EP0609391A1 - Novel alkylpolyosides, compositions containing same, process for their preparation and applications as surface agents - Google Patents

Abstract

The subject of the present invention is new derivatives of alkylpolyosides, compositions containing them, their method of preparation and applications as surfactants. According to the invention, these derivatives are hemisulfosuccinates of alkylpolyosides corresponding to the general formula (I) in which R represents an alkenyl radical or, preferably, an alkyl radical with a straight or branched chain having from 6 to 32 carbon atoms, S represents the residue of a sugar, M represents an alkali metal, one of R1, R2 represents an SO3M group in which M represents an alkali metal, the other represents a hydrogen atom, x represents an integer included between 1 and 10, preferably between 1 and 4. The invention finds particular application in the fields of cosmetics, parapharmacy and household detergents.

Description

New derivatives of alkylpolvosides. Compositions containing them, their preparation process and applications as surfactants.

The present invention relates to new alkylpolyoside derivatives, compositions containing them, their preparation process and applications as surfactants.

It is known that alkylpolyosides are nonionic surfactants already used in a wide range of industrial applications.

It has been discovered, and this constitutes the basis of the present invention, a new family of compounds derived from alkylpolyosides exhibiting particularly advantageous properties as surfactants.

Thus, according to a first aspect, the present invention aims to cover new alkyl polyiside hemisulfosuccinates, corresponding to the general formula:

R_0- (S) _X -CO-CH-CH-C02M (I)

Ri R2

in which :

R represents an alkenyl radical or, preferably, a straight or branched chain alkyl radical having from 6 to 32 carbon atoms,

S represents the remainder of a sugar, M represents an alkali metal, one of Ri, R2 represents a SO3M group in which M represents an alkali metal, the other represents a hydrogen atom, x represents an integer included between 1 and 10, preferably between 1 and 4. In the present description, the term "residue of a sugar" means a bivalent radical resulting from the removal from a sugar molecule, on the one hand of an atom of hydrogen on a hydroxyl group, and on the other hand of the anomeric hydroxyl group.

In the case of glucose, the expression "residue of a sugar" therefore denotes a radical such as:

The sugar is for example chosen from the following compounds: glucose or dextrose, sucrose, fructose, galactose, maltose, maltotriose, lactose, cellobiose, mannose, ribose, dextran, talose, allose, xylose, levoglucosane, cellulose and starch. Among these compounds, glucose, dextrose, fructose and maltose are particularly preferred.

An alkali metal is for example sodium or potassium. It has been found, quite surprisingly, that the new products thus defined have particularly advantageous properties as surfactants.

In particular, the above-mentioned derivatives of formula (C), and more particularly still those in which R represents an alkenyl or alkyl radical having from 8 to 14 carbon atoms, and preferably from 10 to 12 carbon atoms, are foaming, wetting and well tolerated through the skin and mucous membranes.

In general, the derivatives according to the invention will advantageously replace in their applications the polyoxyethylated functional surfactants, the preparation of which leads to toxic impurities, which limits their use. These derivatives will therefore find application in many fields ranging from cosmetics (soaps, toilet bars) and parapharmacy to household detergents, via the textile industry, or paper.

In their applications, the alkylpolyoside derivatives in accordance with the invention can be used alone or as a mixture with hemi-sulfosuccinates fatty alcohols of formula ROCO-CHR1-CHR2-CO2M (II) and optionally alkylpolyosides of formula RO- (S) _x -H; R, RI, R2, M, S and x being as defined above, R 'representing an alkenyl group or, preferably, an alkyl group, with straight or branched chain having from 6 to 32 carbon atoms. Thus, according to a second aspect, the present invention covers a composition which can usually comprise, expressed as a percentage by weight:

- From 20 to 95%, and preferably from 35 to 70%, of at least one alkyl lpolyoside hemi-sulfosuccinate of formula (I) mentioned above; - from 5 to 80%, and preferably from 5 to 30%, of at least one fatty alcohol hemisulfosuccinate of formula II above, and

- from 0 to 30%, and preferably from 10 to 20%, of at least one alkylpolyoside of formula R- (S) x - H, in which R, S and x are as defined above. Such a composition can be obtained by simple mixing of its constituents, but will preferably be prepared by reaction of maleic anhydride on a mixture comprising a polysaccharide of formula RO- (S) _x -H and a fatty alcohol of formula R'OH , in which R ¹ represents an alkenyl group or, preferably, an alkyl group, with a straight or branched chain having from 6 to 32 carbon atoms in the molar proportions indicated above and sulfitation of the product thus obtained in an alkaline medium.

The fatty alcohols that can be used for the preparation of this composition will generally be linear or branched alcohols, of natural origin such as, for example, alcohols from plant materials (copra, palm kernel, palm) or animal materials (tallow), or even synthetic; and whose chain length is between 6 and 32 carbon atoms, preferably between 8 and 14 carbon atoms and more preferably between 10 and 12 carbon atoms.

Preferably the fatty alcohol will have a chain identical to the alkyl chain of the alkylpolyoside hemisulfosuccinate. The above-mentioned alkylpolyoside may be commercial or prepared by any method known to those skilled in the art.

Among the alkylpolyosides currently available on the market, mention may be made of the products known under the trade names Triton CG 110; Triton BG 10, Triton DG 210; Oramix CG 110, Oramix NS 10 and Plantaren APG 600.

Furthermore, two main synthetic routes can be envisaged in the context of the present invention, for the preparation of alkylpolyosides. The first route comprises the reaction, in an acid medium between a fatty alcohol and a sugar having an anomeric hydroxyl group, preferably glucose or dextrose.

The second way consists: - in a first step, to prepare an alkylpolyoside with a light alcohol such as for example methanol or butanol by etherification of a sugar, preferably glucose, to obtain products such as methylglucoside or pentylglucoside; then

- In a second step, to carry out a transethέrifîcation with a heavy fatty alcohol, having for example from 8 to 32 carbon atoms, with distillation of the light alcohol (methanol or butanol).

Whether one chooses the first or the second synthetic route described above, the reaction with heavy fatty alcohol is generally incomplete; one can then proceed, if necessary, to a distillation of the excess fatty alcohol. Examples of acid catalysts which can be used for the preparation of the abovementioned alkylpolyosides are sulfuric, phosphoric, hydrochloric, hypophosphorous acids and their mixtures.

The amount of acid catalyst used will generally be about 0.001 to 0.05 moles per mole of sugar. The reaction temperature will generally be between 90 and 120 ° C, and the reaction time between 3 and 6 hours.

According to a third aspect, the present invention covers a process for the preparation of the alkylpolyoside hemi-sulfosuccinates of the above-mentioned formula (I) or of a composition as defined above, in a container characterized in that it comprises: a- maleic anhydride on an alkylpolyoside of formula RO- (S) xH, in which R, S and x are as defined above; or a _α - the reaction of maleic anhydride on a mixture comprising an alkylpolyoside of formula R-0- (S) _x -H, in which R, S and x are as defined above and a fatty alcohol of formula R'OH wherein R 'represents an' alkenyl or, preferably, straight or branched chain alkyl having from 6 to 32 carbon atoms; b- sulphitation in an alkaline medium of the product thus obtained at the end of step a or a _r In the process according to the present invention, the alkylpolyoside used as starting material can therefore be either an alkylpolyoside alone, or a mixture of alkylpolyoside and fatty alcohol in a molar ratio of between approximately 10/90 and 90/10, that is usually a weight ratio of between 20/80 and 95/5.

The fatty alcohol can come from the synthesis of the alkylpolyoside, or be additive to an alkylpolyoside.

It is possible, for example, to obtain a mixture of alkylpolyoside and fatty alcohol, at the end of the synthesis of the alkylpolyoside using the first route recalled above (reaction in an acid medium between a fatty alcohol and a sugar ), and those skilled in the art knowing the molecular weights of the fatty alcohol and of the ose used as well as the quantity of non-esterified fatty alcohol to be obtained at the end of the reaction, will easily determine the reaction conditions to be used.

The esterification of the alkylpolyoside (step a or a will generally be carried out using a functional anhydride of the maleic type, possibly in the presence of an acid catalyst such as for example sulfuric acid. Generally, 0.7 is used. at approximately 1.8 equivalent of said functional anhydride for an equivalent of primary hydroxide The esterification can be carried out in an appropriate solvent, in an aqueous medium or, preferably, in the absence of any solvent.

The esterification can be carried out at a temperature of between approximately 60 and 130 ° C., preferably between 70 and approximately 100 ° C., for a period of approximately 1 to 15 hours and preferably from 1 hour 30 to 3 hours.

In step b, it is possible to use any known sulphitizing agent and in particular Na2S2O5, Na2SO3 or even SO2 in the gaseous state, preferably Na ₂ S ₂ O ₅ . The amount of said sulphitating agent used can advantageously be of an equivalent for 1 to 2 equivalents of functional anhydride of the maleic type present in the reaction mixture.

The sulfitation reaction is preferably carried out in an aqueous medium, at a pH of between about 4 and 7, preferably between 5.5 and 6.5. This sulfitation reaction can be carried out at a temperature between 60 and

110 * C, preferably between 80 and 100 * C, for a period of 6 hours, and preferably 2 to 4 hours.

According to a fourth aspect, the present invention also aims to cover the use of the alkylpolyoside derivatives defined above or of a composition containing them, as surfactants, in particular as foaming or wetting products.

The invention will be illustrated in more detail by the following examples, given solely by way of illustration and which cannot therefore limit the scope of the invention.

In these examples, the percentages are expressed by weight, unless otherwise indicated. Example 1: Step a: Esterification At 420 g of commercial alkyl glucoside (Oramix CG 110-100%) melted at

105-110 ^* C was added 98 g of maleic anhydride and 1 g of sulfuric acid at 98% dissolved in 2 g of water.

The product thus obtained has the following characteristics: I _A : 108.6 I _S : 235.6

The commercial product Oramix CG 110-100% is a product with 100% of active material obtained by etherification in acid catalysis of glucose by an excess of alcohol (Cg-Gjrj) and elimination of the excess alcohol by distillation on an evaporator to film. Step b: Sulphitation

485 g of the maleic ester obtained in step a are sulfites with 96 g of sodium metabisulfite in the presence of 37 g of sodium hydroxide, at 95-100 ° C. in an aqueous medium (500 g of water) for 3 hours.

A product is thus obtained, the characteristics of which are as follows: Clear Liquid Appearance

Color VCS - Gardner 2 +

Dry extract 53.5% pH in 10% solution 5.55

Anionic active ingredient expressed in meq / g 0.20

Non-ionic content 3.5%

Example 2

Step a ₂ : Esterification

From a C -C ^ Q alcohol cup _. an alkylpolyglucoside containing 51% of active material is prepared in dilution in alcohol. The residual alcohol contents are 23% in Cg alcohol and 26% in C ^ Q- alcohol. To 880 g of the above-mentioned mixture, at 80 ° C., 405 g of maleic anhydride are added and the mixture thus obtained is maintained at 90-100 ^# C for 2 h 30.

The ester obtained has the following characteristics:

I _A : 190.2

IS: 364.8

Step b: Sulphitation

By proceeding in the same way as in Example 1, the ester obtained in step a is sulphited.

The respective amounts of the reaction products are as follows:

Maleic ester 850 g Sodium metabisulfite 282 g Soda 113 g Water 1,200 g

The characteristics of the product thus obtained are as follows:

Clear Liquid Appearance

Color VCS - Gardner 6

Dry extract 47.3% pH in 10% solution 6.35

Anionic active ingredient expressed in meq / g: 0.65 Free alcohol content

Cg: 1.2%

C ₁₀ : 1.4%

Example 3: Example a _χ : Esterification

Preparation of a maleic ester in an aqueous medium. From an alcohol cut in CIO ~ QL2- ° n, an alkylpolyglucoside with 77% dry matter in water is prepared.

6.12 kg of maleic anhydride are added to 30 kg of alkylpolyglucoside thus prepared.

Maleic anhydride is added with stirring to the alkylpolyglucoside placed at 85-90 ° C in a jacketed reactor.

The whole is kept at approximately 100 ° C. with stirring for 11 hours. The medium is then cooled to 40 ° C., then neutralized and diluted with a 10% sodium hydroxide solution.

The characteristics of the maleic ester thus obtained are as follows:

Fluid, cloudy, cloudy appearance

VCS coloring about 7 pH at 10% 6.3 Dry extract 40.5%

Water content 57.1% non-ionic content 11.7%

Viscosity at 25 * C around 5000 cPs (brookfield)

IA: 9.9 IS. 66.3

Step b: Sulphitation

20 kg of maleic ester prepared in step a are added to an alkaline solution of metabisulfite at 45 ^# C

This solution was previously made from 2.10 kg of scale soda, 3.6 kg of sodium metabisulfite and 19.8 kg of water.

The ester-alkaline solution mixture is maintained at 95-100 ^# C with stirring for 4 hours. The product obtained has the following characteristics:

Appearance: Bright clear liquid

Dry matter: 47.3% 8

Example 4: Step a _λ : Esterification From a cut of C12-C14-C16 alcohols, an alylpolyglucoside containing 80% of active material is diluted in alcohol. The residual alcohol contents are 14% in C12 alcohol, 5% in C14 alcohol and 1% in C16 alcohol.

A 15.6 kg of the above mixture, at 95 ^° C, 4.7 kg of maleic anhydride was added and the resulting mixture is maintained at 100-105'C for 4 hours.

The ester obtained has the following characteristic:

I _A : 130.6

Step b: Sulphitation

The maleic ester obtained in stage a ₁ is sulphite with 4.55 kg of sodium metabisulphite, presented with 2.1 kg of soda, at 90 ° C. in an aqueous medium (27 kg) for 3 hours.

The characteristics of the product thus obtained are as follows: - appearance: clear liquid;

- VCS-Gardner color: 4;

- dry extract: 47.8;

- pH in 10% solution: 6.05;

- anionic active ingredient expressed in meq / g: 0.37; - non-ionic content: 14.2

The properties of the products obtained in Examples 1 and 2 were measured and compared to the properties of a polyethoxylated derivative with a structure close to the starting alkylpolyoside. 1. Foaming power

The foaming power was measured by the volume of foam generated 1% of product (dry matter) in water at 30 ^° F of calcium hardness, in the presence of a soil type at 40 ° C, according to standard AFNOR 73403.

The results obtained are as follows:

The foaming power measured by the volume of foam generated by 1% of product (in dry extract) in fresh water (0 * F calcium hardness) at 40 * C and pH 7 gives the following values:

These results show that the products in accordance with the invention have a high and stable foaming power, even in hard water, greater than that of products of neighboring structure. 2. Wetting power

The wetting power was measured according to AFNOR standard NFT 73406 of 0.1% of the product expressed in dry extract at 25 ^° C. It is expressed as a wetting time of the textile disc.

The results obtained are as follows:

These results show that the products of Examples 1 and 2 are more wetting than the starting alkyl glucoside.

3. Eye and skin tolerance

Eye and skin tolerance measurements were carried out on rabbits on products with 10% dry extract according to the standards published in the Official Journal of the French Republic and in particular in the decrees published on 02/21/84 (primary tolerance cutaneous) and 24/10/84 (ocular tolerance).

The results obtained are as follows:

The products of Examples 1 and 2 are classified as very mildly irritant, while the corresponding ethoxylated derivative is moderately irritant, and the reference alkylpolyoside is also moderately irritant.

Quite surprisingly, the derivatives in accordance with the invention therefore exhibit remarkable surfactant properties, superior to those of their known ethoxylated counterparts.

Consequently, the compounds according to the invention can be used to replace these known products in a wide range of applications, in particular in cosmetics, parapharmacy and household detergency. Given the above properties, the compounds of the invention will preferably be used in shampoos, shower gels, bubble baths, to which they impart a creamy foam and which does not attack the skin and scalp during iterative applications.

For example, the following mild shampoo is formulated with the product of Example 1 according to:

Lauryl ether (3) sodium sulfate 2.50%

Cocoyl amido propylhydroxysulfobetaine 2.50%

Product according to example 1 2.50%

Preservative agent (KATHON ^R CG) 0.08% Demineralized water qs 100% whose pH is adjusted to 6 with citric acid. The shampoo is crystal clear. The viscosity obtained is 850 mPas at 20 ° C.

By comparison, a shampoo formulated under the same conditions with sodium alkyl (Cg-C _j ) ethoxy (3) hemisulfosuccinate, in place of the product of Example 1, has a cloudy, non-limpid and fluid appearance without viscosity

(less than 50 mPas).

Doses of 2 to 15% in dry matter of the product according to the invention are recommended for formulating shampoos, shower gels or foam baths having a pleasant foam and a tolerance acceptable by the consumer. Similarly, an antiseptic cleansing liquid for medical skin use has been formulated according to:

Product of Example 2 5.0% Antimicrobial agent 0.5% Demineralized water qs 100% The antimicrobial agent chosen is peracetic acid.

The same composition containing 1% phenoxyethanol as an antimicrobial agent is also effective in removing pathogenic germs from the skin without irritating it.

The products according to the invention can also be used from 10 to 50% as a mild cleaning agent in syndets, soaps and toilet bars.

Claims

1. Alkylpolyoside derivatives, characterized in that they are hemisulfosuccinates corresponding to the general formula

R-0- (S) _x -CO-CH-CH-Cθ2M (I)

It R ₂ in which: R represents an alkenyl radical or, preferably, a straight or branched chain alkyl radical having from 6 to 32 carbon atoms, S represents the remainder of a sugar, M represents an alkali metal, the one of Rχ _} R2 represents an SO3M group in which M represents an alkali metal, the other represents a hydrogen atom, x represents an integer between 1 and 10, preferably between 1 and 4.

2. Derivatives according to claim 1, characterized in that in the above formula I, R represents an alkyl radical, with a straight or branched chain having from 8 to 14 carbon atoms, preferably from 10 to 12 carbon atoms.

3. Derivatives according to claim 1 or 2, characterized in that in the above formula I, the sugar residue is chosen from the residues of glucose, dextrose, fructose, and maltose.

4. Composition, characterized in that it comprises at least one alkylpolyoside hemi-sulfosuccinate of formula (I) as defined in claim and at least one fatty alcohol hemisulfosuccinate of formula R'OCO- CHR1-CHR2-CO2M ( H) and optionally at least one alkylpolyoside of formula RO- (S) xH; R, RI, R2, M, S and x being as defined in claim 1, R 'representing an alkenyl group or, preferably, an alkyl group, straight or branched chain having from 6 to 32 carbon atoms.

5. Composition according to claim 4, characterized in that it comprises, expressed as a percentage by weight: - from 20 to 95%, and preferably from 35 to 70%, of at least one alkylpolyoside hemi-sulfosuccinate of formula (I) as defined in claim 1;

- from 5 to 80%, and preferably from 5 to 30%, of at least one fatty alcohol hemilsulfosuccinate of formula II above, and

- from 0 to 30%, and preferably from 10 to 20% of at least one alkylpolyoside of formula R- (S) x-H, in which R, S and x are as defined in claim 1.

6. Composition according to claim 4 or 5, characterized in that the aforementioned fatty alcohol hέmisulfosuccinate comprises an alkyl chain identical to the alkyl chain of the above-mentioned alkylpolyoside hemisulfosuccmate.

7. Process for the preparation of alkyl polyiside hemi-sulfosuccinates of formula (I) as defined according to any one of Claims 1 to 3, or of a composition as defined according to one of Claims 4 to 6, characterized in that that it comprises: a- the reaction of maleic anhydride on an alkylpolyoside of formula R- O- (S) xH, in which R, S and x are as defined above; or a _x - the reaction of maleic anhydride on a mixture comprising an alkylpolyoside of formula RO- (S) _x -H, in which R, S and x are as defined above and a fatty alcohol of formula R'OH in which R 'represents an alkenyl group or, preferably, a straight or branched chain alkyl group having from 6 to 32 carbon atoms; b- sulphitation in an alkaline medium of the product thus obtained at the end of step a or a _r

8. Method according to claim 7, characterized in that the alkylpolyoside and the fatty alcohol used in mixture in step a _x above are in a molar ratio of between approximately 10:90 and 90:10, ie a weight ratio between 20/80 and 95/5.

9. Method according to claim 7 or 8, characterized in that the sulphiting agent used in the above-mentioned step b is chosen from Na2S2O5 Na2Sθ3 and SO2 gas, preferably Na2S2θ5.

10. Use of an alkylpolyoside derivative according to any one of claims 1 to 3 or of a composition according to one of claims 4 to 6, as surfactant, foaming or wetting product.