EP0454742A1 - Procede pour la fabrication d'alcools de guerbet - Google Patents

Procede pour la fabrication d'alcools de guerbet

Info

Publication number
EP0454742A1
EP0454742A1 EP90902202A EP90902202A EP0454742A1 EP 0454742 A1 EP0454742 A1 EP 0454742A1 EP 90902202 A EP90902202 A EP 90902202A EP 90902202 A EP90902202 A EP 90902202A EP 0454742 A1 EP0454742 A1 EP 0454742A1
Authority
EP
European Patent Office
Prior art keywords
titanium
zirconium
carbon atoms
acid
primary
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP90902202A
Other languages
German (de)
English (en)
Inventor
Manfred Biermann
Uwe Ploog
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0454742A1 publication Critical patent/EP0454742A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/32—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions without formation of -OH groups
    • C07C29/34—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions without formation of -OH groups by condensation involving hydroxy groups or the mineral ester groups derived therefrom, e.g. Guerbet reaction

Definitions

  • the invention relates to a method for producing
  • Guerbet alcohols by condensation of at least one primary or secondary alkanol having 2 to 30 carbon atoms and having a methylene group in the alpha position to the carbon atom bearing the hydroxyl group in the presence of an alkaline catalyst and a cocatalyst at elevated temperature and with removal of the water of reaction, if appropriate using a water-immiscible entrainer.
  • Guerbet alcohols are formed in the condensation of primary and secondary alcohols in the presence of alkali according to the reaction scheme
  • Alkali metals alkali metal hydroxides, alkali metal oxides or alkali metal alcoholates, together with palladium salts as cocatalysts.
  • the main reaction takes place according to the formula scheme above, but in addition, depending on the catalyst, higher molecular alcohols are also formed, namely by further reaction of a Guerbet alcohol formed from two alkanol molecules with one or more further alkanol molecules.
  • the raw condensation product must be fractionally distilled
  • the cocatalyst is a derivative of titanium (IV) or zirconium (IV) acid, selected from that of alkali metal titanates, alkali metal zirconates, esters of titanium (IV) or zirconium (IV) -acid with C 1 -C 4 -alkanols or with polyols with 2 to 12 carbon atoms and 2 to 6 hydroxyl groups,
  • Titanium dioxide zirconium dioxide, mixed anhydrides
  • alkanols having 2 to 30 carbon atoms and having one Methylene group in the alpha position to the carbon atom carrying the hydroxyl group can be converted to the desired Guerbet alcohols, which are essentially free of higher molecular weight condensation products.
  • Alkanols of this type can be represented by the general formula I
  • R 1 -CH (R 2 ) -CH 2 -OH (I) can be reproduced.
  • the radicals R 1 and R 2 which may be the same or different, are hydrogen, aryl or straight-chain or branched alkyl.
  • Typical examples of such alkanols are ethanol, propanol, isopropanol, butanol, pentanol,
  • the aforementioned starting compounds can be of synthetic origin, e.g. so-called Ziegler or oxo alcohols; however, they can also be of natural origin. In this
  • connections of particularly preferred starting compounds are straight-chain primary alkanols having 6 to 22 carbon atoms, such as those derived from fats and oils of vegetable or animal origin
  • Myristyl, cetyl, stearyl, arachidyl and behenyl alcohol Myristyl, cetyl, stearyl, arachidyl and behenyl alcohol.
  • Suitable alkaline catalysts for the process of the invention are oxides, hydroxides and alcoholates (from C 1 -C 4 alkanols) of alkali metals such as lithium, sodium, potassium and cesium; Potassium hydroxide and / or cesium hydroxide are particularly preferred.
  • Titanium or zirconium compounds of the general formula II are Titanium or zirconium compounds of the general formula II
  • M tetravalent titanium or zirconium and R 3 is an alkyl group with at least 2, in particular 2 to 4 carbon atoms, an acyl group with 2 to 14 carbon atoms or a residue of a beta-diketone of the general formula III
  • R 4 and R 5 are identical or different radicals from the group formed by alkyl groups with 1 to 4 carbon atoms and optionally substituted in the p-position phenyl, two of the groups R 3 together from the
  • divalent radical of a dihydric alkanol having 2 to 4 carbon atoms can be formed
  • Titanium (IV) or zirconium (IV) acetylacetonate Condensation products of titanium (IV) or zirconium (IV) tetraalkoxylates of the general formula II, in which M and R 2 are as defined above, with polyfunctional ones
  • Alkanols in particular with 2 to 12 carbon atoms and 2 to 6 hydroxyl groups.
  • Zirconium compounds are known and the majority are commercially available. Condensation products of titanium (IV) or zirconium (IV) tetraalkoxylates with polyfunctional alkanols with 2 to 12 carbon atoms and 2 to 6 hydroxyl groups such as
  • Glycerin, trimethylolpropane and pentaerythritol are examples of Glycerin, trimethylolpropane and pentaerythritol.
  • Esterification and / or transesterification catalysts e.g. in US-C 4,705,764, the contents of which are incorporated herein by reference.
  • a suitable polyalkanol is also polyvinyl alcohol.
  • Titanic acid H 4 TiO 4
  • zirconic acid H 4 ZrO 4
  • mixed anhydrides of titanium or zirconic acid with organic acids of general formula II, in which M Ti or Zr and R 3 is an alkyl group with 1 to 4 carbon atoms or an acyl group derived from a monocarboxylic acid with 2 to 4
  • Titanium or zirconium acetylacetonates of the general formula (IV) can also be used
  • R 6 is an alkyl group with 1 to 4 carbon atoms
  • ACA is an acetylacetonate radical
  • m is the number 0 and n is the number 4 or m is the number 2 and n is the number 2
  • inorganic or organic zinc compounds in particular zinc oxide and zinc acetate, can be used as additional
  • cocatalysts in an amount of 0.1 to 1 wt .-%, based on primary or secondary alkanol.
  • the condensation is preferably carried out at temperatures from 200 to 260 ° C., if appropriate under pressure; working under pressure is particularly necessary in the case of starting alkanols which have an excessively high vapor pressure at the reaction temperatures.
  • Particularly suitable entraining agents which can be used in the process of the invention are toluene, xylene and 1-ethylhexanol, which form azeotropes with water.
  • the method of the invention is preferred based on
  • Distillation head with water separator 633 g (4 mol) of an approximately 99.9% n-decanol were placed in and slowly heated after addition of the catalyst.
  • the potassium hydroxide used was added in the form of a 50% potassium hydroxide solution. After distilling off the water originating from the potassium hydroxide solution at approx. 120 to 150 ° C, the distillation of the water originating from the Guerbet reaction began at approx. 230 ° C. From this point in time, the reaction time was measured and the amount of water formed was used as a measure of the course of the reaction; the reaction was stopped when the water separation practically reached
  • the catalyst / cocatalyst systems used and their amounts (in mmol / 100 g) of the starting product, the reaction time (in min), the water of reaction formed (in% by weight, based on the theoretically expected amount), the composition of the reaction product (in% by weight).
  • % Starting compound and% by weight of C 20 condensation product the degree of conversion (U; in% by weight), the selectivity (S; in% by weight) and the yield (A; in
  • Example catalyst nMol / reaction water.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Un procédé pour la fabrication d'alcools de Guerbet par condensation d'au moins un alcanol primaire ou secondaire avec 2 à 30 atomes de carbone en présence d'un catalyseur alcalin et d'un co-catalyseur à température élevée et avec élimination de l'eau de réaction, dans lequel on utilise comme co-catalyseur des dérivés de l'acide de titane(IV) ou de zirconium(IV), choisis dans le groupe composé des titanates de métaux alcalins, zirconates de métaux alcalins, esters de l'acide de titane(IV) ou de zirconium(IV) avec des alcanols C1-C4 ou avec des polyols ayant de 2 à 12 atomes de carbone et de 2 à 6 groupes OH, dioxyde de titane, dioxyde de zirconium, anhydrides mélangés de l'acide de titane(IV) ou de zirconium(IV) avec des acides monocarboxyliques C2-C4 et des acétylacétonates de titane(IV) ou de zirconium(IV), fournit des alcools de Guerbet avec des rendements élevés, qui sont pratiquement dépourvus de produits de condensation de poids moléculaire très élevé.
EP90902202A 1989-01-16 1990-01-08 Procede pour la fabrication d'alcools de guerbet Withdrawn EP0454742A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3901095A DE3901095A1 (de) 1989-01-16 1989-01-16 Verfahren zur herstellung von guerbet-alkoholen
DE3901095 1989-01-16

Publications (1)

Publication Number Publication Date
EP0454742A1 true EP0454742A1 (fr) 1991-11-06

Family

ID=6372168

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90902202A Withdrawn EP0454742A1 (fr) 1989-01-16 1990-01-08 Procede pour la fabrication d'alcools de guerbet

Country Status (5)

Country Link
EP (1) EP0454742A1 (fr)
JP (1) JPH04502764A (fr)
BR (1) BR9007035A (fr)
DE (1) DE3901095A1 (fr)
WO (1) WO1990008122A1 (fr)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011131549A1 (fr) 2010-04-23 2011-10-27 Basf Se Procédé de production de pétrole utilisant des tensioactifs à base d'un mélange d'alcoxylates d'alkyle contenant un alcool de guerbet en c32, un alcool de guerbet en c34, un alcool de guerbet en c36
BR112014009825A2 (pt) 2011-10-24 2017-05-02 Basf Se mistura tensoativa, formulação tensoativa aquosa, processos para produzir óleo mineral e para preparar uma mistura tensoativa, e, uso de uma mistura tensoativa
IN2014CN03004A (fr) 2011-10-24 2015-07-03 Basf Se
US9475979B2 (en) 2011-10-24 2016-10-25 Basf Se Process for producing mineral oil using surfactants based on a mixture of C20 Guerbet-, C22 Guerbet-, C24 Guerbet-containing hydrocarbyl alkoxylates
CN103998565A (zh) 2011-10-24 2014-08-20 巴斯夫欧洲公司 使用基于含c28格尔伯特、c30格尔伯特、c32格尔伯特的烃基烷氧基化物的混合物的表面活性剂开采矿物油的方法
US9475977B2 (en) 2011-10-24 2016-10-25 Basf Se Process for producing mineral oil using surfactants based on a mixture of C28 Guerbet, C30 Guerbet, C32 Guerbet-containing hydrocarbyl alkoxylates
US9475978B2 (en) 2011-10-24 2016-10-25 Basf Se Process for producing mineral oil using surfactants based on a mixture of C24 guerbet-, C26 guerbet-, C28-guerbet containing hydrocarbyl alkoxylates
JP5856841B2 (ja) * 2011-12-29 2016-02-10 花王株式会社 ゲルベアルコールの製造方法
EP3489212B1 (fr) * 2016-07-21 2022-03-23 Kao Corporation Procédé de production d'alcool de guerbet

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB381185A (en) * 1931-06-25 1932-09-26 Degussa Process for the production of higher alcohols
FR876589A (fr) * 1940-12-23 1942-11-10 Alexander Wacker Dr Procédé d'exécution de réactions entre alcoolates et composés hydroxylés
US4011273A (en) * 1975-08-04 1977-03-08 Henkel Inc. Method for the production of guerbet alcohols utilizing insoluble lead catalysts

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9008122A1 *

Also Published As

Publication number Publication date
BR9007035A (pt) 1991-11-12
WO1990008122A1 (fr) 1990-07-26
JPH04502764A (ja) 1992-05-21
DE3901095A1 (de) 1990-07-19

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