WO1993014060A1 - Process for producing oligomeric fatty acids - Google Patents
Process for producing oligomeric fatty acids Download PDFInfo
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- WO1993014060A1 WO1993014060A1 PCT/EP1993/000041 EP9300041W WO9314060A1 WO 1993014060 A1 WO1993014060 A1 WO 1993014060A1 EP 9300041 W EP9300041 W EP 9300041W WO 9314060 A1 WO9314060 A1 WO 9314060A1
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- acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/367—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of functional groups containing oxygen only in singly bound form
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/31—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of functional groups containing oxygen only in singly bound form
Definitions
- the invention relates to a process for the production of oligomeric fatty acids by reacting epoxidized fatty acid esters with hydroxy compounds and subsequent saponification of the resulting bridged reaction products and dimer fatty acids based on epoxidized fatty acid esters and ricinoleic acid esters.
- Oligomeric fatty acids i.e. H. technical mixtures of acyclic and z. T. also cyclic di-, tri- and oligocarboxylic acids are important products which are used for the production of adhesives, paints, fibers, corrosion inhibitors and lubricants.
- oligomeric fatty acids dimer fatty acids are of particular importance. Such substances are usually obtained by oligomerizing unsaturated fatty acids at temperatures from 180 to 250 ° C. in the presence of clays, for example montmorillonites [fats, soaps, Anstrichstoff, T2, SSI (1970)].
- clays for example montmorillonites [fats, soaps, Anstrichstoff, T2, SSI (1970)].
- the process has the disadvantage that achieving satisfactory yields in the oligomerization requires not only comparatively high catalyst concentrations, but also drastic reaction conditions which are associated with high energy expenditure.
- German patent application DE 33 18 596 A1 reports that bridged species form as undesirable by-products when epoxidized fatty acid esters are reacted with excess polyhydroxy compounds. This publication does not, however, show how a process for the selective production of these substances has to be designed.
- the invention relates to a process for the preparation of oligomeric fatty acids, which is characterized in that epoxidation products of unsaturated fatty acid esters of the formula (I)
- R ⁇ CO for an aliphatic acyl radical with 16 to 22 carbon atoms and 1 to 5 double bonds
- R 2 is a linear or branched alkyl radical having 1 to 4 carbon atoms
- oligomeric, in particular dimeric fatty acids with high selectivity and in good yields can be obtained if, when opening epoxy esters with polyols, the molar conditions are chosen so that at least one oxirane group is available for each hydroxyl group of the polyol.
- Epoxidized fatty acid esters are known substances that can be obtained by the relevant methods of preparative organic chemistry. For their preparation, one can start, for example, from mono- or polyunsaturated fatty acid esters which are known in a manner known per se, e.g. B. be epoxidized by the in situ performic acid process.
- the unsaturated fatty acid esters can be completely or partially, for example 50 to 95 mol%, epoxidized.
- Suitable hydroxy compounds are polyols or lower alkyl ricinoleic acid esters.
- Polyols are understood to mean compounds which have 2 to 15, preferably 2 to 6 carbon atoms and 2 to 4 hydroxyl groups. Typical examples are ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, glycerol, diglycerol, trimethylolpropane, pentaerythritol and bisphenol A.
- Typical examples of lower alkyl ricinoleic esters are esters of ricinoleic acid with linear or branched C1-C4 alcohols. Ricinoleic acid methyl ester is preferred.
- the molar ratio between epoxy compound and hydroxy compound can be 1: 1 to 10: 1.
- a molar ratio of 2: 1 to 5: 1 is preferred.
- the use ratio is selected within the limits specified so that at least one oxirane group is available for each hydroxyl group of the polyol used.
- Typical mineral acids or lower organic carboxylic acids come into consideration as acid catalysts for the ring opening reaction. Typical examples are sulfuric acid, phosphoric acid, formic acid and / or acetic acid.
- the acidic catalysts can be used in concentrations of 0.1 to 5% by weight, based on the starting materials.
- the ring opening reaction can be carried out at temperatures of 80 to 120, preferably 90 to 100 ° C. over a period of 1 to 10, preferably 3 to 6 hours. It is then advantageous to neutralize the catalyst acid with a base, for example sodium hydroxide or sodium methylate.
- a base for example sodium hydroxide or sodium methylate.
- the saponification of the ring opening products can be carried out in a manner known per se. It is recommended that at least for every mole of ester groups present in the crude product Use 1, preferably 1.1 to 2 mol of a base, for example sodium hydroxide solution and carry out the reaction under reflux over a period of 1 to 5 hours.
- the base should then be neutralized by adding a mineral acid, for example sulfuric acid.
- the invention further relates to dimer fatty acids which are obtained by reacting epoxidized fatty acid esters of the formula (I) in the presence of acidic catalysts with lower alkyl ricinoleic acid in a molar ratio of 1: 1 to 1.5: 1 and the resulting bridged ring ⁇ opening products then saponified in a manner known per se.
- the oligomeric fatty acids obtainable by the process according to the invention have pour point-lowering properties and are suitable, for example, for the production of lubricants in which they are present in amounts of 1 to 50, preferably 10 to 25% by weight, based on the composition ⁇ can be hold.
- Tab. 1 Ring opening of 9,10-epoxystearic acid methyl ester Theoretical key figures in () "
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Epoxy Compounds (AREA)
Abstract
Description
Verfahren zur Herstellung oligσmerer Fettsäuren Process for the preparation of oligomeric fatty acids
Gebiet der ErfindungField of the Invention
Die Erfindung betrifft ein Verfahren zur Herstellung oligo- merer Fettsäuren durch Umsetzung von epoxidierten Fettsäure¬ estern mit Hydroxyverbindungen und anschließende Verseifung der resultierenden verbrückten Reaktionsprodukte sowie Dimerfettsäuren auf Basis von epoxidierten Fettsäureestern und Ricinolsäureestern.The invention relates to a process for the production of oligomeric fatty acids by reacting epoxidized fatty acid esters with hydroxy compounds and subsequent saponification of the resulting bridged reaction products and dimer fatty acids based on epoxidized fatty acid esters and ricinoleic acid esters.
Stand der TechnikState of the art
Oligomere Fettsäuren, d. h. technische Gemische acyclischer und z. T. auch cyclischer Di-, Tri- und Oligocarbonsäuren stellen wichtige Produkte dar, die zur Herstellung von Kleb¬ stoffen, Farben, Fasern, Korrosionsinhibitoren und Schmier¬ stoffen dienen.Oligomeric fatty acids, i.e. H. technical mixtures of acyclic and z. T. also cyclic di-, tri- and oligocarboxylic acids are important products which are used for the production of adhesives, paints, fibers, corrosion inhibitors and lubricants.
Unter den oligomeren Fettsäuren kommt den Dimerfettsäuren ei¬ ne besondere Bedeutung zu. Üblicherweise werden solche Stoffe durch Oligomerisierung von ungesättigten Fettsäuren bei Tem¬ peraturen von 180 bis 250°C in Gegenwart von Tonerden, bei¬ spielsweise Montmorilloniten, erhalten [Fette, Seifen, Anstrichmittel, T2 , SSI (1970)]. Das Verfahren ist jedoch mit dem Nachteil behaftet, daß das Erreichen zufriedenstellender Ausbeuten in der Oligomerisierung nicht nur vergleichsweise hohe Katalysatorkonzentrationen, sondern auch drastische Re¬ aktionsbedingungen erforderlich macht, die mit hohem Ener¬ gieaufwand verbunden sind.Among the oligomeric fatty acids, dimer fatty acids are of particular importance. Such substances are usually obtained by oligomerizing unsaturated fatty acids at temperatures from 180 to 250 ° C. in the presence of clays, for example montmorillonites [fats, soaps, Anstrichmittel, T2, SSI (1970)]. However, the process has the disadvantage that achieving satisfactory yields in the oligomerization requires not only comparatively high catalyst concentrations, but also drastic reaction conditions which are associated with high energy expenditure.
In der deutschen Patentanmeldung DE 33 18 596 AI wird be¬ richtet, daß sich bei der Umsetzung von epoxidierten Fett¬ säureestern mit überschüssigen Polyhydroxyverbindungen ver¬ brückte Species als unerwünschte Nebenprodukte bilden. Wie ein Verfahren zur selektiven Herstellung dieser Stoffe ge¬ staltet werden muß, ist dieser Druckschrift jedoch nicht zu entnehmen.German patent application DE 33 18 596 A1 reports that bridged species form as undesirable by-products when epoxidized fatty acid esters are reacted with excess polyhydroxy compounds. This publication does not, however, show how a process for the selective production of these substances has to be designed.
Gemäß der Lehre der Patentschrift US 3,066,159 lassen sich beispielsweise epoxidiertes Butylstearat in Gegenwart eines basischen Katalysators mit einem Diglycerin-8 Mol-Ethylen- oxid-Addukt (Molverhältnis 2 : 1) oder epoxidierter Soja¬ fettsäuremethylester in Gegenwart eines sauren Katalysators mit Diglycerin (MolVerhältnis 2 : 1) zu verbrückten Species umsetzten. Auf eine Verseifung der Reaktionsprodukte findet sich jedoch kein Hinweis.According to the teaching of US Pat. No. 3,066,159, for example, epoxidized butyl stearate in the presence of a basic catalyst with a diglycerol-8 mol ethylene oxide adduct (molar ratio 2: 1) or epoxidized soybean methyl ester in the presence of an acidic catalyst with diglycerol (molar ratio 2 : 1) to form bridged species. However, there is no evidence of saponification of the reaction products.
Aus der deutschen Patentanmeldung DE 32 46 618 AI sind end¬ lich Alkydharze bekannt, die erhältlich sind, indem man bei¬ spielsweise mehrwertige Carbonsäuren mit Ringöffnungsproduk¬ ten von epoxidierten Fettalkoholen kondensiert. Die Aufgabe der Erfindung bestand darin, ein neues Verfahren zur Herstellung oligomerer Fettsäuren zu entwickeln, das frei von den geschilderten Nachteilen ist.From German patent application DE 32 46 618 A1 alkyd resins are finally known which can be obtained by condensing, for example, polyvalent carboxylic acids with ring opening products of epoxidized fatty alcohols. The object of the invention was to develop a new process for the production of oligomeric fatty acids which is free from the disadvantages described.
Beschreibung der ErfindungDescription of the invention
Gegenstand der Erfindung ist ein Verfahren zur Herstellung von oligomeren Fettsäuren, das sich dadurch auszeichnet, daß man Epoxidationsprodukte ungesättigter Fettsäureester der Formel (I)The invention relates to a process for the preparation of oligomeric fatty acids, which is characterized in that epoxidation products of unsaturated fatty acid esters of the formula (I)
in derin the
R^CO für einen aliphatischen Acylrest mit 16 bis 22 Kohlen¬ stoffatomen und 1 bis 5 Doppelbindungen undR ^ CO for an aliphatic acyl radical with 16 to 22 carbon atoms and 1 to 5 double bonds and
R2 für einen linearen oder verzweigten Alkylrest mit 1 bis 4 KohlenstoffatomenR 2 is a linear or branched alkyl radical having 1 to 4 carbon atoms
steht,stands,
in Gegenwart saurer Katalysatoren mit Hydroxyverbindungen im molaren Verhältnis 1 : 1 bis 10 : 1 umsetzt und die resultie¬ renden verbrückten Ringöffnungsprodukte anschließend in an sich bekannter Weise verseift.in the presence of acidic catalysts with hydroxy compounds in a molar ratio of 1: 1 to 10: 1 and the resulting bridged ring-opening products are then saponified in a manner known per se.
Überraschenderweise wurde gefunden, daß sich oligomere, ins¬ besondere dimere Fettsäuren mit hoher Selektivität und in guten Ausbeuten erhalten lassen, wenn man bei der Ringöffnung von Epoxyestern mit Polyolen die molaren Einsatzverhältnisse so wählt, daß für jede Hydroxylgruppe des Polyols mindestens eine Oxirangruppe zur Verfügung steht.Surprisingly, it was found that oligomeric, in particular dimeric fatty acids with high selectivity and in good yields can be obtained if, when opening epoxy esters with polyols, the molar conditions are chosen so that at least one oxirane group is available for each hydroxyl group of the polyol.
Epoxidierte Fettsäureester stellen bekannte Stoffe dar, die nach den einschlägigen Verfahren der präparativen organischen Chemie erhalten werden können. Zu ihrer Herstellung kann man beispielsweise von einfach oder mehrfach ungesättigten Fett¬ säureestern ausgehen, die in an sich bekannter Weise, z. B. nach dem in situ Perameisensäure-Verfahren epoxidiert werden.Epoxidized fatty acid esters are known substances that can be obtained by the relevant methods of preparative organic chemistry. For their preparation, one can start, for example, from mono- or polyunsaturated fatty acid esters which are known in a manner known per se, e.g. B. be epoxidized by the in situ performic acid process.
Die ungesättigten Fettsäureester können vollständig oder auch partiell, beispielsweise zu 50 bis 95 mol.-% epoxidiert vor¬ liegen. Bevorzugt werden Epoxide einfach ungesättigter Fett¬ säureester, insbesondere Ester von technischen ölsäuren mit Methanol ("Epoxymethylstearat"), eingesetzt.The unsaturated fatty acid esters can be completely or partially, for example 50 to 95 mol%, epoxidized. Epoxides of monounsaturated fatty acid esters, in particular esters of technical oleic acids with methanol ("epoxymethyl stearate"), are preferably used.
Als Hydroxyverbindungen kommen Polyole oder Ricinolsäure¬ niedrigalkylester in Betracht.Suitable hydroxy compounds are polyols or lower alkyl ricinoleic acid esters.
Unter Polyole sind dabei Verbindungen zu verstehen, die 2 bis 15, vorzugsweise 2 bis 6 Kohlenstoffatomen und 2 bis 4 Hy¬ droxylgruppen aufweisen. Typische Beispiele sind Ethylenglycol, Diethylenglycol, Propylenglycol, Dipropylengylycol, 1,4-Butandiol, Glycerin, Diglycerin, Trimethylolpropan, Pentaerythrit sowie Bisphenol A.Polyols are understood to mean compounds which have 2 to 15, preferably 2 to 6 carbon atoms and 2 to 4 hydroxyl groups. Typical examples are ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, glycerol, diglycerol, trimethylolpropane, pentaerythritol and bisphenol A.
Typische Beispiele für Ricinolsäureniedrigalkylester sind Ester der Ricinolsäure mit linearen oder verzweigten C1-C4- Alkoholen. Bevorzugt ist Ricinolsäuremethylester. Das molare Einsatzverhältnis zwischen Epoxyverbindung und Hydroxyverbindung kann 1 : 1 bis 10 : 1 betragen. Bei Einsatz von Polyolen ist ein molares Verhältnis von 2 : 1 bis 5 : 1 bevorzugt. Im Hinblick auf eine hohe Ausbeute an verbrückten oligomeren Fettsäuren hat es sich als optimal erwiesen, wenn innerhalb der angegebenen Grenzen das Einsatzverhältnis so gewählt wird, daß für jede Hydroxylgruppe des eingesetzten Polyols mindestens eine Oxirangruppe zur Verfügung steht.Typical examples of lower alkyl ricinoleic esters are esters of ricinoleic acid with linear or branched C1-C4 alcohols. Ricinoleic acid methyl ester is preferred. The molar ratio between epoxy compound and hydroxy compound can be 1: 1 to 10: 1. When using polyols, a molar ratio of 2: 1 to 5: 1 is preferred. In view of a high yield of bridged oligomeric fatty acids, it has proven to be optimal if the use ratio is selected within the limits specified so that at least one oxirane group is available for each hydroxyl group of the polyol used.
Wird die Ringöffnung des Epoxyesters mit einem Ricinolsäu- reester durchgeführt, der nur über eine Hydroxylgruppe ver¬ fügt, ist es ausreichend, ein molares Verhältnis Epoxid zu Hydroxyverbindung von 1 : 1 bis 1,5 : 1 zu wählen.If the ring opening of the epoxy ester is carried out with a ricinoleic acid ester which only has one hydroxyl group, it is sufficient to choose a molar ratio of epoxide to hydroxy compound of 1: 1 to 1.5: 1.
Als saure Katalysatoren für die Ringöffnungsreaktion kommen typische Mineralsäuren oder niedere organische Carbonsäuren in Betracht. Typische Beispiele sind Schwefelsäure, Phosphor¬ säure, Ameisensäure und/oder Essigsäure. Die sauren Kataly¬ satoren können in in Konzentrationen von 0,1 bis 5 Gew.-% - bezogen auf die Ausgangsstoffe - eingesetzt werden.Typical mineral acids or lower organic carboxylic acids come into consideration as acid catalysts for the ring opening reaction. Typical examples are sulfuric acid, phosphoric acid, formic acid and / or acetic acid. The acidic catalysts can be used in concentrations of 0.1 to 5% by weight, based on the starting materials.
Die Ringöffnungsreaktion kann bei Temperaturen von 80 bis 120, vorzugsweise 90 bis 100°C über einen Zeitraum von 1 bis 10, vorzugsweise 3 bis 6 h durchgeführt werden. Anschließend ist es von Vorteil, die Katalysatorsäure mit einer Base, beispielsweise Natriumhydroxid oder Natriummethylat, zu neu¬ tralisieren.The ring opening reaction can be carried out at temperatures of 80 to 120, preferably 90 to 100 ° C. over a period of 1 to 10, preferably 3 to 6 hours. It is then advantageous to neutralize the catalyst acid with a base, for example sodium hydroxide or sodium methylate.
Die Verseifung der Ringöffnungsprodukte kann in an sich be¬ kannter Weise durchgeführt werden. Es empfiehlt sich, für jedes mol im Rohprodukt vorliegender Estergruppen mindestens 1, vorzugsweise 1,1 bis 2 mol einer Base, beispielsweise Na¬ triumhydroxidlösung einzusetzen und die Reaktion unter Rück¬ fluß über einen Zeitraum von 1 bis 5 h durchzuführen. An¬ schließend sollte die Base durch Zusatz einer Mineralsäure, beispielsweise Schwefelsäure, neutralisiert werden.The saponification of the ring opening products can be carried out in a manner known per se. It is recommended that at least for every mole of ester groups present in the crude product Use 1, preferably 1.1 to 2 mol of a base, for example sodium hydroxide solution and carry out the reaction under reflux over a period of 1 to 5 hours. The base should then be neutralized by adding a mineral acid, for example sulfuric acid.
Ein weiterer Gegenstand der Erfindung betrifft Dimerfett¬ säuren, die man dadurch erhält, daß man epoxidierte Fettsäu¬ reester der Formel (I) in Gegenwart saurer Katalysatoren mit Ricinolsäureniedrigalkylestern im molaren Verhältnis 1 : 1 bis 1,5 : 1 umsetzt und die resultierenden verbrückten Ring¬ öffnungsprodukte anschließend in an sich bekannter Weise verseift.The invention further relates to dimer fatty acids which are obtained by reacting epoxidized fatty acid esters of the formula (I) in the presence of acidic catalysts with lower alkyl ricinoleic acid in a molar ratio of 1: 1 to 1.5: 1 and the resulting bridged ring ¬ opening products then saponified in a manner known per se.
Gewerbliche AnwendbarkeitIndustrial applicability
Die nach dem erfindungsgemäßen Verfahren erhältlichen oli- gomeren Fettsäuren weisen stockpunktserniedrigende Eigen¬ schaften auf und eignen sich beispielsweise zur Herstellung von Schmierstoffen, in denen sie in Mengen von 1 bis 50, vorzugsweise 10 bis 25 Gew.-% - bezogen auf die Mittel -ent¬ halten sein können.The oligomeric fatty acids obtainable by the process according to the invention have pour point-lowering properties and are suitable, for example, for the production of lubricants in which they are present in amounts of 1 to 50, preferably 10 to 25% by weight, based on the composition ¬ can be hold.
Die folgenden Beispiele sollen den Gegenstand der Erfindung näher erläutern, ohne ihn darauf einzuschränken. BeispieleThe following examples are intended to explain the subject matter of the invention in more detail without restricting it. Examples
Allgemeine Vorschrift zur Herstellung oligomerer Fettsäuren.General instructions for the production of oligomeric fatty acids.
a) Ringöffnung;a) ring opening;
In einem 1-1-Dreihalskolben wurden 312 g (1 mol) 9,10- Epoxystearinsäuremethylester und 1 bis 3 Mol einer Hy¬ droxyverbindung vorgelegt. Die Reaktionsmischung wurde mit 0,3 Gew.-% - bezogen auf die Einsatzstoffe - 35 gew.-%iger Schwefelsäure versetzt und unter Rühren über einen Zeitraum von 6 h auf 100°C erhitzt. Das Rohprodukt wurde anschließend im Hochvakuum von nichtumgesetzten Anteilen der Hydroxyverbindung befreit. Danach wurde die Katalysatorsäure mit 30 gew.-%iger Natriummethylatlösung neutralisiert und ausgefallenes Natriumsulfat über einen Faltenfilter abgetrennt.312 g (1 mol) of 9,10-epoxystearic acid methyl ester and 1 to 3 mol of a hydroxy compound were placed in a 1 liter three-necked flask. The reaction mixture was mixed with 0.3% by weight, based on the starting materials, of 35% by weight sulfuric acid and heated to 100 ° C. over a period of 6 hours with stirring. The crude product was then freed from unreacted portions of the hydroxy compound in a high vacuum. The catalyst acid was then neutralized with 30% strength by weight sodium methylate solution and precipitated sodium sulfate was separated off using a pleated filter.
b) Verseifung:b) saponification:
Jeweils 1 mol der verbrückten Ringöffnungsprodukte aus a) wurden mit 2 mol Natriumhydroxid in Form einer 15 gew.- %igen wäßrigen Lösung versetzt und über einen Zeitraum von 2 h bei ca. 90°C unter Rückfluß gerührt. Anschließend wurde die Lösung mit 35 gew.-%iger Schwefelsäure auf pH 2 bis 3 eingestellt und mit 2 1 Wasser versetzt. Die ent¬ standene organische Phase wurde abgetrennt und im Was¬ serstrahlvakuum getrocknet.In each case 1 mol of the bridged ring opening products from a) were mixed with 2 mol sodium hydroxide in the form of a 15% strength by weight aqueous solution and stirred under reflux at about 90 ° C. over a period of 2 h. The solution was then adjusted to pH 2 to 3 with 35% strength by weight sulfuric acid and 2 l of water were added. The resulting organic phase was separated off and dried in a water jet vacuum.
Einzelheiten zu den Versuchsansätzen sowie die Kennzahlen der Produkte sind in Tab.l zusammengefaßt. Tab.1: Ringöffnung von 9,10-Epoxystearinsäuremethylester Theoretische Kennzahlen in ( )"Details of the test approaches and the key figures of the products are summarized in Tab. 1. Tab. 1: Ring opening of 9,10-epoxystearic acid methyl ester Theoretical key figures in () "
Legende: E : H Molverhältnis Epoxyester : Hydroxyverbindung OHZ Hydroxylzahl VZ Verseif ngszahl SZ Säurezahl Legend: E: H molar ratio of epoxy ester: hydroxy compound OHZ hydroxyl number VZ saponification number SZ acid number
Claims
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4201343.7 | 1992-01-20 | ||
| DE19924201343 DE4201343A1 (en) | 1992-01-20 | 1992-01-20 | METHOD FOR PRODUCING OLIGOMER FATTY ACIDS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1993014060A1 true WO1993014060A1 (en) | 1993-07-22 |
Family
ID=6449845
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP1993/000041 Ceased WO1993014060A1 (en) | 1992-01-20 | 1993-01-11 | Process for producing oligomeric fatty acids |
Country Status (2)
| Country | Link |
|---|---|
| DE (1) | DE4201343A1 (en) |
| WO (1) | WO1993014060A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007006550A3 (en) * | 2005-07-11 | 2007-05-18 | Plt Patent & Licence Trading L | Oligomers of straight-chain and unbranched fatty acids, and medicaments containing the same |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102004031787A1 (en) | 2004-07-01 | 2006-01-26 | Cognis Deutschland Gmbh & Co. Kg | Viscosity reducer for high-viscosity polyols |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3066159A (en) * | 1960-11-29 | 1962-11-27 | Petrolite Corp | Reaction product of polyols and epoxidized fatty compounds |
| EP0113797A1 (en) * | 1982-12-16 | 1984-07-25 | Henkel Kommanditgesellschaft auf Aktien | Compositions of alkyde resins containing products obtained by the ring opening of epoxidized fatty alcohols or fatty-acid derivatives as the hydroxyl component |
| EP0127810A1 (en) * | 1983-05-21 | 1984-12-12 | Henkel Kommanditgesellschaft auf Aktien | Hydroxyalkoxycarboxylic acids and their salts, their preparation and use |
| EP0353012A1 (en) * | 1988-07-26 | 1990-01-31 | Nabisco Brands, Inc. | Ether bridged polyesters |
| WO1991011424A1 (en) * | 1990-01-26 | 1991-08-08 | Henkel Kommanditgesellschaft Auf Aktien | Alkoxylated compounds produced from epoxylated carboxylic acid derivatives |
-
1992
- 1992-01-20 DE DE19924201343 patent/DE4201343A1/en not_active Withdrawn
-
1993
- 1993-01-11 WO PCT/EP1993/000041 patent/WO1993014060A1/en not_active Ceased
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3066159A (en) * | 1960-11-29 | 1962-11-27 | Petrolite Corp | Reaction product of polyols and epoxidized fatty compounds |
| EP0113797A1 (en) * | 1982-12-16 | 1984-07-25 | Henkel Kommanditgesellschaft auf Aktien | Compositions of alkyde resins containing products obtained by the ring opening of epoxidized fatty alcohols or fatty-acid derivatives as the hydroxyl component |
| EP0127810A1 (en) * | 1983-05-21 | 1984-12-12 | Henkel Kommanditgesellschaft auf Aktien | Hydroxyalkoxycarboxylic acids and their salts, their preparation and use |
| EP0353012A1 (en) * | 1988-07-26 | 1990-01-31 | Nabisco Brands, Inc. | Ether bridged polyesters |
| WO1991011424A1 (en) * | 1990-01-26 | 1991-08-08 | Henkel Kommanditgesellschaft Auf Aktien | Alkoxylated compounds produced from epoxylated carboxylic acid derivatives |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007006550A3 (en) * | 2005-07-11 | 2007-05-18 | Plt Patent & Licence Trading L | Oligomers of straight-chain and unbranched fatty acids, and medicaments containing the same |
| EP2216319A3 (en) * | 2005-07-11 | 2010-11-24 | PLT Patent & Licence Trading Ltd. | Oligomers of straight-chain and unbranched fatty acids, and medicaments containing the same |
| US7964640B2 (en) | 2005-07-11 | 2011-06-21 | Plt Patent & License Trading Ltd. | Oligomers of straight-chain and unbranched fatty acids and drugs containing these |
Also Published As
| Publication number | Publication date |
|---|---|
| DE4201343A1 (en) | 1993-07-22 |
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