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WO1996016924A1 - Procede de fabrication d'esters complexes - Google Patents

Procede de fabrication d'esters complexes Download PDF

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Publication number
WO1996016924A1
WO1996016924A1 PCT/EP1995/004623 EP9504623W WO9616924A1 WO 1996016924 A1 WO1996016924 A1 WO 1996016924A1 EP 9504623 W EP9504623 W EP 9504623W WO 9616924 A1 WO9616924 A1 WO 9616924A1
Authority
WO
WIPO (PCT)
Prior art keywords
weight
acid
fatty acids
condensation
esterification
Prior art date
Application number
PCT/EP1995/004623
Other languages
German (de)
English (en)
Inventor
Andreas Sander
Rainer Von Kries
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
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 Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Publication of WO1996016924A1 publication Critical patent/WO1996016924A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/34—Higher-molecular-weight carboxylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents

Definitions

  • the invention relates to a process for the preparation of complex esters, in which hydroxy fatty acids are initially subjected to self-condensation at high temperatures and the resulting polyhydroxy fatty acids are then esterified with polyols without cooling.
  • glycerol and ricinoleic acid are usually first polymerized separately and the polymers are then esterified with one another.
  • this process is implemented on an industrial scale, it is associated with a high technical outlay in terms of separate boilers or boiler occupancy times.
  • the esterification proceeds more quickly and the proportion of polymeric ricinoleic acids in the complex ester is low.
  • the object of the invention was therefore to provide an improved process for the preparation of polyol polyhydroxy fatty acid esters which is free from the disadvantages described.
  • the invention relates to a process for the preparation of complex esters, in which
  • Particularly suitable hydroxy fatty acids are ricinoleic acid and 12-hydroxystearic acid and mixtures thereof.
  • the latter can be prepared by mixing the two components or partially curing the ricinoleic acid.
  • polyols is understood to mean substances which have at least two, preferably 3 to 12 and in particular 3 to 8 hydroxyl groups and 2 to 12 carbon atoms. Typical examples are:
  • Alkylene glycols such as ethylene glycol, ethylene glycol, propylene glycol;
  • Methyl compounds such as in particular trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol and dipentaerythritol;
  • Alkyl glucosides with 1 to 22, preferably 1 to 8 and in particular 1 to 4 carbons in the alkyl radical, such as methyl and butyl glucoside;
  • Glucose or sucrose *** aminosugars such as glucamine.
  • polyglycerols are used as polyols, in particular those which have the following homolog distribution (the preferred ranges are given in brackets):
  • a polyglycerol of the abovementioned composition can be carried out by self-condensation of glycerol in the presence of suitable catalysts such as, for example, potassium carbonate, silicates according to DE-Al 4029323 (Henkel) or borates according to DE-Al 4117033 (Henkel) at temperatures in the range from 200 to 260 ° C are carried out.
  • suitable catalysts such as, for example, potassium carbonate, silicates according to DE-Al 4029323 (Henkel) or borates according to DE-Al 4117033 (Henkel) at temperatures in the range from 200 to 260 ° C are carried out.
  • suitable catalysts such as, for example, potassium carbonate, silicates according to DE-Al 4029323 (Henkel) or borates according to DE-Al 4117033 (Henkel) at temperatures in the range from 200 to 260 ° C are carried out.
  • Other esterification components such as, for example,
  • alcohols or carboxylic acids such as e.g. Condensate fatty alcohols, fatty acids, fatty alcohol polyglycol ethers and / or fruit acids.
  • fatty alcohols are capronic alcohol, capyl alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palm oleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, linoleylyl alcohol, linoleylyl alcohol, linoleyl alcohol, petol , Gadollyl alcohol, behenyl alcohol and erucyl alcohol and their technical mixtures, which, for example in the high-pressure hydrogenation of technical methyl esters based on fats and oils or aldehydes from Roelen's oxosynthesis and as a monomer fraction in the dimerization of unsaturated fatty alcohols.
  • fatty acids are caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, aradacholeic acid, elaeoleic acid , Behenic acid and erucic acid and their technical mixtures, which are obtained, for example, in the pressure splitting of natural fats and oils, in the reduction of aldehydes from Roelen's oxosynthesis or in the dimerization of unsaturated fatty acids.
  • fatty alcohol polyglycol ethers are the addition products of 1 to 10 moles of ethylene oxide and 0 to 3 moles of propylene oxide to the above-mentioned fatty alcohols.
  • Typical examples of fruit acids are lactic acid, malic acid, tartaric acid and citric acid.
  • the proportion by weight of the above-mentioned further esterification components can be 1 to 10, preferably 2 to 5,% by weight, based on the complex ester.
  • the use of catalysts is not absolutely necessary.
  • the self-condensation of the hydroxy fatty acids is usually autocatalytic.
  • polyglycerol is used as the polyol component, it usually contains an alkaline catalyst content which is advantageous for the esterification.
  • the reactions can be accelerated by using catalysts.
  • Alkali and / or alkaline earth compounds such as, for example, sodium hydroxide, sodium carbonate, sodium hydrogen carbonate, potassium hydroxide, potassium carbonate, calcium oxide or magnesium oxide are suitable for this.
  • Other suitable catalysts are tin compounds such as tin oxalate or aluminum compounds such as basic aluminum hydroxide.
  • mineral acids can also be used However, because of possible elimination reactions, their use is associated with disadvantages.
  • the catalysts can be used in amounts of 1 to 10, preferably 2 to 5,% by weight, based on the starting materials.
  • hypophosphorous acid and / or its alkali metal salts such as sodium hypophosphite as stabilizers.
  • concentration of these substances can be 0.1 to 5, preferably 0.5 to 2% by weight, based on the starting materials.
  • the condensation with subsequent esterification is usually carried out in a closed tank with a cooler attached.
  • the hydroxy fatty acid and, if appropriate, the catalyst and / or the stabilizer are initially introduced, the reactor is closed and the mixture is heated to 200 to 280, preferably 220 to 250 ° C.
  • the desired degree of self-condensation can be determined by the amount of water discharged or by taking samples and determining the acid number.
  • polyhydroxy fatty acids with 2 to 10 and in particular whose 2 to 8 fatty acid units are formed.
  • the following distribution (GPC method) is typically achieved:
  • the preheated polyol component is metered into the reactor using pumps. Due to the high temperatures, the esterification occurs spontaneously, i.e. the water released evaporates suddenly and has to be removed without pressure building up in the reactor. In order to avoid this, the polyol is preferably metered into the reaction batch at such a rate as the water released during the esterification can be removed via the cooler.
  • the resulting complex esters - insofar as they contain ricinoleic acid units - can be characterized by their iodine number.
  • Typical examples are polyesters with an iodine number ⁇ 10 (based on 99% 12-hydroxystearic acid) or 70 to 110 (based on 90% 12-hydroxystearic acid, 10% ricinoleic acid).
  • the complex esters according to the invention are distinguished by a particularly advantageous emulsifying power.
  • the resulting emulsions have a higher storage and in particular heat stability than the products of the prior art.
  • W / O emulsifiers for cosmetic and / or pharmaceutical preparations such as e.g. Skin creams, body lotions, sunscreens and the like are used, in which they can be contained in concentrations of 1 to 20, preferably 2 to 10% by weight, based on the composition.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé de fabrication d'esters complexes, consistant (a) à soumettre des hydroxy-acides gras à une autocondensation à des températures de l'ordre de 200 à 280 °C et (b) à estérifier, avec des polyols, les polyhydroxy-acides gras obtenus, sans les faire refroidir.
PCT/EP1995/004623 1994-12-02 1995-11-23 Procede de fabrication d'esters complexes WO1996016924A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP4442988.6 1994-12-02
DE4442988A DE4442988C1 (de) 1994-12-02 1994-12-02 Verfahren zur Herstellung von Komplexestern

Publications (1)

Publication Number Publication Date
WO1996016924A1 true WO1996016924A1 (fr) 1996-06-06

Family

ID=6534776

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1995/004623 WO1996016924A1 (fr) 1994-12-02 1995-11-23 Procede de fabrication d'esters complexes

Country Status (2)

Country Link
DE (1) DE4442988C1 (fr)
WO (1) WO1996016924A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114149322A (zh) * 2021-10-29 2022-03-08 南京中威生物材料研究院有限公司 一种中链脂肪酸单双甘油酯的制备工艺

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112778135B (zh) * 2021-01-14 2022-03-08 郑州大河食品科技有限公司 一种聚甘油蓖麻醇酸酯的制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1524782A (en) * 1976-01-24 1978-09-13 Indian Space Res Org Production of estertype polyols
GB2073232A (en) * 1980-04-09 1981-10-14 Magdeburg Oel & Margarine Method of preparing polyglycerol polyricinoleic fatty acid esters
DE4409569C1 (de) * 1994-03-21 1995-08-10 Henkel Kgaa Polyglycerinpolyricinoleate

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3928397A1 (de) * 1989-08-28 1991-03-07 Henkel Kgaa Verfahren zur herstellung von salzfreien estern von fettsaeuren mit oligoglycerinen bzw. mit anlagerungsprodukten von ethylenoxid und/oder propylenoxid an oligoglycerine

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1524782A (en) * 1976-01-24 1978-09-13 Indian Space Res Org Production of estertype polyols
GB2073232A (en) * 1980-04-09 1981-10-14 Magdeburg Oel & Margarine Method of preparing polyglycerol polyricinoleic fatty acid esters
DE4409569C1 (de) * 1994-03-21 1995-08-10 Henkel Kgaa Polyglycerinpolyricinoleate

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114149322A (zh) * 2021-10-29 2022-03-08 南京中威生物材料研究院有限公司 一种中链脂肪酸单双甘油酯的制备工艺

Also Published As

Publication number Publication date
DE4442988C1 (de) 1996-02-08

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