WO1992013819A1 - Process for producing branched dialkyl ethers - Google Patents
Process for producing branched dialkyl ethers Download PDFInfo
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- WO1992013819A1 WO1992013819A1 PCT/EP1992/000178 EP9200178W WO9213819A1 WO 1992013819 A1 WO1992013819 A1 WO 1992013819A1 EP 9200178 W EP9200178 W EP 9200178W WO 9213819 A1 WO9213819 A1 WO 9213819A1
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- alcohols
- branched
- dialkyl ethers
- formula
- hydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/09—Preparation of ethers by dehydration of compounds containing hydroxy groups
Definitions
- the invention relates to a process for the preparation of branched dialkyl ethers by condensation of branched alcohols with hydroxy compounds in the presence of acidic catalysts.
- Dialkyl ethers are important products of the chemical industry.
- the use of diisoalkyl ethers as heat exchanger liquids is known from German patent application DE 34 24 702 A1.
- Dialkyl ethers, in particular those with at least one long, branched alkyl radical, are also found as auxiliaries in the photo industry [JP 84/33 369], solvents for the suspension polymerization of vinyl acetate [JP 83/109 504] or components of skin creams [JP 73/5941] use.
- a process for their preparation is based on aldehydes from Roelen 1 see oxosynthesis, which in the first stage condenses to the alpha, beta-unsaturated aldehydes, then in the presence of phosphoric acid are reacted with alcohols and finally hydrogenated [DE 2945050 AI] .
- this process is not very economical from an economic point of view.
- it is practically only suitable for the preparation of 2-ethylhexyl ethers, since 2-ethylhexanal is the only branched oxoaldehyde which is available in large quantities.
- Another possibility for the production of dialkyl ethers is the reaction of alcohols with alkyl chlorides according to WILLIAMSON.
- German patent application DE 39 11004 AI describes the condensation of branched alcohols in the presence of a catalyst system consisting of sulfuric acid or sulfonic acids and phosphorous acid. At temperatures around 240 ° C, however, branched olefins and no ethers are obtained in practically quantitative amounts.
- the object of the invention was therefore to develop a process for the preparation of dialkyl ethers which is free from the disadvantages.
- the invention relates to a process for the preparation of branched dialkyl ethers, which is characterized in that branched primary alcohols of the formula (I),
- R - * and R2 independently of one another represent linear alkyl radicals having 2 to 20 carbon atoms, in the presence of sulfonic acids condensed with hydroxy compounds at temperatures of 150 to 200 ° C.
- dialkyl ethers with high selectivity are formed in the acid-catalyzed condensation of branched alcohols with hydroxy compounds if the reaction is carried out in the temperature range from 150 to 200.degree. This overcome the prejudice that only olefins are produced in this type of implementation.
- Branched primary alcohols for the preparation of the dialkyl ethers are branched oxo alcohols which are accessible via Roelen's oxosynthesis (hydroformylation).
- short-chain olefins such as propylene, butene-1 or pentene-1
- synthesis gas in the presence of rhodium / triphenylphosphine catalysts.
- the resulting aldehydes are subjected to base-catalyzed aldol condensation and hydrogenation, in which beta-alkyl-branched alcohols are obtained.
- beta-alkyl-branched alcohols are obtained.
- Typical examples of this are 2-ethylhexanol, 2-propylheptanol or 2-butyloctanol.
- Preferred branched oxo alcohols as starting materials for the preparation of dialkyl ethers are alcohols of the formula (II) in which R 1 and R 2 represent alkyl radicals having 2 to 8 carbon
- Guerbet alcohols which are formed in the base-catalyzed condensation of linear saturated or unsaturated alcohols having 6 to 22 carbon atoms via the intermediate stages of the aldehydes and aldols can also be used as branched primary alcohols for the preparation of the dialkyl ethers [Soap Cosm.Chem. Spec, 52 (1987)]. Typical examples are 2- butyloctanol, 2-hexyldecanol, 2-0ctyldodecanol, 2-decyltetra- decanol, 2-dodecylhexadecanol or 2-tetradecyloctadecanol.
- Preferred Guerbet alcohols for the production of dialkyl ethers are alcohols of the formula (II) in which R 1 and R 2 are alkyl radicals
- Branched and linear alcohols are suitable as hydroxy compounds.
- the branched alcohols are self-condensed; in this case the hydroxy compounds used correspond to the alcohols of the formula (I).
- Dialkyl ethers with branches in both alkyl chains are formed.
- hydroxy components are primary, predominantly linear alcohols of the formula (II),
- R3 is an aliphatic hydrocarbon radical having 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds.
- Typical examples are capronic alcohol, caprylic alcohol, capric alcohol, myristyl alcohol, lauryl alcohol, cetyl alcohol, palmitoleyl alcohol, stearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linolyl alcohol, linolenyl alcohol, behenyl alcohol or erucyl alcohol.
- R 3 represents alkyl radicals having 8 to 18 carbon atoms.
- the alcohols can also be used in the form of technical cuts, such as those obtained by high-pressure hydrogenation of fatty acid methyl esters based on fats and oils. Furthermore, the Largely linear oxo alcohols from Roelen 1 see oxosynthesis as suitable if they have a corresponding chain length.
- the condensation takes place in the presence of acidic catalysts of the sulfonic acid type.
- the sulfonic acids can be used in concentrations of 0.1 to 5% by weight, based on the starting alcohols. In view of a high reaction rate and minimal formation of undesired olefinic by-products, it has proven to be optimal to use the sulfonic acids in amounts of 1 to 2% by weight.
- the condensation is carried out at temperatures in the range from 150 to 200.degree. In view of a sufficient reaction rate and a minimal formation of undesired olefinic by-products, it has proven to be optimal to carry out the reaction at temperatures from 160 to 190 ° C.
- the reaction time is determined by the catalyst concentration and the reaction temperature.
- the reaction can usually be carried out over a period of 1 to 36 h, preferably 2 to 30 h.
- the starting materials and the catalyst are introduced and heated.
- the crude product can then, if appropriate after neutralizing the acid catalyst, be purified by distillation in vacuo.
- the dialkyl ethers obtainable by the process according to the invention are high-boiling, temperature-resistant substances which are suitable, for example, as heat exchanger liquids.
- Octyloxy-2-hexyldecane 758.3 g (2.9 mol) of 2-hexyldecanol and 64.7 g of a 70% by weight aqueous solution of sulfosuccinic acid were heated to 170 to 184 ° C. over 6 h and in four portions with 1508 g (11, 6 mol) of n-octanol are added.
- the crude reaction product was worked up analogously to Example 2. There were 400 g Obtain 1-octyloxy-2-hexyldecane in the form of a colorless oil (bp 160 ° C / 0.06 mbar).
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Abstract
Branched dialkyl ethers may be produced by condensing branched primary alcohols of the formula (I), in which R?1 and R?2 are mutually independently linear alkyl radicals with 2 to 20 carbon atoms, in the presence of sulphonic acids at temperatures of 150 to 200 C with hydroxy compounds. The products are suitable as heat exchanger liquids.
Description
Verfahren zur Herstellung von verzweigten Dialkylethern Process for the preparation of branched dialkyl ethers
Gegenstand der Erfindung ist ein Verfahren zur Herstellung von verzweigten Dialkylethern durch Kondensation von verzweigten Al¬ koholen mit Hydroxyverbindungen in Gegenwart saurer Katalysatoren.The invention relates to a process for the preparation of branched dialkyl ethers by condensation of branched alcohols with hydroxy compounds in the presence of acidic catalysts.
Dialkylether stellen wichtige Produkte der chemischen Industrie dar. Aus der deutschen Patentanmeldung DE 34 24 702 AI ist der Einsatz von Diisoalkylethern als Wärmetauscherflüssigkeiten be¬ kannt. Dialkylether, insbesondere solche mit mindestens einem langen, verzweigten Alkylrest, finden ferner als Hilfsmittel in der Photoindustrie [JP 84/33 369], Lösungsmittel für die Suspen¬ sionspolymerisation von Vinylacetat [JP 83/109 504] oder Bestand¬ teil von Hautcremes [JP 73/5941] Verwendung.Dialkyl ethers are important products of the chemical industry. The use of diisoalkyl ethers as heat exchanger liquids is known from German patent application DE 34 24 702 A1. Dialkyl ethers, in particular those with at least one long, branched alkyl radical, are also found as auxiliaries in the photo industry [JP 84/33 369], solvents for the suspension polymerization of vinyl acetate [JP 83/109 504] or components of skin creams [JP 73/5941] use.
Ein Verfahren zu ihrer Herstellung geht von Aldehyden aus der Roelen1sehen Oxosynthese aus, die in der ersten Stufe zu den alpha, beta-ungesättigten Aldehyden kondensiert, danach in Gegen¬ wart von Phosphorsäure mit Alkoholen umgesetzt und schließlich hydriert werden [DE 2945050 AI]. Infolge des hohen Syntheseauf¬ wandes ist dieses Verfahren vom wirtschaftlichen Standpunkt jedoch wenig rentabel. Es ist zudem praktisch nur für die Herstellung von 2-Ethylhexylethern geeignet, da 2-Ethylhexanal den einzige ver¬ zweigte Oxoaldehyd darstellt, der in großtechnischen Mengen zur Verfügung steht.
Eine weitere Möglichkeit zur Herstellung von Dialkylethern besteht in der Umsetzung von Alkoholen mit AlkylChloriden nach WILLIAMSON. Da hierzu jedoch mindestens stöchio etrische Mengen Alkali benö¬ tigt werden, weisen entsprechende Verfahren den Nachteil auf, daß die anfallenden Salzmengen entweder mit hohem technischen Aufwand abgetrennt werden müssen oder zu einer unerwünscht hohen Elektro¬ lytbelastung der Produkte führen. Ein weiterer Nachteil, gerade für die Herstellung von verzweigten Dialkylethern besteht darin, daß die entsprechenden Alkylchloride schwer zugänglich sind.A process for their preparation is based on aldehydes from Roelen 1 see oxosynthesis, which in the first stage condenses to the alpha, beta-unsaturated aldehydes, then in the presence of phosphoric acid are reacted with alcohols and finally hydrogenated [DE 2945050 AI] . However, due to the high expenditure on synthesis, this process is not very economical from an economic point of view. In addition, it is practically only suitable for the preparation of 2-ethylhexyl ethers, since 2-ethylhexanal is the only branched oxoaldehyde which is available in large quantities. Another possibility for the production of dialkyl ethers is the reaction of alcohols with alkyl chlorides according to WILLIAMSON. However, since at least stoichiometric amounts of alkali are required for this purpose, corresponding processes have the disadvantage that the resulting amounts of salt either have to be separated with a high level of technical complexity or lead to an undesirably high load of electrolytes on the products. Another disadvantage, especially for the production of branched dialkyl ethers, is that the corresponding alkyl chlorides are difficult to access.
In der deutschen Patentanmeldung DE 39 11004 AI wird die Konden¬ sation verzweigter Alkohole in Gegenwart eines Katalysatorsystems bestehend aus Schwefelsäure oder Sulfonsäuren und Phosphoriger Säure beschrieben. Bei Temperaturen um 240°C werden dabei jedoch in praktisch quantitativen Mengen verzweigte Olefine und keine Ether erhalten.The German patent application DE 39 11004 AI describes the condensation of branched alcohols in the presence of a catalyst system consisting of sulfuric acid or sulfonic acids and phosphorous acid. At temperatures around 240 ° C, however, branched olefins and no ethers are obtained in practically quantitative amounts.
Die Aufgabe der Erfindung bestand somit darin, ein Verfahren zur Herstellung von Dialkylethern zu entwickeln, das frei von den ge¬ sch lderten Nachteilen ist.The object of the invention was therefore to develop a process for the preparation of dialkyl ethers which is free from the disadvantages.
Gegenstand der Erfindung ist ein Verfahren zur Herstellung von verzweigten Dialkylethern, das sich dadurch auszeichnet, daß man verzweigte primäre Alkohole der Formel (I),The invention relates to a process for the preparation of branched dialkyl ethers, which is characterized in that branched primary alcohols of the formula (I),
RZRZ
II.
R1-CH2-CH2-CH-CH2θH (I)R 1 -CH 2 -CH2-CH-CH2θH (I)
in der R--* und R2 unabhängig voneinander für lineare Alkylreste mit 2 bis 20 Kohlenstoffatomen stehen, in Gegenwart von Sulfonsäuren
mit Hydroxyverbindungen bei Temperaturen von 150 bis 200°C kon¬ densiert.in which R - * and R2 independently of one another represent linear alkyl radicals having 2 to 20 carbon atoms, in the presence of sulfonic acids condensed with hydroxy compounds at temperatures of 150 to 200 ° C.
Überraschenderweise wurde gefunden, daß bei der sauer katalysier¬ ten Kondensation von verzweigten Alkoholen mit Hydroxyverbindungen Dialkylether mit hoher Selektivität gebildet werden, wenn man die Reaktion im Temperaturbereich von 150 bis 200°C durchführt. Damit konnte das Vorurteil überwunden werden, daß bei dieser Art der Umsetzung grundsätzlich nur Olefine entstehen.Surprisingly, it was found that dialkyl ethers with high selectivity are formed in the acid-catalyzed condensation of branched alcohols with hydroxy compounds if the reaction is carried out in the temperature range from 150 to 200.degree. This overcome the prejudice that only olefins are produced in this type of implementation.
Als verzweigte primäre Alkohole für die Herstellung der Dialkyl¬ ether kommen verzweigte Oxoalkohole in Betracht, die über die Roelen'sche Oxosynthese (Hydroformylierung) zugänglich sind. Hierzu werden zunächst kurzkettige Olefine, wie beispielsweise Propylen, Buten-1 oder Penten-1, in Gegenwart von Rhodium/Tri- phenylphosphin-Katalysatoren mit Synthesegas umgesetzt. Die dabei anfallenden Aldehyde werden einer basenkatalysierten Aldolkon- densation und einer Hydrierung unterworfen, bei der man beta-al- kylverzweigte Alkohole erhält. Typische Beispiele hierfür sind 2-Ethylhexanol, 2-Propyl- heptanol oder 2-Butyloctanol. Bevorzugte verzweigte Oxoalkohole als Einsatzstoffe für die Herstellung von Dialkylethern sind Alkohole der Formel (II), in der R1 und R2 für Alkylreste mit 2 bis 8 Kohlenstoffatomen stehen.Branched primary alcohols for the preparation of the dialkyl ethers are branched oxo alcohols which are accessible via Roelen's oxosynthesis (hydroformylation). For this purpose, short-chain olefins, such as propylene, butene-1 or pentene-1, are first reacted with synthesis gas in the presence of rhodium / triphenylphosphine catalysts. The resulting aldehydes are subjected to base-catalyzed aldol condensation and hydrogenation, in which beta-alkyl-branched alcohols are obtained. Typical examples of this are 2-ethylhexanol, 2-propylheptanol or 2-butyloctanol. Preferred branched oxo alcohols as starting materials for the preparation of dialkyl ethers are alcohols of the formula (II) in which R 1 and R 2 represent alkyl radicals having 2 to 8 carbon atoms.
Weiterhin können als verzweigte primäre Alkohole für die Herstel¬ lung der Dialkylether auch Guerbetalkohole verwendet werden, die bei der basenkatalysierten Kondensation linearer gesättigter oder ungesättigter Alkohole mit 6 bis 22 Kohlenstoffatomen über die Zwischenstufen der Aldehyde und Aldole gebildet werden [Soap Cosm.Chem. Spec, 52 (1987)]. Typische Beispiele hierfür sind 2— Butyloctanol , 2-Hexyldecanol , 2-0ctyldodecanol, 2-Decyltetra-
decanol, 2-Dodecyl- hexadecanol oder 2-Tetradecyloctadecanol. Be¬ vorzugte Guerbetalkohole für die Herstellung von Dialkylethern sind Alkohole der Formel (II), in der R1 und R2 für Alkylreste mitGuerbet alcohols which are formed in the base-catalyzed condensation of linear saturated or unsaturated alcohols having 6 to 22 carbon atoms via the intermediate stages of the aldehydes and aldols can also be used as branched primary alcohols for the preparation of the dialkyl ethers [Soap Cosm.Chem. Spec, 52 (1987)]. Typical examples are 2- butyloctanol, 2-hexyldecanol, 2-0ctyldodecanol, 2-decyltetra- decanol, 2-dodecylhexadecanol or 2-tetradecyloctadecanol. Preferred Guerbet alcohols for the production of dialkyl ethers are alcohols of the formula (II) in which R 1 and R 2 are alkyl radicals
4 bis 20, insbesondere 6 bis 16 Kohlenstoffatomen stehen.4 to 20, in particular 6 to 16 carbon atoms.
Als Hydroxyverbindungen kommen verzweigte und lineare Alkohole in Betracht. Im einfachsten Fall findet eine Eigeπkondensation der verzweigten Alkohole statt; in diesem Fall entsprechen die einge¬ setzten Hydroxyverbindungen den Alkoholen der Formel (I). Dabei werden Dialkylether mit Verzweigungen in beiden Alkylketten ge¬ bildet.Branched and linear alcohols are suitable as hydroxy compounds. In the simplest case, the branched alcohols are self-condensed; in this case the hydroxy compounds used correspond to the alcohols of the formula (I). Dialkyl ethers with branches in both alkyl chains are formed.
Als Hydroxykomponenten eignen sich ebenfalls primäre, überwiegend lineare Alkohole der Formel (II),Also suitable as hydroxy components are primary, predominantly linear alcohols of the formula (II),
R3-0H (II)R3-0H (II)
in der R3 für einen aliphatischen Kohlenwasserstoffrest mit 6 bis 22 Kohlenstoffatomen und 0, 1, 2 oder 3 Doppelbindungen steht. Typische Beispiele sind Capronalkohol, Caprylalkohol, Caprinal- kohol, Myristylalkohol, Laurylalkohol, Cetylalkohol, Palmitoleyl- alkohol, Stearylalkohol, Oleylalkohol, Elaidylalkohol, Petroseli- nylalkohol, Linolylalkohol, Linolenylalkohol, Behenylalkohol oder Erucylalkohol. Bevorzugt ist die Verwendung von Alkoholen der Formel (II), in der R3 für Alkylreste mit 8 bis 18 Kohlenstoff¬ atomen steht.in which R3 is an aliphatic hydrocarbon radical having 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds. Typical examples are capronic alcohol, caprylic alcohol, capric alcohol, myristyl alcohol, lauryl alcohol, cetyl alcohol, palmitoleyl alcohol, stearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linolyl alcohol, linolenyl alcohol, behenyl alcohol or erucyl alcohol. Preference is given to using alcohols of the formula (II) in which R 3 represents alkyl radicals having 8 to 18 carbon atoms.
Wie in der Fettchemie üblich, können die Alkohole dabei auch in Form technischer Schnitte eingesetzt werden, wie man sie bei¬ spielsweise durch Hochdruckhydrierung von Fettsäuremethylestern auf Basis von Fetten und Ölen erhält. Weiterhin sind auch die
weitgehend linearen Oxoalkohole aus der Roelen1sehen Oxosynthese geeignet, sofern sie eine entsprechende Kettenlänge aufweisen.As is usual in fat chemistry, the alcohols can also be used in the form of technical cuts, such as those obtained by high-pressure hydrogenation of fatty acid methyl esters based on fats and oils. Furthermore, the Largely linear oxo alcohols from Roelen 1 see oxosynthesis as suitable if they have a corresponding chain length.
Die Kondensation findet in Gegenwart von sauren Katalysatoren des Typs der Sulfonsäuren statt. Hierzu sind aliphatische und aroma¬ tische Sulfonsäuren, wie beispielsweise Methansulfonsäure, Butan- sulfonsäure, p-Toluolsulfonsäure zu zählen. Bevorzugt ist die Verwendung von Sulfobernsteinsäure, die sich als besonders effi¬ zient erwiesen hat.The condensation takes place in the presence of acidic catalysts of the sulfonic acid type. This includes aliphatic and aromatic sulfonic acids, such as methanesulfonic acid, butanesulfonic acid, p-toluenesulfonic acid. Preferred is the use of sulfosuccinic acid, which has proven to be particularly efficient.
Die Sulfonsäuren können in Konzentrationen von 0,1 bis 5 Gew.-% - bezogen auf die Einsatzalkohole - eingesetzt werden. Im Hinblick auf eine hohe Reaktionsgeschwindigkeit und eine minimale Bildung unerwünschter olefinischer Nebenprodukte hat es sich als optimal erwiesen, die Sulfonsäuren in Mengen von 1 bis 2 Gew.-% einzuset¬ zen.The sulfonic acids can be used in concentrations of 0.1 to 5% by weight, based on the starting alcohols. In view of a high reaction rate and minimal formation of undesired olefinic by-products, it has proven to be optimal to use the sulfonic acids in amounts of 1 to 2% by weight.
Die Kondensation wird bei Temperaturen im Bereich von 150 bis 200°C durchgeführt. Im Hinblick auf eine ausreichende Reaktions¬ geschwindigkeit und eine minimale Bildung unerwünschter olefi¬ nischer Nebenprodukte hat es sich als optimal erwiesen, die Re¬ aktion bei Temperaturen von 160 bis 190°C durchzuführen.The condensation is carried out at temperatures in the range from 150 to 200.degree. In view of a sufficient reaction rate and a minimal formation of undesired olefinic by-products, it has proven to be optimal to carry out the reaction at temperatures from 160 to 190 ° C.
Die Reaktionsdauer wird durch die Katalysatorkonzentration und die Reaktionstemperatur bedingt. Üblicherweise kann die Reaktion über einen Zeitraum von 1 bis 36 h, vorzugsweise 2 bis 30 h durchge¬ führt werden. Hierzu werden die Einsatzstoffe und der Katalysator vorgelegt und erhitzt. Anschließend kann das Rohprodukt, gegebe¬ nenfalls nach Neutralisation des sauren Katalysators, im Vakuum destillativ gereinigt werden.
Die nach dem erfindungsgemäßen Verfahren erhältlichen Dialkylether stellen hochsiedende, temperaturbeständige Stoffe dar, die sich beispielsweise als Wärmetauscherflüssigkeiten eignen.The reaction time is determined by the catalyst concentration and the reaction temperature. The reaction can usually be carried out over a period of 1 to 36 h, preferably 2 to 30 h. For this purpose, the starting materials and the catalyst are introduced and heated. The crude product can then, if appropriate after neutralizing the acid catalyst, be purified by distillation in vacuo. The dialkyl ethers obtainable by the process according to the invention are high-boiling, temperature-resistant substances which are suitable, for example, as heat exchanger liquids.
Die folgenden Beispiele sollen den Gegenstand der Erfindung näher erläutern, ohne ihn darauf einzuschränken.
The following examples are intended to explain the subject matter of the invention in more detail without restricting it.
BeispieleExamples
Beispiel 1:Example 1:
Bis-(2-ethylhexy1)-ether. 1000 g (7,67 mol) 2-Ethylhexanol wurden mit 14,3 g einer 70gew.-%igen wäßrigen Lösung von Sulfobernstein¬ säure versetzt und 16 h unter Rückfluß am Wasserabscheider er¬ hitzt. Nach 10 h wurden weitere 3,6 g der Sulfobernsteinsäure-Lö- sung zugegeben. Das Rohprodukt wurde im Wasserstrahlvakuum (T = 220°C/0,05 mbar) destilliert, wobei 282 g des Bis-(2-ethylhexyl)- ethers erhalten wurden.Bis (2-ethylhexyl) ether. 14 g of a 70% strength by weight aqueous solution of sulfosuccinic acid were added to 1000 g (7.67 mol) of 2-ethylhexanol and the mixture was heated under reflux for 16 hours on a water separator. After 10 h, a further 3.6 g of the sulfosuccinic acid solution were added. The crude product was distilled in a water jet vacuum (T = 220 ° C./0.05 mbar), 282 g of the bis (2-ethylhexyl) ether being obtained.
Beispiel 2;Example 2;
Bis-(2-hexyldecyl)-ether. 2200 g (8,41 mol) 2-Hexyldecanol wurden mit 62,9 einer 70gew.-%igen wäßrigen Lösung von Sulfobernstein¬ säure versetzt und 7 h auf 165 bis 185°C erhitzt. Das dabei an¬ fallende goldgelbe Rohprodukt wurde über einen Zeitraum von 30 min bei 95°C mit 267 g 50 gew.-%iger Natriumhydroxidlösung behandelt. Die organische Phase wurde abgetrennt und einer fraktionierten Destillation unterworfen, wobei 500 g des Bis-(2-hexylethyl)ethers (Sdp. 220°C/0,05 mbar) erhalten wurden.Bis (2-hexyldecyl) ether. 2200 g (8.41 mol) of 2-hexyldecanol were mixed with 62.9% of a 70% strength by weight aqueous solution of sulfosuccinic acid and heated to 165 to 185 ° C. for 7 hours. The resulting golden-yellow crude product was treated with 267 g of 50% strength by weight sodium hydroxide solution at 95 ° C. over a period of 30 minutes. The organic phase was separated and subjected to fractional distillation, whereby 500 g of the bis (2-hexylethyl) ether (bp. 220 ° C./0.05 mbar) were obtained.
Beispiel 3:Example 3:
0ctyloxy-2-hexyldecan. 758,3 g (2,9 mol) 2-Hexyldecanol und 64,7 g einer 70gew.-%igen wäßrigen Lösung von Sulfobernsteinsäure wurden über 6 h auf 170 bis 184°C erhitzt und dabei in vier Portionen mit 1508 g (11,6 mol) n-Octanol versetzt. Das rohe Umsetzungsprodukt wurde analog Beispiel 2 aufgearbeitet. Es wurden 400 g
l-0ctyloxy-2-hexyldecan in Form eines farblosen Öles (Sdp. 160°C/0,06 mbar) erhalten.
Octyloxy-2-hexyldecane. 758.3 g (2.9 mol) of 2-hexyldecanol and 64.7 g of a 70% by weight aqueous solution of sulfosuccinic acid were heated to 170 to 184 ° C. over 6 h and in four portions with 1508 g (11, 6 mol) of n-octanol are added. The crude reaction product was worked up analogously to Example 2. There were 400 g Obtain 1-octyloxy-2-hexyldecane in the form of a colorless oil (bp 160 ° C / 0.06 mbar).
Claims
1. Verfahren zur Herstellung von verzweigten Dialkylethern, da¬ durch gekennzeichnet, daß man verzweigte primäre Alkohole der Formel (I),1. Process for the preparation of branched dialkyl ethers, characterized in that branched primary alcohols of the formula (I),
R2R2
II.
R-L-CH2-CH2-CH-CH2OH (1)R-L-CH2-CH2-CH-CH2OH (1)
in der R* und R2 unabhängig voneinander für lineare Alkylreste mit 2 bis 20 Kohlenstoffatomen stehen, in Gegenwart von Sul¬ fonsäuren bei Temperaturen von 150 bis 200°C mit Hydroxyver¬ bindungen kondensiert.in which R * and R 2 independently of one another represent linear alkyl radicals having 2 to 20 carbon atoms, condensed with hydroxy compounds in the presence of sulfonic acids at temperatures of 150 to 200 ° C.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man als Hydroxyverbindungen verzweigte Alkohole der Formel (I) ein¬ setzt.2. The method according to claim 1, characterized in that one uses as hydroxy compounds branched alcohols of formula (I) ein¬.
3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man als Hydroxyverbindungen primäre, überwiegend lineare Alkohole der Formel (II) einsetzt,3. The method according to claim 1, characterized in that primary, predominantly linear alcohols of the formula (II) are used as hydroxy compounds,
R3-0H (II)R3-0H (II)
in der R-*-* für einen aliphatischen Kohlenwasserstoffrest mit 6 bis 22 Kohlenstoffatomen und 0, 1, 2 oder 3 Doppelbindungen steht. in which R - * - * represents an aliphatic hydrocarbon radical having 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds.
4. Verfahren nach mindestens einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß man die Sulfonsäuren in Konzentrationen von 0,1 bis 5 Gew.-% - bezogen die eingesetzten Alkohole - einsetzt. 4. The method according to at least one of claims 1 to 3, characterized in that one uses the sulfonic acids in concentrations of 0.1 to 5 wt .-% - based on the alcohols used.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4103489.9 | 1991-02-06 | ||
| DE19914103489 DE4103489A1 (en) | 1991-02-06 | 1991-02-06 | METHOD FOR PRODUCING BRANCHED DIALKYL ETHERS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1992013819A1 true WO1992013819A1 (en) | 1992-08-20 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP1992/000178 WO1992013819A1 (en) | 1991-02-06 | 1992-01-28 | Process for producing branched dialkyl ethers |
Country Status (2)
| Country | Link |
|---|---|
| DE (1) | DE4103489A1 (en) |
| WO (1) | WO1992013819A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL1008796C2 (en) * | 1997-04-02 | 1998-11-03 | Snam Progetti | Process for the preparation of ethers from alcohols. |
| WO2009064828A1 (en) * | 2007-11-13 | 2009-05-22 | E. I. Du Pont De Nemours And Company | Process for making a composition comprising at least two different dialkyl ethers |
| SE2151462A1 (en) * | 2021-12-01 | 2023-06-02 | Colabitoil Sweden Ab | Biofuel and method of synthesis of the same |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4301820C2 (en) * | 1993-01-23 | 1996-04-25 | Henkel Kgaa | Foaming emulsions, processes for their preparation and their use |
| DE4308794C1 (en) * | 1993-03-18 | 1994-04-21 | Henkel Kgaa | Prepn. of solid esterquat used as hair care compsn. by quaternising fatty acid tri:ethanolamine ester - with alkylating agent, in presence of fatty alcohol, fatty acid mono:glyceride or di:alkyl ether as dispersant and opt. emulsifier |
| DE4311445C1 (en) * | 1993-04-07 | 1994-10-06 | Henkel Kgaa | Multiple W / O / W emulsions, process for their preparation and their use |
| DE19517049B4 (en) * | 1995-05-10 | 2005-06-16 | Cognis Deutschland Gmbh & Co. Kg | Process for the preparation of dialkyl ethers |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2844534A (en) * | 1952-10-20 | 1958-07-22 | Exxon Research Engineering Co | High molecular weight branched-chain ethers of lubricating grade |
| EP0170076A1 (en) * | 1984-07-05 | 1986-02-05 | BASF Aktiengesellschaft | Heat transfer fluids |
-
1991
- 1991-02-06 DE DE19914103489 patent/DE4103489A1/en not_active Withdrawn
-
1992
- 1992-01-28 WO PCT/EP1992/000178 patent/WO1992013819A1/en active Application Filing
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2844534A (en) * | 1952-10-20 | 1958-07-22 | Exxon Research Engineering Co | High molecular weight branched-chain ethers of lubricating grade |
| EP0170076A1 (en) * | 1984-07-05 | 1986-02-05 | BASF Aktiengesellschaft | Heat transfer fluids |
Non-Patent Citations (1)
| Title |
|---|
| BULLETIN DE LA SOCIETE CHIMIQUE DE FRANCE. 1949, PARIS FR Seiten 333 - 337; R. PERRON UND C.PAQUOT: 'Préparation des éthers-oxydes symétriques dérivés des alcools aliphatiques saturés à longue chaine' * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL1008796C2 (en) * | 1997-04-02 | 1998-11-03 | Snam Progetti | Process for the preparation of ethers from alcohols. |
| US6218583B1 (en) | 1997-04-02 | 2001-04-17 | Snamprogetti S.P.A. | Process for the production of ethers from alcohols |
| WO2009064828A1 (en) * | 2007-11-13 | 2009-05-22 | E. I. Du Pont De Nemours And Company | Process for making a composition comprising at least two different dialkyl ethers |
| SE2151462A1 (en) * | 2021-12-01 | 2023-06-02 | Colabitoil Sweden Ab | Biofuel and method of synthesis of the same |
| WO2023101592A1 (en) * | 2021-12-01 | 2023-06-08 | Colabitoil Sweden Ab | Biofuel and method of synthesis of the same |
Also Published As
| Publication number | Publication date |
|---|---|
| DE4103489A1 (en) | 1992-08-13 |
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