NL8102734A - METHOD FOR PREPARING A STABLE WATER-OIL EMULSION USING A COMPOUND CONTAINING A SULFOXY GROUP - Google Patents

Description

* 4 * I: 813139 / vdV / kd

Short designation: Process for the preparation of a stable water-oil emulsion using a compound containing a sulfoxy group.

The invention relates to novel compounds containing sulfoxy in the molecule having emulsifying properties which are particularly capable of providing stable water-oil emulsions.

Despite the large number of known emulsifying surfactants, there remains a need for an emulsifier which can prepare water-oil emulsions that are sufficiently stable to prevent phase separation. This is important if the water-oil emulsions are to be stored for a long time, such as in cosmetics, for example, of creams with improved moisturizing and skin-protecting properties, which consist of a dispersion of very fine water droplets in a fat phase. It is now often the case that the known emulsifiers have a risk of mixing, while the composition of new recipes containing such emulsions is always difficult and the long-term retention of the properties becomes uncertain.

The compounds which are suitable in practice for such water-oil emulsions consist of an aliphatic fat chain bonded mixed with a hydrophilic part. The aliphatic chain can be unsaturated and contain a hydrophilic function that is free or ethoxylated. The hydrophilic part can be a carboxylate, a glycerol, sorbitol or ethylene polyoxide ester or a phosphate.

* and

Also the compounds derived from oleic acid, ricinoleic acid / Lanolin are known as emulsifiers used in cosmetic recipes. These compounds are oil-soluble and provide water-oil emulsions. The cohesion of the thin boundary layer between the oil and the water phase is the result of van der Waals forces or of hydrogen bonds. However, these cohesive forces are low, and the stability of these emulsions is difficult to maintain. Thus, the preparation of water-oil emulsions is difficult, especially if one tries to reduce the content of the oil phase.

The object of the present invention is to provide an improved emulsion with which the above-mentioned drawbacks can be overcome and with which, in particular, very stable, in particular water-oil, emulsions can be obtained. As for cosmetic applications, the present invention provides a product that better protects the surface by the greater affinity of the new emulsifiers to the skin.

The invention is based on the finding of compounds which consist of a lipophilic part with a sulfoxy function and of a hydrophilic part. It has been found that by introducing the group - § - into the molecule of a compound with a hydro-

II

file function (the compound can be a surface-active compound known per se), this compound forms water-oil emulsions and stabilizes the emulsions formed. It may be that the influence of the sulfoxy function must be attributed to its polarizing effect, added to the known intermediate van der Waalsse and dipolar bonds, thereby stabilizing the interfaces between the phases of the emulsion. Either way, entering the - S - group / one

II

A compound containing a hydrophilic group cannot be derived from the prior art.

The new emulsifiers according to the invention thus consist of compounds with a hydrophilic part, the chain of this hydrophilic part containing a sulfoxy group which is connected to the lipophilic part of the hydrocarbon molecule.

These emulsifiers are new chemical compounds of the general formula 1 of the formula sheet, wherein Row represents a hydrocarbon group and Rg represents a hydrogen atom or a hydrocarbon substituent, n is an integer of 1 to 20 while A represents the hydrophilic part of the compound.

More specifically, R ^ may represent an alkyl, alkenyl, aryl, alkaryl, aralkyl, or cycloalkyl group having in x 2 * generally 1-20 carbon atoms, while R may be equal to r \ The most common values for n are 4-18.

Although the structure of the hydrophilic portion of the surfactant compound is known to be 1%, in most 10 cases A represents the following. First of all, a carboxylic acid group-COOH, a sulfonic acid group -S0 ^, a sulfuric acid group -SO ^ or a phosphoric acid group -P0 ^ optionally esterified, in particular with a polyol, for example glycerol or sorbitol, or in the form of a salt of an alkali or alkaline earth metal, an amine 15 or a quaternary imidazolinium salt, or a salt of another nitrogen-containing base, or a polyoxyalkylene chain, in particular polyoxyethylene (-C ^ CHpO- ^ H or polyoxypropylene, where m preferably is a number from 2 to 20. Furthermore, A may represent, for example, an amino acid group of formula 2 or 3 of formula sheet 20.

In order for the emulsifier according to the invention to properly form and stabilize an emulsion with a dispersed aqueous phase, the sulfoxy group must be sufficiently far from the hydrophilic part A. The compounds which give the best results have a sulphoxy function which is included in the fat phase and which can be effective in stabilizing the thin surface-active layer of the interface. The value of n is above 4 and preferably above 6.

The new sulfoxide emulsifiers are used in the same manner as the known emulsifiers, so that there is no need to go into them. It is only noted here that the best results are achieved with, for example, a content of 0.01 to 10% by weight, based on the emulsion to be prepared, with 81 02 734-4 being the optimum ratio of 1 to 3%.

In order to adapt the emulsifier system to the compounds to be emulsified, one or more known emulsifiers must be used. However, this stabilizing effect is always very striking, so it is advisable to add a sulfoxide compound according to the invention to stabilize the emulsion, whereby the new emulsifiers according to the invention can be mixed with one another or with known emulsifiers, insofar as allow the surface-active agents to be mixed together, i.e., it is not possible to mix two surface-active agents with an opposite ionic character.

The new agents according to the invention are suitable not only for the preparation of emulsions of which one of the phases is an aqueous phase, but also for the emulsification of immiscible non-aqueous products, for example for the emulsification of halobenzenes or other organic chlorine compounds (" Chlordan "," DDT%, etc.) with petroleum, xylene, etc.

The invention is now further illustrated by the following examples.

Although the preparation of the corresponding sulfides and sulfoxides is generally known, in the examples known processes are used in the preparation of the products according to the invention.

EXAMPLE I

Preparation of dodecyl sulfoxy undecanoic acid.

a) Chemical preparation of the sulfide.

In a reactor equipped with a stirrer, a heating element and a reflux condenser, 300 ml of ethanol, 450 ml of water with 120 g of sodium hydroxide solution, 398 g (1.5 mol) of bromo undecanoic acid and 303.6 g (1.5 mol) are successively charged. lauryl mercaptan.

The temperature rises to about 80 ° C during mixing. The reaction mixture is stirred vigorously at this temperature to prevent the molded product from crystallizing and the foam formed during cooking from boiling over.

After a reaction lasting 6 hours, the mixture is acidified at pH 80 with concentrated hydrochloric acid to pH 2. Two layers are formed. The bottom aqueous layer is removed and the top layer is poured into benzene.

The product which crystallizes at ambient temperature is suctioned, washed with benzene and dried at 50 ° and 133 Pa. This gives 434 g (yield = 7 ($)) of a crystalline product with a melting point of 70-72 ° C.

Elemental analysis of the product.

Found C% 71.92 H% 12.68

Calculation 71.50 11.92 15 b) Photochemical preparation of the sulfide.

A heated 3 liter reactor, provided with an average pressure, uses a mercury vapor lamp of 125 Watt. The optical path of the reactor is 7 cm. Stirring takes place by means of an external recirculation pipe.

1288 g (7 mol) of undecylenic acid, 14.14 g (7 mol) of lauryl mercaptan, 5.4 g of benzophenone and 5.4 g of trimethyl phosphite are added to this reactor. The reaction lasts at 80 ° C, 3 hours.

After the reaction has ended, the reactor is poured into 4.5 liters of petroleum ether and the product is allowed to crystallize at ambient temperature. After suction and washing the crystals with petroleum ether, 2361 g of product are obtained (yield 87.5).

c) Conversion to sulfoxide.

A solution of 965 g (2.5 moles) of dodecyl thioundecanoic acid in 3000 ml of acetone is refluxed with acetone under very vigorous stirring and slowly added 270 ml of ~ 33% hydrogen peroxide (2.6 moles of HgOg). . The reaction is finished after 3 hours. After cooling, the crystals are filtered off, washed 8102734-6 with acetone and dried at 50 ° C and 133 Pa. The product obtained melts at 95-96 ° C and has an acidity of 99.6% of theory.

Basic analysis.

5 Found C% 68.85 H% 11.54 S% 11.50

Calculation 68.66 11.44 11.94

Chemical preparation of methylthioundecanoic acid.

To a stirred, heated, and refluxed reactor, a solution is added containing 1600 g (40 moles) of caustic soda, 960 g (20 moles) of methyl mercets and 4500 ml of water, and then a solution containing 5300 g (20 moles) bromo undecanoic acid in 1200 ml of methanol. The mixture is refluxed for 3 hours, then 20 liters of hexane are added and the temperature of the reaction mixture is kept at 40 ° C for 6 hours. It is acidified to pH 2 with 1900 ml of 13% hydrochloric acid, the aqueous phase is drained and the organic phase is neutralized by washing with water at 40-50 ° C. 13 L of hexane is evaporated and the solution crystallizes at about 5 ° C. After suction and drying, 4450 g (yield 95.5%) of a crystalline product melting at 45 ° C with an acidity of 100% of theory are obtained.

Basic analysis.

Found C% 62.15 H% 10.70

Calculated 62.06 10.54 Photochemical preparation of methyltoundecanoic acid.

A heated reactor of 3 liters is used with an average pressure mercury vapor lamp of 125 watts. The optical path of the reactor is 7 cm. It is stirred by means of an extensive recirculation pipe. 2245 g of 30 (12 mole) of undecyl acid, 5.4 g of benzophenone, 5.4 g of trimethyl phosphite are added to the reaction. The atmosphere is replaced by nitrogen.

Once everything is melted, the mixture is circulated 8102734 - 7 - through the external loop and the temperature is set at 55 ° C. The lamp is lit and introduced into the bottom of the reactor through a sintered gas plate of methyl mercaptan.

After a 7-hour reaction, the excess methyl-5-mercaptan is expelled with nitrogen and the reactor is poured into 3 l of hexane. The solution crystallizes out at 5 ° C, is filtered off and washed with cold hexane. After drying, 2637 g (yield 93.7%) of crystalline product melting at 44.5 ° C are obtained. The acidity is 99.6% of theory.

10 Analysis of the product.

Found C% 62.04 H% 10.67

Calculated 62.06 10.34

Methyl sulfoxy undecanoic acid.

A solution of 1000 g (4.31 mpl) of methyl 15-thioundecanoic acid in 2350 ml of acetone was boiled for 6 hours with 449 ml of 33% hydrogen peroxide (4.3 mol HgOg).

After evaporation of the acetone and drying, 1070 g of crystalline product with a melting point of 85-87 ° C are obtained.

The acidity is 100 ^ of theory.

20 Basic analysis.

Found C% 50.03 H% 9.35

Calculated 50.08 9.68

EXAMPLE III

Glyceryl monomethyl thioundecanoate.

In a reactor equipped with a reflux condenser, 696 g (3 mol) of methylthioundecanoic acid and 828 g (9 mol) of glycerol are heated at 180 ° C and 2660 Pa. After 8 hours, the residual acidity is 0.06 mol. After cooling to 60 ° C, the reaction mixture is divided into two layers which are separated.

The top layer is dissolved in 1 liter of ether and washed with water. After evaporation of the ether and drying, 831 g of a pasty product are obtained. (Yield 90.5%), 81 0 2 7 3 »» - 8 -

The bottom layer is added to the next feed. Glycerol monomethylsulfoxundcano decanoate.

A solution of 770 g (2.5 mol) of glyceryl monomethylthioundecanoate, 260 ml of 33% hydrogen peroxide in 1500 ml of acetone is refluxed for 4 hours.

After evaporation of acetone and drying, 810 g of crystalline product are obtained.

Melting point3 49-52 ° C saponification number = .184 10 C% = 55.89 (56.42) H% = 9.49 (9.33)

EXAMPLE IV

Olycervlmonododecylthioundecanoate.

The mixture is heated in a reactor equipped with a reflux condenser, a mixture of 965 g (2.5 mol) dodecylthioundecanoic acid and 696 g (2.5 mol) glycerol at 2660 Pa at a temperature of 195-200 ° C.

After a 7-hour reaction, the reaction medium no longer contains any acid.

After cooling to 75 ° C, the reaction medium divides into two layers. The bottom layer is used for the following preparation. The top layer consists of a solid mass which melts at 62-71 ° C and whose saponification number is 128. Glyceryl monododecyls ulphoxy undecanoate.

A solution of 874 g (2 mol) of glyceryl monode decyl undecanoate and 200 ml (2 mol) of 33% hydrogen peroxide in 1500 ml of acetone was refluxed for 6 hours.

The acetone is evaporated and the crystallized product is dried. 910 g of product with a melting point of 95-100 ° C are obtained.

Saponification number: 122.

30 Basic analysis.

Found C% 64.87 H% 16.72

Calculated 65.54 16.81 8102734 - 9 -

EXAMPLE V

0/2

45 parts by weight of petroleum jelly are added at 20 ° C / wt. parts of the emulsion mentioned below. After adding 55 wt. parts of distilled water, stirring with a rotary stirrer for 3 minutes, the resulting emulsion is poured into a 100 ml test tube, which is placed in an oven at 40 ° C. The creation of the emulsion is checked every day.

An emulsifier commercially available under the name NOINIC 10 218 and a corresponding sulfoxide compound are being investigated.

N0NI0NIC 218: tert.dodeoyl polyethylene glycol thioether

C12H25-S- (C H20) 12H

SULFOXYDE tert.dodecyl sulfoxy polyethylene glycol

C12H25 < CH2 CH2 < 12H

0

The NNN0NIC emulsion remains stable for about 17 days while the SULFOXYDE emulsion does not show any separation after 40 days.

EXAMPLE VI

2o -

The foaming power of an aqueous medium according to the ROSS MILES method of 0.1% of one of the following compounds should be obtained with the following results.

Emulsifier Height of the foam 25 in mm

In the beginning After 10 min.

Lauryl ether sulfate of triethanolamine 180 120 "+ lauramide (0.1 $). 230 190

Methyl sphoxy undecanoate of triethanolamine 230 200 81 02 734 - 10 -

It can be observed here that the sulfoxide compound according to the invention is much better than the known lauryl sulfate and that it even produces a slightly more stable foam than with the ether to which lauryl amide has been added.

EXAMPLES VII AND VIII

Emulsions for cosmetic creams, in particular night creams, are prepared from the usual ingredients to which the sulfoxide compounds according to the invention are partly added. The creams are subjected to centrifugation, stewing and storage tests. The results of the tests with these preparations are shown in the table.

EXAMPLE VII

Preparations (weight percent)

IA IB

Arlacel 481 (Sorbitan sesquistearate) 6.80 6.80

Vaseline 1.40 1.40

Cholesterol 0.08 0.08

Marcol 82 (Vaseline oil) 41 40

Beeswax 2.20 2.20 20 Paraffin 50/52 10.50 10.50

Stearin (triple pressure). 1.60 1.60

Cetyl alcohol 0.47 0.47 p-propyl hydroxybenzoate 0.15 0.15

Dodecyl sulfoxy undecanoic acid - 1 25 Water 34.70 34.60

Magnesium sulfate 0.50 0.50

Triethanolamine - 0.10

Preserval LL (preservative) 0.20 0.20 T 100 860 (Perfume) 0.40 0.40 100.00 100.00 8102734 -11-

EXAMPLE VIII

(weight percent)

Preparation IIA IIB

Vegetable laundry 8 8

Vegetable butter 5 5 5 Isododecane 10 10

Isopropyl myristate 5 5

Imwitor 780 K (glycerol monoisostearate) 2 2

Montane 73 (sorbitan sesquiisostearate) 1 1

Simulsol 989 (hydrogenated ethoxylated castor oil) 0.5 0.5

Dodecyl sulfoxy undecanoic acid - 1

Hostaphat K0 300 N (trioleyl phosphate) 2 1

Bentone 27 (Hectorite dimethylbenzyzstearyl ammonium) 1.5 1.5 15 Bentone 38 (Hectorite quaternium-18) 2 2

Preservative 0.2 0.2

Water 56.2 56.1

Magnesium sulfate 1 1

Magnesium Hydroxide - 0.1 20 Glycerin 5 5

Preservative 0.6 0.6 100 100 81 02 73 4

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Q Ο_ ^ * · _ Ή_ 81 02 734 - 13 -

The fact that creams IB and IIB are better than creams IA and IIA is clearly due to the addition of the decylsulfoxy undecanoic acid, one of the compounds of the present invention.

5 EXAMPLES IX and X

In the previous examples, in which the preparation of cosmetic creams has been described, dodecyl sulfoxide undecanoic acid is replaced by methyl sulfoxy undecanoic acid (Example IX) and by glyceryl monododecyl sulfoxide undecanoate (Example X).

As has been shown in Example V, the creams containing a sulfoxide compound have much greater and longer lasting stability than the creams not containing this compound.

EXAMPLE XI.

15 Composition of the cream wt

Isododecane 12.00

Lawyer oil 2.00

Corn germ oil 1.00 PPG 3 myristyl ether 2.00 20 Ethylhexyl acetoxystearate 1.50

Sorbitan monooleate 0.50

Polyglycerol ether from a soybean oil dinner 1.00

Soy lecithin 0.40

Oodecyl sulfoxy undecanoic acid 0.90 25 Glyceryl monododecyl sulfoxy undecanoate 1.00

Propyl parahydroxybenzoate 0.10

Sodium hydroxide 10 $ 1.00

Glycerin 2.50

Magnesium sulfate 0.50 30 Methyl parahydroxybenzoate 0.20

Distilled water 73.40 81 02 7 3 4

% »V

- Η -

This cream, which contains two sulfoxide compounds according to the invention, has a much longer lasting stability.

Incidentally, this preparation with a continuous oil phase is particularly striking because it contains 75% water.

Such a 75% aqueous continuous oil phase composition has not been previously prepared with the known emulsifiers and is thus particularly representative of the products prepared according to the present invention.

8102734

Claims (5)

Emulsifier suitable for the preparation of stable vascular emulsions containing a lipophilic and a hydrophilic part, characterized in that the lipophilic part of these compounds contains a sulfoxy function. r 2. An emulsifier according to claim 1, characterized in that the sulfoxylated emulsifiers correspond to the formula 1 of the formula sheet, wherein R represents a hydrocarbon group 2 and R represents a hydrogen atom or a hydrocarbon substituent, n is a number from 2 to 20, preferably 4 to 18 and A 10 represents a hydrophilic group, for example an acid in the form of an ester or salt, a polyoxyolefin chain, a tetravalent nitrogen cation or an amino acid group. Emulsifier according to claim 2, characterized in that R 1 represents an alkyl, alkenyl, aryl, alkaryl, aralkyl or cycloalkyl group, preferably with 1 to 20 carbon atoms. Emulsifier according to claim 2 or 3, characterized in that R represents a hydrocarbon group, which may or may not be equal to D1 to R. Emulsifier according to one or more of claims 2-4, 20, characterized in that A represents -C00H, -50 ^, -S0 ^ or -P0 ^, whether or not in the form of an ester or salt. e. Emulsifier according to claim 5, characterized in that A is westernized with a polyol, in particular glycerol or sorbitol. 81 02 734 -16- * y v Emulsifier according to claim 5, characterized in that A is a salt of an alkali base, an amine or a quaternary ammonium. Emulsifier according to one or more of claims 2 to 5, 5, characterized in that A represents a cationic nitrogen group, in particular a quaternary ammonium or imidazolio. 9. Emulsifier according to one or more of claims 2 to 5, characterized in that A represents a polyoxyalkylene chain, in particular polyoxyethylene or polyoxypropylene, preferably 2 to 20 oxygen atoms. Emulsifier according to one or more of claims 1 to 5, characterized in that A represents an amino acid group, in particular the group of formula 2 of the formula sheet, of which nitrogen may be substituted. Emulsifier according to one or more of claims 1 to 10, characterized in that the emulsifier is dodecyl sulfoxy undecanoic acid, methyl sulfoxy undecanoic acid or glyceryl monododecyl sulfoxy undecanoate. 12. Stable water-in-oil emulsion, in particular a cosmetic preparation consisting of a stable water-oil emulsion, characterized in that the preparation contains an emulsifier according to claims 1 to 11. 81 02 734. R 1 - R 1 - S - CH - (CH 3) - A 5 R2 (1) nk2 "HC \ (2) 'COOH yalkyl / N \ ** HC ^ alkyl COOH 5 81 02 7 34