their use Download PDFInfo
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- EP0511982B1 EP0511982B1 EP91902087A EP91902087A EP0511982B1 EP 0511982 B1 EP0511982 B1 EP 0511982B1 EP 91902087 A EP91902087 A EP 91902087A EP 91902087 A EP91902087 A EP 91902087A EP 0511982 B1 EP0511982 B1 EP 0511982B1
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- fatty acids
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- alkanols
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
- C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
- C10M129/26—Carboxylic acids; Salts thereof
- C10M129/28—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M129/38—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms
- C10M129/40—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms monocarboxylic
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
- C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
- C10M129/68—Esters
- C10M129/70—Esters of monocarboxylic acids
Definitions
- the invention relates to saturated, branched fatty acids with 21 to 28 carbon atoms or esters thereof with C1-C36 alkanols, obtainable by hydrogenation of olefinically unsaturated adducts of propylene with polyunsaturated fatty acids with 18 to 22 carbon atoms or esters thereof with C1-C36 -Alkanols in molar ratios of ethylene to fatty acids or fatty acid esters in the range from 1: 1 to 2: 1.
- Fatty acids of the Guerbet acid type branched in the alkyl chain obtainable by Guerbetification of the corresponding fatty alcohols and oxidation of the Guerbet alcohols to the corresponding acids, are technologically interesting intermediates because they or their alkyl esters have significantly lower pour points compared to the corresponding unbranched isomers.
- the production of guerbet acids is technologically complex and can only be carried out with unsatisfactory yields. It therefore has no attempts failed to produce, starting from fatty acids or esters thereof, corresponding fatty acid derivatives which have branches in the alkyl chain.
- a typical example of this is layered silicate-catalyzed fatty acid dimerization, in which, however, considerable amounts of trimeric fatty acids and of methyl-branched fatty acids, so-called isofatty acids, are also formed.
- branched fatty acid derivatives from conjuene fatty acids in the trans, trans form with activated dienophiles under the conditions of a Diels-Alder reaction; for example, a branched C21-dicarboxylic acid can be produced from linoleic acid and acrylic acid in this way, cf. US-B 3,734,859, US-B 3,753,968, DE-B 2 253 930 .
- EP-A1 0 010 807 discloses branched monocarboxylic acids which are obtained by telomerization of one mole of acetic anhydride and at least three moles of an olefin having at least 6 and up to 30 carbon atoms in the presence of a trivalent manganese compound.
- branched fatty acid derivatives have been obtained by thermal or acid-catalyzed addition of activated enophiles to unsaturated fatty acid derivatives.
- activated enophiles For example, maleic anhydride can be added with acid catalysis in up to 70% yield of oleic acid, cf. Fat. Sci. Technol., 1 , 1 (1988) .
- the presence of more than one carboxyl group often proves to be troublesome in the reaction products mentioned above.
- the saturated, branched fatty acids or esters thereof can be prepared in a simple manner and with good yields become.
- the compounds provided according to the invention are new products which are derived, for example, from naturally occurring ethyl-branched fatty acids with a total of 12 to 18 carbon atoms, described in A. Smith et al, Biomed. Mass Spectrom., 6 (8), 347-349 , already differ by their chain length.
- the saturated, branched fatty acids of the invention or esters thereof can be obtained by hydrogenating olefinically unsaturated adducts of propylene with polyunsaturated fatty acids having 18 to 22 carbon atoms or with esters thereof with C1-C3 Alk alkanols in molar ratios of propylene to fatty acids or fatty acid esters in the range of 1: 1 to 2: 1 can be obtained.
- Suitable starting products for the preparation of the olefinically unsaturated adducts of the abovementioned patent application are unsaturated fatty acids with 18 to 22 carbon atoms and more than one olefinic double bond such as linoleic acid, isomerized linoleic acid with conjugated double bonds (so-called C18: 2 conjuene fatty acid), linolenic acid, arachidonic acid, docosadienoic acid, docosaic acid and eicosapentaenoic acid, in the form of their technical mixtures with others
- Fatty acids renewable natural raw materials for example from sunflower oil, tall oil or fish oil, can be obtained.
- polyunsaturated fatty acids are, as is customary in fat chemistry, generally not in the form of their pure compounds, but in the form of their technical mixtures for the preparation of the adducts of the invention.
- the aforementioned fatty acids are preferably used not only as such, but also in the form of their esters with C1-C36 alkanols, especially with C1-C4 alkanols.
- Typical examples of such alkanols for the formation of esters with the aforementioned fatty acids are methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, decanol, dodecanol, tetradecanol, hexadecanol, octadecanol and higher fatty alcohols or fatty alcohol derivatives with up to 36 carbon atoms, e.g. C36 Guerbet alcohols.
- the aforementioned polyunsaturated fatty acids or fatty acid esters accumulate at elevated temperature and pressure in the presence of compounds of transition metals from the group consisting of Ru, Rh, Pd, Ir and Pt and propylene.
- Typical examples of catalysts that can be used are the following: RhCl3.3H2O RhBr3.3H2O [(C2H4) 2RhCl] 2 Rh (NO3) 3.2H2O Rh (OOCCH3) 2.2H2O Rh (acetylacetonate) 3 RhF3.6H2O RhJ3 Rh (CN) 3.3H2O Rh2 (SO4) 3 Rh2 (CO3) 3 [(1.5-Cyclooctadiene) RhCl] 2 [(C2H4) 2Rh (acetylacetonate)] [(1,3-butadiene) RhCl] 2 Cyclopentadienyl olefin complexes such as [(n-C5H5) Rh (C2H4) 2].
- the catalysts which can be used are in anhydrous form, it may be expedient to add a small amount of water to the reaction mixture.
- catalysts which can be used in the process of the patent application mentioned are, for example PdCl2 PtCl2 IrCl3 Ru (acetylacetonate) 3.
- Mixtures of 1: 1 and 2: 1 adducts of propylene with the fatty acids or fatty acid esters are generally formed with the aforementioned catalysts.
- the proportions of the various adducts can be varied by changing the reaction conditions, such as pressure, temperature and reaction time.
- suitable phosphine or phosphite ligands for example, are added to the reaction mixture P (C4H9) 3 P (OC4H9) 3 P (C6H5) 3 P (OC6H5) 3 or other ligands known from the last discussed prior art and DE-B 20 16 133 , it is possible in certain circumstances to influence the composition of the adduct mixtures in a targeted manner. Similar effects can be achieved in part by adding promoters such as LiCl, FeCl3 or AgBF4 to the reaction system, which are also known as such from the last-mentioned prior art.
- the structure of the olefinically unsaturated adducts described in the cited patent application is not uniform.
- the addition of the first propylene molecule takes place between positions 9 and 12 of the carbon chain of linoleic acid, the 1: 1 adduct having the same number of double bonds as has the fatty acid used as the starting material.
- the position of the double bonds is uncertain.
- the double bonds are in no case more than 4 carbon atoms away from the branch and are always in the alpha, delta or alpha, gamma positions.
- the second and optionally the third propylene molecule is then attached to a double bond located in the branch. It can be assumed that the adducts obtained have at least partially one of the structures shown below; analogous carbon skeletons are present in the saturated compounds obtained according to the present invention.
- the polyunsaturated fatty acids optionally used in the form of their esters have 2 to 5, in particular 2 to 3, olefinic double bonds.
- the adducts are obtained at a propylene pressure in the range from 5 to 60 bar and a temperature in the range from 50 to 140 ° C., where appropriate in the presence of inert organic solvents such as hexane, chloroform or the like.
- the catalysts are used in an amount in the range from 0.02 to 2 mol%, based on fatty acids or fatty acid esters.
- rhodium compounds are advantageously used as catalysts, rhodium compounds from the group formed by RhCl3 and RhBr3 (including hydrates thereof) and [(C2H4) 2RhCl] 2 being preferred as catalysts.
- the invention relates to the use of the saturated, branched fatty acids or esters thereof as pour point depressants in lubricants.
- the starting materials explained above can be hydrogenated according to the invention to saturated, branched fatty acids having 21 to 28 carbon atoms or esters thereof with C1-C36 alkanols. Preferred exemplary embodiments are given below for this.
- a starting material according to H1) was completely cured with the addition of 1 mol%, based on palladium, of a catalyst containing 5% by weight palladium on activated carbon at 70 ° C. and 10 bar hydrogen pressure.
- the hardened reaction mixture contained exclusively stearic acid. The hardened addition products could be obtained in high purity by distillation.
- Example 2 A starting material according to H2) was cured in the manner described in Example 1. The desired mixture of hydrogenated adducts of the same composition was obtained.
Abstract
Description
Die Erfindung betrifft gesättigte, verzweigte Fettsäuren mit 21 bis 28 Kohlenstoffatomen bzw. Ester derselben mit C₁-C₃₆-Alkanolen, erhältlich durch Hydrierung von olefinisch ungesättigten Addukten von Propylen an mehrfach ungesättigte Fettsäuren mit 18 bis 22 Kohlenstoffatomen bzw. an Ester derselben mit C₁-C₃₆-Alkanolen in molaren Verhältnissen von Ethylen zu Fettsäuren bzw. Fettsäureestern im Bereich von 1 : 1 bis 2 : 1.The invention relates to saturated, branched fatty acids with 21 to 28 carbon atoms or esters thereof with C₁-C₃₆ alkanols, obtainable by hydrogenation of olefinically unsaturated adducts of propylene with polyunsaturated fatty acids with 18 to 22 carbon atoms or esters thereof with C₁-C₃₆ -Alkanols in molar ratios of ethylene to fatty acids or fatty acid esters in the range from 1: 1 to 2: 1.
In der Alkylkette verzweigte Fettsäuren vom Typ der Guerbetsäuren, erhältlich durch Guerbetisierung der entsprechenden Fettalkohole und Oxidation der Guerbetalkohole zu den entsprechenden Säuren, sind technologisch interessante Zwischenprodukte, weil sie bzw. ihre Alkylester, im Vergleich zu den entsprechenden unverzweigten Isomeren, deutlich erniedrigte Stockpunkte aufweisen. Die Herstellung von Guerbetsäuren ist jedoch technologisch aufwendig und nur mit unbefriedigenden Ausbeuten durchführbar. Es hat daher nicht an Versuchen gefehlt, ausgehend von Fettsäuren bzw. Estern derselben entsprechende Fettsäurederivate herzustellen, die in der Alkylkette Verzweigungen aufweisen. Ein typisches Beispiel hierfür ist die schichtsilikatkatalysierte Fettsäuredimerisierung bei der jedoch auch erhebliche Mengen an trimeren Fettsäuren sowie an methylverzweigten Fettsäuren, sogenannten Isofettsäuren, gebildet werden.Fatty acids of the Guerbet acid type branched in the alkyl chain, obtainable by Guerbetification of the corresponding fatty alcohols and oxidation of the Guerbet alcohols to the corresponding acids, are technologically interesting intermediates because they or their alkyl esters have significantly lower pour points compared to the corresponding unbranched isomers. However, the production of guerbet acids is technologically complex and can only be carried out with unsatisfactory yields. It therefore has no attempts failed to produce, starting from fatty acids or esters thereof, corresponding fatty acid derivatives which have branches in the alkyl chain. A typical example of this is layered silicate-catalyzed fatty acid dimerization, in which, however, considerable amounts of trimeric fatty acids and of methyl-branched fatty acids, so-called isofatty acids, are also formed.
Ein weiteres, wenn auch aufwendiges Verfahren liefert aus Konjuenfettsäuren in der trans,trans-Form mit aktivierten Dienophilen unter den Bedingungen einer Diels-Alder-Reaktion verzweigte Fettsäurederivate; so läßt sich z.B. auf diesem Wege aus Linolsäure und Acrylsäure eine verzweigte C₂₁-Dicarbonsäure herstellen, vgl. US-B 3,734,859, US-B 3,753,968, DE-B 2 253 930.Another, albeit complex, process gives branched fatty acid derivatives from conjuene fatty acids in the trans, trans form with activated dienophiles under the conditions of a Diels-Alder reaction; for example, a branched C₂₁-dicarboxylic acid can be produced from linoleic acid and acrylic acid in this way, cf. US-B 3,734,859, US-B 3,753,968, DE-B 2 253 930 .
Des weiteren sind aus der EP-A1 0 010 807 verzweigte Monocarbonsäuren bekannt, die durch Telomerisation von einem Mol Acetanhydrid und mindestens drei Mol eines Olefins mit mindestens 6 und bis zu 30 Kohlenstoffatomen in Gegenwart einer dreiwertigen Manganverbindung erhalten werden.Furthermore, EP-A1 0 010 807 discloses branched monocarboxylic acids which are obtained by telomerization of one mole of acetic anhydride and at least three moles of an olefin having at least 6 and up to 30 carbon atoms in the presence of a trivalent manganese compound.
Weitere, verzweigte Fettsäurederivate sind durch thermische oder säurekatalysierte Addition von aktivierten Enophilen an ungesättigte Fettsäurederivate erhalten worden. So läßt sich z.B. Maleinsäureanhydrid unter Säurekatalyse mit bis zu 70 % Ausbeute an Ölsäure addieren, vgl. Fat. Sci. Technol., 1, 1 (1988). Bei den vorstehend genannten Reaktionsprodukten erweist sich die Anwesenheit von mehr als einer Carboxylgruppe jedoch häufig als störend.Further branched fatty acid derivatives have been obtained by thermal or acid-catalyzed addition of activated enophiles to unsaturated fatty acid derivatives. For example, maleic anhydride can be added with acid catalysis in up to 70% yield of oleic acid, cf. Fat. Sci. Technol., 1 , 1 (1988) . However, the presence of more than one carboxyl group often proves to be troublesome in the reaction products mentioned above.
Schließlich hat man auch versucht, gesättigte Kohlenwasserstoffe durch thermisch initiierte radikalische Addition von gesättigten Kohlenwasserstoffen an Fettsäuren anzulagern; die Addition von Cyclohexan an Ölsäuremethylester führt bei 340°C und 200 bar mit 70%-iger Selektivität, jedoch mit einer Ausbeute von lediglich 2,8 %, zu alkylverzweigten Fettsäuren, vgl. J.O. Metzger, et al., Fat. Sci. Technol. 1 (1989), 18. Finally, attempts have also been made to add saturated hydrocarbons to fatty acids by means of thermally initiated radical addition of saturated hydrocarbons; the addition of cyclohexane to oleic acid methyl ester leads to alkyl-branched fatty acids at 340 ° C and 200 bar with 70% selectivity, but with a yield of only 2.8%, cf. JO Metzger, et al., Fat. Sci. Technol. 1 (1989), 18.
Gegenstand der Erfindung sind gesättigte verzweigte Fettsäuren mit 21 bis 28 Kohlenstoffatomen bzw. Ester derselben mit C₁-C₃₆-Alkanolen, die dadurch erhältlich sind, daß man
- a) ungesättigte Fettsäuren mit 18 bis 22 Kohlenstoffatomen und mehr als einer olefinischen Doppelbindung bzw. Ester derselben mit C₁-C₃₆-Alkanolen bei erhöhter Temperatur und erhöhtem Druck in Gegenwart von Verbindungen von Übergangsmetallen aus der von Ru, Rh, Pd, Ir und Pt gebildeten Gruppe mit Propylen umsetzt, wobei das molare Verhältnis von Propylen zu Fettsäure bzw. Fettsäureester 1 : 1 bis 2 : 1 beträgt, und
- b) die resultierenden olefinisch ungesättigten Addukte bei einer Temperatur im Bereich von 70 bis 120°C und einem Wasserstoffdruck im Bereich von 10 bis 30 bar in Gegenwart von Hydrierkatalysatoren hydriert.
- a) Unsaturated fatty acids with 18 to 22 carbon atoms and more than one olefinic double bond or ester thereof with C₁-C₃₆ alkanols at elevated temperature and pressure in the presence of compounds of transition metals from those formed by Ru, Rh, Pd, Ir and Pt Reacts group with propylene, the molar ratio of propylene to fatty acid or fatty acid ester being 1: 1 to 2: 1, and
- b) the resulting olefinically unsaturated adducts are hydrogenated at a temperature in the range from 70 to 120 ° C. and a hydrogen pressure in the range from 10 to 30 bar in the presence of hydrogenation catalysts.
Die gesättigten, verzweigten Fettsäuren bzw. Ester derselben können auf einfache Weise und mit guten Ausbeuten hergestellt werden. Die erfindungsgemäß bereitgestellten Verbindungen sind neue Produkte, die sich z.B. von in der Natur vorkommenden ethylverzweigten Fettsäuren mit insgesamt 12 bis 18 Kohlenstoffatomen, beschrieben in A. Smith et al, Biomed. Mass Spectrom., 6 (8), 347-349, bereits durch ihre Kettenlänge unterscheiden.The saturated, branched fatty acids or esters thereof can be prepared in a simple manner and with good yields become. The compounds provided according to the invention are new products which are derived, for example, from naturally occurring ethyl-branched fatty acids with a total of 12 to 18 carbon atoms, described in A. Smith et al, Biomed. Mass Spectrom., 6 (8), 347-349 , already differ by their chain length.
Die gesättigten, verzweigten Fettsäuren der Erfindung bzw. Ester derselben können durch Hydrierung von olefinisch ungesättigten Addukten von Propylen an mehrfach ungesättigte Fettsäuren mit 18 bis 22 Kohlenstoffatomen bzw. an Ester derselben mit C₁-C₃₆-Alkanolen in molaren Verhältnissen von Propylen zu Fettsäuren bzw. Fettsäureestern im Bereich von 1:1 bis 2:1 erhalten werden.The saturated, branched fatty acids of the invention or esters thereof can be obtained by hydrogenating olefinically unsaturated adducts of propylene with polyunsaturated fatty acids having 18 to 22 carbon atoms or with esters thereof with C₁-C₃ Alk alkanols in molar ratios of propylene to fatty acids or fatty acid esters in the range of 1: 1 to 2: 1 can be obtained.
Diese Propylenaddukte sind Gegenstand der zeitgleichen Patentanmeldung DE-A1 40 02 008 der Anmelderin, auf die hier ausdrücklich Bezug genommen und deren wesentlicher Inhalt im folgenden zusammengefaßt ist :
Als Ausgangsprodukte zur Herstellung der olefinisch ungesättigten Addukte der genannten Patentanmeldung eignen sich ungesättigte Fettsäuren mit 18 bis 22 Kohlenstoffatomen und mehr als einer olefinischen Doppelbindung wie Llnolsäure, isomerisierte Linolsäure mit konjuierten Doppelbindungen (sogenannte C18:2-Konjuenfettsäure), Linolensäure, Arachidonsäure, Docosadiensäure, Docosahexaensäure und Eicosapentaensäure, die in Form ihrer technischen Gemische mit anderen Fettsäuren nachwachsenden natürlichen Rohstoffen, z.B. aus Sonnenblumenöl, Tallöl oder Fischöl, erhalten werden können. Diese mehrfach ungesättigten Fettsäuren werden, wie in der Fettchemie üblich, im allgemeinen nicht in Form ihrer reinen Verbindungen, sondern in Form ihrer technischen Gemische zur Herstellung der Addukte der Erfindung eingesetzt. Die vorgenannten Fettsäuren werden bevorzugt nicht nur als solche, sondern auch in Form ihrer Ester mit C₁-C₃₆-Alkanolen, insbesondere mit C₁-C₄-Alkanolen, eingesetzt. Typische Beispiele für derartige Alkanole zur Bildung von Estern mit den vorgenannten Fettsäuren sind Methanol, Ethanol, Propanol, Butanol, Pentanol, Hexanol, Octanol, Decanol, Dodecanol, Tetradecanol, Hexadecanol, Octadecanol sowie höhere Fettalkohole bzw. Fettalkoholderivate mit bis zu 36 Kohlenstoffatomen, z.B. C₃₆-Guerbetalkohole.These propylene adducts are the subject of the applicant's simultaneous patent application DE-A1 40 02 008 , to which reference is expressly made here and the essential content of which is summarized below:
Suitable starting products for the preparation of the olefinically unsaturated adducts of the abovementioned patent application are unsaturated fatty acids with 18 to 22 carbon atoms and more than one olefinic double bond such as linoleic acid, isomerized linoleic acid with conjugated double bonds (so-called C18: 2 conjuene fatty acid), linolenic acid, arachidonic acid, docosadienoic acid, docosaic acid and eicosapentaenoic acid, in the form of their technical mixtures with others Fatty acids renewable natural raw materials, for example from sunflower oil, tall oil or fish oil, can be obtained. These polyunsaturated fatty acids are, as is customary in fat chemistry, generally not in the form of their pure compounds, but in the form of their technical mixtures for the preparation of the adducts of the invention. The aforementioned fatty acids are preferably used not only as such, but also in the form of their esters with C₁-C₃₆ alkanols, especially with C₁-C₄ alkanols. Typical examples of such alkanols for the formation of esters with the aforementioned fatty acids are methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, decanol, dodecanol, tetradecanol, hexadecanol, octadecanol and higher fatty alcohols or fatty alcohol derivatives with up to 36 carbon atoms, e.g. C₃₆ Guerbet alcohols.
Die vorgenannten mehrfach ungesättigten Fettsäuren bzw. Fettsäureester lagern gemäß der genannten Patentanmeldung bei erhöhter Temperatur und erhöhtem Druck in Gegenwart von Verbindungen von Übergangsmetallen aus der von Ru, Rh, Pd, Ir und Pt gebildeten Gruppe Propylen an.According to the patent application mentioned, the aforementioned polyunsaturated fatty acids or fatty acid esters accumulate at elevated temperature and pressure in the presence of compounds of transition metals from the group consisting of Ru, Rh, Pd, Ir and Pt and propylene.
Typische Beispiele für dabei einsetzbare Katalysatoren sind die folgenden:
RhCl₃.3H₂O
RhBr₃.3H₂O
[(C₂H₄)₂RhCl]₂
Rh(NO₃)₃.2H₂O
Rh(OOCCH₃)₂.2H₂O
Rh(acetylacetonat)₃
RhF₃.6H₂O
RhJ₃
Rh(CN)₃.3H₂O
Rh₂(SO₄)₃
Rh₂(CO₃)₃
[(1.5-Cyclooctadien)RhCl]₂
[(C₂H₄)₂Rh(acetylacetonat)]
[(1.3-Butadien)RhCl]₂
Cyclopentadienyl-Olefin-Komplexe wie [(n-C₅H₅)Rh(C₂H₄)2].Typical examples of catalysts that can be used are the following:
RhCl₃.3H₂O
RhBr₃.3H₂O
[(C₂H₄) ₂RhCl] ₂
Rh (NO₃) ₃.2H₂O
Rh (OOCCH₃) ₂.2H₂O
Rh (acetylacetonate) ₃
RhF₃.6H₂O
RhJ₃
Rh (CN) ₃.3H₂O
Rh₂ (SO₄) ₃
Rh₂ (CO₃) ₃
[(1.5-Cyclooctadiene) RhCl] ₂
[(C₂H₄) ₂Rh (acetylacetonate)]
[(1,3-butadiene) RhCl] ₂
Cyclopentadienyl olefin complexes such as [(n-C₅H₅) Rh (C₂H₄) 2].
Sofern die einsetzbaren Katalysatoren in wasserfreier Form vorliegen, kann es zweckmäßig sein, dem Reaktionsgemisch eine geringe Menge von Wasser zuzusetzen.If the catalysts which can be used are in anhydrous form, it may be expedient to add a small amount of water to the reaction mixture.
Die im Rahmen der genannten Patentanmeldung einsetzbaren Katalysatoren sind als solche für die Anlagerung von Propylen an Alkadiene bekannt, vgl. US-B 3,636,122; M. Bockmann et al., Journal of Molecular Catalysis, 22 (1984) 363-365; G. Wilkinson (Ed.), Comprehensive Organometallic Chemistry. S. 414-429, Pergamon Press (1982); A.C.L. Su, Advances in Organometallic Chemistry, Vol. 17, S. 271-283; wobei diese Veröffentlichungen, auf deren Inhalt im übrigen ausdrücklich Bezug genommen wird, sich jedoch nicht mit der Anlagerung von Alkenen an Fettsäuren bzw. Fettsäurederivate oder andere Fettstoffe befassen.The catalysts which can be used in the context of the aforementioned patent application are known as such for the addition of propylene to alkadienes, cf. US-B 3,636,122; M. Bockmann et al., Journal of Molecular Catalysis, 22 (1984) 363-365; G. Wilkinson (Ed.), Comprehensive Organometallic Chemistry. Pp. 414-429, Pergamon Press (1982); ACL Su, Advances in Organometallic Chemistry, Vol. 17, pp. 271-283 ; however, these publications, the content of which is expressly referred to, do not deal with the attachment of alkenes to fatty acids or fatty acid derivatives or other fatty substances.
Weitere, im Verfahren der genannten Patentanmeldung einsetzbare Katalysatoren sind z.B.
PdCl₂
PtCl₂
IrCl₃
Ru(acetylacetonat)₃.Other catalysts which can be used in the process of the patent application mentioned are, for example
PdCl₂
PtCl₂
IrCl₃
Ru (acetylacetonate) ₃.
Mit den vorgenannten Katalysatoren entstehen im allgemeinen Gemische von 1:1- und 2:1-Addukten von Propylen an die Fettsäuren bzw. Fettsäureester. Durch Veränderung der Reaktionsbedingungen wie Druck, Temperatur und Reaktionszeit lassen sich jedoch die Anteile an den verschiedenen Addukten variieren. Setzt man dem Reaktionsgemisch jedoch neben den Katalysatoren geeignete Phosphin- oder Phosphitliganden, z.B.
P(C₄H₉)₃
P(OC₄H₉)₃
P(C₆H₅)₃
P(OC₆H₅)₃
oder andere, aus dem zuletzt diskutierten Stand der Technik sowie der DE-B 20 16 133 bekannte Liganden zu, kann man unter Umständen gezielt die Zusammensetzung der Adduktgemische beeinflussen. Änliche Effekte lassen sich zum Teil dadurch erreichen, daß man dem Reaktionssystem Promotoren wie LiCl, FeCl₃ oder AgBF₄ zusetzt, die als solche ebenfalls aus dem zuletzt genannten Stand der Technik bekannt sind.Mixtures of 1: 1 and 2: 1 adducts of propylene with the fatty acids or fatty acid esters are generally formed with the aforementioned catalysts. However, the proportions of the various adducts can be varied by changing the reaction conditions, such as pressure, temperature and reaction time. However, in addition to the catalysts, suitable phosphine or phosphite ligands, for example, are added to the reaction mixture
P (C₄H₉) ₃
P (OC₄H₉) ₃
P (C₆H₅) ₃
P (OC₆H₅) ₃
or other ligands known from the last discussed prior art and DE-B 20 16 133 , it is possible in certain circumstances to influence the composition of the adduct mixtures in a targeted manner. Similar effects can be achieved in part by adding promoters such as LiCl, FeCl₃ or AgBF₄ to the reaction system, which are also known as such from the last-mentioned prior art.
Die Struktur der in der genannten Patentanmeldung beschriebenen olefinisch ungesättigten Addukte ist nicht einheitlich. Im Falle der Linolsäure (bzw. der von dieser abgeleiteten C₁₈-Konjuenfettsäure) konnte gezeigt werden, daß die Anlagerung des ersten Propylenmoleküls zwischen den Positionen 9 und 12 der Kohlenstoffkette der Linolsäure erfolgt, wobei das 1:1-Addukt die gleiche Anzahl von Doppelbindungen wie die als Ausgangsmaterial eingesetzte Fettsäure aufweist. Die Stellung der Doppelbindungen ist jedoch unsicher. Die Doppelbindungen sind in keinem Fall mehr als 4 Kohlenstoffatome von der Verzweigung entfernt und stehen grundsätzlich in alpha,delta- oder in alpha,gamma-Stellung zueinander. Das zweite und gegebenenfalls das dritte Propylenmolekül wird dann an eine in der Verzweigung befindliche Doppelbindung angelagert. Es ist zu vermuten, daß die erhaltenen Addukte mindestens teilweise eine der nachstehend wiedergegebenen Strukturen aufweisen; bei den gemäß der vorliegenden Erfindung erhaltenen gesättigten Verbindungen liegen analoge Kohlenstoffgerüste vor.The structure of the olefinically unsaturated adducts described in the cited patent application is not uniform. In the case of linoleic acid (or the C₁₈ conjuene fatty acid derived from this) it could be shown that the addition of the first propylene molecule takes place between positions 9 and 12 of the carbon chain of linoleic acid, the 1: 1 adduct having the same number of double bonds as has the fatty acid used as the starting material. However, the position of the double bonds is uncertain. The double bonds are in no case more than 4 carbon atoms away from the branch and are always in the alpha, delta or alpha, gamma positions. The second and optionally the third propylene molecule is then attached to a double bond located in the branch. It can be assumed that the adducts obtained have at least partially one of the structures shown below; analogous carbon skeletons are present in the saturated compounds obtained according to the present invention.
Gemäß einer Ausführungsform der genannten Patentanmeldung weisen die gegebenenfalls in Form ihrer Ester eingesetzten mehrfach ungesättigten Fettsäuren 2 bis 5, insbesondere 2 bis 3 olefinische Doppelbindungen auf.
Gemäß einer weiteren Ausführungsform der genannten Patentanmeldung erhält man die Addukte bei einem Propylendruck im Bereich von 5 bis 60 bar und einer Temperatur im Bereich von 50 bis 140°C, wobei man gegebenenfalls in Anwesenheit inerter organischer Lösemittel wie Hexan, Chloroform oder dergleichen, arbeitet.According to one embodiment of the patent application mentioned, the polyunsaturated fatty acids optionally used in the form of their esters have 2 to 5, in particular 2 to 3, olefinic double bonds.
According to a further embodiment of the patent application mentioned, the adducts are obtained at a propylene pressure in the range from 5 to 60 bar and a temperature in the range from 50 to 140 ° C., where appropriate in the presence of inert organic solvents such as hexane, chloroform or the like.
Gemäß einer weiteren Ausführungsform der genannten Patentanmeldung verwendet man die Katalysatoren in einer Menge im Bereich von 0,02 bis 2 Mol-%, bezogen auf Fettsäuren bzw. Fettsäureester.According to a further embodiment of the patent application mentioned, the catalysts are used in an amount in the range from 0.02 to 2 mol%, based on fatty acids or fatty acid esters.
Vorteilhafterweise verwendet man gemäß der genannten Patentanmeldung als Katalysatoren Rhodiumverbindungen, wobei wiederum Rhodiumverbindungen aus der von RhCl₃ und RhBr₃ (einschließlich Hydraten derselben) sowie [(C₂H₄)₂RhCl]₂ gebildeten Gruppe als Katalysatoren bevorzugt sind.According to the patent application mentioned, rhodium compounds are advantageously used as catalysts, rhodium compounds from the group formed by RhCl₃ and RhBr₃ (including hydrates thereof) and [(C₂H₄) ₂RhCl] ₂ being preferred as catalysts.
Ein weiterer Gegenstand der Erfindung betrifft ein Verfahren zur Herstellung gesättigter verzweigter Fettsäuren mit 21 bis 28 Kohlenstoffatomen bzw. Ester derselben mit C₁-C₃₆-Alkanolen, das sich dadurch auszeichnet, daß man
- a) ungesättigte Fettsäuren mit 18 bis 22 Kohlensoffatomen und mehr als einer olefinischen Doppelbindung bzw. Ester derselben mit C₁-C₃₆-Alkanolen bei erhöhter Temperatur und erhöhtem Druck in Gegenwart von Verbindungen von Übergangsmetallen aus der von Ru, Rh, Pd, Ir und Pt gebildeten Gruppe mit Propylen umsetzt, wobei das molare Verhältnis von Ethylen zu Fettsäure bzw. Fettsäureester 1 : 1 bis 2 : 1 beträgt, und
- b) die resultierenden olefinisch ungesättigten Addukte bei einer Temperatur im Bereich von 70 bis 120°C und einem Wasserstoffdruck im Bereich von 10 bis 30 bar in Gegenwart von Hydrierkatalysatoren hydriert.
- a) Unsaturated fatty acids with 18 to 22 carbon atoms and more than one olefinic double bond or ester thereof with C₁-C₃₆ alkanols at elevated temperature and pressure in the presence of compounds of transition metals from Ru, Rh, Pd, Ir and Pt formed group is reacted with propylene, the molar ratio of ethylene to fatty acid or fatty acid ester being 1: 1 to 2: 1, and
- b) the resulting olefinically unsaturated adducts are hydrogenated at a temperature in the range from 70 to 120 ° C. and a hydrogen pressure in the range from 10 to 30 bar in the presence of hydrogenation catalysts.
Schließlich betrifft die Erfindung die Verwendung der gesättigten, verzweigten Fettsäuren bzw. Ester derselben als Stockpunktserniedriger in Schmiermitteln.Finally, the invention relates to the use of the saturated, branched fatty acids or esters thereof as pour point depressants in lubricants.
Die Erfindung wird im folgenden anhand bevorzugter Ausführungsbeispiele näher erläutert.The invention is explained in more detail below on the basis of preferred exemplary embodiments.
Zunächst wird in den nichterfindungsgemäßen Herstellbeispielen H1 bis H5 die Herstellung der Ausgangsverbindungen für die Verbindungen der Erfindung gemäß DE-A1 40 02 008 beschrieben.
- H1) 8,2 g eines technischen Fettsäureestergemisches mit einem Gehalt von 67,8 Gew.-% Linolsäuremethylester (19 mmol), 100 mg RhCl₃.3H₂O und 10 ml Chloroform wurden 20 h bei 100°C in Gegenwart von überschüssigem Propen in einem 75 ml-Autoklaven umgesetzt. Man erhielt 27,6 % (gaschromatografisch ermittelt) an 1:1-Addukten, bezogen auf Linolsäuremethylester.
- H2) 8,2 g einer technischen Fettsäure, enthaltend 56,0 % C18:2-Konjuensäuren, 100 mg RhCl₃.3H₂O und 10 ml Hexan wurden 20 h bei 100°C in Gegenwart eines Propylenüberschusses in einem 75 ml-Autoklaven umgesetzt. Man erhielt 70,5 % 1:1-Addukte, bezogen auf Konjuenfettsäure.
- H3) Ein technisches Fettsäuremethylestergemisch (8,2 g) mit einem Gehalt von 62,4 % an konjugierten C18:2-Fettsäuremethylestern, 100 mg RhCl₃.3H₂O und 10 ml Hexan wurde 20 h bei 100°C in Gegenwart eines Propylenüberschusses in einem 75 ml-Autoklaven erhitzt. Man erhielt 58,5 % 1:1-Addukte, bezogen auf konjugierte Fettsäuremethylester.
- H4) 300 g eines Fettsäuremethylesters gemäß Beispiel 3, 3,0 g RhCl₃.3H₂O und 350 ml Hexan wurden 20 h bei 100°C in Gegenwart eines Propylenüberschusses in einem 1 l-Rührautoklaven mit Turbinenrührer umgesetzt. Es wurden 98,2 % 1:1-Addukte, bezogen auf konjugierte Fettsäuremethylester, erhalten.
- H5) 301 g eines Fettsäuremethylestergemisches, enthaltend 60,3 % C18:2-Konjuenmethylester (197 g; 0,76 mol), 6,2 % Linolsäuremethylester und 24,4 % Ölsäuremethylester, 881,6 mg (3,35 mmol) RhCl₃.3H₂O (263,5 g/mol) und 350 ml Hexan wurden in einem 1 l-Rührautoklaven mit Turbinenrührer gegeben. Anschließen wurden ca. 100 g Propylen einkondensiert. Das Reaktionsgemisch wurde 20 h bei 100°C gerührt. Man erhielt 91,9 %, bezogen auf Konjuenfettsäureester, an Propylenaddukten, davon 85,2 % 1:1-Addukte und 6,7 % 2:1-Addukte.
- H1) 8.2 g of a technical fatty acid ester mixture containing 67.8% by weight of linoleic acid methyl ester (19 mmol), 100 mg RhCl₃.3H₂O and 10 ml chloroform were 20 h at 100 ° C in the presence of excess propene in a 75th ml autoclaves implemented. This gave 27.6% (determined by gas chromatography) of 1: 1 adducts, based on methyl linoleic acid.
- H2) 8.2 g of a technical fatty acid containing 56.0% C18: 2-conjugate acids, 100 mg RhCl₃.3H₂O and 10 ml hexane were reacted for 20 h at 100 ° C in the presence of an excess of propylene in a 75 ml autoclave. 70.5% 1: 1 adducts, based on conjuene fatty acid, were obtained.
- H3) A technical fatty acid methyl ester mixture (8.2 g) containing 62.4% of conjugated C18: 2 fatty acid methyl esters, 100 mg RhCl₃.3H₂O and 10 ml hexane was in a 75 at 100 ° C in the presence of an excess of propylene in a 75th ml autoclave heated. 58.5% 1: 1 adducts were obtained, based on conjugated fatty acid methyl esters.
- H4) 300 g of a fatty acid methyl ester according to Example 3, 3.0 g of RhCl₃.3H₂O and 350 ml of hexane were reacted for 20 h at 100 ° C in the presence of an excess of propylene in a 1 l stirred autoclave with a turbine stirrer. 98.2% 1: 1 adducts, based on conjugated fatty acid methyl esters, were obtained.
- H5) 301 g of a fatty acid methyl ester mixture containing 60.3% C18: 2 conjunct methyl ester (197 g; 0.76 mol), 6.2% methyl linoleate and 24.4% methyl oleic acid, 881.6 mg (3.35 mmol) RhCl₃ .3H₂O (263.5 g / mol) and 350 ml of hexane were placed in a 1 l stirred autoclave with a turbine stirrer. Approx. 100 g of propylene were then condensed in. The reaction mixture was stirred at 100 ° C for 20 h. 91.9%, based on conjuene fatty acid esters, of propylene adducts were obtained, of which 85.2% 1: 1 adducts and 6.7% 2: 1 adducts.
Die vorstehend erläuterten Ausgangsmaterialien lassen sich erfindungsgemäß zu gesättigten, verzweigten Fettsäuren mit 21 bis 28 Kohlenstoffatomen bzw. Estern derselben mit C₁-C₃₆-Alkanolen hydrieren. Hierfür werden im folgenden bevorzugte Ausführungsbeispiele angegeben.The starting materials explained above can be hydrogenated according to the invention to saturated, branched fatty acids having 21 to 28 carbon atoms or esters thereof with C₁-C₃₆ alkanols. Preferred exemplary embodiments are given below for this.
Ein Ausgangsmaterial gemäß H1) wurde unter Zugabe von 1 mol-%, bezogen auf Palladium, eines 5 Gew.-% Palladium auf Aktivkohle enthaltenden Katalysators bei 70°C und 10 bar Wasserstoffdruck vollständig gehärtet. Die gehärtete Reaktionsmischung enthielt neben den hydrierten Addukten und den schon im Ausgangsmaterial enthaltenen Verunreinigungen ausschließlich Stearinsäure. Die gehärteten Additionsprodukte konnten durch Destillation in hoher Reinheit erhalten werden.A starting material according to H1) was completely cured with the addition of 1 mol%, based on palladium, of a catalyst containing 5% by weight palladium on activated carbon at 70 ° C. and 10 bar hydrogen pressure. In addition to the hydrogenated adducts and the impurities already contained in the starting material, the hardened reaction mixture contained exclusively stearic acid. The hardened addition products could be obtained in high purity by distillation.
Ein Ausgangsmaterial gemäß H2) wurde in der in Beispiel 1 beschriebenen Weise gehärtet. Man erhielt das gewünschte Gemisch von hydrierten Addukten der analogen Zusammensetzung.A starting material according to H2) was cured in the manner described in Example 1. The desired mixture of hydrogenated adducts of the same composition was obtained.
Claims (3)
- Saturated branched c₂₁₋₂₈ fatty acids or esters thereof with C₁₋₃₆ alkanols obtainable bya) reaction of unsaturated fatty acids containing 18 to 22 carbon atoms and more than one olefinic double bond or esters thereof with C₁₋₃₆ alkanols with propylene at elevated temperature and pressure in the presence of compounds of transition metals from the group consisting of Ru, Rh, Pd, Ir and Pt, the molar ratio of propylene to fatty acid or fatty acid ester being from 1:1 to 2:1, andb) hydrogenation of the resulting olefinically unsaturated adducts in the presence of hydrogenation catalysts at a temperature of 70 to 120°C and under a hydrogen pressure of 10 to 30 bar.
- A process for the production of saturated branched c₂₁₋₂₈ fatty acids or esters thereof with C₁₋₃₆ alkanols, characterized in thata) unsaturated fatty acids containing 18 to 22 carbon atoms and more than one olefinic double bond or esters thereof with C₁₋₃₆ alkanols are reacted with propylene at elevated temperature and pressure in the presence of compounds of transition metals from the group consisting of Ru, Rh, Pd, Ir and Pt, the molar ratio of propylene to fatty acid or fatty acid ester being from 1:1 to 2:1, andb) the resulting olefinically unsaturated adducts are hydrogenated in the presence of hydrogenation catalysts at a temperature of 70 to 120°C and under a hydrogen pressure of 10 to 30 bar.
- The use of the saturated branched fatty acids or esters claimed in claim 1 as pour point depressants in lubricants.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4002009A DE4002009A1 (en) | 1990-01-24 | 1990-01-24 | SATURATED, BRANCHED FATTY ACIDS WITH 21 TO 28 CARBON ATOMS OR ESTER THE SAME WITH C (DOWN ARROW) 1 (DOWN ARROW) -C (DOWN ARROW) 3 (DOWN ARROW) (DOWN ARROW) 6 (DOWN ARROW) ALKANOLS, METHOD FOR THEIR PRODUCTION AND THEIR USE |
| DE4002009 | 1990-01-24 | ||
| PCT/EP1991/000051 WO1991011425A1 (en) | 1990-01-24 | 1991-01-15 | Saturated, branched fatty acids with 21 to 28 carbon atoms or esters of the same with c1-c36 alkanols, process for producing them and their use |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0511982A1 EP0511982A1 (en) | 1992-11-11 |
| EP0511982B1 true EP0511982B1 (en) | 1995-01-25 |
Family
ID=6398678
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP91902087A Expired - Lifetime EP0511982B1 (en) | 1990-01-24 | 1991-01-15 | Saturated, branched fatty acids with 21 to 28 carbon atoms or esters of the same with c1-c36 alkanols, process for producing them and their use |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US5401865A (en) |
| EP (1) | EP0511982B1 (en) |
| JP (1) | JPH05503693A (en) |
| DE (2) | DE4002009A1 (en) |
| WO (1) | WO1991011425A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6897325B2 (en) | 2001-01-11 | 2005-05-24 | Cognis Deutschland Gmbh & Co. Kg | Method of producing branched fatty substances |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BR0211058B1 (en) | 2001-07-10 | 2013-10-01 | Fatty acids, processes for the isomerization thereof, derivatives from the same derivatives from them and fabric softening composition. | |
| US6946567B2 (en) | 2002-04-02 | 2005-09-20 | Akzo Nobel N.V. | Skeletal isomerization of alkyl esters and derivatives prepared therefrom |
| FI122428B2 (en) * | 2002-08-05 | 2021-01-29 | Arizona Chemical | Fatty acid composition and its use |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3640898A (en) * | 1969-04-11 | 1972-02-08 | Du Pont | Rhodium based catalysts for the synthesis of 1 4-dienes |
| US3636122A (en) * | 1970-05-28 | 1972-01-18 | Du Pont | Preparation of 1 4-hexadiene from ethylene and butadiene with selected cyclopentadienylrhodium catalysts |
| US3753968A (en) * | 1971-07-01 | 1973-08-21 | Westvaco Corp | Selective reaction of fatty acids and their separation |
| US3734859A (en) * | 1971-10-12 | 1973-05-22 | Westvaco Corp | Dicarboxylic acid soaps |
| BE794530A (en) * | 1972-01-25 | 1973-07-25 | Unilever Nv | HYDROGENATION OF UNSATURATED FATTY ACIDS |
| DE2253930A1 (en) * | 1972-11-03 | 1974-05-22 | Westvaco Corp | Dicarboxylic acid prodn - from fatty acids mixt contg conj and non-conj linoleic acids |
| CA1204755A (en) * | 1978-10-26 | 1986-05-20 | Jacobus J. Zeilstra | Derivatives of branched-chain monocarboxylic acids, engine lubricating oils, lubricant compositions for polymers, wax compositions in which these derivatives are incorporated and a process for preparing said branched-chain monocarboxylic acids |
| US4371469A (en) * | 1981-04-28 | 1983-02-01 | The United States Of America As Represented By The Secretary Of Agriculture | Process for the preparation of branched chain fatty acids and esters |
| EP0116621B1 (en) * | 1982-08-26 | 1987-05-13 | Dragoco Gerberding & Co. GmbH | Utilisation of branched chain carbonic acid esters with branched chain alcohols as components of cosmetic products |
| DE3807409A1 (en) * | 1988-03-07 | 1989-09-21 | Henkel Kgaa | METHOD FOR INSULATION OR CLEANING OF METHYL-BRANCHED, SATURATED C (ARROW DOWN) 1 (ARROW DOWN) (ARROW DOWN) 4 (ARROW DOWN) -C (ARROW DOWN) 2 (ARROW DOWN) (ARROW DOWN). 4 (ARROW DOWN) |
-
1990
- 1990-01-24 DE DE4002009A patent/DE4002009A1/en not_active Withdrawn
-
1991
- 1991-01-15 WO PCT/EP1991/000051 patent/WO1991011425A1/en active IP Right Grant
- 1991-01-15 US US07/910,351 patent/US5401865A/en not_active Expired - Fee Related
- 1991-01-15 JP JP3502438A patent/JPH05503693A/en active Pending
- 1991-01-15 EP EP91902087A patent/EP0511982B1/en not_active Expired - Lifetime
- 1991-01-15 DE DE59104425T patent/DE59104425D1/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6897325B2 (en) | 2001-01-11 | 2005-05-24 | Cognis Deutschland Gmbh & Co. Kg | Method of producing branched fatty substances |
Also Published As
| Publication number | Publication date |
|---|---|
| WO1991011425A1 (en) | 1991-08-08 |
| JPH05503693A (en) | 1993-06-17 |
| EP0511982A1 (en) | 1992-11-11 |
| DE59104425D1 (en) | 1995-03-09 |
| DE4002009A1 (en) | 1991-07-25 |
| US5401865A (en) | 1995-03-28 |
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