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WO1995011251A1 - Ethers glyceriques d'alkyl- et/ou d'alkenyloligoglucosides oligomeres - Google Patents

Ethers glyceriques d'alkyl- et/ou d'alkenyloligoglucosides oligomeres Download PDF

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Publication number
WO1995011251A1
WO1995011251A1 PCT/EP1994/003378 EP9403378W WO9511251A1 WO 1995011251 A1 WO1995011251 A1 WO 1995011251A1 EP 9403378 W EP9403378 W EP 9403378W WO 9511251 A1 WO9511251 A1 WO 9511251A1
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WO
WIPO (PCT)
Prior art keywords
alkyl
glycerol
alkenyl
carbon atoms
formula
Prior art date
Application number
PCT/EP1994/003378
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German (de)
English (en)
Inventor
Manfred Weuthen
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 WO1995011251A1 publication Critical patent/WO1995011251A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H15/00—Compounds containing hydrocarbon or substituted hydrocarbon radicals directly attached to hetero atoms of saccharide radicals
    • C07H15/02—Acyclic radicals, not substituted by cyclic structures
    • C07H15/04—Acyclic radicals, not substituted by cyclic structures attached to an oxygen atom of the saccharide radical
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/662—Carbohydrates or derivatives

Definitions

  • the invention relates to a new oligomeric alkyl and / or alkenyl oligoglycoside glycerol ether, a process for their preparation in which alkyl and / or alkenyl oligoglycosides are reacted with glycerol and / or technical oligoglycerol mixtures, and their use for the production of surface coatings tive means.
  • Alkyl oligoglycosides and in particular alkyl oligoglucosides are nonionic surfactants that are becoming increasingly important due to their natural raw material base - fatty alcohol and sugar - and are used, for example, in manual dishwashing detergents or cosmetic products [cf. Tens. Surf.Det. .28, 413 (1991)]. Nevertheless, alkyl oligoglycosides show in some applications that their foaming power is not completely satisfactory. The solubility in cold water and the crystallization behavior are also in need of improvement. In the past, there has been no lack of attempts to chemically derivatize alkyl oligoglycosides and in this way to bring about an improvement in the properties mentioned by hydrophilizing the molecule.
  • the object of the invention was therefore to provide new nonionic derivatives of the alkyl and / or alkenyl oligoglycosides which are free from the disadvantages described.
  • the invention relates to oligomeric alkyl and / or alkenyl oligoglycoside glycerol ethers which are obtained by adding alkyl and / or alkenyl oligoglycosides of the formula (I)
  • the new ethers have greater foaming power, better solubility in cold water and a reduced tendency to crystallize compared to alkyl oligoglycosides. In addition, they are well tolerated by the skin and are completely biodegradable.
  • the invention includes the knowledge that under the specified process conditions, self-condensation of the glycerol and etherification with the glycosides take place simultaneously.
  • the invention further relates to a process for the preparation of oligomeric alkyl and / or alkenyl oligoglycoside glycerol ethers, in which alkyl and / or alkenyl oligoglycosides of the formula (I),
  • R 1 is an alkyl and / or alkenyl radical having 1 to 22 carbon atoms or a glycerol, ethylene glycol, propylene glycol or sorbitol radical
  • G is a sugar having 5 or 6 carbon atoms
  • p is a number from 1 to 10 , with glycerol and / or technical oligoglycerol mixtures.
  • Alkyl and alkenyl oligoglycosides are known substances which can be obtained by the relevant processes in preparative organic chemistry. Representative of the extensive literature, reference is made here to the publications EP-Al-0 301 298 and WO 90/3977.
  • the alkyl and / or alkenyl oligoglycosides can be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose.
  • the preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides.
  • the alkyl or alkenyl radical R 1 can be derived from primary alcohols having 1 to 11, preferably 8 to 10, carbon atoms. Typical examples are methanol, butanol, capron alcohol, caprylic alcohol, capric alcohol and undecyl alcohol as well as their technical mixtures, such as are obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis. Alkyl oligoglucosides are preferred
  • the alkyl or alkenyl radical R-1- can also be derived from primary alcohols having 12 to 22, preferably 12 to 14, carbon atoms. Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and their technical mixtures, which can be obtained as described above. Alkyl oligoglucosides based on hydrogenated Ci2 / i4 coconut alcohol with a DP of 1 to 3 are preferred.
  • the starting materials can also be polyoligoglycosides, preferably glycerol, ethylene glycol, propylene glycol or sorbitol oligoglucosides.
  • oligoglycerol mixtures preferably those which have a high diglycerol content, become more basic through self-condensation of glycerol in the presence Catalysts obtained by methods of the prior art. Oligoglycerol mixtures which have an average degree of condensation of 1.5 to 10 are preferably used.
  • the alkyl and / or alkenyl oligoglycosides and the glycerol or the oligoglycerols can usually be used in a molar ratio of 3: 1 to 1:30. This means that the stoichiometric conversion of the reactants is not always sought. In particular, there is an interest in mixtures in which only a certain proportion of the alkyl and / or alkenyl oligoglycosides are etherified. Conversely, an excess of glycerol or oligoglycerin is required if the reaction is to be carried out as completely as possible. Usually, however, an application ratio of 3: 1 to 1:10 and in particular 1 ⁇ 3 to 1: 5 is recommended.
  • the etherification can also be carried out purely thermally, the use of catalysts is recommended.
  • both acidic and basic compounds come into consideration; in view of the acetal bond present in the alkyl and / or alkenyl oligoglycosides, the use of basic catalysts, for example alkali and / or alkaline earth oxides, hydroxides, is of course not recommended.
  • carbonates or C ⁇ .-C4 alcoholates are sodium hydroxide, sodium hydrogen carbonate, sodium methoxide, potassium hydroxide and potassium carbonate.
  • the operational The amount of the alkaline catalysts can be 0.5 to 5, preferably 1 to 2, mol%, based on the glycoside.
  • glycoside and glycerol or oligoglycerol are introduced, heated, mixed with an optionally aqueous or alcoholic solution of the catalyst at the reaction temperature and the solvent introduced is optionally removed in vacuo.
  • oligoglycerols which can react with the glucosides in the same form as the glycerol. Portions of such higher oligomers are even expressly desired since they further improve the hydrophilicity and therefore water solubility of the products.
  • the oligomers according to the invention are in any case complex mixtures of etherification products between the glycosides and oligoglycerols, regardless of whether the oligoglycerols are used directly or are prepared in situ.
  • the reaction is preferably carried out at temperatures in the range from 180 to 230, preferably 180 to 200 ° C; the reaction time can be between 1 and 35 hours.
  • the reaction is preferably carried out in an inert gas atmosphere and the water of reaction is continuously removed from the equilibrium. After etherification, the products can be dissolved in water or pasted with water and in themselves known manner, e.g. B. be bleached by adding hydrogen peroxide.
  • the oligomeric alkyl and / or alkenyl oligoglycoside glycerol ethers according to the invention have surface-active properties. They promote the wetting of hard surfaces and the emulsification of otherwise immiscible phases.
  • Another object of the invention therefore relates to the use of the oligomeric alkyl and / or alkenyl oligoglycoside glycerol ethers according to the invention for the production of surface-active agents, in particular detergents, dishwashing detergents and cleaning agents and products for hair and body care, are used in which they can contain in amounts of 1 to 50, preferably 5 to 30% by weight, based on the composition.
  • the temperature was raised further to 210 ° C. within 4 h.
  • the heat source was then removed, the gas discharge pipe was replaced by a distillation attachment and unconverted glycerol was distilled off under reduced pressure (approx. 1 mbar); in order to avoid excessive foaming, the stirrer speed was also increased.
  • the crude oligomeric dodecylglucoside glycerol ether was mixed with 450 g of water at a temperature of 60 ° C. at 120 ° C., the solution cooling to a mixing temperature of 80 ° C.
  • the product was then bleached by adding 40 g of hydrogen peroxide (30% by weight aqueous solution).

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Biochemistry (AREA)
  • Biotechnology (AREA)
  • General Health & Medical Sciences (AREA)
  • Genetics & Genomics (AREA)
  • Saccharide Compounds (AREA)

Abstract

On obtient des éthers glycériques d'alkyl- et/ou d'alkényloligoglucosides oligomères en faisant réagir avec de la glycérine et/ou des mélanges techniques d'oligoglycérines des alkyl- et/ou des alkényloligoclucosides de la formule (I): R1-O-[G]¿p?, dans laquelle R?1¿ désigne un reste alkyle et/ou alkényle avec 1 à 22 atomes de carbone ou un reste glycérine, éthylèneglycol, propylèneglycol ou sorbitol, G un sucre avec 5 ou 6 atomes de carbone et p des nombres compris entre 1 et 10. Les produits se caractérisent par des propriétes détergentes exceptionnelles.
PCT/EP1994/003378 1993-10-21 1994-10-13 Ethers glyceriques d'alkyl- et/ou d'alkenyloligoglucosides oligomeres WO1995011251A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4335956A DE4335956A1 (de) 1993-10-21 1993-10-21 Oligomere Alkyl- und/oder Alkenyloligoglykosidglycerinether
DEP4335956.6 1993-10-21

Publications (1)

Publication Number Publication Date
WO1995011251A1 true WO1995011251A1 (fr) 1995-04-27

Family

ID=6500696

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1994/003378 WO1995011251A1 (fr) 1993-10-21 1994-10-13 Ethers glyceriques d'alkyl- et/ou d'alkenyloligoglucosides oligomeres

Country Status (2)

Country Link
DE (1) DE4335956A1 (fr)
WO (1) WO1995011251A1 (fr)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04325596A (ja) * 1991-04-26 1992-11-13 Kao Corp 洗浄剤組成物
DE4131281A1 (de) * 1991-09-20 1993-03-25 Henkel Kgaa Verfahren zur herstellung von alkyl- und/oder alkenylpolyglycosidether

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04325596A (ja) * 1991-04-26 1992-11-13 Kao Corp 洗浄剤組成物
DE4131281A1 (de) * 1991-09-20 1993-03-25 Henkel Kgaa Verfahren zur herstellung von alkyl- und/oder alkenylpolyglycosidether

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 9252, Derwent World Patents Index; Class A96, AN 429064 *

Also Published As

Publication number Publication date
DE4335956A1 (de) 1995-04-27

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