DE1793123B2 - Polyoxyalkylenecarboxylic acids, processes for their production and cosmetic agents based on them - Google Patents

Description

or

-C ₂ H ₃ (CH ₂ OH) -
-CH ₂ CHOH-CH ₂ residue

and A "one

or

-CH ₂ CHOH-CH ₂ -, -CH ₂ CH ₂ CH ₂ -
-CH ₂ CH (CH ₃ ) residue

15th

20th

25th

mean, where in the compound at least one A 'or A "with the meaning

-CH ₂ CHOH-CH ₂ - or C ₂ H ₃ (CH ₂ OH) -

is contained, m and η each have a mean statistical value from zero to 10, where, if m and π are zero at the same time, X 'must be the sulfoxide group, as well as their alkali, alkaline earth, ammonium or organic ammonium salts.

2. Process for the preparation of the compounds according to claim 1, characterized in that a saturated mercaptocarboxylic acid or a salt or a lower ester of such an acid is used
either in the presence of an alkaline catalyst with a glycidyl ether of the general formula (II)

RX- (AOk- (AO) S-CH ₂ - CH CH ₂ (II)

40

wherein

have interpretations and

A '"is identical to A' or is a C ₂ H ₃ (CH ₂ Cl) or C ₂ H ₃ (CH ₂ Br) radical,
or with an allyl ether of the general formula III:

(III)

wherein

R, X, A and A '", m and π have the meanings given above,

to a compound of the formula I in which X 'is sulfur, then optionally carries out a hydrolysis and / or saponification of the product obtained, and optionally in the presence a carboxylic acid is oxidized to a compound of the formula I in which X 'is a sulfoxide group, or that one alcoholates of polyether alcohols of the general formula IV:

(IV)

wherein

R, X, A, A ", A '", m and π have the meanings given above and M is an alkali metal,
with a salt of a haloalkanecarboxylic acid of the formula V:

Y-CH ₂ -COOM '

R, X, A, m and η are the values given in claim 1

M 'an alkali metal and

Y is a Halpgen atom,

to a compound of the formula I in which X 'is a 0 atom.

3. A process for the preparation of compounds according to claim 1, in which X 'is oxygen, A' is a -C ₂ H ₃ (CH ₂ OH) -GrUpPe and A "is a

-CH ₂ CHOH-CH ₂ -GmPPe
means, characterized in that a glycidyl ether of the general formula VIII:

RX- (AO) nrfC ₂ H., O- (CH ₂ Z)] "- CH ₂ - CH CH ₂

(VIII)

in which R, X, A, m and π have the meanings given in claim 1 and Z is halogen,
with a haloalkanecarboxylic acid of the general formula:

Y-CH, -COOH

(VI)

in which Y is a halogen atom, the product obtained is treated with alkali metal hydroxide, if appropriate with an aqueous solution of a strong mineral acid produces the free acid from its salt and finally the halogen atoms Z in the product thus obtained are replaced by hydroxyl groups.

4. Cosmetic agent, characterized by a content of at least one compound according to Claim 1 in aqueous solution.

The invention is based on the objects characterized in the claims.

The products according to the invention have a mono- or polyetherified and mono- or polyhydroxyated chain in the molecule between the lipophilic part and the carboxylic acid group. A polyoxyalkylene group can be located in front of this muiio- or polyhydroxylated chain. _{If only a single radical —CH 2} CHOH — CH ₂ - is present between the lipophilic part and the carboxylic acid group, it is present either together with a sulfoxide group or at least one alkylene group.

The general properties of the products according to the invention are of the same type as the polyoxyalkylenecarbonic acids described earlier, but they are generally more pronounced They are also easily dispersible or soluble in water. They can even be used with hard water, since the alkaline earth metal salts of the polyoxyalkylenecarbonic acids according to the invention are dispersible or soluble in water provided that the parameter η in the given general formula I has a value greater than or equal to 0.5, namely when X is oxygen or sulfur. Finally, the solubility in an acidic medium and compatibility with cationic surface-active agents of the products according to the invention are particularly good

As for the use of the products of the invention in hard water, those are those given above Properties completely unexpected, as comparable compounds do not have this property. So was found by the comparison test described in more detail below that the in the JA-PS 16 376 (1966) on page 10 by adding calcium chloride even at significantly lower levels Calcium chloride levels precipitate as a representative compound of the invention. Furthermore, was found that the known compounds

C ₁₂ H ₂₅ -S-CH ₂ -COONa C ₁₂ H ₂₅ -S-CH ₂ -COONa or C ₁₂ H ₂₅ -S-CH ₂ -CH ₂ -COONa

after dissolving at a concentration of 0.5% o in demineralized water by adding a solution of calcium chloride to 0.1% cause a turbidity,

while the compound according to the invention of the comparable formula:

Ci ₂ H ₂₅ -OCH ₂ -CHOH-CH ₂ -S-CH ₂ -COONa

in the same experiment after an approximately 100% excess of calcium chloride, based on the for the double conversion theoretically required amount, only a slight cloudiness results. In addition, one obtains in this case even in the presence of a considerable excess of calcium ions (more than 10 times the equivalent amount) a non-cloudy dispersion, while in the case of the aforementioned known compounds the cloudiness of the solution changes very quickly to the point of being completely opaque

The compounds according to the invention have foaming and cleaning properties and can consequently be used in cosmetic products for shampoos. Their application to hair confers them a much softer feel than when using alkyl sulfates in the same field the compounds according to the invention can also be used as color carriers for hair.

However, the compounds according to the invention can also be used in other areas, in particular for degreasing wool, desizing cotton and mercerising.

If the preparation of the compounds according to the invention with glycidyl ethers of the general formula (II), the esters or salts of saturated mercaptocarboxylic acid give the best results. The molar ratio between saturated mercaptocarboxylic acid, its salts or its esters and the one used Glycidyl ether is in the order of magnitude from 1 to 1.5, preferably from 1 to 1.1.

The reaction of glycidyl ethers with the esters or the salts of saturated mercapto carboxylic acids is carried out at a temperature of 20 ° to 15O ⁰ C, preferably at 100 ° to 120 ⁰ C.

In order to obtain good yields within a few hours, alkaline catalysts are used, such as Alcoholates, mercaptides, hydroxides or tertiary amines. Of the tertiary amines that can be used are named for example: triethylamine, tripropylamine, N, N'-tetra! T! ethy! biitan-d! a! T! in- {1,3) and N, N'-tetramethylethylenediamine. With these tertiary amines, starting from the esters of the saturated mercaptocarboxylic acids, thioethers of the general formula are obtained I in the form of the methyl or ethyl esters in virtually quantitative yields. The ones used as a catalyst tertiary amines are in the reaction mass in an amount of 1 to 5%, based on the rest Respondents, before.

If the radical A '"of the general formula II is halogenated and esters of the saturated mercaptocarboxylic acid are used, the thioether obtained is polyhalogenated. To obtain the product of the general formula I, the halogen atoms must be replaced by a hydroxyl group and the thioalkanecarboxylic acid ester obtained must be saponified.
If η is less than 2, the halogen atom can be replaced by a hydroxyl group and, at the same time, the saponification can be carried out in one step by treating with an alkaline reagent such as sodium or potassium hydroxide. These bases are used in stoichiometric amounts with respect to the ester and halide groups and, when working at a temperature of about 120 ° C., after a reaction time of 4 to 5 hours receives a more than 90% conversion. The fluidity of the reaction mass is sufficient so that the addition of a solvent is not indispensable. If the medium contains little water, it is also not necessary to carry out the reaction under pressure.

When π is greater than or equal to 2, the alkali salt of a carboxylic acid is ζ first. B. in a hydroxyl-containing solvent, the halogen atom is replaced by a hydroxyl group. Then, after the inorganic halide formed has been filtered off, the thioalkanecarboxylic acid ester is saponified. The replacement of the halogen by hydroxyl is analogous to the procedure described in French patent specification 14 77 048.

If the preparation of the compounds according to the invention starting from the Aüv'äthern of the general

NEN Formula III takes place, the reaction is preferably carried out using the free saturated mercaptocarboxylic acids. The products of the general formula I are immediately after a few hours by simply heating the mixture to a temperature of 25 ° to 150 ⁰ C, preferably from 100 to 130 ⁰ C, received.

The allyl ethers of the general formula III can either by reacting allyl glycidyl ethers with Compounds of the general formula

RX-fAOfcr-H,

in which m has an average statistical value from 0 to 10 inclusive and R, X and A have the meanings given above, or are obtained by reacting glycidyl ethers of the general formula II with allyl alcohol.

Used as catalysts for these two reactions one alkali metals, alkali hydroxides, alkali alcoholates, alkylimercaptides or tertiary amines. Man can also be acidic catalysts such as boron trifluoride, tin chloride or ammonium pentachloride.

For the preparation of the compounds of the general formula I in which X 'denotes a sulfoxide group one prepares the corresponding compound in which X 'is a thioether group and then oxidizes this compound with hydrogen peroxide in the presence of a carboxylic acid, for example acetic acid. Because of the difficulty To remove this carboxylic acid, it is preferably used in a small amount, for example in an amount of about 1 to 2% by weight, based on the dry extract the reaction, used. The oxidation is carried out at a temperature of 0 ° to 50 ° C, preferably at 30 ° to 35 ° C.

When operating the process according to claim 3, haloalkanecarboxylic acids are used. When treating of the product of the general formula VIII with an alkali metal hydroxide is obtained "in situ" Alkali salt of haloalkanecarboxylic acid and the alcoholate of glycerol ether of the general formula VI

RX - (A (% rfC ₂ H., _{O (CH 2} Z) Ji-CH ₂ CHOH-CH ₂ OH

(Vl)

in which R, X, A, m and η have the meanings given above and Z is halogen.

The alkali salt of the polyether carboxylic acid obtained is treated with an aqueous solution of a strong mineral acid, such as sulfuric acid, converted into the free acid, whereby one at the same time a purification of the product jo achieved.

An excess of haloalkanecarboxylic acid of from 10 to 100% of the stoichiometric acid is preferably used Lot. For the final phase, a procedure is used, that of making connections with thioether bond selected working method is analogous.

The cosmetic agent according to the invention can be used, for example, as a shampoo for hair. It can contain the compound of the general formula I, for example, in an amount of 0.1 to 20%. The pH of the cosmetic agent can be 3 to 10, for example. The agent can be mixed dyes commonly used to dye hair, especially nitro, azo and anthraquinone dyes, contain.

Preparation examples Example 1

C ₁₂ H ₂₅ -O-CH ₂ -CHOH-CH ₂ -S-CH ₂ -COONa

3.5 ml of triethylamine are added to 120 g (1 mol) of ethyl thioglycolate under a nitrogen atmosphere. It is heated to IOC "C and dropwise add 242 g (1 mol) of distilled dodecyl glycidyl ether added. Then you heat for about three hours. The implementation is then practically finished. The excess of ethyl thioglycolate is removed in vacuo.

The ester thus obtained is taken up again in 200 cm ^{3 of} acetic acid, and 1 mol of 39% strength hydrogen peroxide, which is half diluted with acetic acid, is added dropwise. The reaction is exothermic. the

The temperature is maintained at 30 ° to 35 ° C.

After one night at room temperature, there are no more free peroxides present. Then you heat in the Vacuum to remove the acetic acid. The sulfoxide crystallizes on cooling.

The product is taken up in 200 to 250 cm ^{3 of} CH ₃ OH and 100 g of 40% strength NaOH are added. The sodium soap is precipitated with acetone. A white, odorless powder is obtained in this way. Basicity Index (-COO-): 2.6 meq / g.

55

Example 2 Preparation of the compound of formula

RO-EC ₂ H ₃ O (CH ₂ OH) Js-CH ₂ -CHOH-CH ₂ -S-CH ₂ COONa

in which R is an aliphatic radical with 12 to 14 carbon atoms and η has a mean statistical value of 0.5.

To 396 g (2 fvioi) of a mixture of Feiiäikonülcn,

b5 which essentially contain dodecanol and tetradecanol, 1.6 ml of boron fluoride-acetic acid complex and then 277 g dropwise at 75 ° to 80 ° C Epich'iorhydnn added. If the

settlement b

ends, the product is dissolved in 675 g of tert-butyl alcohol! and 300 g of 40% NaOH are added. It is heated at 75 ° C for one hour. By adding the necessary to dissolve the salt formed Amount of water causes precipitation of the epoxy.

300 g (1 mol) of the epoxide obtained by distilling the tert-butyl alcohol are added dropwise at 105 ° to 115 ° C. under nitrogen to 132 g (1.1 mol) of ethyl thioglycolate and 4.5 cm ^{3 of} triethylamine. This temperature is maintained for three hours. The reaction is now complete. The excess ethyl thioglycolate is removed by heating in vacuo.

To carry out the hydrolysis of the remaining chlorinated. Bandaging is carried out in a reaction vessel equipped with a powerful stirrer. 150 g of 40% NaOH (1.5 mol) are added to 420 g of the ester obtained (1 mol). The released alcohol and then some of the water introduced are distilled off up to a temperature of 120 ° to 125 ° C. This temperature is maintained for 4 1/2 hours. The hydrolysis number is now approximately 95%. In this way, a soap is obtained in the form of a hard paste with approximately 80% active material.

In order to produce the corresponding sulfoxide, the soap obtained is taken up with 250 cm ^{3 of} water in order to obtain sufficient flowability for the oxidation. The thioetbar is oxidized with 39% H2O2 in a stoichiometric amount in the presence of acetic acid as a catalyst (1.5 cm ³ per 100 g of active material).

The product obtained is a white cream with approximately 50% active material with a basicity index of 1.2 meq / g.

Example 3

Preparation of the compound of the formula RO- ^ C ₂ H ₃ O (CH ₂ OH) Ji-CH ₂ CHOH-CH ₂ - S - CH ₂ -COONlI

in which R is an oleyl radical and η is an average statistical value of 3.

The procedure given in Example 2 is used to prepare an epoxide from the compound prepared by reacting 4 moles of epichlorohydrin with oleyl alcohol. 240 g of the epoxide thus obtained are added dropwise to 53 g of ethyl thioglycolate and 2 cm ^{3 of} triethylamine at HO ⁰ C under a nitrogen atmosphere. A quantitative conversion is obtained after 5 hours.

Within 30 minutes under nitrogen 180 ° C. 285 g of the chlorinated ester obtained previously were added to 115 g of potassium acetate in 285 g of dipropylene glycol. It is heated for a further four hours. The salt obtained is filtered off at 100 ° C. and it is mixed with dipropylene glycol flushed. Distillation is carried out at up to 190 ° C. under a pressure of 20 mbar.

The residue is taken up with 250 cm ^{3 of} absolute alcohol and 750 mg of CH ₃ ONa. After one night at room temperature, the ethyl acetate and alcohol formed are distilled off. Is distilled in vacuo to 18O ⁰ C and then distillation was finished.

The ester is again taken up in a little alcohol and in a stoichiometric amount 40% sodium hydroxide solution saponified. By distilling off the alcohol, a paste is obtained that is immersed in pure water and is soluble in concentrated aqueous sodium hydroxide solutions. The aqueous solution of this product does not foam much.

That obtained by double reaction of the sodium salt and the magnesium chloride in an alcoholic medium Corresponding magnesium salt is completely soluble in water.

Basicity index: 1.8 meq / g (Na-Salz)
1.2 meq / g (Mg salt).

Example 4

Preparation of the compound of the formula C ₁ JH ₃ -O-CH ₂ -CHOH-CH ₂ -O-CH ₂ - (C ₂ H ₄ IS-CH ₂ -COONa

The reaction takes place by adding thioglycolic acid to allyl (2-hydroxy-3-lauryloxypropyl) ether.

The latter is made by condensing lauryl alcohol with allyl glycidyl ether in the presence of sodium methylate manufactured in the following way:

To 186 g of lauryl alcohol and 1.2 g of sodium methylate, which are heated to 120 ° to 140 ° C are added dropwise 115 g of allyl glycidyl ether were added over the course of 20 minutes The mixture is then heated to 160 ° C. for 4 hours The alljl- (2-hydroxy-3-lauryloxypropyl) ether is separated off by distillation of the crude product thus obtained This distilled at 150 ° to 170 ° C under a pressure of 133 mbar.

60 g (0.2 mole) des; Äthylenderivats and 10 g (0.2 mol) of thioglycolic acid are mixed and heated 8 to 9 hours at 100 ⁰ C, the conversion ratio is about 90%. The acid number shows that the product is partially esterified. It is neutralized and saponified with stoichiometric amounts of 40% strength NaOH in the presence of alcohol. After the alcohol has been distilled off, a water-soluble, slightly colored wax is obtained.

Basicity index: 2.4 meq / g.

Example 5

Preparation of the compound of the formula C ₁₂ Ha-S-CH ₂ -CHOH-CH ₂ -O-CH ₂ - (C ₂ Hi) -S-CH ₂ -COONa

The product is obtained as described in Example 4 by adding thioglycolic acid to the corresponding ethylene derivative, this ethylene derivative is prepared by adding lauryl mercaptan dropwise at 100 ° to 110 ° C. while passing nitrogen through to allyl glycidyl ether in excess (200%) in

the presence of triethylamine (0.5% based on the reaction mass) is added. The addition is complete in 30 minutes. The implementation is almost instant.

The excess allyl glycidyl ether is removed. The desired ethylene derivative is then distilled at 170 ° to 185 ° C. at 0.67 mbar. The stoichiometric amount of thioglycolic acid (7.2 g) is added dropwise ^{at 70 °} C. under nitrogen to 28 g of the compound thus obtained. After the addition, the mixture is ^{heated at 100 °} C. for 5 minutes. The unreacted acid

10

is removed in vacuo. The condensation product is crystallized by cooling. It is made with petroleum ether washed, and in this way a beautiful white powder is obtained.

Basicity index: 2.3 meq / g.

The sodium soap is made by neutralization
50% sodium hydroxide solution in an alcoholic environment
obtained by precipitation with acetone.

with and

Example 6
Preparation of the compound of formula

CpH, ₅ -S-CH, -CHOH-CH, -O-CH -, - (C ₂ H ₄ ) -S-CH, -COONa

Il "Il

ο ο

To prepare the Disulfoxids 12 g of the compound obtained in Example 5 product in the form of the acid with heating in 5 cm ³ of acetic acid and added dropwise to 5.2 cm ³ H2O2 to 11.2 moles per liter added, the temperature is at 30 ° to 40 ⁰ C held. After one night at room temperature, no more peroxides are present. The acetic acid is distilled, it is neutralized with 50% NaOH in alcohol and precipitated with acetone.

The desired product is obtained as a white powder which is readily soluble in water.
Basicity index: 2.25 meq / g.

Example 7
Preparation of the compound of formula

RO-EC ₂ H ₃ O (CH ₂ OH) CH ₂ Jr CHOH-CH ₂ -O-CH ₂ -COONa

in which R is an aliphatic radical with 12 to 14 carbon atoms and π has a mean statistical value of 0.5

400 g of the epoxide prepared according to Example 2 (1.33 mol) are added to 151 g of monochloroacetic acid in the presence of 11 cm ^{3 of} triethylamine in the course of 30 minutes at 120 ^{° C.} The mixture is then heated to 150 ° C. for 3 hours. After cooling to 6O ⁰ C 127.5 g of sodium hydroxide pellets are added. The implementation is exothermic. This temperature is maintained until the sodium hydroxide has completely reacted. 84 g of sodium hydroxide pellets and 101 g of monochloroacetic acid are added alternately in three parts

The mixture is taken up in 1500 cm ^{3 of} water and 400 g of 1.8 η-sulfuric acid are added. The acid is precipitated by heating to 100 ⁰ C. 528 g of the acid thus obtained are taken up in 150 g of alcohol at 96 ^° C. and 40% strength sodium hydroxide solution is added for neutralization and hydrolysis of the chlorine.

The alcohol and part of the water are distilled off until a temperature of 120 ^° C. is reached, which is maintained for 4 hours. A 96% hydrolysis is obtained.

Cooling gives a hard product that is suitable for molding, but somewhat fragile. Basic index: 2.7 meq / g.

Example 8
Preparation of the compound of formula

R -O-fC ₂ H ₃ O (CH ₃₎ MC ₂ H ₃ O (CH ₂ OH)] _n CH ₂ -CHOH- CH ₂ -O-CH ₂ -COONa

where R is a stearyl and m and π respectively ethylamine are heated to 100 ° to 110 ⁰ C within the statistical average values of 5.25 or have. 1 from V / 2 hours 308 g of the corresponding

52 g of monochloroacetic acid (0.55 mol) and 7 ml of tri-55 epoxide of the formula

RO- [C ₂ H ₃ O (CH ₃ ) MC ₂ H ₃ O (CH ₂ CI) Jr-CH ₂ -CH CH ₂

at 75 ° to 8O ⁰ C. The propylene oxide is added over IV2 to Wa hours

The condensation of the epichlorohydrin takes place immediately after the oxypropylenation. The condensation takes place always at 75 ° to 80 ° C and takes 30 minutes. The so polychlorinated polyethers produced have a hydroxyl number from 90.

The chlorinated derivative is given equal weight

in which R, m and η have the above meanings and which was prepared as described below, added

_{6.25 ml of BF 3} -acetic acid complex and then 5.25 mol of propylene oxide are added dropwise to one mole of stearyl alcohol, which has been melted and dehydrated by heating in a boiling water bath under 20 mbar. The implementation is exothermic. It takes place

share tert-butyl alcohol and over the course of 10 minutes 150 g of 40% sodium hydroxide solution at room temperature. The mixture is then heated to 65 ° C. for 30 minutes. One Minimum amount of water is added to dissolve the salt formed, and the aqueous phase is through Separated decanting. The organic phase is dried over sodium sulfate. One filtered and the tert-butyl alcohol is distilled off. In this way, an epoxide with 1.62 meq / g oxirane groups is obtained.

The mixture is heated for 6 hours at 120 ° to 160 ⁰ C. Subsequently, are introduced at a temperature of 60 ⁰ C. 42 g of sodium hydroxide pellets and the mixture is heated for 5 hours at 60 ° to 8O ⁰ C. Alternately, of three portions 76 g of sodium hydroxide in Cookie form and 89 g monochloroacetic acid added

10

15 With the simultaneous addition of 800 ml of water, the mixture is acidified with 41.5 ml of sulfuric acid with a density of 1.8. The mixture is heated in a water bath for 1 hour while stirring. The carboxylic acid is completely precipitated. It is separated off and drained in vacuo.

The corresponding sodium salt is produced by adding 40% sodium hydroxide solution in an alcoholic medium for salt formation and hydrolysis of the remaining chlorine added.

It is refluxed for 10 minutes, the alcohol is distilled off and it is then like in Example 2, heated to 125 ° C. for 4/2 hours.

Basicity index: 1.2 meq / g.

Example 9
Preparation of the compound of formula

RO [C ₂ H ₃ O (CH ₃ ) L ₁ [C ₂ H ₃ O (CH ₂ OH)] ,, - CH ₂ -CHOh-CH ₂ -O-CH ₂ -COO-

Mg ^{2 +} RO [C ₂ H ₃ O (CH ₃ ) MC ₂ H ₃ O (CH ₂ OHQ _n - CH ₂ -CHOh-CH ₂ -O-CH ₂ -COO-

in which R, m and π have the meanings given in Example 8.

This compound is prepared from the above-obtained sodium salt 0.2 moles of salt are dissolved in 50 ml of water and 50 ml of alcohol at 60 ° C, 40 g in 100 ml of water dissolved MgCl ₂ (100% excess) added is I ¹ / 2 hours ^{heated to 7O 0} C, and the mixture obtained is in 700 bis

30 800 ml previously heated to 90 ° C poured water.

The aqueous phase is removed and the magnesium salt, which is in the form of a brown paste, becomes dried. The determination of the magnesium in the product and in the precipitation water shows that the exchange reaction The product contains 1.2% Mg. This product can be used as an emulsifier be used.

example

Preparation of the compound of formula
R-O- [C ₂ H ₃ O (C ₂ H ₅ )] ₃ -CH ₂ -CH-O-CH ₂ -CH-CH ₂ -S-CH ₂ COONa

CH ₂ OH OH

in which R stands for a stearyl radical

First stage

Preparation of the chlorinated polyether of the formula RO- [C ₂ H ₃ O (C ₂ H ₅ I] ₃ - [C ₂ H ₃ O (CH ₂ CD] ₂ -H)

(R = stearyl)

0.22 ml of boron trifluoride-acetic acid complex are added to 0.04 mole (11 ^ g) of stearyl alcohol, which has previously been melted and dehydrated in vacuo, and then 8.64 g (0.12 mole) of butylene oxide are added dropwise under a stream of nitrogen , keeping the temperature during the addition at 75 to 8O ⁰ C.

Then allowed to cool to ambient temperature and determined by measuring the epoxide number that the Butylene oxide is bound

The mixture is heated again to 80 ° and 7.4 g (0.08 mol) of epichlorohydrin are added dropwise, with the temperature is kept at 80.degree. C. It is allowed to cool to ambient temperature and is put on the so obtained product that the epoxide number is zero

The hydroxyl number is 1.45 meq / g.

Second step
Manufacture of the thioether of the formula

RO- [C ₂ H ₃ O (C ₂ H ₅ Q ₃ -CH ₂ -CH-O-CH ₂ -CH-CH ₂ -S-CH ₂ COONa

CH ₂ OH OH

1032 g (0.015 mol) of chlorinated polyether 65 are dissolved. The mixture is heated to 70 to 75 ° and for one hour

which was previously prepared in 10.32 g of tert-butyl alcohol. then add 10 cm ^{3 of} water to the sodium chloride, the

This mixture is heated to 75 ^° C. and has formed to dissolve

dropwise 2 ^ 5 ml of a 10 N sodium hydroxide solution The mixture separates into two phases:

13 14

The solvent phase is isolated and washed. Inorganic salts are filtered off and the di-

once with 10 ml of water. After removing the tert-propylene glycol under a vacuum of 40 to 53.3 mbar

Butyl alcohol is isolated in vacuo, 8.6 g of a yellow one is distilled off.

Oil, in which one has an epoxide number of 1.50 meq / g. 6.82 g of red-brown compound are isolated, which one

notices; calculated: 153 meq / g. 5 subjected to alcoholysis by being at 4O ⁰ C in

To 1.62 g (0.013 mol) of ethyl thioglycolate in 0.1 ml of 17 ml of absolute alcohol in the presence of 0.34 meq

Triethylamine is added dropwise at 105 ° to 110 °, and 8 g of sodium methylate are dissolved.

(0.012 mole) of the epoxide obtained previously. ^{After stirring at 40 °} C. for 14 hours, the mixture is heated

for 3 hours further at 105 to 115 ° and allowed to add 1.23 cm ^{3 of} 10n sodium hydroxide to the mixture,

Then cool the mixture to ambient temperature, ι ο so that the sodium salt forms, which you then through

The hydrolxylation reaction is then carried out in the same way as adding 50 cm ^{3 of} acetone to precipitate

followed by: A light beige-colored precipitate is formed, the

To 3.6 g (0.037 mol) of potassium acetate, dissolved in 8.83 g, it is suctioned off and dried in vacuo. You get

Dipropylene glycol, which is heated to 180 ⁰ C are, to a thioether index of 1.24 meq / g; calculated

the previously obtained chlorinated 15 1.33 meq / g for 20 minutes.

Ester. This compound is in a concentration of 1%

The temperature is kept in water at ambient temperature for 4 hours and 30 minutes

at 180 ^° C. and then lowers it to 100 ^° C. The boiling point soluble.

Application examples

Example 11
The following means are made:

CpH ₁₅ OCH ₁ -CHOH-CH ₁ -S-CH ₁ -COONa 10 g

Il ο

Lauryl dialhanolamide 2 g

Soy lecithin 0.5 g

2-buloxyethanol 0.5 g

Hydroxypropyl methyl cellulose 0.2 g

Make up to 100 g with water

The agent has a pH of 7. It is transparent, has good foaming properties and can be used as a shampoo for hair ^{in an amount of approximately 20 cm 3.}

Example 12
The following means are made:

C _n H ₂₅ OCH ₁ -CHOH-CH ₁ -S-CH ₁ -COONa 5 si

"Il ο

Sodium salt of poly- 5 g with 2 moles of ethylene oxide

ethoxylated laiiryl alcohol sulfuric acid ester
Lauryl diethanolamide 2.5 g

Hydroxypropyl methyl cellulose 0.3 g

Fill up with water to KX) g "

The agent has a pH of 7. It is transparent, has good foam properties and can ii. an amount of about 20 cm ^{3 can be used} as a shampoo for hair.

Example 13
The following means are made:

C ₁₂ H ₂₅ OCH ₂ CHOH-CH ₂ -OCH ₂ - (C ₂ H ₄ ) -S-CH ₂ -COONa 15g

Lauryl diethanolamide 2.5 g

Soy lecithin 0.5 g

2-methyloxyethanol 0.5 g

Hydroxypropyl methyl cellulose 0.25 g

Make up to 100 g with water

The agent has a pH of 7. It is transparent, has good foaming properties and can be used as a shampoo for hair ^{in an amount of approximately 20 cm 3.}

13 14

Example 14
The following means are made:

C ₁₂ H ₂₅ OCH ₂ CHOH-CHj-OCH ₂ - (QH ₄ IS-CH ₂ -COONa 6 g

Sodium salt / des mil 2 moles of ethylene oxide polväthowlierten 5 g

Launl alcohol sulfate

Lauryl diethanolamide 2.5 a

Acetylated Lanolin 0.5 »

With water outlets on KX) g "

The agent has a pH of 7. It is transparent, has good foaming properties and can be used as a shampoo for hair ^{in an amount of approximately 20 cm 3.}

Example 15
The following means are made:

RO- [C ₂ H ₃ O (CH ₂ OHI] ₁₁ -CH ₂ -CHOH-CH ₂ -OCH ₂ -COONa 15 g

wherein R is an alkyl radical having 12 to 14 carbon atoms
and (j has a mean statistical value of 0.5

Acetylated Lanolin I g

Hydroxypropyl meth \ leellulose 0.25 g

Make up to 100 g with water

The agent has a pH of 7. It is transparent, has good foaming properties and can be used as a shampoo for hair ^{in an amount of approximately 20 cm 3.}

Example 16
The following means are made:

RO - [C ₂ H _.; 0 <CH ₂ OH)] "- CH ₂ --CHOH - CH ₂ - OCH ₂ --COONa 8 g

wherein R is an alkyl radical having 12 to 14 carbon atoms
and »has a mean statistical value of 0.5

Sodium salt of polyälhow liereni with 2 moles of ethylene oxide 5 g

Lauryl alcohol sulfuric acid ester

Lauryl diethanolamide 2 g

Hydroxypropyl methyl cellulose 0.2 g

Make up to 100 g with water

The agent has a pH of 7. It is transparent, has good foaming properties and can be used as a shampoo for hair ^{in an amount of approximately 20 cm 3.}

Example 17
The following dye is made:

bis-methyl-EKS-ly-trimethyl-animoniuml-propylaminoanthracliinon] - 1.65 g sulfate

C ₁₂ H ₂₅ -OCH ₂ -CHOH-CH ₂ -S-CH ₂ -COONa 2.00 g

Isooetylphenylpolyäthoxyäthanol in 20% solution 4.60 g

Monoethanolamine up to a pH of 8

With water on spouts to 100 g

1.65 g of bis-methyl-fUS - ^ - trimethyl-ammo- of 100 g / liter are dissolved
nium j-propylaminoanthraquinone sulfate in the minimum amount of water and brings the solution with Mono- CuH ₂₅ OCH ₂ - CHOH - CH _{2 -SCH 2} - COONa ethanolamine to a pH value of 7. To this solution ||

a solution O is added drop by drop with a burette

Precipitation of a dark red colored product can be seen as soon as the first drops are added This precipitation is followed by spotting on filter paper and it is noted that the precipitate is growing depending on the amount of added product of the above formula increases while the solution becomes clearer. At 20 ml of the solution of the surface-active By means of the precipitation is maximal. The solution is now colorless.

A slight excess of the product of the formula given above can cause the precipitate to be dissolved again. The complex formed will

IO

dissolved in the minimum amount of Isooctylphenylpolyäthoxyäthanol in 20% solution. One follows the re-dissolution by spotting on filter paper by dropwise adding the solution with the burette are 23 cm ³ of a 20% solution of Isooctylphenylpolyäthoxyäthanol required the complex completely dissolve. The pH is adjusted to 8 with monoethanolamine, the solution is made up to 100 g and it is determined by testing that no new precipitate is formed. The complex contains approximately 2.2 molecules of the product of the formula

CpH ₂₅ OCr ^ -CHOH-CH ₁ -S-CH ₁ -COONa

on a molecule of the dye what stoichiometry comes very close, since the bis-methyl- [l, 5- (y-trimethylammonium) propylaminoanthraquinone] sulfate is dibasic.

This remedy is applied to auburn hair. The product foams well. It is left for 15 minutes act, washes with a shampoo and rinsed. A strong mahogany color is obtained.

example

Using the procedure given in Example 17, anthraquinone sulfate is used in this way an anion-cation complex is produced, the following means being produced: bis-methyl- [l, 5 - (}> - methyl-ammonium) -propylamino-

bis-methyl ^ l.S-iy-trimethyl-ammoniumj-propylaminoanthraquinone] - 1.65 g sulfate

R-EOC ₂ Hj (CH ₂ OH) Jr-OCH ₂ -CHOH-CH ₂ -S-CH ₂ -COONa

wherein R is an aliphatic radical having 12 to 14 carbon atoms, 2.30 g

means and η has the value 0.5

Isooctylphenylpolyethoxyethanol in 20% solution 4.30 g

Monoethanolamine up to a pH of

Make up to 100 g with water

In this example the anion excess is 8 to 45 applied and results in a very nice mahogany 10%, based on the stoichiometry. hue.

This agent is described as in Example 17

The following means are made:

example

4-N-methylamino-3-nitro-N-0-aminoethylamino-1-ben7ol 0.29 g

R-EOC ₂ Hj (CH ₂ OH) Jr-OCH ₂ -CHOH-CH ₂ -S-CH ₂ COONa

where R is an oleyl radical and 11 has the value I 0.72 g

Isooctylphenylpolyethoxyethanol in 20% solution 1.60 g

Monoethanolamine up to a pH of

Make up to 100 g with water

The complex is obtained as a partially soluble paste, although it does not succeed in being a complete one To obtain precipitate in a colorless solution. However, it will be very accurate which the maximum rainfall supplying amount of anions from the point in time at which a slight excess of anions dissolves the complex again, certainly. The anion excess in relation to the stoichiometry is 10%. The product foams well. b5 This remedy is applied to auburn hair, Left on for 15 minutes, it is rinsed and washed with a shampoo. You get a dark purple hue.

17 18

B is ρ ie 1 20
The following means are made:

^ N-methylamino-S-nitro-1-N-Zi-aminoethylamino-benzene 0.29 g

R-EOC ₂ H ₃ (CH ₂ OH)] S-OCH ₂ -CHOH-CH ₂ -S-CH ₂ -COONa

where R is an oleyl radical and η is 0.53 g

Isooctylphenylpolyethoxyethanol in 20% solution 1.60 g
Monoethanolamine up to a pH of 8

Make up to 100 g with water

In the preparation of the complex one notes 15 if this means as described in Example 18

hardly any precipitate, since the complex is applied very soluble, one also gets a purple one

H is. It is therefore the stoichiometric amount of anion hue, but a little less red than in the previous

§ uses outgoing FaIL

| Example 21

gj Make the following remedy (working as in Example 17):

Ij bis-methyl- [1,5 - (}> - trimethylammonium) propylaminoanthraquinone] - 1.65 g

'■? sulfate

I R-EOC ₂ H ₃ (CH ₂ OH) Jr-OCH ₂ -CHOH-CH ₂ -S-CH ₂ -COONa 2.6 g

p where R is an aliphatic radical having 12 to 14 carbon atoms

, 1 and η has the value 0.5

■ f $ Isooctylphenylpolyäthoxyäthanol in 20% solution 3.20 g

: Monoethanolamine up to a pH of 8

I Make up to 100 g with water

•?: In this case there is an anion excess of 20%, carried. It is left to act for 15 minutes, rinsed and

If based on the stoichiometry, before. The agent foams 35 washes with a shampoo. You get a lot

good strong mahogany shade.
This remedy is applied to auburn hair.

Comparative experiment
The compound according to Example 1 of the present application of the formula:

C ₁₂ H ₂₅ -O-CH ₂ -CHOH-CH ₂ -S-CH ₂ -COONa

compared with the compound described on page 10 of Japanese Patent Publication No. 16,376 (1966) and has the following formula:

C ₁₂ H ₂₅ -O-CH ₂ -CHOH-CH ₂ -S-CH ₂ COONa.

With these two compounds, solutions were obtained from In the solution, which is described in the Japanese patent

0.5 per cent made in distilled water. If you contain the described connection, you have to

takes 100 ml of this solution and adds _{3 m} with the burette, add calcium chloride solution with it

a 0.1 o / o solution of calcium chloride in water, 55, _{eichte Down} ^ _and

until a slight cloudiness occurs and then continues with the _{10 ml until the} ^ _vö , _{ü is opaque} .
Adding continues until the solution is completely opaque

is. The compound according to the invention thus has a

To the solution that the compound according to the invention has better compatibility with calcium ions - d. H. with

contains, one must 60 hard water - on as the connection according to the

Japanese Patent 16,376 (1966). So she has

Add 20 ml of calcium chloride solution until you get the benefit of using it in shampoos or

can observe a slight cloudiness; and foam baths not in the water or even on the hair

100 ml until the solution is completely opaque. or the skin falls out.

Claims (1)

Patent claims: 1. Polyoxyalkylenecaric acids of the general Formula: RX-fAOfe-fAOfe-A "—X— CH ₂ -COOH (I) in which R is an alkyl or alkenyl radical each having 8 to 22 carbon atoms, X and X ', the can be the same or different, oxygen, sulfur or the sulfoxide group, A is an ethylene, Propylene or butylene radical, A 'one