DE4033209A1 - SURFACE-ACTIVE ETHERCARBONIC ACID DERIVATIVES - Google Patents

Abstract

Surface-active ether carboxylic acid derivatives of the formula (I) R<1>O-(CmH2mO)x-(CnH2nO)y-CH2-CONR<2>-[A]-COOM, which can be produced by the reaction of an amino acid or a water-soluble oligo or polypeptide or their salts of the formula HNR<2>-(A)-COOM with an ether carboxylic acid chloride of the formula R<1>O(CmH2mO)x-(CnH2nO)y-CH2-COCl in which: R<1> is an alkyl or alkenyl group with 6 to 22 C atoms or a p-alkylphenyl group with 6 to 15 C atoms in the alkyl group and R<2> is hydrogen, an alkyl group with 1 to 4 C atoms, a hydroxylalkyl group with 2 to 4 C atoms or together with the nitrogen atom and a C atom of the group (A) forms a pyrrolidine or hydroxy-pyrrolidine ring; m and n are mutually independently 2 or 3; x and y are mutually independently 0 or numbers from 1 to 30; and (A) is the radical of an amino acid, an oligo or polypeptide; and M is hydrogen or a salt-forming cation; exhibit better washing and foaming properties, especially in hard water as against the corresponding fatty acid derivatives. The preferred oligo or polypeptides are protein hydrolysates with an average molecular weight of 200 to 20,000.

Description

The invention relates to surface-active condensation products Acylation of amino acids or water-soluble oligo- or polypeptides are available with ether carboxylic acid chlorides.

It is known that the skin compatibility of surfactants and surfactants Preparations by adding water-soluble proteins or Protein breakdown products can be significantly improved. You already have one Amino acids and protein breakdown products built into surfactants, e.g. B. by Acylation of amino acids or protein hydrolyzates with fatty acid chlorides or by condensation of fatty acid methyl esters with protein hydrolyzates. Acylated amino acids are e.g. B. under the trade name Medialan® known, acylated oligopeptides are under the trade name Lamepon® and Maypon®.

The known fatty acid-protein hydrolyzate condensation products have but technical disadvantages, e.g. B. an unsatisfactory Washability and foaming power, high sensitivity of the foam to Water hardness and against grease in the wash liquor. Now it became one new group of surface-active amino acid, oligo or polypeptide Derivatives found which are derived from ether carboxylic acids and which in Improved washing and washing compared to the corresponding fatty acid derivatives Have foaming properties, especially in hard water.

The invention relates to surface-active ether carboxylic acid derivatives of formula I.

R¹O- (C _m H₂ _m O) _x - (C _n H₂ _n O) _y -CH₂-CONR²- [A] -COOM (I)

in which R¹ is an alkyl or alkenyl group with 6-22 carbon atoms or one p-alkylphenyl group with 6-15 C atoms in the alkyl group and R² is hydrogen, an alkyl group with 1-4 C atoms, a hydroxylalkyl group with 2- 4 carbon atoms or together with the nitrogen atom and a carbon atom of Group [A] forms a pyrrolidine or hydroxypyrrolidine ring, m and n independently 2 or 3, x and y independently 0 or Numbers from 1-30 are and [A] the residue of an amino acid, an oligo or polypeptide and M is hydrogen or a salt-forming cation.

The preparation of the ether carboxylic acid derivatives of the formula according to the invention I is preferably carried out by using an aqueous solution of an amino acid or a water-soluble oligo- or polypeptide or their salts Formula II

HNR²- [A] -COOM (II)

with an ether carboxylic acid chloride of the formula III

R¹O (C _m H₂ _m O) _x - (C _n H₂ _n O) _y -CH₂-COCl (III)

in the presence of a base, preferably from the group of alkali or alkaline earth metal hydroxides brings to implementation. The production can, however, if necessary also be done in such a way that an amino acid or a water-soluble Oligo- or polypeptide of formula II with an ether carboxylic acid methyl ester of formula IV

R¹O (C _m H₂ _m O) _x - (C _n H₂ _n O) _y -CH₂-COCH₃ (IV)

condensed.

Both amino acids known as natural protein building blocks can be used as amino acids α-amino acids, such as. B. glycine, alanine, sarcosine, valine, leucine, Isoleucine, serine, threonine, cysteine, methionine, lanthionine, phenylalanine, basic amino acids such as B. ornithine, arginine, lysine, acidic amino acids such as B. aspartic acid, glutamic acid can be used. But it can  β-amino acids and other synthetic amino acids are also used, whose amino group is still further from the carboxyl group, e.g. B. β-alanine (β-aminopropionic acid), β-aminobutyric acid or ε-aminocaproic acid. Other synthetic amino acids with up to 8 are also suitable C atoms, such as B. N-2-hydroxyethylglycine or N-2-hydroxypropylalanine.

In general, protein fragments of 2-9 amino acids, understood as polyseptides with 10-100 amino acids. To Preparation of the ether carboxylic acid derivatives according to the invention are suitable preferably water-soluble oligo- and polypeptides. Such can be passed through The hydrolysis of protein substances on an industrial scale is and still is available as commercial products.

Preferred surface-active ether carboxylic acid derivatives are those of the Formula I, wherein [A] is the remainder of a protein hydrolyzate having an intermediate Molecular weight is 200-20,000. Suitable protein hydrolyzates are those that are derived from animal, vegetable and microbial protein raw materials with the lowest possible amount of by-products such as fat and Let carbohydrates win. Such suitable proteins are e.g. B. Collagen from skin or connective tissue, gelatin, casein, albumin from blood, Milk or eggs, keratin made of hair, wool, horn, claws or feathers, Proteins from leather waste, vegetable proteins from soybeans, wheat gluten, Almonds and unicellular proteins. The hydrolysis of such proteins can be carried out according to various methods known per se, e.g. B. by acidic, alkaline or enzymatic cleavage in water dispersed proteins. Suitable commercial products are e.g. B.

• - Nutrilan®I, a medium molecular weight collagen hydrolyzate of 1412 and a solids content of 50- 52% by weight in water.
• - Keratin W®, a medium molecular weight keratin hydrolyzate of 995 and a solids content of 35 % By weight in water.  
• - Gluadin AGP®, a medium protein wheat hydrolyzate Molecular weight of 1827 (95% powder).

The basis of the suitable ether carboxylic acid chlorides of the formula III Ether carboxylic acids

R¹O- (C _m H₂ _m O) _x - (C _n H₂ _n O) _y -CH₂-COOH

are substances known from the literature that are also commercially available. they but can also be easily manufactured by implementing linear or branched, saturated or unsaturated primary alcohols with 6-22 C atoms or of alkylphenols with 6-15 C atoms in the alkyl group or their ethylene oxide and / or propylene oxide adducts with the sodium salt chloroacetic acid. Commercial products of this type are under the trademark Sandopan® and Akypo® offered. Leave the ether carboxylic acids by known methods, e.g. B. by reaction with acid chlorides of phosphorus or sulfur, e.g. B. with PCl₃, PCl₅, POCl₃, SO₂Cl or Convert SO₂Cl₂ into the ether carboxylic acid chlorides of formula III.

Those ether carboxylic acid chlorides of the formula III are preferably used in which R¹ is a linear alkyl or alkenyl group with 10-18 C atoms, m = 2, x = 1-30 and y = 0, i.e. H. from investment products of 1- 30 moles of ethylene oxide on fatty alcohols with 10-18 carbon atoms after the reaction available with sodium chloroacetate and conversion to acid chloride Ether carboxylic acid chlorides.

The implementation of the amino acids, oligo- or polypeptides of formula II with The ether carboxylic acid chlorides of the formula III are preferably carried out in aqueous Solution in the presence of a base. The amino acids are in these solutions, Oligo or polypeptides in the form of the salts of these bases. As a base preferably sodium hydroxide used. However, z. B. Potassium hydroxide or calcium hydroxide. Basically all bases are suitable the salts which are water-soluble with the amino acids, oligo- or polypeptides form. In the case of protein hydrolysates obtained by alkaline protein hydrolysis the base used for protein hydrolysis is preferred used. The base should be in an amount of at least 2 moles per mole  Amino acid, oligo- or polypeptide can be used in order to To bind the condensation to hydrochloric acid that has split off. It can be beneficial be, the base gradually according to the progress of the reaction in the to form the hydrochloric acid split off and to maintain a Add pH of 7-8 required amount. When using of protein hydrolyzates, the aqueous solutions of these are preferred Products with a solids content in the range of 5-50 wt .-% used.

The ether carboxylic acid chloride is preferably obtained in an equimolar amount used on the free amino groups of the amino acid, oligo- or polypeptides. The content of α-amino groups in a protein hydrolyzate can be e.g. B. by potentiometric titration (in mVal / g) based on the solids content determine in a pH range of 6-8.5. The contained in the protein basic amino acid histidine is also included. When implementing with the ether carboxylic acid chloride the omega-amino groups of Histidine, ornithine, lysine and hydroxylysine, their share from amino acid analysis of the protein is known, mitacyliert.

As a side reaction, hydrolysis of the ether carboxylic acid chloride takes place to a lesser extent instead of forming the salt of ether carboxylic acid and, when sodium hydroxide was used as the base, sodium chloride. Appropriate amounts of non-acylated amino acids, oligo- or polypeptides remain in the end product. However, these by-products do not interfere the application properties of the ether carboxylic acid Derivatives.

The ether carboxylic acid derivatives according to the invention are new, good foaming and particularly skin and mucous membrane compatible surfactants. Preferred Such ether carboxylic acid derivatives have application properties in particular of formula I, wherein [A] is the remainder of a protein hydrolyzate an average molecular weight of 200-20,000. Furthermore are those products of formula I are particularly preferred in which R 1 is a linear one Alkyl or alkenyl group with 10-18 C atoms, m = 2, x = 1-30 and y = 0. These products are stable even in hard water Foaming power and good fat dispersibility.  

The ether carboxylic acid derivatives according to the invention are suitable for use as surfactants in detergents and cleaning agents, especially in body cleaning agents for the skin and hair. But also in manual dishwashing detergents or in detergents and cleaning agents used in the application come into contact with the skin, the use of the new ether carboxylic acid Derivatives are an advantage. The products are with all known anionic, non-ionic, amphoteric and zwitterionic surfactants without any problems bearable. They also have the advantage of being in mixtures with strongly foaming anionic surfactants, especially with alkyl sulfates and alkyl ether sulfates, whose foaming power when 5- 50% by weight of the ether carboxylic acid derivative, based on the surfactant mixture, do not affect negatively. Conversely, the foaming power of the Ether carboxylic acid derivatives, by adding 1-50 wt .-% of such foam-rich anionic surfactant, based on the surfactant mixture, considerably increase. They are therefore excellent as a surfactant partner for Improvement of the dermatological and hair cosmetic properties cosmetic surfactant preparations, e.g. B. of shampoos, foam bath preparations, Shower baths, washing lotions and liquid soaps.

The following examples are intended to explain the subject of the invention in more detail, without restricting him to this.  

Examples 1. Preparation of the ether carboxylic acid condensation products 1.1 Preparation of the ether carboxylic acid chloride

From the adduct of x moles of ethylene oxide and 1 mole of n-dodecanol (prepared by ethoxylation at 175 ° C in the presence of sodium methylate as a catalyst) by reaction with sodium chloroacetate Dodecyloxy-polyethoxy-acetic acid is produced by known processes. This was converted into the corresponding reaction with thionyl chloride Dodecyloxy-polyethoxy-acetyl chloride transferred.

1.2 Condensation product A

To 46.8 g of an aqueous, 35.4 wt .-% collagen hydrolyzate (medium Molar mass (MW) 658, acid hydrolyzed) containing solution (25 mmol) 5.2 g of aqueous (25% by weight) sodium hydroxide solution and 20 ml of water were added. After heating to 70 ° C were stirred within 25 minutes 22.3 g (50 mmol) of dodecyloxy tetrakis (ethoxy) acetyl chloride dripped. The pH of the reaction solution dropped continuously and was finally at pH = 7 by simultaneous addition of 25 % by weight, aqueous sodium hydroxide solution kept at pH = 7. Subsequently the reaction mixture was stirred at 70 ° C. for a further 30 minutes. It a yellowish, clear, highly foaming solution was obtained. These had the following salary:

Condensation product: 35.5% by weight
Sodium chloride: 3.1% by weight.

Condensation products B-H

The same procedure was followed using hydrolyzates the molecular weight (MW) given in Table I from the given Proteins and ether carboxylic acid chlorides of the specified alkyl chain R¹ and the specified degree of oxyalkylation (x, m, y, n) aqueous  Solutions of ether carboxylic acid condensates according to the invention in Obtain the composition indicated in Table II.

2. Testing the foam properties

The foaming power was tested according to DIN 53902-T01. The test procedure is that by beating 200 ml for 30 seconds Solution of the surfactant in a 1 liter standing cylinder with one on a stick attached perforated plate with 1 blow per second foam is generated. The foam volume of the sample solution is 30 seconds after the end of the Measured.

In Table III the foam volume is at 40 ° C for a product concentration of 1.0 g / l, with a water hardness of 0 ° d, 10 ° d and 20 ° d specified.

Table I

Table II

Table III

Claims (6)

1. Surface active ether carboxylic acid derivatives of the formula I R¹O- (C _m H₂ _m O) _x - (C _n H₂ _n O) _y -CH₂-CONR²- [A] -COOM (I) in which R¹ has an alkyl or alkenyl group 6-22 carbon atoms or a p-alkylphenyl group with 6-15 carbon atoms in the alkyl group and R² is hydrogen, an alkyl group with 1-4 carbon atoms, a hydroxylalkyl group with 2-4 carbon atoms or together with the nitrogen atom and a C atom of group [A] forms a pyrrolidine or hydroxypyrrolidine ring, m and n are independently 2 or 3, x and y are independently 0 or numbers from 1-30 and [A] is the residue of an amino acid, one Oligo- or polypeptide and M is hydrogen or a salt-forming cation. 2. Surface-active ether carboxylic acid derivatives according to claim 1, characterized characterized in that [A] the rest of a protein hydrolyzate with a average molecular weight of 200-20,000. 3. Surface-active ether carboxylic acid derivatives according to claim 1 or 2, characterized in that R¹ is a linear alkyl or alkenyl group with 10-18 C atoms, m = 2, x = 1-30 and y = 0. 4. Process for the preparation of surface-active ether carboxylic acid derivatives of the formula I R¹O- (C _m H₂ _m O) _x - (C _n H₂ _n O) _y -CH₂-CONR²- [A] -COOM (I) in which R¹ is an alkyl - Or alkenyl group with 6-22 carbon atoms or a p-alkylphenyl group with 6-15 carbon atoms in the alkyl group and R² is hydrogen, an alkyl group with 1-4 carbon atoms, a hydroxylalkyl group with 2-4 carbon atoms or together forms a pyrrolidine or hydroxypyrrolidine ring with the nitrogen atom and a carbon atom from group [A], m and n are independently 2 or 3, x and y are independently 0 or numbers from 1-30 and [A] the rest an amino acid, an oligo- or polypeptide and M is hydrogen or a salt-forming cation, characterized in that an aqueous solution of an amino acid or a water-soluble oligo- or polypeptide or its salts of the formula (II) HNR²- [A] -COOM ( II) with an ether carboxylic acid chloride of the formula IIIR¹O- (C _m H₂ _m O) _x - (C _n H₂ _n O) _y - CH₂-COCl (III) in the presence of a base to implement. 5. The method according to claim 4, characterized in that as an oligo or polypeptide is an average molecular weight protein hydrolyzate from 200-20,000. 6. Use of the surface-active ether carboxylic acid derivatives according to claim 1 or 2 as skin-friendly surfactants in detergents and cleaning agents, especially in liquid personal cleansers.