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EP0548104A1 - Method of preparing oligoglycerine mixtures with a high diglycerine content - Google Patents

Method of preparing oligoglycerine mixtures with a high diglycerine content

Info

Publication number
EP0548104A1
EP0548104A1 EP19910914912 EP91914912A EP0548104A1 EP 0548104 A1 EP0548104 A1 EP 0548104A1 EP 19910914912 EP19910914912 EP 19910914912 EP 91914912 A EP91914912 A EP 91914912A EP 0548104 A1 EP0548104 A1 EP 0548104A1
Authority
EP
European Patent Office
Prior art keywords
silicate compounds
water
condensation
formula
glycerol
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Withdrawn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
EP19910914912
Other languages
German (de)
French (fr)
Inventor
Udo Hees
Reinhard Bunte
Johannes Hachgenei
Andreas Botulinski
Arno Behr
Manfred Biermann
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 EP0548104A1 publication Critical patent/EP0548104A1/en
Withdrawn legal-status Critical Current

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Classifications

    • 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 oligoglycerol mixtures with a high diglycerol content by condensation of glycerol in the presence of silicate compounds.
  • Diglycerin has gained great importance as a starting material for the production of fatty acid esters.
  • esters are used as emulsifiers in the food industry and cosmetics and in various technical applications, for example as a lubricant or stabilizer for PVC [J.Am.Oil. Che. Soc. 66, 153 (1989)].
  • diglycerin is generally based on glycerin which is reacted with glycidol [fats, soaps, paints, 88 101 (1986)] or epichlorohydrin [EP-A-0 333 984].
  • glycidol fats, soaps, paints, 88 101 (1986)
  • epichlorohydrin EP-A-0 333 984.
  • the reaction is not very selective, and glycidol and epichlorohydrin are difficult to handle and place high demands on occupational safety.
  • glycerol can be condensed in the presence of alkali bases. In this way, however, only mixtures are obtained which, in addition to diglycerol, contain even higher homologues and not negligible amounts of unreacted glycerol. Since the diglycerin has to be separated from these mixtures by distillation, which is associated with a high expenditure of time and energy, the object of the invention was to develop an improved process according to which oligoglycerol mixtures with a high diglycerol content are made available can.
  • the invention relates to a process for the preparation of oligoglycerol mixtures with a high diglycerol content, characterized in that glycerol is condensed in the presence of silicate compounds, the water of condensation is continuously removed from the reaction mixture and the reaction is terminated as soon as that theoretically required for the formation of diglycerol Amount of water has been separated.
  • M stands for lithium, sodium or potassium
  • n stands for whole or fractional numbers greater than 0 as well
  • n 1 and x is 0 or integers from 1 to 20,
  • the amorphous alkali silicates are glassy, water-soluble salts of silicic acid which have solidified from the melt flow. Their production is described, for example, in R ⁇ MPP's Chemie Lexikon, 8th edition, Franckh-Kosmos, Stuttgart, Vol. 6, p. 4593.
  • alkali silicates with a low SiO 2: M2O or m: n ratio (“basic” water glasses), as well as those with a high m: n ratio ("neutral” or “acidic” Water glasses ") are used.
  • the ratio SiO 2: M 0 is also referred to as the" module "of the silicate.
  • the crystalline alkali metal silicates are also known substances. They have a layered structure and are accessible, for example, by sintering alkali water glass or by hydrothermal reactions [Glastechn.Ber., 37 194 (1964)].
  • crystalline alkali metal silicates which catalyze the self-condensation of glycerol in the sense of the process according to the invention, z. B. Makatit (Na S ⁇ ' 4 ⁇ g • 5 H 2 0), Kenyait (Na2Si 22 ⁇ 45 • 10 H 2 0) or Ilerit (Na 2 S ⁇ * 8 ⁇ i7 • 9 H 2 0) into consideration [American mineral. 38, 163 (1953)].
  • the silicate compounds can be used as solids or also in the form of aqueous solutions with solids contents of 1 to 80, preferably 30 to 60% by weight, based on the silicate compound.
  • the silicate compounds are used in the condensation in amounts of 1 to 10, preferably 2 to 5,% by weight, based on the glycerol.
  • the condensation of the glycerol is carried out at temperatures from 200 to 260, preferably 240 to 250 ° C.
  • glycerol and silicate compound are introduced and heated to the reaction temperature in an inert gas atmosphere.
  • the water of condensation formed is separated off, for example, using a water separator.
  • the reaction is stopped when the amount of water theoretically required for the formation of diglycerin has been separated off.
  • the catalysts are used in the form of aqueous solutions in the condensation reaction, their water content must be taken into account when calculating the theoretical amount of condensation water for diglycerol formation.
  • the reaction time is 1 to 30, preferably 3 to 15 hours.
  • the catalyst can be separated from the reaction mixture, for example by filtering or centrifuging; this can also be dispensed with for a large number of applications.
  • the diglycerin is separated from the oligoglycerol mixture formed, for example, by distillation in a high vacuum. For a large number of applications, however, the oligoglycerol mixtures according to the invention can be used without further separation.
  • VI potassium hydroxide was used instead of a silicate compound.
  • module weight ratio Si0 2 : Na 2 0
  • Tri triglycerin
  • Tetra tetraglycerin

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Cosmetics (AREA)

Abstract

On peut obtenir des mélanges d'oligoglycérines à teneur élevée en diglycérine en condensant de la glycérine en présence de composés de silicate, en enlevant en continu l'eau de condensation du mélange de réaction et en interrompant la réaction dès que la quantité d'eau théoriquement requise pour former la diglycérine a été extraite.Mixtures of oligoglycerins with a high diglycerin content can be obtained by condensing glycerin in the presence of silicate compounds, by continuously removing the water of condensation from the reaction mixture and by stopping the reaction as soon as the amount of water theoretically required to form diglycerin has been extracted.

Description

Verfahren zur Herstellung von Oligoglyceringemischen mit hohem Process for the preparation of high oligoglycerol mixtures
DiglyceringehaltDiglycerin content
Die Erfindung betrifft ein Verfahren zur Herstellung von Oligo¬ glyceringemischen mit hohem Diglyceringehalt durch Kondensation von Glycerin in Gegenwart von Silicatverbindungen.The invention relates to a process for the preparation of oligoglycerol mixtures with a high diglycerol content by condensation of glycerol in the presence of silicate compounds.
Diglycerin hat als Ausgangsmaterial für die Herstellung von Fett¬ säureestern große Bedeutung erlangt. Derartige Ester finden Ver¬ wendung als Emulgatoren in der Nahrungsmittelindustrie und der Kosmetik sowie in verschiedenen technischen Anwendungen, bei¬ spielsweise als Schmierstoff oder Stabilisator für PVC [J.Am.Oil. Che .Soc. 66, 153 (1989)].Diglycerin has gained great importance as a starting material for the production of fatty acid esters. Such esters are used as emulsifiers in the food industry and cosmetics and in various technical applications, for example as a lubricant or stabilizer for PVC [J.Am.Oil. Che. Soc. 66, 153 (1989)].
Zur Herstellung von Diglycerin wird in der Regel von Glycerin ausgegangen, das mit Glycidol [Fette,Seifen,Anstrichmitt., 88 101 (1986)] oder Epichlorhydrin [EP-A-0 333 984] umgesetzt wird. Die Reaktion verläuft jedoch wenig selektiv, zudem sind Glycidol und Epichlorhydrin schwer zu handhaben und stellen hohe Anforderungen an den Arbeitsschutz.The production of diglycerin is generally based on glycerin which is reacted with glycidol [fats, soaps, paints, 88 101 (1986)] or epichlorohydrin [EP-A-0 333 984]. However, the reaction is not very selective, and glycidol and epichlorohydrin are difficult to handle and place high demands on occupational safety.
Alternativ hierzu kann Glycerin in Gegenwart von Alkalibasen kon¬ densiert werden. Man erhält auf diesem Wege jedoch nur Gemische, die neben Diglycerin noch höhere Homologe sowie nicht zu vernach¬ lässigende Mengen an nichtumgesetztem Glycerin enthalten. Da das Diglycerin aus diesen Gemischen destillativ abgetrennt werden muß, was mit einem hohem Aufwand an Zeit und Energie ver¬ bunden ist, bestand die Aufgabe der Erfindung darin, ein verbes¬ sertes Verfahren zu entwickeln, nach dem Oligoglyceringemische mit hohem Diglyceringehalt zur Verfügung gestellt werden können.Alternatively, glycerol can be condensed in the presence of alkali bases. In this way, however, only mixtures are obtained which, in addition to diglycerol, contain even higher homologues and not negligible amounts of unreacted glycerol. Since the diglycerin has to be separated from these mixtures by distillation, which is associated with a high expenditure of time and energy, the object of the invention was to develop an improved process according to which oligoglycerol mixtures with a high diglycerol content are made available can.
Gegenstand der Erfindung ist ein Verfahren zur Herstellung von Oligoglyceringemischen mit hohem Diglyceringehalt, dadurch ge¬ kennzeichnet, daß man Glycerin in Gegenwart von Silicatverbin- dungen kondensiert, das Kondensationswasser kontinuierlich aus der Reaktionsmischung entfernt und die Reaktion abbricht, sobald die zur Bildung von Diglycerin theoretisch erforderliche Menge Wasser abgeschieden worden ist.The invention relates to a process for the preparation of oligoglycerol mixtures with a high diglycerol content, characterized in that glycerol is condensed in the presence of silicate compounds, the water of condensation is continuously removed from the reaction mixture and the reaction is terminated as soon as that theoretically required for the formation of diglycerol Amount of water has been separated.
Unter Silicatverbindungen sind im folgendenBelow are silicate compounds
a) amorphe Alkalisilicate der Formel (I),a) amorphous alkali silicates of the formula (I),
(Si02)π,(M2θ)π (I)(Si0 2 ) π, (M2θ) π (I)
in der M für Lithium, Natrium oder Kalium, und n für ganze oder gebrochene Zahlen größer 0 steht sowiewhere M stands for lithium, sodium or potassium, and n stands for whole or fractional numbers greater than 0 as well
b) kristalline Alkalidisilicate der Formel (II),b) crystalline alkali disilicates of the formula (II),
(Si02)m(M2θ)n(H20)x (ii)(Si0 2 ) m (M2θ) n (H 2 0) x (ii)
in der M und m die oben angegebenen Bedeutung besitzen, n für 1 und x für 0 oder ganze Zahlen von 1 bis 20 steht,in which M and m have the meaning given above, n is 1 and x is 0 or integers from 1 to 20,
zu verstehen. Bei den amorphen Alkalisilicaten handelt es sich um aus dem Schmelzfluß erstarrte, glasige, wasserlösliche Salze der Kiesel¬ säure. Ihre Herstellung ist beispielsweise im RÖMPP's Chemie Le¬ xikon, 8.Aufl., Verlag Franckh-Kosmos, Stuttgart, Bd.6, S. 4593 beschrieben. Im Sinne des erfindungsgemäßen Verfahrens können so¬ wohl Alkalisilicate mit niedrigem Siθ2 : M2O-, beziehungsweise m:n-Verhältnis ("basische" Wassergläser), als auch solche mit ho¬ hem m:n-Verhältnis ("neutrale" oder "saure" Wassergläser") einge¬ setzt werden. Das Verhältnis Siθ2 : M 0 wird auch als "Modul" des Silicats bezeichnet.to understand. The amorphous alkali silicates are glassy, water-soluble salts of silicic acid which have solidified from the melt flow. Their production is described, for example, in RÖMPP's Chemie Lexikon, 8th edition, Franckh-Kosmos, Stuttgart, Vol. 6, p. 4593. In the sense of the process according to the invention, alkali silicates with a low SiO 2: M2O or m: n ratio ("basic" water glasses), as well as those with a high m: n ratio ("neutral" or "acidic" Water glasses ") are used. The ratio SiO 2: M 0 is also referred to as the" module "of the silicate.
Auch die kristallinen Alkalidisilicate stellen bekannte Stoffe dar. Sie besitzen einen schichtförmigen Aufbau und sind bei¬ spielsweise durch Sintern von Alkaliwasserglas oder durch hydrothermale Reaktionen zugänglich [Glastechn.Ber., 37 194 (1964)]. Als kristalline Alkalidisilicate, die im Sinne des erfindungsgemäßen Verfahrens die Eigenkondensation des Glycerins katalysieren, kommen z. B. Makatit (Na Sι'4θg • 5 H20), Kenyait (Na2Si22θ45 • 10 H20) oder Ilerit (Na2Sι*8θi7 • 9 H20) in Betracht [Amer.Mineral. 38, 163 (1953)].The crystalline alkali metal silicates are also known substances. They have a layered structure and are accessible, for example, by sintering alkali water glass or by hydrothermal reactions [Glastechn.Ber., 37 194 (1964)]. As crystalline alkali metal silicates, which catalyze the self-condensation of glycerol in the sense of the process according to the invention, z. B. Makatit (Na Sι ' 4θg • 5 H 2 0), Kenyait (Na2Si 22 θ45 • 10 H 2 0) or Ilerit (Na 2 Sι * 8θi7 • 9 H 2 0) into consideration [American mineral. 38, 163 (1953)].
Als besonders aktive Katalysatoren in der Kondensation von Glyce¬ rin zu Oligoglycerinen mit hohem Diglyceringehalt haben sich Silicatverbindungen der Formeln (I) und (II) erwiesen, bei denen M für Natrium und x für 0 steht und deren Modul, d. h. deren m:n- Verhältnis, 1,9 bis 4, vorzugsweise 1,9 bis 2,5 beträgt.Silicate compounds of the formulas (I) and (II) in which M is sodium and x are 0 and their modulus, ie. H. whose m: n ratio is 1.9 to 4, preferably 1.9 to 2.5.
Die Silicatverbindungen können als Feststoffe oder auch in Form wäßriger Lösungen mit Feststoffgehalten von 1 bis 80, vorzugsweise 30 bis 60 Gew.-%, bezogen auf die Silicatverbindung, eingesetzt werden. Die Silicatverbindungen werden in der Kondensation in Mengen von 1 bis 10, vorzugsweise 2 bis 5 Gew.-%, bezogen auf das Glycerin, eingesetzt. Die Kondensation des Glycerins wird bei Temperaturen von 200 bis 260, vorzugsweise 240 bis 250°C durchgeführt.The silicate compounds can be used as solids or also in the form of aqueous solutions with solids contents of 1 to 80, preferably 30 to 60% by weight, based on the silicate compound. The silicate compounds are used in the condensation in amounts of 1 to 10, preferably 2 to 5,% by weight, based on the glycerol. The condensation of the glycerol is carried out at temperatures from 200 to 260, preferably 240 to 250 ° C.
Zur Durchführung der Kondensationsreaktion werden Glycerin und Silicatverbindung vorgelegt und in einer Inertgasatmosphäre auf die Reaktionstemperatur erhitzt. Zur Verlagerung des Gleichge¬ wichtes wird das entstehende Kondensationswasser beispielsweise über einen Wasserabscheider abgetrennt. Die Reaktion wird abge¬ brochen, wenn die zur Bildung von Diglycerin theoretisch erfor¬ derliche Menge Wasser abgeschieden worden ist. Werden die Kata¬ lysatoren in Form von wäßrigen Lösungen in die Kondensationsreak¬ tion eingesetzt, muß deren Wassergehalt bei der Berechnung der theoretischen Menge Kondensationswasser zur Diglycerinbildung be¬ rücksichtigt werden. Im allgemeinen beträgt die Reaktionszeit 1 bis 30, vorzugsweise 3 bis 15 h. Der Katalysator kann aus dem Re¬ aktionsgemisch beispielsweise durch Filtrieren oder Zentrifugieren angetrennt werden; für eine Vielzahl von Anwendungen kann hierauf auch verzichtet werden. Die Abtrennung des Diglycerin aus dem ge¬ bildeten Oligoglyceringemisch erfolgt beispielsweise durch De¬ stillation im Hochvakuum. Für eine Vielzahl von Anwendungen können jedoch die erfindungsgemäßen Oligoglyceringemische ohne weitere Auftrennung eingesetzt werden.To carry out the condensation reaction, glycerol and silicate compound are introduced and heated to the reaction temperature in an inert gas atmosphere. To shift the equilibrium, the water of condensation formed is separated off, for example, using a water separator. The reaction is stopped when the amount of water theoretically required for the formation of diglycerin has been separated off. If the catalysts are used in the form of aqueous solutions in the condensation reaction, their water content must be taken into account when calculating the theoretical amount of condensation water for diglycerol formation. In general, the reaction time is 1 to 30, preferably 3 to 15 hours. The catalyst can be separated from the reaction mixture, for example by filtering or centrifuging; this can also be dispensed with for a large number of applications. The diglycerin is separated from the oligoglycerol mixture formed, for example, by distillation in a high vacuum. For a large number of applications, however, the oligoglycerol mixtures according to the invention can be used without further separation.
Die nachfolgenden 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
Beispiele 1 bis 6:, Veroleichsbeispiel 1Examples 1 to 6: Comparative Example 1
Allgemeine Vorschrift zur Herstellung von Oligoglyceringemischen mit hohem Diglyceringehalt. In einem 250-ml-Dreihalskolben mit Rückflußkühler, Wasserabscheider und Innenthermometer wurden 184 g (2 mol) Glycerin (99,5 gew.-%ig) vorgelegt und mit 2 bis 5 Gew.-% einer Silicatverbindung versetzt. Die Reaktionsmischung wurde in einer Stickstoffat osphäre auf 240°C erhitzt, wobei das Kondensa¬ tionswasser über den Wasserabscheider entfernt wurde. Die Reaktion wurde abgebrochen, nachdem die für die Bildung von Diglycerin er¬ forderliche Menge abgeschieden worden war. Die Zusammensetzung des Oligoglyceringemisches mittels HPLC ermittelt. Einzelheiten zu den Katalysatoren, der Versuchsdurchführung sowie den Produktzusam¬ mensetzungen sind in Tab.l zusammengefaßt. Im VergleichsbeispielGeneral instructions for the preparation of oligoglycerol mixtures with a high diglycerol content. 184 g (2 mol) of glycerol (99.5% by weight) were placed in a 250 ml three-necked flask with a reflux condenser, water separator and internal thermometer, and 2 to 5% by weight of a silicate compound were added. The reaction mixture was heated to 240 ° C. in a nitrogen atmosphere, the condensation water being removed via the water separator. The reaction was stopped after the amount necessary for the formation of diglycerin had been separated. The composition of the oligoglycerol mixture was determined by HPLC. Details on the catalysts, the test procedure and the product compositions are summarized in Tab. 1. In the comparative example
VI wurde Kaliumhydroxid anstelle einer Silicatverbindung einge¬ setzt. VI potassium hydroxide was used instead of a silicate compound.
Tab. l : Versuchsdurchführun en und Produktzusammensetzun enTab. 1: Experiments and product compositions
VI K0H 100 2,4 7 32 29 16VI K0H 100 2.4 7 32 29 16
Legende: Modul = Gewichtsverhältnis Si02:Na20Legend: module = weight ratio Si0 2 : Na 2 0
EM = Einsatzmenge Katalysator, bezogen auf GlycerinEM = amount of catalyst used, based on glycerol
FG = Feststoffgehalt des Katalysators t = ReaktionszeitFG = solids content of the catalyst t = reaction time
Gly = GlycerinGly = glycerin
Di = DiglycerinDi = diglycerin
Tri = TriglycerinTri = triglycerin
Tetra = TetraglycerinTetra = tetraglycerin
* = sprühgetrocknet, amorph* = spray dried, amorphous
# = wäßrige Lösung# = aqueous solution
+ = wasserfrei, kristallin, delta-Modifikation + = anhydrous, crystalline, delta modification

Claims

Patentansprüche Claims
1. Verfahren zur Herstellung von Oligoglyceringemischen mit hohem Diglyceringehalt, dadurch gekennzeichnet, daß man Glycerin in Gegenwart von Silicatverbindungen kondensiert, das Kondensa¬ tionswasser kontinuierlich aus der Reaktionsmischung entfernt und die Reaktion abbricht, sobald die zur Bildung von Diglycerin theoretisch erforderliche Menge Wasser abgeschieden worden ist.1. A process for the preparation of oligoglycerol mixtures with a high diglycerol content, characterized in that glycerol is condensed in the presence of silicate compounds, the water of condensation is continuously removed from the reaction mixture and the reaction is terminated as soon as the amount of water theoretically required for the formation of diglycerol has been separated .
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man als Silicatverbindungen amorphe Alkalisilicate der Formel (I),2. The method according to claim 1, characterized in that amorphous alkali silicates of the formula (I) are used as silicate compounds,
(Si02)m(M20)n (I)(Si0 2 ) m (M 2 0) n (I)
in der M für Lithium, Natrium oder Kalium, m und n für ganze oder gebrochene Zahlen größer 0 steht, einsetzt.in which M stands for lithium, sodium or potassium, m and n stands for whole or fractional numbers greater than 0.
3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man als Silicatverbindungen kristalline Alkalidisilicate der Formel (II),3. The method according to claim 1, characterized in that crystalline alkali disilicates of the formula (II) as silicate compounds,
(Si02)m(M2θ)n(H20)x (II)(Si0 2 ) m (M2θ) n (H 2 0) x (II)
in der M für Lithium, Natrium oder Kalium, für ganze oder gebrochene Zahlen größer 0, n für 1 und x für 0 oder ganze Zahlen von 1 bis 20 steht, einsetzt. where M stands for lithium, sodium or potassium, for integers or fractional numbers greater than 0, n for 1 and x for 0 or integers from 1 to 20.
4. Verfahren nach mindestens einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß man Silicatverbindungen der Formel (I) oder (II) einsetzt, in denen M für Natrium steht.4. The method according to at least one of claims 1 to 3, characterized in that silicate compounds of the formula (I) or (II) are used in which M is sodium.
5. Verfahren nach mindestens einem der Ansprüche 1 bis 4,dadurch gekennzeichnet, daß man Silicatverbindungen der Formel (I) oder (II) einsetzt, deren Modul 1,9 bis 4 beträgt.5. The method according to at least one of claims 1 to 4, characterized in that silicate compounds of formula (I) or (II) are used, the modulus of which is 1.9 to 4.
6. Verfahren nach mindestens einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß man die Silicatverbindungen in Form wä߬ riger Lösungen mit Feststoffgehalten von 1 bis 80 Gew.-%, be¬ zogen auf die Silicatverbindung, einsetzt.6. The method according to at least one of claims 1 to 5, characterized in that the silicate compounds are used in the form of aqueous solutions having solids contents of 1 to 80% by weight, based on the silicate compound.
7. Verfahren nach mindestens einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß man die Silicatverbindungen in Mengen von 1 bis 10 Gew.-%, bezogen auf das Glycerin, einsetzt.7. The method according to at least one of claims 1 to 6, characterized in that one uses the silicate compounds in amounts of 1 to 10 wt .-%, based on the glycerol.
8. Verfahren nach mindestens einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß man die Kondensation bei Temperaturen von 200 bis 260°C durchführt. 8. The method according to at least one of claims 1 to 6, characterized in that one carries out the condensation at temperatures of 200 to 260 ° C.
EP19910914912 1990-09-15 1991-09-06 Method of preparing oligoglycerine mixtures with a high diglycerine content Withdrawn EP0548104A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19904029323 DE4029323A1 (en) 1990-09-15 1990-09-15 METHOD FOR THE PRODUCTION OF OLIGOGLYCERINE MIXTURES WITH A HIGH DIGLYCERINE CONTENT
DE4029323 1990-09-15

Publications (1)

Publication Number Publication Date
EP0548104A1 true EP0548104A1 (en) 1993-06-30

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Family Applications (1)

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Country Status (5)

Country Link
EP (1) EP0548104A1 (en)
JP (1) JPH06500773A (en)
CA (1) CA2091687A1 (en)
DE (1) DE4029323A1 (en)
WO (1) WO1992005133A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2743337A1 (en) 2012-12-14 2014-06-18 Cognis IP Management GmbH Surface-active polyglycerine derivatives

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5349094A (en) * 1992-06-12 1994-09-20 Henkel Kommanditgesellschaft Auf Aktien Process for the production of oligoglycerol mixtures of increased diglycerol content
DE4409569C1 (en) * 1994-03-21 1995-08-10 Henkel Kgaa New poly:glycerol poly:ricinoleate ester(s)
DE4420516C2 (en) * 1994-06-13 1998-10-22 Henkel Kgaa Polyglycerol polyhydroxystearates
EP0732318B1 (en) * 1995-03-15 2003-11-19 Nexus A/S A process of preparing oligomeric and/or polymeric polyol compounds and their use in the production of emulsifying agents and surfactants
DE19533539A1 (en) 1995-09-11 1997-03-13 Henkel Kgaa O / W emulsifiers
DE19641604C1 (en) 1996-10-09 1998-03-12 Goldschmidt Ag Th Polyglycerol partial esters of fatty acids and polyfunctional carboxylic acids, their preparation and use

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB265147A (en) * 1926-01-27 1928-02-09 Henkel & Cie Gmbh Improved manufacture of a glycerine poor in poly-glycerines and containing di-glycerine
US2487208A (en) * 1946-12-23 1949-11-08 Colgate Palmolive Peet Co Preparation of diglycerol

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9205133A1 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2743337A1 (en) 2012-12-14 2014-06-18 Cognis IP Management GmbH Surface-active polyglycerine derivatives

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Publication number Publication date
CA2091687A1 (en) 1992-03-16
JPH06500773A (en) 1994-01-27
WO1992005133A1 (en) 1992-04-02
DE4029323A1 (en) 1992-03-19

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