EP1572617A1 - Procede pour produire des esters d'acide hydroxycarboxylique - Google Patents

Procede pour produire des esters d'acide hydroxycarboxylique

Info

Publication number
EP1572617A1
EP1572617A1 EP03789193A EP03789193A EP1572617A1 EP 1572617 A1 EP1572617 A1 EP 1572617A1 EP 03789193 A EP03789193 A EP 03789193A EP 03789193 A EP03789193 A EP 03789193A EP 1572617 A1 EP1572617 A1 EP 1572617A1
Authority
EP
European Patent Office
Prior art keywords
alcohol
hydroxycarboxylic acid
alcohols
alkyl radical
hydroxycarboxylic
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Withdrawn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
EP03789193A
Other languages
German (de)
English (en)
Inventor
Ansgar Behler
Almud Folge
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.)
Cognis IP Management GmbH
Original Assignee
Cognis IP Management GmbH
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 Cognis IP Management GmbH filed Critical Cognis IP Management GmbH
Publication of EP1572617A1 publication Critical patent/EP1572617A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/37—Esters of carboxylic acids
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0208—Tissues; Wipes; Patches
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • 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

Definitions

  • the present invention relates to a process for the preparation of selected hydroxycarboxylic acid esters and mixtures of hydroxycarboxylic acid esters and their use in cosmetic compositions.
  • Hydroxycarboxylic acid esters have been known for a long time.
  • the monoalkyl hydroxycarboxylic acid esters have long been used in cosmetic products.
  • B. EP 282289 AI a cosmetic composition that contains monoalkyl citric acid salts.
  • alkyl oxide compounds of citric acid are also disclosed in this document.
  • WO 94/10970 describes a solubilizer, the monoalkyl citrates with alkyl groups, which contain 7 to 10 carbon atoms, as an ingredient in perfumes, cosmetic compositions, such as cleaning and care agents for body and textiles.
  • DE 199 45 478 A1 discloses cosmetic and / or pharmaceutical preparations which contain, in addition to alkyl and or alkyl oligoglycosides, partial hydroxycarboxylic esters or their salts.
  • alkyl citrates known from the prior art are frequently not clearly formulated together with anionic surfactants, and even when combined with certain nonionic surfactants, such as alkyl polyglycosides, there may be disadvantages in the formulation.
  • the pure alkyl citrates are pastes that melt at room temperature. It was therefore the object of the present invention to improve the disadvantages of the alkyl citrates and hydroxycarboxylic acid esters known from the prior art. It has been found that alkyl citrates which do not have the disadvantages indicated above can be obtained by selecting the alcohol component.
  • a first subject of the present invention relates to a process for the preparation of hydroxycarboxylic acid esters by combining hydroxycarboxylic acids or their salts with a mixture of alcohols of the general formulas (I) R ! -OH and (II) R 2 - (C 2 H) n -OH, where R 1 and R 2 independently of one another, for a saturated or unsaturated, branched or unbranched alkyl radical having 6 to 22 C atoms and n for a number between 1 and 20, at temperatures of 120 to 180 ° C., characterized in that the compounds of the formulas (I) and (II) are used in a weight ratio of 10: 1 to 1:10.
  • the so Compounds obtained, which are mixtures of different isomeric esters, are also the subject of the present invention.
  • the process according to the invention relates in principle to all hydroxycarboxylic acids, particularly preferred hydroxycarboxylic acids being selected from the group formed by lactic acid, tartaric acid, malic acid and citric acid and their self-condensation products.
  • Citric acid is particularly preferred for the purposes of the present invention.
  • the partial esters of hydroxycarboxylic acids for the purposes of the present invention are surfactants which preferably still contain a free carboxyl group. Accordingly, it can also be acidic esters or their neutralization products.
  • the partial esters are then preferably in the form of alkali metal, alkaline earth metal, ammonium, alkylammonium, alkanolammonium and / or glucammonium salts.
  • the esters themselves are preferably derived from fatty alcohols of the formula (I) which are used in a mixture with ethoxylated fatty alcohols of the general formula (II).
  • the weight ratio between the alcohols of the formula (I) and the ethoxylated alcohols of the formula (II) is selected in the range from 10: 1 to 1:10. It has proven to be particularly preferred to use the alcohols of the formulas (I) and (II) in a weight ratio of from 10: 1 to 1: 1 and in particular from 9: 1 to 1: 1, preferably 4: 1 to 1: 1 in particular to use 1: 1.
  • esters according to the present invention are polyesters, since several carboxyl functions can be esterified. Typically, for production reasons, mixtures of the esters are present, it being possible for about 25 to 30% monoesters, 30 to 40% diesters and 5 to 15% triesters to be present. The rest up to 100% is in the form of free hydroxycarboxylic acid.
  • Another object of the present invention therefore relates to mixtures of isomeric compounds of the general formula (III)
  • the mixtures contain mono- Di- and triesters side by side, with monoesters and diesters preferably being side by side in a ratio of 1: 1 to 1: 2.
  • the proportion of free citric acid can be up to 20%, based on the mixtures, but the mixtures preferably contain less free citric acid, with less than 10% preferred.
  • the production process as such corresponds to the prior art, although it may be essential that the reaction takes place in a nitrogen atmosphere. It may furthermore be advantageous to set the temperatures in the reaction in the range from 150 to 170 and preferably from 160.degree.
  • the monoalkyl esters of hydroxycarboxylic acids according to the invention are obtained as the end product and can be removed from the batch, for example, by distillation.
  • the esters can be free or in the form of salts.
  • there is always a small proportion of unesterified hydroxycarboxylic acid preferably at most 20% by weight and in particular at most 10% by weight. Reaction products which contain a maximum of 8% and in particular a maximum of 5% of unesterified citric acid are particularly preferred.
  • the acid number (DIN 51963) of the products obtained according to the invention is preferably 200 to 300, the OH number is preferably in the range from 180 to 250, the ester number is preferably in the range from 100 to 160 and the saponification number is preferably in the range from 380 to 500 Measurements according to DIN).
  • hydroxycarboxylic acid esters produced according to the invention and preferably the esters of citric acid can advantageously be formulated with aqueous and / or anionic and / or nonionic surfactants.
  • the particularly preferred nonionic surfactants include fatty alcohols, alcohol ethoxylates and alkyl polyglycosides.
  • fatty alcohols As particularly suitable anionic surfactants, reference is made to the alkyl ether sulfates, without any restriction with regard to the selection of the anionic surfactants.
  • fatty alcohols As particularly suitable anionic surfactants, reference is made to the alkyl ether sulfates, without any restriction with regard to the selection of the anionic surfactants.
  • Fatty alcohols which are also used in the synthesis of the hydroxycarboxylic acids according to the invention are primary aliphatic alcohols of the formula (I)
  • R 1 represents an aliphatic, linear or branched hydrocarbon radical having 6 to 22 carbon atoms and 0 and / or 1, 2 or 3 double bonds.
  • Typical examples are capronic alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linoleyl alcohol alcohol, linoleyl alcohol alcohol, linoleyl alcohol alcohol, linoleyl alcohol alcohol, linoleyl alcohol alcohol, linoleyl alcohol alcohol, linoleol alcohol alcohol, linoleol alcohol alcohol, linoleol alcohol alcohol, linoleyl alcohol alcohol, linoleyl alcohol alcohol, linoleyl alcohol alcohol, linoleo
  • alcohol ethoxylates are referred to as fatty alcohol or oxo alcohol ethoxylates and preferably follow the formula (II),
  • R 2 is a linear or branched alkyl and / or alkenyl radical having 6 to 22 carbon atoms and n is a number from 1 to 50.
  • Compounds of formula (II) with a degree of ethoxylation of 1 to 20 are used for synthesis in the process according to the invention for the preparation of hydroxycarboxylic acid esters.
  • Typical examples are the adducts of on average 1 to 20, preferably 1 to 10 and in particular 1 to 5, moles of ethylene oxide with capron alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl 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 brassidyl alcohol and their technical mixtures, which are used, 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.
  • Alkyl and alkenyl oligoglycosides are known nonionic surfactants which have the formula
  • R 3 is an alkyl and / or alkenyl radical having 4 to 22 carbon atoms
  • G is a sugar radical having 5 or 6 carbon atoms
  • p is a number from 1 to 10. They can be obtained according to the relevant preparative organic chemistry methods.
  • 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.
  • alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and is in particular between 1.2 and 1.4.
  • the alkyl or alkenyl radical R 3 can be derived from primary alcohols having 4 to 11, preferably 8 to 10, carbon atoms. Typical examples are butanol, capro alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and 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.
  • the alkyl or alkenyl radical R 3 can also be derived from primary alcohols having 12 to 22, preferably 12 to 14, carbon atoms.
  • Typical examples are lauryl alcohol, my- ristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol and their technical mixtures, which can be obtained as described above.
  • Alkyl oligoglucosides based on hardened C 12/14 coconut alcohol with a DP of 1 to 3 are preferred.
  • ether sulfates are known anionic surfactants which are produced on an industrial scale by SO 3 - or chlorosulfonic acid (CSA) sulfation of fatty alcohol or oxo alcohol polyglycol ethers and subsequent neutralization.
  • CSA chlorosulfonic acid
  • ether sulfates which follow the formula (V) are suitable
  • R 4 represents a linear or branched alkyl and / or alkenyl radical having 6 to 22 carbon atoms
  • m represents numbers from 1 to 10
  • X represents an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.
  • Typical examples are the sulfates of addition products with an average of 1 to 10 and in particular 2 to 5 moles of ethylene oxide with caprone alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostalkyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, Petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and their technical mixtures in the form of their sodium and / or magnesium salts.
  • the ether sulfates can have both a conventional and a narrow homolog distribution. Or C 12/18 - - particularly preferred to use ether sulfates based on adducts of on average 2 to 3 moles of ethylene oxide with technical C12 / 14 coconut fatty alcohol fractions in the form of their sodium and / or magnesium salts.
  • the surfactant mixtures according to the invention can be used for the production of cosmetic preparations, such as hair shampoos, hair lotions, foam baths, shower baths, creams, gels, lotions, alcoholic and aqueous / alcoholic solutions, emulsions, wax / fat masses, stick preparations, powders or ointments.
  • cosmetic preparations such as hair shampoos, hair lotions, foam baths, shower baths, creams, gels, lotions, alcoholic and aqueous / alcoholic solutions, emulsions, wax / fat masses, stick preparations, powders or ointments.
  • the hydroxycarboxylic acid esters of the present invention can furthermore be used in combination with further auxiliaries and additives customary in cosmetics, such as, for example, mild surfactants, oil bodies, emulsifiers, Superfatting agents, pearlescent waxes, consistency enhancers, thickening agents, polymers, silicone compounds, fats, waxes, lecithins, phosphorus lipids, stabilizers, biogenic agents, deodorants, antiperspirants, antidandruff agents, film formers, swelling agents, UV light protection factors and the like. ⁇ . can be combined.
  • mild surfactants such as, for example, mild surfactants, oil bodies, emulsifiers, Superfatting agents, pearlescent waxes, consistency enhancers, thickening agents, polymers, silicone compounds, fats, waxes, lecithins, phosphorus lipids, stabilizers, biogenic agents, deodorants, antiperspirants, antidandruff agents, film formers, swelling agents,
  • a further embodiment of the present invention relates to the use of hydroxycarboxylic acid esters which have been prepared by the process according to claim 1 as auxiliaries for the preparation of cosmetic compositions, preferably those which contain either alkyl ether sulfates or alkyl oligoglycosides or fatty alcohol ethoxylates or mixtures of these surfactants.
  • Aqueous formulations are particularly preferred, especially if they are slightly acidic and preferably have a pH between 5 and 6.5.
  • the saponification number was 432, the acid number was measured at 284, the OH number was 210, the ester number was 148.
  • the proportion of free citric acid was 3.7% by weight.
  • a mixture of an ether sulfate (Texapon N from the applicant) was used both with pure lauryl citrates (VI) and with lauryl / C12-14 fatty alcohol + 3-EO citrate according to the invention in a weight ratio of 3: 1 or 9: 1 (el and E4) (based on active substance) in water, the pH of the solution being adjusted to 6.

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  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Public Health (AREA)
  • Organic Chemistry (AREA)
  • Veterinary Medicine (AREA)
  • Chemical & Material Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Birds (AREA)
  • Epidemiology (AREA)
  • Biomedical Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Dermatology (AREA)
  • Emergency Medicine (AREA)
  • Cosmetics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé pour produire des esters d'acide monoalkylhydroxycarboxylique. Selon ce procédé, on fait réagir des acides hydroxycarboxyliques ou leurs sels avec un mélange constitué d'alcools de formules générales (I) R<1>-OH et (II) R<2>-(C2H4)n-OH, dans lesquelles R<1> et R<2> représentent, indépendamment de l'autre, un groupe alkyle saturé ou insaturé, ramifié ou non ramifié, comportant 6 à 22 atomes de carbone, et n est compris entre 1 et 20, à des températures comprises entre 120 et 180 DEG C, les composés des formules (I) et (II) étant utilisés dans des rapports en poids compris entre 10:1 et 1:10.
EP03789193A 2002-12-19 2003-12-10 Procede pour produire des esters d'acide hydroxycarboxylique Withdrawn EP1572617A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10260131 2002-12-19
DE10260131A DE10260131A1 (de) 2002-12-19 2002-12-19 Verfahren zur Herstellung von Hydroxycarbonsäureestern
PCT/EP2003/013978 WO2004056741A1 (fr) 2002-12-19 2003-12-10 Procede pour produire des esters d'acide hydroxycarboxylique

Publications (1)

Publication Number Publication Date
EP1572617A1 true EP1572617A1 (fr) 2005-09-14

Family

ID=32404094

Family Applications (1)

Application Number Title Priority Date Filing Date
EP03789193A Withdrawn EP1572617A1 (fr) 2002-12-19 2003-12-10 Procede pour produire des esters d'acide hydroxycarboxylique

Country Status (5)

Country Link
US (1) US20060078576A1 (fr)
EP (1) EP1572617A1 (fr)
JP (1) JP2006512341A (fr)
DE (1) DE10260131A1 (fr)
WO (1) WO2004056741A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102004054036A1 (de) 2004-11-05 2006-05-11 Cognis Ip Management Gmbh Verwendung von alkoxylierten Hydroxycarbonsäureestern zur Lösungsvermittlung von Parfümölen in Wasser

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2361716A1 (de) * 1973-12-12 1975-06-26 Henkel & Cie Gmbh Kosmetische zubereitungen, insbesondere hautcremes
IT1098010B (it) * 1978-08-04 1985-08-31 S I S A S Spa Derivati dell'acido citrico utili come ammorbidenti
IT1201411B (it) * 1985-03-26 1989-02-02 Rol Raffineria Olii Lubrifican Tesnioattivi derivati dall'acido citrico
DE3886432T2 (de) * 1987-03-10 1994-05-11 Unilever N.V., Rotterdam Kosmetisches Mittel.
DE69313127T2 (de) * 1992-11-09 1998-01-08 Quest Int Solubilisierungsmittel
FR2755369B1 (fr) * 1996-11-04 1998-12-04 Oreal Composition moussante pour le nettoyage de la peau sous la forme d'un gel transparent
FR2758261A1 (fr) * 1997-01-10 1998-07-17 Oreal Compositions cosmetiques presentant une rincabilite amelioree

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2004056741A1 *

Also Published As

Publication number Publication date
WO2004056741A1 (fr) 2004-07-08
US20060078576A1 (en) 2006-04-13
DE10260131A1 (de) 2004-07-01
JP2006512341A (ja) 2006-04-13

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