WO1996008501A1 - Melange comprenant des produits d'alkylation de monosaccharides acetalises et des epoxydes - Google Patents

Melange comprenant des produits d'alkylation de monosaccharides acetalises et des epoxydes Download PDF

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Publication number
WO1996008501A1
WO1996008501A1 PCT/EP1995/003466 EP9503466W WO9608501A1 WO 1996008501 A1 WO1996008501 A1 WO 1996008501A1 EP 9503466 W EP9503466 W EP 9503466W WO 9608501 A1 WO9608501 A1 WO 9608501A1
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WO
WIPO (PCT)
Prior art keywords
products
alkyl
weight
monosaccharides
mixture according
Prior art date
Application number
PCT/EP1995/003466
Other languages
German (de)
English (en)
Inventor
Alfred Oftring
Martin Aus Dem Kahmen
Günter OETTER
Richard Baur
Richard Schmidt
Hendrik Wulff
Original Assignee
Basf Aktiengesellschaft
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 Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Priority to JP8509867A priority Critical patent/JPH10505129A/ja
Priority to EP95932657A priority patent/EP0781292A1/fr
Publication of WO1996008501A1 publication Critical patent/WO1996008501A1/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

Definitions

  • the present invention relates to a mixture of alkylation products of monosaccharides acetalized in the 1-position with long-chain epoxides, processes for their preparation and their use as surfactants or emulsifiers in detergents, cleaning products or personal care products.
  • nonionic surface-active substances based on renewable raw materials have increasingly come to the fore in recent years. Such substances generally have good biodegradability, low toxicity and therefore good environmental compatibility.
  • Alkylglycosides in which the long-chain hydrophobic alkyl radical is attached directly to the hydrophilic carbohydrate part of the molecule in the 1-position by means of an acetal bond.
  • Such products already largely meet the expectations placed on them, but they still prove to be in need of improvement in some properties, such as the foam and wetting capacity, the interfacial or surface tension or the fat loss capacity.
  • US Pat. No. 4,011,389 discloses a mixture of reaction products of long-chain 1,2-epoxyalkanes with glycosides which carry an acetally bound short-chain alkyl, hydroxyalkyl or alkoxyalkyl group in the 1-position.
  • the molar ratio of glycosides to 1,2-epoxyalkanes in the reaction is 4: 1 to 0.83: 1.
  • the 1,2-epoxyalkanes can react with any free hydroxyl group in glycoside. This results in a more or less statistical mixture of the possible reaction products, in which no enrichment of a particular species can be observed.
  • the mixture thus obtained is recommended as a nonionic surfactant for a wide variety of uses.
  • the object of the present invention was to provide nonionic surfactants or emulsifiers based on renewable raw materials with improved application properties. Accordingly, a mixture of alkylation products of monosaccharides acetalized in the 1-position by the radical R 1 was of the general formula I
  • n represents the number 5 or 6 and R 1 is a C 1 - to C 4 -alkyl group, a mono- or dihydroxy-C 1 - to C 3 -alkyl group or a methoxy or ethoxy-C 1 - to C 3 -alkyl group, with epoxides of the general formula II
  • the acetalized monosaccharides I are based on conventional ones
  • Aldopentoses such as ribose, arabinose, xylose and lyxose, aldohexoses such as allose, old rose, glucose, mannose, gulose, idose, galactose and talose and ketohexoses such as are preferably used as such carbohydrates
  • Fructose Of these, mannose, glucose, galactose and fructose are preferred. Glucose is particularly preferred.
  • the naturally occurring carbohydrates of the D series are normally considered, but representatives of the L series can also be used.
  • the radical R 1 denotes in particular methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl, but also are
  • terminal epoxides ie those in which R 2 is a C 4 to C 33 alkyl or alkenyl radical and R 3 is hydrogen;
  • each represent a C 4 to C 30 alkyl or alkenyl radical, it being possible for the two radicals to be the same or different;
  • Glycidyl ether ie those compounds in which R 2 is a C 3 to C 29 alkyl or alkenyloxymethyl radical and R 3 is hydrogen.
  • a long-chain radical R 2 or R 3 represents branched or preferably linear alkyl or alkenyl having 4 to 30 C atoms, in particular 6 to 20 C atoms, especially 8 to 16 C atoms.
  • alkyl and alkenyl groups are listed as examples of linear long-chain radicals R 2 and R 3 : n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-t ⁇ decyl, n-tetradecyl, n-pentadecyl, n- Hexadecyl, n-heptadecyl, n-octadecyl, eicosyl, hexadec-7-enyl, hexadeca-7, 10-dienyl and hexadeca-7,10,13-t ⁇ enyl.
  • R 2 or R 3 can also occur, for example mixtures of n-decyl and n-dodecyl or n-dodecyl and n-tetradecyl.
  • C 1 to C 4 alkyl ester radicals in (c) are n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl and in particular
  • Alkylation products are products in which one or more of the free hydroxyl groups in the acetalized monosaccharides I have been replaced by groups of the formula -O-CHR 3 -CH (OH) -R 2 .
  • groups of the formula -O-CHR 3 -CH (OH) -R 2 When one hydroxyl group is replaced, there are monoalkylation products, and when two or more hydroxyl groups are replaced, higher alkylation products are present.
  • pentose-based acetalized monosaccharides I (n 5) exist
  • the mixture described is enriched with at least one, in particular one or two, of the respective regioisomeric monoalkylation products.
  • the enrichment can go so far that a regioisomeric monoalkylation product is present in the mixture according to the invention in practically pure form, that is to say 95 95% by weight.
  • high levels of enrichment can generally only be achieved by additional complex cleaning or work-up steps such as chromatographic techniques, so that they are normally no longer interesting for large-scale production of the mixture according to the invention.
  • the application properties of the practically pure regioisomeric monoalkylation products usually exceed the already excellent application properties of the, as above described, at least 30 wt .-% or 40 wt .-% enriched monoalkylation products.
  • a mixture according to the invention is therefore preferred which is enriched in these two species or in one of them.
  • the mixture according to the invention can contain up to 50% by weight, in particular up to 35% by weight, especially up to 20% by weight, based on the mixture as a whole, of higher alkylation products. These levels of higher alkylation products can have advantages in certain applications because they have a foam-suppressing effect.
  • the mixture according to the invention can be prepared in a simple manner by reacting the acetalized monosaccharides I with the epoxides II in a molar ratio of 5: 1 to 25: 1, in particular 6: 1 to 15: 1. Through the excess
  • Glycoside I is presumably directed the reaction in such a way that a certain one or more certain regioisomeric monoalkylation products preferentially form, in the case of aldohexose derivatives I these are mostly the 4- and / or 6-alkylation products. Another favorable effect is the only small to nonexistent proportion of higher alkylation products in the mixture according to the invention.
  • the mixture according to the invention can also be more simple
  • this can be achieved in that the epoxide II in a suitable manner, i.e. finely distributed and with thorough mixing, is continuously introduced into the reaction mixture, for example by slow injection.
  • Pumping systems via an external liquid circuit, into which the epoxy II is fed by means of a liquid jet pump, are particularly effective.
  • this invention are particularly effective.
  • monosaccharide I and epoxide II are prepared in a molar ratio of 0.5: 1 to 5: 1, preferably 1: 1 to 3: 1.
  • customary emulsifiers such as further alkyl glycosides or fatty alcohol ethoxylates or alkyl phenol ethoxylates can be used become.
  • concentrations of such emulsifiers in the reaction mixture are normally 0.5 to 30% by weight, in particular 1 to 15% by weight.
  • the two measures of the excess procedure on monosaccharide I and the formation of an emulsion can also be combined.
  • Epoxides II is advantageously made without solvent at higher temperatures, for example at 120 to 250 ° C, in particular at 150 to 200 ° C, i.e. in the melt. But you can also work in inert, sufficiently polar solvents at about 80 to 200 ° C. The reaction is more successful if suitable catalysts are used in the usual amounts, e.g. of alcoholates such as potassium tert-butoxide.
  • the crude product is usually in a solvent, e.g. an alcohol or an alcohol-containing solvent mixture, added and a basic or acidic catalyst used, if appropriate, neutralized. Unreacted monosaccharide I can normally be removed by filtration.
  • the mixture according to the invention is then obtained by distilling off the solvent or the solvent mixture. Further purification with further enrichment or isolation of individual species can be carried out using chromatographic techniques.
  • the crude product still containing monosaccharide I can also be used directly for various applications.
  • the mixture according to the invention is used as a surface-active substance, i.e.
  • non-ionic surfactant in detergents and cleaning agents, for example for cleaning processes in technology and household as for textile washing or for cleaning processes in the food sector such as cleaning beverage bottles or in hand dishwashing detergents. It also serves as an emulsifier in personal care products such as skin creams, lotions, gels, skin oils or hair shampoos.
  • the present invention also relates to detergents, cleaning agents and personal care products which, in addition to the usual constituents, contain 0.5 to 50% by weight, preferably 1 to 30% by weight, of the mixture according to the invention.
  • the usual constituents and composition of detergents and cleaning agents and of personal care products are known to the person skilled in the art and therefore need not be discussed further here.
  • the mixture according to the invention is a nonionic surfactant or emulsifier, which usually has an unusually low interfacial tension, especially against essential oils (for applications in cosmetics as a solubilizer), non-polar oils such as motor oils (for applications in technical cleaners) or fatty oils such as olive oil (when used in hand dishwashing detergents), which correlates very well with a high fat ablation ability, and effectively lowers the surface tension and has a very low critical micelle formation concentration. It shows a good wetting ability of hard surfaces such as glass, metal, ceramic or plastic, which they are suitable for
  • the mixture according to the invention is particularly suitable as an emulsifier or solubilizer for essential oils.
  • Essential oils such as spruce needle oil, rosemary oil or pine needle oil are dissolved in water or, for example, in aqueous ethanol at a suitable weight ratio of the mixture according to the invention to ethereal oil, usually 0.1: 1 to 10: 1, in particular 1: 1 to 5: 1, water-clear solubilized.
  • the emulsions produced in this way are stable almost indefinitely.
  • Such aqueous or aqueous-alcoholic formulations of essential oils are used, for example, in cosmetic or pharmaceutical preparations. As a rule, washing, cleaning and personal care products
  • the mixture according to the invention is a valuable building block for setting a certain property profile in these agents.
  • the mixture according to the invention is based on pure monosaccharides and thus does not have the known problems which occur with alkyl polyglycosides in the production and use in terms of purity, color or reproducibility of the composition.
  • the mixture according to the invention is biodegradable, non-toxic and therefore has good environmental compatibility. Manufacturing examples
  • Example 1 38.8 g (200 mmol) of anhydrous ⁇ -methylglucoside were melted under a nitrogen atmosphere at a bath temperature of 180 ° C., 1.12 g (10 mmol) of potassium tert-butoxide were added and the mixture was dissolved with stirring. Then 3.68 g was added dropwise
  • Example 2 The mixture of the 4 monoalkylation products from Example 1 was separated into the 4 individual species according to the above general working instructions, which were then each present in approximately 95% by weight purity (Example 2: 2 isomer, Example 3: 3 -Isomer, example 4: 4-isomer, example 5: 6-isomer).
  • Example 6 The mixture of the 4 monoalkylation products from Example 1 was separated into the 4 individual species according to the above general working instructions, which were then each present in approximately 95% by weight purity (Example 2: 2 isomer, Example 3: 3 -Isomer, example 4: 4-isomer, example 5: 6-isomer).
  • Example 6 Example 6
  • the 2-isomer behaves similarly to the 3-isomer (example 3)
  • the 4-isomer behaves similarly to the 6-isomer in terms of application technology
  • Aqueous formulation for an essential oil 1 g of rosemary oil and 3 g of the mixture from Example 6 were mixed with 96 g of water and stirred at room temperature for 5 min.
  • a clear liquid was obtained which remained stable over a period of at least 6 weeks.

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

Abstract

Mélange comprenant des produits d'alkylation de monosaccharides acétalisés en position 1 par le radical R1, de la formule (I): (C¿n?H2n-1On)-R?1¿, dans laquelle n est égal à 5 ou à 6, et R1 désigne un groupe alkyle en C¿1? à C4, un groupe alkyle monohydroxy ou dihydroxy en C1 à C3 ou un groupe alkyle méthoxy ou éthoxy en C1 à C3, et des époxydes de formule (II) dans laquelle R?2 et R3¿ désignent, indépendamment l'un de l'autre, de l'hydrogène ou un radical alkyle ou alcényle pouvant porter en outre des groupements alkylesters d'acide carboxylique en C¿1? à C4 et pouvant être interrompu par des atomes d'oxygène non voisins, la somme des atomes de carbone des deux radicaux R?2 et R3¿ devant être comprise entre 4 et 60, ledit mélange renfermant 50 à 100 % en poids de produits de monoalkylation et 0 à 50 % en poids de produits d'alkylation supérieurs, au moins l'un des produits de monoalkylation éventuels régio-isomères étant présent en une quantité d'au moins 30 % en poids dans le cas où n = 6, ou d'au moins 40 % en poids dans le cas où n = 5, ces pourcentages étant donnés par rapport à la somme de tous les produits de monoalkylation formés.
PCT/EP1995/003466 1994-09-14 1995-09-02 Melange comprenant des produits d'alkylation de monosaccharides acetalises et des epoxydes WO1996008501A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP8509867A JPH10505129A (ja) 1994-09-14 1995-09-02 アセタール化された単糖類とエポキシドとのアルキル化生成物からなる混合物
EP95932657A EP0781292A1 (fr) 1994-09-14 1995-09-02 Melange comprenant des produits d'alkylation de monosaccharides acetalises et des epoxydes

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP4432689.0 1994-09-14
DE4432689A DE4432689A1 (de) 1994-09-14 1994-09-14 Mischung aus Alkylierungsprodukten von acetalisierten Monosacchariden mit Epoxiden

Publications (1)

Publication Number Publication Date
WO1996008501A1 true WO1996008501A1 (fr) 1996-03-21

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PCT/EP1995/003466 WO1996008501A1 (fr) 1994-09-14 1995-09-02 Melange comprenant des produits d'alkylation de monosaccharides acetalises et des epoxydes

Country Status (4)

Country Link
EP (1) EP0781292A1 (fr)
JP (1) JPH10505129A (fr)
DE (1) DE4432689A1 (fr)
WO (1) WO1996008501A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7993877B2 (en) 1999-01-30 2011-08-09 Novozymes Biopharma Dk A/S Process for the purification of recombinant albumin

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4011389A (en) * 1975-03-21 1977-03-08 Basf Wyandotte Corporation Glycoside polyethers
WO1993021196A1 (fr) * 1992-04-10 1993-10-28 Basf Aktiengesellschaft Procede de production d'alkylglucosides
WO1993021197A1 (fr) * 1992-04-21 1993-10-28 Basf Aktiengesellschaft Procede de production d'alkylglucosides et leur utilisation
DE4223581A1 (de) * 1992-07-17 1994-01-20 Henkel Kgaa Polyhydroxyverbindungen

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4011389A (en) * 1975-03-21 1977-03-08 Basf Wyandotte Corporation Glycoside polyethers
WO1993021196A1 (fr) * 1992-04-10 1993-10-28 Basf Aktiengesellschaft Procede de production d'alkylglucosides
WO1993021197A1 (fr) * 1992-04-21 1993-10-28 Basf Aktiengesellschaft Procede de production d'alkylglucosides et leur utilisation
DE4223581A1 (de) * 1992-07-17 1994-01-20 Henkel Kgaa Polyhydroxyverbindungen

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7993877B2 (en) 1999-01-30 2011-08-09 Novozymes Biopharma Dk A/S Process for the purification of recombinant albumin
US9029102B2 (en) 1999-01-30 2015-05-12 Novozymes Biopharma Dk A/S Process for the purification of recombinant albumin
US9555344B2 (en) 1999-01-30 2017-01-31 Albumedix A/S Process for the purification of recombinant albumin

Also Published As

Publication number Publication date
DE4432689A1 (de) 1996-03-21
JPH10505129A (ja) 1998-05-19
EP0781292A1 (fr) 1997-07-02

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