WO1991001321A1 - Polyolesters d'acide carboxylique etherique tensio-actifs - Google Patents

Polyolesters d'acide carboxylique etherique tensio-actifs Download PDF

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Publication number
WO1991001321A1
WO1991001321A1 PCT/EP1990/001144 EP9001144W WO9101321A1 WO 1991001321 A1 WO1991001321 A1 WO 1991001321A1 EP 9001144 W EP9001144 W EP 9001144W WO 9101321 A1 WO9101321 A1 WO 9101321A1
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WO
WIPO (PCT)
Prior art keywords
carboxylic acid
ether carboxylic
mol
formula
atoms
Prior art date
Application number
PCT/EP1990/001144
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German (de)
English (en)
Inventor
Uwe Ploog
Rolf Kawa
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 WO1991001321A1 publication Critical patent/WO1991001321A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/04—Ortho-condensed systems

Definitions

  • the invention relates to surface-active ether carboxylic acid polyol esters and a process for their production by esterification of hexites and / or anhydrohexites with surface-active ether carboxylic acids.
  • Fatty acid esters of anhydrohexites e.g. B. from Sorbitan
  • B. from Sorbitan
  • the sorbitan fatty acid esters are by esterification of z.
  • B. sorbitol accessible in the presence of acidic or basic catalysts, but are obtained as relatively strongly colored products which are not suitable for use in cosmetic and pharmaceutical products without additional bleaching.
  • DE-0S-31 19 553 z.
  • a method for the preparation of such esters of anhydrohexites is indicated, which includes bleaching with hydrogen peroxide.
  • anhydrosorbitol esters or mixtures of sorbitol, anhydrosorbitol and dianhydrosorbitol esters in which the average degree of dehydration is S 1-1.5.
  • the degree of dehydration is understood to mean the molar amount of arihydrohexite rings per mole of hexite used. According to S. Ropuszynski, such degrees of dehydration can be achieved by successive use of basic catalysts (eg NaOH) and acidic catalysts (eg H3PO4).
  • hexite esters of ether carboxylic acids can also be prepared in a light color and with degrees of dehydration of 1-1.5 without the use of catalyst under mild conditions. These products also have very advantageous technical properties, especially since their hydrophilicity can be controlled within wide limits by the glycol ether content of the ether carboxylic acids.
  • the invention therefore relates to surface-active ether carboxylic acid polyol esters of the formula I.
  • R is an alkyl or alkenyl group with 6-22 C atoms or a p-alkylphenyl group with 6 - 15 C atoms in the alkyl group and m and n independently of one another 2 or 3, x and y independently of one another 0 or Numbers from 1 - 30, z an average value has from 1 to 2 and (A) is the remainder of a hexite, anhydrohexite or dianhydrohexite.
  • ether carboxylic acid polyol esters can be prepared by a conventional method by adding 1 mole of a hexite or anhydrohexite with 1-2 moles of an ether carboxylic acid of the formula II
  • Suitable hexites for the production of the products according to the invention are e.g. B. sorbitol, mannitol and dulcitol. These hexites tend to form so-called anhydrohexites (by splitting off 1 mole of water) or even dianhydrohexites (by splitting off 2 moles of water) by intramolecular dehydration.
  • the anhydrohexites are also called hexitanes, the dianhydrohexites also called hexides. This intramolecular dehydration is a known secondary reaction in the esterification of the hexites to hexite esters.
  • the preferred hexite for producing the compounds according to the invention is sorbitol.
  • sorbitol By intramolecular dehydration, it forms sorbitan (by splitting off 1 mol of water) and sorbide (or isosorbide) by splitting off 2 mol of water.
  • an equilibrium mixture is formed during the esterification in the preparation of the polyol esters according to the invention, so that in formula I group (A) consists of a mixture of residues of sorbitol, anhydrosorbitol (sorbitan) and dianhydrosorbitol (Sorbide) exists.
  • This mixture shows in a preferred embodiment, namely in the case of esterification in the absence of acidic catalysts, has an average degree of dehydration S of 1-1.5.
  • Ether carboxylic acids of the general formula II are commercially available.
  • Commercial products belonging to this type of connection are offered under the trademarks SandopanW and Akypo (R). The preparation of the ether carboxylic acids used as the starting product is described in more detail in Example 1.
  • sorbitol is used as hexite, then the commercially available 70% sorbitol solution can be used, from which the solution water is then first removed. The sorbitol can then first be wholly or partly converted into the anhydrosorbitol. However, it is preferred that the dehydration of the sorbitol coincides with that - 5 -
  • the esterification is preferably carried out at a temperature of about 200 ° C. in an inert atmosphere, e.g. B. in a nitrogen atmosphere, with constant removal of the split-off esterification water and the water which originates from the intramolecular dehydration of the hexite.
  • the reaction has largely ended when the acid number of the reaction mixture has dropped to values below 15 (residual acid number).
  • the esterification takes place under the specified conditions in a time of 5-8 hours.
  • ethereal carboxylic acid sorbitan esters whose degree of dehydration is at values of 1-1.5, have more favorable application properties.
  • the preferred production process for the ether carboxylic acid polyesters according to the invention is therefore that sorbitol is used as the hexite and with 1-1.5 mol of an ether carboxylic acid of the formula II in the absence of acidic catalysts, preferably in the absence of acidic and ba ⁇ sic catalysts with elimination of 0.8-1 mol of esterification water per mol of ether carboxylic acid and 1-1.5 mol of dehydration water per mol of sorbitol.
  • the residual acid number of the reaction mixture indicates that the ether carboxylic acid is not - 6 -
  • esterification of polyols with fatty acids even if it is carried out in a stoichiometric molar ratio of 1: 1, always runs to a mixture of monoesters, diesters and a small proportion of free polyols.
  • Such an equilibrium mixture also forms in the preparation of the ether carboxylic acid polyol esters according to the invention, so that the value for z in general formula I is always an average, the level of which is given by the ratio of ether carboxylic acid to hexite and by the degree of esterification.
  • the ether carboxylic acid polyol esters according to the invention are obtained in a light color and with very good emulsifier properties.
  • the products according to the invention can be prepared in a very wide range of hydrophilicity by the selection of the ether carboxylic acids. This makes it possible to provide suitable emulsifiers for numerous oils, fats, waxes, paraffins, for water-immiscible solvents and active ingredients for the pharmaceutical, cosmetic, agricultural and industrial sector.
  • the readily water-soluble ether carboxylic acid polyol esters of the present invention are also suitable as skin and mucous membrane-friendly surfactants for body wash lotions, shampoos, foam baths and for the production of liquid soaps.
  • the following examples are intended to explain the subject of the invention in more detail, without restricting it thereto.
  • the ether carboxylic acid was released by adding 0.5-0.6 mol of sulfuric acid (in the form of a 20% strength aqueous sulfuric acid); this separated out as an organic phase above the aqueous phase, was separated from the aqueous phase, dried and filtered.
  • the ether carboxylic acids prepared in this way were obtained as clear, light yellow liquids.
  • the following ether carboxylic acids of the formula III were prepared by the process described
  • Example 2.2 The preparation was carried out analogously to Example 2.1, starting from 1 mol of sorbitol and 1.5 mol of ether carboxylic acid according to Example 1.1.
  • the reaction product obtained showed the following key figures:
  • Residual acid number 3.1 S (degree of dehydration): 1.2 - 10 -
  • the ether carboxylic acid polyol esters were tested in the following test formulation:
  • Paraffin oil thin 50 g
  • the fat components and the emulsifier were heated together to 75 ° C.
  • the water, heated to 80 ° C. was gradually incorporated into the melt, which had been homogenized with stirring, with stirring.
  • ge ⁇ schmoope skin creams that were stable at temperatures between -6 ° C and +40 ° C for several weeks were formed.

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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)

Abstract

Des polyolesters d'acide carboxylique éthérique tensio-actifs de formule (I): [RO-(CmH2mO)x-(CnH2nO)y-CH2-COO]z-(A), dans laquelle R est un groupe alkyle ou alkényle avec 6-22 atomes de C ou un groupe p-alkylphényle avec 6-15 atomes de C dans le groupe alkyle, m et n indépendamment l'un de l'autre valent 2 ou 3, x et y indépendamment l'un de l'autre valent 0 ou des nombres de 1 à 30, z a une valeur moyenne de 1-2 et (A) est le résidu d'une hexite, anhydrohexite ou dianhydrohexite, sont fabriqués par estérification d'hexites ou d'anhydrohexites avec des acides carboxyliques éthériques, de préférence en l'absence de catalyseurs. Ces produits conviennent de préférence comme émulsifiants.
PCT/EP1990/001144 1989-07-21 1990-07-12 Polyolesters d'acide carboxylique etherique tensio-actifs WO1991001321A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP3924201.3 1989-07-21
DE3924201A DE3924201A1 (de) 1989-07-21 1989-07-21 Oberflaechenaktive ethercarbonsaeure-polyolester

Publications (1)

Publication Number Publication Date
WO1991001321A1 true WO1991001321A1 (fr) 1991-02-07

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Application Number Title Priority Date Filing Date
PCT/EP1990/001144 WO1991001321A1 (fr) 1989-07-21 1990-07-12 Polyolesters d'acide carboxylique etherique tensio-actifs

Country Status (2)

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DE (1) DE3924201A1 (fr)
WO (1) WO1991001321A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0778822A1 (fr) * 1994-08-29 1997-06-18 Henkel Corporation Nouveaux esters de polyol d'acides ether carboxyliques et procedes d'appretage de fibres

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102004010505A1 (de) * 2004-03-04 2005-09-29 Clariant Gmbh Verfahren zur lösungsmittelfreien Herstellung von Ethercarbonsäuren mit niedrigem Restsalzgehalt

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3119553A1 (de) * 1981-05-16 1982-12-02 Hoechst Ag, 6000 Frankfurt "verfahren zur herstellung von carbonsaeureestern von anhydrohexiten"
GB2189787A (en) * 1986-04-30 1987-11-04 Sandoz Ltd Alkyl polyoxyalkylene carboxylate esters

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3119553A1 (de) * 1981-05-16 1982-12-02 Hoechst Ag, 6000 Frankfurt "verfahren zur herstellung von carbonsaeureestern von anhydrohexiten"
GB2189787A (en) * 1986-04-30 1987-11-04 Sandoz Ltd Alkyl polyoxyalkylene carboxylate esters

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0778822A1 (fr) * 1994-08-29 1997-06-18 Henkel Corporation Nouveaux esters de polyol d'acides ether carboxyliques et procedes d'appretage de fibres
EP0778822A4 (fr) * 1994-08-29 1997-11-19 Henkel Corp Nouveaux esters de polyol d'acides ether carboxyliques et procedes d'appretage de fibres

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DE3924201A1 (de) 1991-01-24

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