FR2733982A1 - ALKYL ETHER OLIGOMERIC SULFATES AND THEIR USES IN CLEANING COMPOSITIONS - Google Patents

Abstract

Oligomeric alkyl ether sulphates of mean general formula (I) are described. A method for preparing products of formula (I) and the use thereof as surfactants in cleaning, cosmetic and toothpaste compositions are also described.

Description

ALKYL ETHER OGOMERIC SULFATES AND THEIR USE
IN CLEANING COMPOSITIONS
The present invention relates to new surfactants belonging to the group of alkyl ether sulfates containing at least two hydrophilic poles of anionic character and at least two hydrophobic poles, and their use as emulsifiers, detergents, dispersants, hydrotropes, wetting agents, foaming agents in cleaning compositions containing them.

Surfactants are a broad class of chemicals generally described as consisting of a hydrophilic moiety and a hydrophobic moiety. These compounds constitute a large class which is decomposed into subclasses according to the nature of the hydrophilic pole. Nonionic, anionic, cationic and amphoteric surfactants are distinguished. These products find many applications in particular as emulsifiers, detergents, dispersants, or solubilizers in the fields of personal hygiene, textile treatment, industrial or household cleaning, or anticorrosion.

Anionic surfactants carry a negative charge in their hydrophilic pole, usually in the form of a carboxylate, phosphate, sulfate or sulfonate. These products find applications in the fields of emulsion polymerization, personal hygiene or household and industrial cleaning products.

Surfactants are generally compounds having a hydrophilic pole and a hydrophobic pole. Recently, a new group of compounds having two hydrophilic poles and two hydrophobic poles has been described. These novel compounds have been referred to as Gemini surfactants and described in Chemtech, March 1993, p30-33 and J. Am.

Chem. Soc., 115, 10083-10090 (1993). Sulphate, phosphate and carboxylate surfactants have been described in the literature as in J. Am. Oil. Chem. Soc., Fiz., 459 (1990), J. Am. Oil. Chem. Soc., Fia, 268 (1991), J. Am. Oil. Chem. Soc., Fia. 539 (1991), J. Am. Oil. Chem. Soc., 69, 626 (1992). In all cases, a secondary hydroxyl is sulfated, carboxymethylated, or phosphated.

There are also examples where, by the use of propane sultone, it is possible to access sulphonate surfactants. However, this road has major drawbacks on an industrial scale due to the very high toxicity and instability of propane sultone.

All these surfactants do not fulfill all the requirements for use, in particular those related to sensitivity to alkaline earth metals and even more importantly those relating to biological tolerance.

A solution exists in the case of monomeric surfactants with the alkyl ether sulfates resulting from the sulfation of ethoxylated fatty alcohols. These products find major applications particularly in the areas of personal hygiene as primary constituents of shampoos, or industrial cleaning or household especially in the liquid dishes by hand. However, these products are not completely satisfactory and contribute in a substantial way to skin and eye irritation phenomena.

dans laquelle: m identiques ou différents représentent un nombre entier ou décimal égal ou supérieur à let inférieur à 20,
M représente un cation choisi parmi un métal alcalin, un métal alcalinoterreux ou un groupe ammonium quaternaire,
W représente le radical -CH2-Z-CH2- dans lequel Z représente le groupe:

dans lequel p a la même signification que m défini précedemment et peut être en outre égal à 0,
le radical R3 est choisi parmi un atome d'hydrogène, un radical R1 un radical R2 définis ci-dessous, et un motif de formule:: O(CH2CH20),-S03M où q a la même signification que m défini précedemment et M a la même signification qu'à la formule (1) avec R1 et R2 identiques ou différents représentent le groupe:

où R4 représente un atome d'hydrogène ou un motif O(CH2CH2O)q~SO3M où q et M sont tels que définis précedemment où Q représente un radical alkyle1 alkényle, alkyloxy, alkényloxy, linéaire ou branché, cyclique ou acyclique comprenant de 4 à 18 atomes de carbone
De façon préférentielle, pour les produits répondant à la formule générale (I), R3 représente un atome d'hydrogène, p et q un nombre entier ou décimal compris entre 0 et 10, plus préférentiellement entre 0 et 5, M un atome de sodium ou de potassium, et m un nombre entier ou décimal compris entre 1 et 10, plus préférentiellement entre 1 et 3, encore plus préférentiellement égal à 1.The products described in the present invention provide excellent levels of biological tolerance while improving application performance. This new class of oligomeric alkyl ether sulfates correspond to the average general formula (I)

in which: m identical or different represent an integer or decimal number equal to or greater than let less than 20,
M represents a cation chosen from an alkali metal, an alkaline earth metal or a quaternary ammonium group,
W represents the radical -CH2-Z-CH2- in which Z represents the group:

in which pa has the same meaning as m defined above and may also be equal to 0,
the radical R3 is chosen from a hydrogen atom, a radical R1 a radical R2 defined below, and a unit of formula :: O (CH2CH2O), - SO3M where q has the same meaning as m defined previously and M has the Same meaning as in formula (1) where R1 and R2 are the same or different and represent the group:

where R4 represents a hydrogen atom or a unit O (CH2CH2O) q ~ SO3M where q and M are as defined previously, where Q represents an alkyl1 alkenyl, alkyloxy, alkenyloxy, linear or branched, cyclic or acyclic radical comprising from 4 to 18 carbon atoms
Preferably, for the products corresponding to the general formula (I), R3 represents a hydrogen atom, p and q an integer or decimal number between 0 and 10, more preferably between 0 and 5, M a sodium atom or potassium, and m an integer or decimal number between 1 and 10, more preferably between 1 and 3, even more preferably equal to 1.

avec Q et M définis précédemment
De façon préférentielle, Q représente un radical alkyle ou alkyloxy comprenant de 6 à 14 atomes de carbone, plus préférentiellement un radical alkyle ayant de 8 à 12 atomes de carbone.Preferably, the products corresponding to the general formula (I) correspond to the general formula (II):

with Q and M previously defined
Preferably, Q represents an alkyl or alkyloxy radical comprising from 6 to 14 carbon atoms, more preferably an alkyl radical having from 8 to 12 carbon atoms.

avec n entier compris entre 4 et 18 et M tels que définis précédemment
Les produits décrits par la formule générale (I) peuvent être préparés par réaction du sulfate d'éthylène avec les composés généralement décrits dans la littérature et répondant à la formule générale (V):

avec R1, R2, et W tels que définis précédemment
Le sulfate d'éthylène est un réactif d'hydroxyalkylation permettant d'obtenir de manière séquentielle controllée, par réaction avec une fonction hydroxyle, le résidu hydroxyéthyle correspondant, comme décrit dans New J. Chem., 16, 107-112(1992). Il s'agit d'un substitut de l'oxyde d'éthylène permettant d'éviter les réactions consécutives de polycondensation.Appliqué à la synthèse de tensioactifs, il permet l'accès direct aux éther sulfates par neutralisation in situ de l'intermédiaire, ou après hydrolyse aux tensioactifs non ioniques correspondants comme décrit dans le schéma ci-après:

The following products corresponding to formulas (III) and (IV) are cited as representative but non-limiting examples of the invention:

with n integer between 4 and 18 and M as previously defined
The products described by the general formula (I) can be prepared by reaction of ethylene sulphate with the compounds generally described in the literature and corresponding to the general formula (V):

with R1, R2, and W as previously defined
Ethylene sulfate is a hydroxyalkylation reagent for sequentially controlling, by reaction with a hydroxyl group, the corresponding hydroxyethyl residue, as described in New J. Chem., 16, 107-112 (1992). It is a substitute for ethylene oxide which makes it possible to avoid the subsequent reactions of polycondensation.Applied to the synthesis of surfactants, it allows direct access to ether sulphates by neutralization in situ of the intermediate, or after hydrolysis to the corresponding nonionic surfactants as described in the diagram below:

Nu-O-CH2CH2-OSO3H + NaOH

Nu-O-CH2CH2-OS03Na NU-o-CH2CH2-oSO3H + H20

Nu-O-CH2CH2-OH
Nu is a nucleophilic radical, preferably a hydroxyl group.

avec R1, R2, et W ayant la signification donnée précédemment et m = 1.This reaction applied to the products described in the general formula (V) makes it possible to obtain the following reaction intermediate corresponding to the general formula (VI)

with R1, R2, and W having the meaning given above and m = 1.

Ethylene sulphate can be easily prepared by oxidation of ethylene sulphite with bleach in the presence of catalytic ruthenium as described in EP-A 332521 and EP-A 399899.

The hydroxyethylenation reaction of the products of general formula (V) with ethylene sulphate is generally carried out in the presence of a third solvent but can be carried out in the absence of any solvent. As the inert solvent, it is possible to use ester-type solvents such as ethylene glycol diacetate, ether such as tert-butyl methyl ether, ketone such as methyl isobutyl ketone, nitrile such as acetonitrile, aromatic such as toluene and xylene, or chlorinated like chloroform. Preferably, we will work in the mass. The reaction is generally carried out under atmospheric or autogenous pressure at temperatures that are compatible with the productivity constraints. It is preferable to work at reflux of the solvent or in a temperature range of between 20 and 1800 ° C., more preferably between 50 and 100 ° C., even more preferentially. between 70 and 900C.

The reaction is carried out by portionwise addition of the ethylene sulphate in solution or not in a compatible solvent to the product of general formula (V) in solution or not in a compatible solvent, previously heated to the required temperature. The reaction is then conducted at the required temperature for about 0.5-10 hours, more usually 1-4 hours.

avec m, R1, R2, et W ayant la signification indiquée précédemment. Pour obtenir le produit de formule (Vl) avec m = 2, on fait réagir de nouveau le produit deformule ('Il) avec m = 1 sur le sulfate d'éthylène en vue d'obtenir le produit de formule (Vl) avec m = 2, suivi éventuellement d'une hydrolyse pour obtenir le produits de formule générale (VIl) avec m = 2. On procède ainsi de façon réitérée autant de fois qu'il est nécessaire pour atteindre les valeurs de m désirées.Ainsi, de façon générale quelles que soient les valeurs de m, on hydrolyse le produit de formule (1) ayant une valeur de m inférieure d'une unité à la valeur désirée et on le fait réagir sur du sulfate d'éthylène.At this stage, the product of general formula (VI) precipitates but it is more convenient not to isolate If necessary, the hydrolysis can be chained directly leading to the products of general formula (VIl)

with m, R1, R2, and W having the meaning indicated above. To obtain the product of formula (VI) with m = 2, the product of formula (II) is reacted with m = 1 on ethylene sulphate in order to obtain the product of formula (VI) with m = 2, followed optionally by hydrolysis to obtain the products of general formula (VIl) with m = 2. This is done repeatedly as many times as necessary to reach the desired values of m. Thus, so Generally, irrespective of the values of m, the product of formula (1) having a value of m less than one unit is hydrolyzed to the desired value and reacted with ethylene sulphate.

The products of general formula (I) are obtained by in situ neutralization of the products of general formula (VIl) with an appropriate base according to methods known to those skilled in the art. The base can be introduced as or in aqueous or alcoholic solution. It is preferred to use the bases in solution, particularly in aliphatic light alcohols such as methanol or ethanol.

The product of general formula (I) will then be isolated by conventional methods after optional separation of the third solvent. It will be preferred to isolate it by crystallization in a suitable solvent.

avec R1, R2, R3, et n définis précédemment avec un époxyde de formule générale (IX)

avec R1 et R2 définis précédemment
La réaction d'ouverture des époxydes par des alcools est connue par ailleurs. On préférera cependant utiliser des catalyseurs de type basique comme les métaux alcalins, les hydroxydes de métaux alcalins ou alcalinoterreux, les alcoolates de métaux alcalins ou alcalinoterreux, des amides de métaux alcalins. De préférence, on utilisera les hydroxydes de métaux alcalins comme l'hydroxyde de sodium ou de potassium.The products of general formula (V) can be obtained by reaction of a diol of general formula (VIII)

with R1, R2, R3, and n defined previously with an epoxide of general formula (IX)

with R1 and R2 defined previously
The reaction of opening epoxides with alcohols is known elsewhere. However, preference will be given to using basic type catalysts such as alkali metals, alkali metal or alkaline earth metal hydroxides, alkali or alkaline earth metal alkoxides, and alkali metal amides. Preferably, alkali metal hydroxides such as sodium or potassium hydroxide will be used.

The opening reaction of the epoxides of the general formula (IX) will generally be carried out by preparing a solution of the diols of the general formula (VIII) in a compatible solvent. As inert solvent, it is possible to use ether-type solvents such as tert-butyl methyl ether, ketone such as methyl isobutyl ketone, nitrile such as acetonitrile, aromatic such as toluene and xylene, or chlorinated as chloroform.

This reaction can also be carried out in the absence of a solvent. The catalyst is introduced as is or in solution in a third solvent. In the case of alkali metal hydroxides, it is necessary to carry out a drying step at a temperature of 60-160 ° C at atmospheric pressure or under reduced pressure. The catalyst will be present in amounts of between 0.05% and 20 mol% relative to the diol of formula (VIII), preferably between 0.1-5 mol%.

The residual reaction medium is then heated to temperatures between 80 ° C. and 180 ° C., preferably between 100 ° C. and 140 ° C. The epoxide of formula (IX) is introduced in portions as is or in solution in a third solvent. It is preferable to introduce the epoxide as it is.The epoxide is used in quantities of between 0.5 and 5 molar equivalents relative to the diol of formula (Ylil), preferably between 0.8 and 1.2 molar equivalents.The reaction is then carried out at the temperatures described. above for periods varying between 0.5 and 25 hours.

The reaction medium is then neutralized with a compatible acid. By way of example, it is possible to use hydrochloric acid, acetic acid or para-toluenesulphonic acid.

It will be preferred to use acetic acid, the excess of which will be removed by distillation.

The reaction product of general formula (V) will then be purified by methods known to those skilled in the art. It will be preferred to use liquid-liquid extraction methods followed by distillation.

The products of general formula (VIII) are prepared by methods known to those skilled in the art and are for some commercially available as in the case of 1,2-diols obtained by hydrolysis of the corresponding epoxides. For non-zero values of n, the products of formula (VIII) are obtained from 1,2-diols or by polycondensation obtained using an excess of the epoxides of formula (IX).

It will be preferred to use 1,2-diols, in particular 1,2-alkyl diols such as hexanediol 1,2, heptanediol-1,2, octanediol-1,2, nonanediol-1,2, decanediol. -1, 2,
1,2-dimethiolediol, 1,2-dodecanediol, and glycerol monoalkyl ethers, such as
O-hexyl-1 glycerol, 0-heptyl-1 glycerol, 0-octyl-1 glycerol, 0-nonyl-1 glycerol,
O-decyl-1 glycerol, 0-undecyl-1 glycerol1 and 0-dodecyl-1 glycerol.

The epoxides of general formula (IX) are for the most part commercial products.

They can also be prepared by epoxidation of ethylenic derivatives by methods known to those skilled in the art or by reaction of activated derivatives of glycerol with alcohols described in the Q descriptor. By activated derivatives of glycerol is meant halohydrins and epihalohydrins . It will be preferred to use epichlorohydrin in the presence of basic type catalysts. It is preferred to use epoxides such as 1,2-alkyl epoxides, such as hexylene-1,2-oxide, heptylene-1,2-oxide, octylene-1,2-oxide, 1,2-nonylene, 1,2-decylene oxide, 1,2-undecylene oxide, 1,2-dodecylene oxide, and glycerol glycidyl ether ethers such as hexyl glycidyl ether. Heptyl glycidyl ether, octyl glycidyl ether, nonyl glycidyl ether, decyl glycidyl ether, undecyl glycidyl ether, and dodecyl glycidyl ether.

This new class of oligomeric alkyl ether sulphates corresponding to the general formula (I) have extremely low critical micellar concentrations (cmc) relative to monomeric alkyl ether sulphates such as lauryl ether sulphate 3 ethylene oxides, this being due to the simultaneous presence of at least two hydrophilic poles and at least two hydrophobic poles in the molecule. These products are able to lower the surface tension extremely efficiently and being very soluble in water, the products described in this invention exert their activity at much lower levels than the monomeric species.

 It has also been unexpectedly found that the products described in this invention, in admixture with conventional surfactants such as anionic, nonionic or cationic surfactants, exhibit synergistic effects in relation to critical micelle concentration and the ability to lower the surface tension.

This exceptional performance predisposes the products described in this invention to a large number of applications of which representative but not limiting examples are set forth below.

In addition to the oligomeric alkyl ether sulfates, other additives of the type described below may be present in said detergent compositions: - other surfactants, in amounts corresponding to approximately 3-40% by weight relative to detergent composition, surfactants such as anionic surfactants. the alkyl ester sulphonates of formula R-CH (SO 3 M) -COOR ', where R represents a C 8-20 alicyl radical, preferably C 10 -C 18 R 1, a C 1 -C 6 alkyl radical, preferably a C 1 -C 3 alkyl radical, and M alkaline cation (sodium, potassium, lithium), substituted or unsubstituted ammonium (methyl-, dimethyl-, trimethyl-, tetramethylammonium, dimethylpiperidinium ...) or derivative of an alkanolamine (monoethanolamine, diethanolamine, triethanolamine ...). mention may particularly be made of methyl ester sulphonates whose R radical is C 14 -C 18;
alkyl sulphates of formula ROSO 3 M, in which R represents a C 10 -C 24, preferably C 12 -C 20, and especially C 1 -C 18 alkyl or hydroxyalkyl radical, M representing a hydrogen atom or a cation of the same definition as above, as well as their ethoxylenated (EO) and / or propoxylenated (PO) derivatives, having on average from 0.5 to 6 units, preferably from 0.5 to 3 EO and / or OP units; . alkylamidesulfates of formula RCONHR'OSO3M where R represents a C2-C22 alkyl radical, preferably C6-C20 radical R 'a C2-C3 alkyl radical, M represents a hydrogen atom or a cation of the same definition as ci above, as well as their ethoxylenated (EO) and / or propoxylenated (PO) derivatives, having on average from 0.5 to 60 EO and / or OP; saturated or unsaturated C8-C24 fatty acid salts, preferably C1-C20, C8-C20 alkylbenzenesulfonates, C8-C8 primary or secondary alkylsulfonates;
C22, the alkylglycerol sulfonates, the sulfonated polycarboxylic acids described in
GB-A-1 082 179, paraffin sulfonates, N-acyl N-alkyltaurates, alkylphosphates, alkylisethionates, alkylsuccinamates, alkylsulfosuccinates, sulfosuccinates monoesters or diesters, N-acyl sarcosinates, alkylglycoside sulfates the polyethoxycarboxylates, the cation being an alkali metal (sodium, potassium, lithium), a substituted or unsubstituted ammonium residue (methyl-, dimethyl-, trimethyl-, tetramethylammonium, dimethylpiperidinium ...) or an alkanolamine derivative (monoethanolamine, diethanolamine, triethanolamine ...); nonionic surfactants polyoxyalkylenated (polyethoxyethylenated, polyoxypropylenated, polyoxybutylenated) alkylphenols wherein the alkyl substituent is C 6 -C 12 and containing from 5 to 25 oxyalkylene units; by way of example, mention may be made of TRITON X45, X-1 14, X-100 or
X-102 marketed by Rohm & Haas Cy .; glucosamide, glucamide; glycerolamides derived from N-alkylamines (US-A-5,223,179 and FR-A-1,585,966) C 6 -C 22 aliphatic polyoxyalkylenated alcohols containing from 1 to 25 oxyalkylene units (oxyethylene, oxypropylene); for example, we can mention the
TERGITOL 15-S-9, TERGITOL 24-L-6 NMW marketed by Union Carbide Corp.,
NEODOL 45-9, NEODOL 23-65, NEODOL 45-7, NEODOL 45-4 marketed by
Shell Chemical Cy., KYRO EOB marketed by The Procter & Gamble Cy.

the products resulting from the condensation of ethylene oxide with a hydrophobic compound resulting from the condensation of propylene oxide with propylene glycol, such as PLURONIC marketed by BASF; the products resulting from the condensation of ethylene oxide the compound resulting from the condensation of propylene oxide with ethylenediamine, such as TETRONIC marketed by BASF; amine oxides such as C1-C18 alkyl dimethylamine oxides, C8-C22 alkoxy ethyl dihydroxy ethylamine oxides; the alkylpolyglycosides described in US-A-4,565,647; C 8 -C 20 fatty acid amides ethoxylated fatty acids ethoxylated fatty amides ethoxylated amines catlalkyl surfactants alkyldimethylammonium halides amphoteric and zwitterionic surfactants
alkyldimethylbetaines, alkylamidopropyldimethylbetaines, alkyltrimethylsulfobetaines, condensation products of fatty acids and protein hydrolysates.

- BUILDERS AGENTS, in amounts corresponding to about 5-50%, preferably about 5-30% by weight for liquid detergent formulations, or about 10-80%, preferably about 15-50% by weight for detergent formulations in powders, builders such as builders Inorganlques
polyphosphates (tripolyphosphates, pyrophosphates, orthophosphates, hexametaphosphates) of alkali metals, ammonium or alkanolamines. tetraborates or borate precursors. silicates, in particular those having a SiO 2 / Na 2 O ratio of the order of 1.6 / 1 to 3.2 / 1 and the layered silicates described in US-A-4 664839. alkali or alkaline earth carbonates (bicarbonates, sesquicarbonates). cogranulates of hydrated alkali metal silicates and alkali metal carbonates (sodium or potassium) rich in silicon atoms in O2 or Q3 form, described in EP-A488 868. crystalline or amorphous aminosilicates of alkali metals (sodium, potassium) or ammonium, such as zeolites A, P, X, etc .; particle size zeolite A of the order of 0.1-10 micrometers is preferred organic bullders. water-soluble polyphosphonates (ethane 1-hydroxy-1,1-diphosphonates, methylene diphosphonate salts, etc.). water-soluble salts of carboxylic polymers or copolymers or their water-soluble salts such as
. polycarboxylate ethers (oxydisuccinic acid and its salts, monosuccinic acid tartrate and its salts, disuccinic acid tartrate and its salts
. the hydroxypolycarboxylate ethers
. Citric acid and its salts, mellitic acid, succinic acid and their salts
. salts of polyacetic acids (ethylenediaminetetraacetates, nitrilotriacetates,
N- (2 hydroxyethyl) -nitrilodiacetates)
. succinic C5-C20 alkyl acids and their salts (2-dodecenylsuccinates, lauryl succinates)
. Polyacetate carboxylic esters
Polyaspartic acid, polyglutamic acid and their salts. polyimides derived from the polycondensation of aspartic acid and / or glutamic acid. polycarboxymethyl derivatives of glutamic acid or other amino acids - BLANCHING AGENTS, in amounts of about 0.1-20%, preferably about 1-10% by weight, optionally associated with WHITENING ACTIVATORS, in amounts of about 0.1-60%, preferably about 0.540% by weight, agents and activators such as: perborate bleaches such as sodium perborate monohydrate or tetrallydrate. peroxygen compounds such as sodium carbonate peroxyhydrate, pyrophosphate peroxyhydrate, urea peroxyhydrate, sodium peroxide, sodium persulfate preferably associated with a bleach activator generating in situ in the washing medium, a peroxy carboxylic acid; ; among these activators, there may be mentioned tetraacetyethylenediamine, tetraacetyl methylene diamine, tetraacetyl glycoluryl, sodium p-acetoxybenzene sulfonate, pentaacetyl glucose and octaacetyl lactose. percarboxylic acids and their salts (called zpercarbonates) such as magnesium monoperoxy phthalate hexahydrate, magnesium metachloroperbenzoate, 4-nonylamino-4-oxoperoxybutyric acid, 6-nonylamino-6-oxoperoxycaproic acid, diperoxydodecanedioic acid, nonylamide of peroxysuccinic acid, decyldiperoxysuccinic acid.

These agents may be combined with at least one of the anti-fouling or anti-redeposition agents mentioned below.

May also be mentioned non-oxygenated bleaching agents, acting by photoactivation in the presence of oxygen, agents such as aluminum phthalocyanines and / or sulphonated zinc
ANTI-SOFTENING AGENTS, in amounts of the order of 0.01-10%, preferably about 0.1-596, and most preferably of the order of 0.2-3% by weight, agents such as. cellulose derivatives such as cellulose hydroxyethers, methylcellulose,
Ethylcellulose, hydroxypropyl methylcellulose, hydroxybutyl methylcellulose. polyvinyl esters grafted on polyalkylene trunks such as polyvinylacetates grafted on polyoxyethylene trunks (EP-A-219 048). polyvinyl alcohols. polyester copolymers based on ethylene terephthalate and / or propylene terephthalate and polyoxyethylene terephthalate units, with a molar ratio (number of units) of ethylene terephthalate and / or propylene terephalate / (number of units) polyoxyethylene terephthalate of the order of 1/10 to 10/1 , preferably of the order of from 111 to 9/1, the polyoxyethylene terephthalates having polyoxyethylene units having a molecular weight of the order of 300 to 5000, preferably of the order of 600 to 5000 (US-A-3 959,230, US-A-3,893,929, US-A-4,116,896, USA4,702,857, US-A-4,770,666); . sulfonated polyester oligomers obtained by sulfonation of an oligomer derived from ethoxylated allyl alcohol, dimethylterephthalate and 1,2-propylene diol having from 1 to 4 sulfonated groups (US-A-4,968,451). polyester copolymers based on propylene terephthalate and polyoxyethylene terephthalate units and terminated with ethyl, methyl units (US-A-4,711,730) or polyester oligomers terminated by alkylpolyethoxy groups (US-A-4,702,857) or groups sulfopolyethoxy anionics (US-A-4,721,580), sulfoaroyles (US-A-4,877,896). polyesterspolyurethanes obtained by reaction of a polyesters of number 3004000 molecular weight obtained from adipic acid and / or tereptalic acid and / or sulfoisophthalic acid and a diol of mass less than 300, on a prepolymer with terminal isocyanate groups obtained from a polyoxyethylene glycol having a molecular weight of 6004000 and a diisocyanate (FR-A-2 334 698) anti-redeishing agents, in amounts of approximately 0.01-10% by weight for a powdered detergent composition, about 0.01-5% by weight for a liquid detergent composition, agents such as ethoxylated monoamines or polyamines, ethoxylated amine polymers (US-AQ 597 898, EP-A Carboxymethylcellulose, sulfonated polyester oligomers obtained by condensation of isophthalic acid, dimethyl sulfosuccinate and diethylene glycol (FR-A-2,236,926), polyvinylpyrollidones - CHELATING AGENTS of iron and magnesium in amounts of the order of 0.1-10%, preferably of the order of 0.1-3% by weight, agents such as
aminocarboxylates such as ethylenediaminetetraacetates, hydroxyethylethylenediaminetriacetates, nitrilotriacetates. aminophosphonates such as nitrilotris (methylene phosphonates). polyfunctional aromatic compounds such as dihydroxydisulfobenzenes - POLYMERIC DISPERSIENT AGENTS, in an amount of the order of 0.1-7% by weight, for controlling the hardness of calcium and magnesium, agents such as. water-soluble salts of polycarboxylic acids with a molecular mass of the order of 2,000 to 100,000, obtained by polymerization or copolymerization of ethylenically unsaturated carboxylic acids such as acrylic acid, maleic acid or anhydride, fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid, methylenemalonic acid, and most particularly polyacrylates with a molecular mass of about 2,000 to 10,000 (US-A-3,308,067), copolymers of aryl and maleic anhydride mass molecular weight of the order of 5,000 to 75,000 (EP-A-66,915). polyethylene glycols with a molecular weight of the order of 1000 to 50,000 - FLUORESCENCE AGENTS (BRIGHTENERS), in an amount of approximately 0.05-1.2% by weight, agents such as stilbene, pyrazoline and coumarin derivatives, fumaric acid, cinnamic acid, azoles, methinecyanines, thiophenes ... ("The production and application of fluorescent brightening agents" - M.Zahradnik, published by John Wiley & Sons, NY-1982-) - FOAM SUPPRESSOR AGENTS, in amounts up to 5% by weight, such as monocarboxylic fatty acids C1-C24 or their alkaline salts, ammonium or alkanolamines, triglycerides of fatty acids, saturated or unsaturated aliphatic hydrocarbons, alicyclic, aromatic or heterocyclic, such as paraffins, waxes, N-alkylaminotriazines, monostearylphosphates, monostearyl alcohol phosphates, polyorganosiloxane oils or resins, which have been combined with silica particles this - SOFTENING AGENTS, in amounts of approximately 0.5-10% by weight, agents such as clays - ENZYMES in an amount of up to 5 mg by weight, preferably of the order of 0.05-3 mg of d active enzyme / g detergent composition, enzymes such as proteases, amylases, lipases, cellulases, peroxidases (US-A-3,553,139,
US-A-4,101,457, US-A4 507 219, US-A4 261 868 - OTHER ADDITIVES such as. alcohols (methanol, ethanol, propanol, isopropanol, propanediol, ethylene glycol, glycerin). buffering agents. perfumes .pigments
In the field of household detergency, the present invention relates more particularly to the compositions for dishwashing liquid by hand.

 Said compositions contain, on the order of 0.1 to 20%, preferably of the order of 0.5 to 10%, of their weight of oligomeric alkyl ether sulphates of formula (I) and of the order of 0, 5 to 40%, preferably of the order of 1 to 20% of their weight of at least one anionic or nonionic surfactant.

 Preferred oligomeric alkyl ether sulfates are those already mentioned above.

Among the anionic surfactants that may be present, there may be mentioned alkylsulfates, alkylethersuffates, alkylsulfonates, alkylbenzenesulfonates, soaps, alkylethercarboxylates, N-acylsarcosinates, alkylisethionates, N-acyl N-alkyltaurates, alkylphosphates, alkylsulfosuccinates, alkylsulfosuccinamates, sulfonated derivatives of fatty acids
Among the nonionic surfactants that may be present, there may be mentioned amine oxides, alkylglucamides, alkylpolyglycosides, oxyalkylenated derivatives of fatty alcohols such as PLANTAREN%) marketed by HENKEL
In addition to the oligomeric alkyl ether sulfates and anionic surfactants may be present in the compositions for dishwashing liquid by hand, other additives such as. amphoteric and zwitterionic surface-active agents such as alkyl-dimethyl betaines, alkyl-amidopropyl betaines, alkyl sulfates, fatty acid condensation products on proteins or protein hydrolysates, amphoteric derivatives of alkylpolyamines, such as AMPHIONIC XL 6 sold by RHONE-
POULENC, AMPHOLAC 7T / X23) and AMPHOLAC 7C / X) marketed by BEROL
NOBEL. bactericidal or disinfecting agents such as triclosan. synthetic cationic polymers such as MIRAPOL A550, MIRAPOL A15't) marketed by RHONE-POULENC, MERQUAT 550 marketed by
CALGON. the polymers used to control the viscosity of the mixture and / or the stability of foams formed in use, such as cellulose or guar derivatives (carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylguar, carboxymethylguar, carboxymethylhydroxypropylguar, etc.).

. hydrotropic agents, such as C 2 -C 8 short alcohols, in particular ethanol, diols and glycols such as ethylene glycol dipropylene glycol, skin moisturizing or humectant agents such as glycerol, urea or skin-protecting agents, such as proteins or protein hydrolysates, cationic polymers such as cationic derivatives of guar (JAGUAR Cl 3S,
JAGUAR C162, HICARE 1000Q9 marketed by RHONE-POULENC,. dyes, perfumes, preservatives
The term "cosmetic composition or formulation" is intended to mean all cosmetic products or preparations such as those described in Annex I ("Illustrative list of the category of cosmetic products") of European Directive 76/768 / EEC of 27 July 1976 referred to as 1 cosmetic directive ".

Oligomeric alkyl ether sulfates, which are the subject of this invention, can be used more particularly in lotions formulations, toilet milks, cleansing compositions, creams care or creams or lotions for protection against the sun and ultraviolet radiation. violet, mousses, styling gels or any formulation used for styling or to facilitate the combing of hair, shampoos for hair or the body, facial or body cleansing gels, liquid soaps, bubble bath compositions, formulations used for the treatment of hair, cleaning teeth or oral cavity such as mouthwashes or toothpastes. Said oligomeric alkyl ether sulphates can also be used alone or in combination in the formulation of soaps or toilet rolls. Because of their cationic activity at acidic pH, they can also be used for the preparation of rinse or balm formulations. conditioners for hair or skin.

 The cosmetic compositions generally contain surfactants which serve to disperse, emulsify, solubilize and stabilize various compounds used for their emollient or humectant properties. Surfactants are used in these compositions at concentrations ranging from 0.05 to 10% by weight of the preparation.

Among the humectants, mention may be made of glycerol, sorbitol, urea, collagen, gelatin, aloe vera, hyaluronic acid,
The emollients are generally chosen from alkylmonoglycerides, alkyldiglycerides and triglycerides, such as oils extracted from plants and plants (palm, coconut, cottonseed, soybean, sunflower, olive, grapeseed oils). , sesame, peanut, castor oil ...) or oils of animal origin (tallow, fish oils, ...), derivatives of these oils such as hydrogenated oils, lanolin derivatives, mineral oils or paraffinic oils, perhydrosqualane, squalene, diols such as 1-2-propanediol, 1-3-butanediol,
Cetyl alcohol, stearyl alcohol, oleic alcohol, polyethylene glycols or polypropylene glycols, fatty esters such as isopropyl palmitate, ethyl 2-hexyl cocoate, myristyl myristate, lactic acid esters, Stearic acid, behenic acid, isostearic acid, silicone oils comprising cyclic polydimethylsiloxanes, as hydroxylated polydimethylsiloxanes, trimethylsilylated polydimethylsiloxanes, polyorganosiloxanes such as polyalkylmethylsiloxanes, polymethylphenylsiloxanes, polydiphenylsiloxanes, amino derivatives of silicones, silicone waxes, silicone copolyethers (such as the oil SILBIONE 70646 marketed by RHONE-POULENC or DC 1 90 marketed by Dow Corning) or mixed silicone derivatives such as mixed polyalkylmethylsiloxane-silicone copolyether copolymers.

To these compounds, it is possible to add powders or mineral particles such as calcium carbonate, mineral oxides in the form of powder or in colloidal form (particles of smaller size or of the order of a micrometer, sometimes of a few tens of nanometers ) as titanium dioxide, silica, aluminum salts generally used as antiperspirants, kaolin, talc, clays and their derivatives,
Preservatives such as methyl, ethyl, propyl and butyl esters of p-hydroxybenzoic acid, sodium benzoate, GERMABENe or any chemical agent which avoids bacterial growth or mold and is traditionally used in cosmetic compositions are generally introduced into these products. compositions of 0.01 to 3% by weight.

In contrast to these chemical agents, it is sometimes possible to use agents that modify the activity of water and strongly increase the osmotic pressure, such as carbohydrates or salts.

To protect the skin or the hair from the aggressions of the sun and the UV rays, one can add to these formulations sunscreens which are either chemical compounds strongly absorbing the UV radiation like the compounds authorized in the European directive N "76/768 / EEC, its Annexes and subsequent amendments to that Directive, either titanium dioxide or cerium oxides in the form of powder or colloidal particles.

Perfumes, dyes or pigments can also be added.

Viscose or gelling polymers (such as CARBOPOL6 crosslinked polyacrylates marketed by GOODRICH-, cellulose derivatives such as hydroxypropylcellulose, carboxymethylcellulose, guars and their derivatives, carob, tartar gum or cassia gum may also be present). xanthan gum, alginates, carrageenans, chitin derivatives such as chitosan
A toothpaste may contain, in addition to abrasive agents such as silica or calcium carbonate (used at 5 to 25% by weight of the total composition), 0.1 to 5% by weight of said surfactants of the invention, taken alone or in admixture with the usual surfactants such as anionic, nonionic or zwitterionic surfactants such as alkylbetaines or alkylamidopropyl betaines or amphoters or combinations thereof. These surfactants which are used as foaming agents during the use of the composition, as well as for their cleaning, disinfecting power. Sometimes they are used specifically for a therapeutic action such as sarcosinate alkyls that protect the teeth by inhibiting the enzymatic activity of the bacteria responsible for infections of the teeth or gums.

The dentifrice compositions also comprise from 5 to 85% of so-called humectant agents such as glycerol, sorbitol, polyethylene glycols, lactilol and xylitol.

The rheological behavior of the dental paste, that is to say its viscosity, its resistance on the brush, the ease of its extrusion at the outlet of the tube or the dispenser, the non-spinning nature of the paste is controlled by thickeners as some silica used for this purpose (TIXOSIL 43 sold by RHONE-POULENC) and / or polymers used alone or in combination such as Xanthan gum, guar gum, cellulose derivatives (carboxymethylcellulose for example), crosslinked polyacrylates such as CARBOPOLs (8) distributed by GOODRICH, alginates or canagenenans, of the VlSCARIN. The total of thickening agents represents from 0.1 to 15% by weight of the composition of a toothpaste.

Therapeutic agents such as certain fluorine or potassium salts, weapons, sweetening agents and water are also generally associated with these various components.

 The oligomeric alkyl ether sulfates of this invention can also be used in toilet roll formulations called soaps or soaps.

Conventional bath towel compositions generally comprise fatty acid salts used in combination with surfactants of the invention and optionally surfactants other than the fatty acid salts or the fatty acids themselves. These compositions may even contain no fatty acid or fatty acid salt and their formulations are then based on other surfactants such as, for example, C 8 -C 22 sodium alkyl isethionates or C 8 -C 22 sodium alkyl sulphates.

To these compositions can also be added various constituents useful for reducing irritation or aggression of the skin such as alkali metal salts or isethionates or to promote the hydration of the skin as some carbohydrates (glycerol, sorbitol for example) polyethylene glycol or polypropylene glycol, alkoxylated derivatives of sugars or their derivatives (methyl glucose for example), water-soluble or water-dispersible polymers such as collagen or certain non-allergenic derivatives of animal or vegetable proteins (for example wheat protein hydrolisates). ), natural hydrocolloids (guar gum, carob, tara ...) or from fermentation processes such as xanthan gum and derivatives of these polycarbohydrates such as modified celluloses (for example hydroxyethylcellulose, carboxymethylcellulose, cationic celluloses such as POLYMER JR marketed by UNION CARBIDE), derivatives guar or carob as their cationic derivatives (JAGUAR C13S JAGUAR Ci 6 marketed by RHONE-POULENC) or nonionic derivatives (for example hydroxypropylguar), anionic derivatives (carboxymethylguar) or mixed nonionic / anionic derivatives such as carboxy-hydroxypropyl-guars or nonionic / cationic polymers. Synthetic polymers such as polyacrylates or synthetic cationic polymers, known under the generic name CTFA of Polyquatemium ", for example the polymers MIRAPOL A15 or MIRAPOL 5506 of the company RHONE-POULENC.

It is also advantageous to add to these compositions metal sequestering agents, more particularly those sequestering calcium such as citrate ions or emollient agents such as silicones or oils or fats used for this purpose in the cosmetics industry (mineral oils, esters of fatty acids, triglycerides, silicones, etc.).

To these ingredients is generally added one or more perfumes, dyes and / or opacifying agents such as pigments (titanium oxide particles). It is also possible to incorporate in the composition bactericidal or fungicidal agents in order to improve the disinfection of the skin.

In a toilet bar whose formulation consists mainly of monocarboxylic fatty acid soaps (sodium, potassium, mono-, di- or triethanolammonium salts); the levels of fatty acid soaps are generally greater than 25% by weight of the formulation, generally 30 to 95% by weight.

In a toilet roll whose formulation is based on other main constituents than fatty acid soaps, the formulation contains from 0 to 50% by weight, preferably from 1 to 40% by weight of these acid soaps. fat.

These toilet roll compositions may also contain from 0 to 95%, preferably from 0 to 60% surfactants other than soaps, especially C8-
C22 alkyl or alkenyl isethionates, as well as alkyl ether sulfates, alkyl betaines, alkyl amidopropyl betaines, alkyl ampho acetates, diacetates, propionates or dipropionates used to reduce irritation which may be caused by other surfactants, principally anionic surfactants .

From 1 to 15% C 8 -C 22 free fatty acids can also be introduced into the soap compositions as superfatting agents or to modify the appearance and creaminess of the foam during washing.

It is also possible to find in these compositions waxes such as paraffin waxes, natural waxes such as beeswax or ozokerite or silicone waxes. These waxes are advantageously used to improve the appearance, the hold, the processability and storage retention of toilet rolls.

 Shampoos, and more generally detergent compositions for personal use may contain, besides the amidoamines of the invention, the usual additives present in these types of formulation.

There may be mentioned in particular: anionic surfactants, such as water-soluble salts of alkyl sulphates, alkyl ether sulphates, alkyl isethionates and alkyl taurates or their salts, alkyl carboxylates, alkyl sulphosuccinates or alkyl succinamates, alkyl sarcosinates, derivatives thereof; alkyllates of protein hydrolysates, acylaspartates - zwitterionic or amphoteric surfactants, such as alkylbetaines, alkylamidopropylbetaines, imidazoline derivatives such as alkylamphoacetates, alkylamphodiacetates, alkylamphopropionates, alkylamphodipropionates, alkylsultaines or alkylamidopropylhydroxysultaines - agents nonionic surfactants, such as the polyoxyethylenated derivatives of C 6 -C 22 aliphatic or arylaliphatic alcohols, the alkylpolysaccharides having a C 6 -C 30, preferably C 10 -C 18, hydrophobic group and a polysaccharide group, for example polyglycoside, as a grouping hydrophil as well as from 1 to 3 sugar units, the alkylated derivatives of aminosugars, such as the alkylglucamides produced by the amidation reaction of a fatty acid on N-methylglucamine - amides derived from fatty acids generally used for their suitability to improve the foaming of the compositions or to increase the viscosity of said compositions; these amides are generally chosen from cationic polymers (such as synthetic cationic polymers of the MIRAPOL AD1 or MIRAPOL A550M type) marketed by RHONE-POULENC, cationic polymers (improving the combability, the styling, the touch and the volume of the hair). as cationic derivatives of guar (JAGUAR C135M), JAGUAR CI 62 @ marketed by RHONE-POULENC) or cationic derivatives of cellulose (POLYMER JR400 marketed by UNION CARBIDE).

organopolysiloxanes used as such or in solution in one of their usual solvents (low-mass silicone oils, highly branched paraffinic oils, fatty esters, for example of the isopropyl palmitate type, etc.), as conditioning or glossing agents; .

anti-dandruff agents, such as pyridinethiones, more especially zinc pyridinethione, selenium-based compounds such as selenium sulphide or OCTOPYROX (8), marketed by HOECHST; anti-parasite agents (anti-lice), such as UNDANE or different pyrethrins used for this purpose.

These compositions may also contain agents that modify the appearance or the viscosity of the formulations such as pearl-containing compounds based on polyethylene glycol stearate or viscosity-enhancing or stability-enhancing polymers such as CARBOPOLQ9 marketed by GOODRICH, hydrocolloids and their derivatives, such as guar or modified guars, carob, xanthan gum, cellulose derivatives (hydroxyethylcellulose, marboxymethylcellulose).

The conventional compositions of shampoos containing the oligomeric alkyl ether sulfates of the invention may consist of (percentages by weight)
. Oligomeric alkyl ether sulfates of the invention 1-15%
. anionic surfactant G15%
. amphoteric surfactant 0-10%
. 0-5% fatty acid alkanolamide
. thickening agent 0-5%
. conditioner 0-3%
0-2% perfume
.conservator 0-2%
. 0-2% anti-dandruff agent
water 100% supplement
The oligomeric alkyl ether sulfates of the invention can also be used in formulations where it is necessary to maintain in suspension in water finely divided solids, such as agrochemical active ingredient formulations (herbicides, insecticides, fungicides, etc.). known as the generic name of concentrated suspensions ".

In addition to a dispersing surfactant, additives such as those described in the commercial brochure "Auxiliaries for agrochemical formulations" published by RHONE-POULENC are found as additives in a concentrated suspension formulation.
GERONAZZO SpA.

There may be mentioned, for example, a wetting surfactant, taken from the alkoxylated derivatives of arylaliphatic alcohols, aryl sulphonated derivatives such as sodium isopropyinaphthalene sulphonate, sold under the name SUPRAGIL WPe by Rhone.
POULENC GERONAZZO, dialkyl sulfosuccinates such as sodium di-ethyl-2-hexyl sulfosuccinate, dispersing polymers, such as polyacrylic acids and their salts, anhydride (or acid) maleic-diisobutylene copolymers and their salts, such as GEROPON T36 (RHONE -POULENC GERONAZZO), the condensed sodium methylnaphthalenesulfonate SUPRAGIL MNS909 (RHONE-POULENC
GERONAZZO), dispersant polymers derived from lignin such as lignosulfonates of sodium or calcium or other dispersing surfactants such as alkoxylated derivatives, optionally sulfated or phosphated with tristytylphenols. In addition, these formulations may contain antifreeze additives such as propylene glycol and thickening additives which modify the rheological behavior of the suspension, such as xanthan gum, cellulose derivatives (carboxymethylcellulose), guar gum or its derivatives, and clays. or modified clays such as bentonite and bentones.

 Among the active materials that can be formulated in this way, there are generally those whose melting point is greater than 45 ° C., preferably greater than 60 ° C. and whose solubility in water is less than 10 g / l, preferably less than 10 g / l. 1 g / l.

The phytosanitary active ingredients concerned are herbicides, fungicides and insecticides, such as those described in THE PESTICIDE MANUAL (9 "edition
WORKLING and RJ HANCE, editors, published by The British Crop Protection Council) and meeting the above criteria.

EXAMPLE 1 Preparation of bis (2-hydroxy-dodecyl) ether
To a solution of 1,2-dodecanediol (50 g, 0.247 mol) in toluene (100 ml) is added potassium hydroxide (0.69 g, 0.012 mol). The medium is dehydrated by azeotropic distillation. The residual reaction medium is refluxed and a solution of 1,2-epoxy dodecane (54.62 g, 0.296 mol) dissolved in toluene (50 ml) is added. The reaction medium is then stirred at reflux for 5 hours until the two starting products disappear (analysis by gas chromatography).

After cooling, the organic phase is washed three times with distilled water until neutral. After drying over magnesium sulphate, the solvent is evaporated off under reduced pressure. This is followed by distillation under reduced pressure and the bis (2-hydroxy-dodecyl) ether is obtained in the form of a white solid.

Example 2 Preparation of bis (2-hydroxy-tetradecyl) ether
To a solution of 1,2-tetradecanediol (50 g, 0.217 mol) in toluene (100 ml) is added potassium hydroxide (0.607 g, 0.011 mol). The medium is dehydrated by azeotropic distillation. The residual reaction medium is refluxed and a solution of 1,2-epoxy tetradecane (55.34 g, 0.260 mol) dissolved in toluene (50 ml) is added. The reaction medium is then stirred at reflux for 5 hours until the two starting products disappear (analysis by gas chromatography).

After cooling, the organic phase is washed three times with distilled water until neutral. After drying over magnesium sulphate, the solvent is evaporated off under reduced pressure. This is followed by distillation under reduced pressure and the bis (2-hydroxy-tetradecyl) ether is obtained in the form of a white solid.

Exemole 3: Prenaration of bis (1-decyloxy-1-hydroxy-2-hydroxyl) ether
To a solution of 1,2-dihydroxy-3-decyloxypropane (50 g, 0.215 mol) in toluene (100 ml) was added potassium hydroxide (0.538 g, 0.010 mol). The medium is dehydrated by azeotropic distillation. The residual reaction medium is refluxed and a solution of decyl glycidyl ether (48.13 g, 0.258 mol) dissolved in toluene (50 ml) is added. The reaction medium is then stirred under reflux for 6 hours until the two starting products disappear (analysis by gas chromatography).

After cooling, the organic phase is washed three times with distilled water until neutral. After drying over magnesium sulphate, the solvent is evaporated off under reduced pressure. Distillation is then carried out under reduced pressure and the bis (decyloxy-1-hydroxy-2-propyl) ether is obtained in the form of a white solid.

EXAMPLE 4: Prenaration of bis (dodecyloxy-1-hydroxy-2-DroDyl) ether
To a solution of 1,2-dihydroxy-3-dodecyloxy propane (50 g, 0.192 mol) in toluene (100 ml) was added potassium hydroxide (0.538 g, 0.010 mol). The medium is dehydrated by azeotropic distillation. The residual reaction medium is refluxed and a solution of dodecyl glycidyl ether (55.75 g, 0.23 mol) dissolved in toluene (50 ml) is added. The reaction medium is then stirred at reflux for 7 hours until the two starting products disappear (analysis by gas chromatography).

After cooling, the organic phase is washed three times with distilled water until neutral. After drying over magnesium sulphate, the solvent is evaporated off under reduced pressure. This is followed by distillation under reduced pressure and the bis (1-dodecyloxy-2-hydroxypropyl) ether is obtained in the form of a white solid.

EXAMPLE 5: Prenaration of tndodecylene glycol
To a solution of 1,2-dodecanediol (50%, 0.247 mol) in toluene (100 ml) was added potassium hydroxide (0.69 g, 0.012 mol). The medium is dehydrated by azeotropic distillation. The residual reaction medium is heated under reflux and 1,2-dodecane epoxide (184.4 g, 1.235 mol) is added over a period of one hour. The reaction medium is then stirred under reflux for 8 hours until the two starting products disappear (analysis by gas chromatography).

After cooling, the organic phase is washed three times with distilled water until neutral. After drying over magnesium sulphate, the solvent is evaporated off under reduced pressure. Tridodecylene glycol is purified by chromatography on silica gel (eluent hexane / acetone).

EXAMPLE 6: Prenaration of Ethylene Sulfate
The ethylene sulphite (6.959, 62.5 mmol) is dissolved in 54 ml of distilled water.

This stirred solution is cooled to 0 ° C. A commercial solution of 2M sodium hypochlorite (33.5 ml) containing RuO 2, 2H 2 O (1.3 mg, 0.0076 mmol) is then added over 40 minutes. It is necessary to regulate the temperature in order to maintain the reaction medium at 0 ° C. A white precipitate is formed as the batch is poured in. At the end of the addition, after filtration, washing and drying under vacuum, 5.90 g are obtained. of ethylene sulphate (yield 76%) as white crystals with a melting point of 92 ° C.

EXAMPLE 7 Preparation of bis ((2-hydroxy-2-ethoxy) -2-dodecyl) ether
To a solution of bis (2-hydroxy-dodecyl) ether (50 g, 0.129 mol) in toluene (100 ml) was added potassium hydroxide (0.36 g, 0.006 mol). The medium is dehydrated by azeotropic distillation. The residual reaction medium is heated to 90 ° C. and the ethylene sulphate (32 g, 0.258 mol) is added portionwise After five minutes of reaction, the reaction medium becomes cloudy and at the end of the reaction, the precipitate formed is important. The hydrolysis is carried out by adding water (50 ml) and concentrated sulfuric acid (10 ml) The medium is maintained at 80 ° C. for one hour.After decantation and washing of the organic phase, the bis (( 2-hydroxy-ethoxy) -2-dodecyl ether is obtained in the form of a viscous oil after evaporation of the solvent under reduced pressure.

EXAMPLE 8 Preparation of bis ((sodium ethoxy sulfate) -2 dodecyl) ether
To a solution of bis (2-hydroxy-dodecyl) ether (50 9, 0.129 mol) in toluene (100 ml) is added potassium hydroxide (0.36 g, 0.006 mol). The medium is dehydrated by azeotropic distillation. The residual reaction medium is heated to 90 ° C. and the ethylene sulphate (32 g, 0.258 mol) is added portionwise. After five minutes of reaction, the reaction medium becomes cloudy and at the end of the reaction, the precipitate formed is important. The reaction medium is then cooled to 40 ° C. and an aqueous sodium hydroxide solution (50%, 0.258 mol) is slowly added and after stirring for a few minutes, the precipitate is filtered off and dried under vacuum.The bis ((ethoxy) is thus obtained. sodium sulphate) -2 dodecyl ether as a hygroscopic white powder.

EXAMPLE 9: PreDaratlon of bis ((sodium ether sulphate) -2 tetradecyl) ether
To a solution of bis (2-hydroxy-tetradecyl) ether (50 g, 0.120 mol) in toluene (100 ml) was added potassium hydroxide (0.36 g, 0.006 mol). The medium is dehydrated by azeotropic distillation. The residual reaction medium is heated to 90 ° C. and the ethylene sulphate (29.8 g, 0.24 mol) is added portionwise After five minutes of reaction, the reaction medium becomes cloudy and at the end of the reaction, the precipitate formed is important. The reaction medium is then cooled to 40 ° C. and an aqueous sodium hydroxide solution (50%, 0.24 mol) is slowly added. After stirring for a few minutes, the precipitate is filtered off and dried under vacuum. The bis ((sodium ethoxy sulfate) -2-tetradecyl) ether is thus obtained in the form of a hygroscopic white powder.

EXAMPLE 10 PREPARATION OF bis (decoxy) ((sodium ethoxy sulphate) -2) -2 nn (nn) ether
To a solution of bis (decyloxy-1-hydroxy-2-propyl) ether (50 g, 0.106 mol) in toluene (100 ml) was added potassium hydroxide (0.28 g, 0.005 mol). The medium is dehydrated by azeotropic distillation. The residual reaction medium is heated to 900 ° C. and the ethylene sulphate (26.3 g, 0.212 mol) is added portionwise. After five minutes of reaction, the reaction medium becomes cloudy and at the end of the reaction, the precipitate formed is important. The reaction medium is then cooled to 40 ° C. and an aqueous sodium hydroxide solution (50%, 0.212 mol) is slowly added and after stirring for a few minutes, the precipitate is filtered off and dried under vacuum to give the bis (decyloxy) Sodium ethoxy sulfate -2-2 propyl ether as a hygroscopic white powder.

EXAMPLE II: Preparation of bis (dodecyloxy-ethoxy sodium sulphate) -2) -2-eoeyl) ether
To a solution of bis (dodecyloxy-1-hydroxy-2-propyl) ether (50 μg 0.1 mol) in toluene (100 ml) was added potassium hydroxide (0.28 g, 0.005 mol). The medium is dehydrated by azeotropic distillation. The residual reaction medium is heated to 90 ° C. and the ethylene sulphate (24.8 g, 0.2 mol) is added portionwise. After five minutes of reaction, the reaction medium becomes cloudy and at the end of the reaction, the precipitate formed is important. The reaction medium is then cooled to 40 ° C. and an aqueous sodium hydroxide solution (50%, 0.2 mol) is added slowly. After stirring for a few minutes, the precipitate is filtered and dried under vacuum. There is thus obtained bis (dodecyloxy-1 - ((sodium ethoxy sulfate) -2) -2 propyl) ether in the form of a hygroscopic white powder.

Example 12: Preparation of tetraoxa-3.6.9.12tridecyl-4.8.11 sodium disulfate-1.14 tetradecane
To a solution of tridodecylene glycol (30 g, 0.0525 mol) in toluene (100 ml) was added potassium hydroxide (0.147 g, 0.0026 mol). The medium is dehydrated by azeotropic distillation. The residual reaction medium is heated to 90 ° C. and the ethylene sulphate (13 g, 0.105 mol) is added portionwise. After five minutes of reaction, the reaction medium becomes cloudy and at the end of the reaction, the precipitate formed is important. The reaction medium is then cooled to 40 ° C. and an aqueous sodium hydroxide solution (50%, 0.105 mol) is slowly added. After stirring for a few minutes, the precipitate is filtered off and dried in vacuo. Thus, tetraoxa-3,6,9,12 tridecyl, 8,11-sodium disulphate-1,14 tetradecane is obtained in the form of a white solid.

EXAMPLE 13 Surface Properties of Alkylene Diphenylsulfates (20 ° C)
The critical micelle concentration (cmc) and static surface tension measured in mN / m (milinewton per meter) at the critical micelle concentration (y cmc) at room temperature are determined using a PROLABO "Tensimat n" tensiometer. 3 "equipped with a platinum blade

<tb><SEP> x <SEP> n <SEP> R81. <SEP> cnìc
<tb><SEP> x
## EQU1 ## 28
<tb><SEP> 2 <SEP> 12 <SEP> ewmpb11 <SEP> 0fl17 <SEP> 31
<tb><SEP> 10 <SEP>) <SEP> S <SEP> 3 <SEP> 10 <SEP> ta) <SEP> 0fil33 <SEP> 28
<tb><SEP> 12 <SEP> (a) <SEP> 0fil14 <SEP> 30
<tb><SEP> 14 <SEP> (a) <SEP> ome <SEP> 375
<tb><SEP> x
<tb><SEP> Cn <SEP> H <SEP> 2n4b1-CH <SEP> CH <SEP> 2 <SEP>'<SEP> 2 <SEP> OCH2CH2 <SEP> -OSO3 <SEP> Na <SEP> 10 <SEP> ::::: <SEP> 8 <SEP> 0.045 <SEP> 275
<tb><SEP> example <SEP> 9 <SEP> OQn <SEP> 295
<tb><SEP> n <SEP> H <SEP> x <SEP> OSO <SEP> 3No <SEP> 12 <SEP> (a) <SEP> 82 <SEP> 385
<tb><SEP> 50 <SEP> 3No <SEP> 12 <SEP> (a) <SEP> gd <SEP> 39
<tb> (a) Okahara et al., J. Jpn. Oil Chem. Soc., 40,473 (1991)
Surface properties of alkyl trimeric sulphates (20 C)

<tb><SEP> x <SEP> I <SEP> X <SEP> I <SEP> Ret. <SEP> cmo <SEP> ycrnc
<tb><SEP> x <SEP> RBS. <SEP> I <SEP> old <SEP> ranc
<tb><SEP> c10 <SEP> C10 <SEP> H21 <SEP> cH-X <SEP> | <SEP> OCH2CH2 <SEP> OSO3 <SEP> Na <SEP> | <SEP> exemde <SEP> 12 <SEP> O012 <SEP> 27
<tb><SEP> AT
<tb><SEP> c10 <SEP> C10
<tb><SEP> (o
<tb><SEP> c10 <SEP> 10 <SEP> cH-x
<tb><SEP> C1OH21 <SEP> C10H21 <SEP> ocH2CH-x <SEP> | <SEP> 4su3 <SEP> Na <SEP> (b) <SEP> Q0009 <SEP> 27
<tb><SEP> AT
<tb><SEP> C1OH21 <SEP> OCH2CH
<tb> I <SEP> CrOH21 <SEP> 4CH2-CH
<tb> I <SEP> P
<tb><SEP> c10 <SEP> H21 <SEP> 0CH2CH-X
<b> (b) Okahara et al., J. Am.

 Oil Chem. Soc., 69, 626 (1992)

Claims (10)

 Claims .1 Oligomeric alkyl sulphates having the general formula (I)

 in which: m identical or different represent an integer or decimal number equal to or greater than let less than 20, M represents a cation chosen from an alkali metal, an alkaline earth metal or a quaternary ammonium group, W represents the radical -CH2-Z-CH2- in which Z represents the group:

 in which p has the same meaning as m defined above and may also be equal to 0,  the radical R3 is chosen from a hydrogen atom, a radical R1. a radical R2 defined below, and a unit of formula :: O (CH2CH2O), - SO3M where q has the same meaning as m defined previously and M has the same meaning as in formula (1) with R1 and R2 identical or different represent the group:

 where R4 represents a hydrogen atom or a unit O (CH2CH2O) q-SO3M where m and M are as defined previously, where Q represents an alkyl, alkenyl, alkyloxy, alkenyloxy, linear or branched, cyclic or acyclic radical comprising from 4 to at 18 carbon atoms  2. Alkyl ether sulfates according to claim 1, characterized in that R3 represents a hydrogen atom, p and q an integer or decimal number between 0 and 10, more preferably between 0 and 5, M a sodium or potassium, and m an integer or decimal number between 1 and 10, more preferably between 1 and 3, even more preferably equal to 1.  3. Alkyl ether sulfates according to claim 1, characterized in that they correspond to the general formula (II):

 with Q and M previously defined  Alkyl ether sulphates according to Claim 1, characterized in that they correspond to the formula:

  with n and M as previously defined  5. Process for the preparation of the products of formula (1) defined in claim 1 and wherein m = 1, characterized in that they are prepared by reaction of ethylene sulphate with the compounds t corresponding to the general formula (! /):

 with R1, R2, and W as previously defined.  6. Process for the preparation of the products of formula (1) defined in claim (1) and wherein m = 2, characterized in that the product of formula (1) obtained by the process according to claim 5 is hydrolysed and the product obtained is reacted with ethylene sulphate.  7. Process for the preparation of the products of formula (1) defined in claim (1), characterized in that the product of formula (1) having a value of m less than one unit is hydrolyzed to the desired value and is reacted on ethylene sulphate.  8. Surfactant composition, characterized in that it comprises at least one product of formula (1) as defined in any one of claims 1 to 4, and optionally at least one surfactant chosen from anionic surfactants. , nonionic, cationic, amphoteric and zwitterionic.  9. A detergent composition comprising a surfactant composition as defined in claim 8.  10. Cosmetic composition or dentifrice comprising a surfactant composition as defined in claim 8.