MXPA98000778A

MXPA98000778A - Polyhydroxyalkylamidobetai

Info

Publication number: MXPA98000778A
Application number: MXPA/A/1998/000778A
Authority: MX
Inventors: Papenfuhs Bernd
Original assignee: Hoechst Ag 65929 Frankfurt De
Priority date: 1995-07-28
Filing date: 1998-01-27
Publication date: 1999-04-06

Abstract

The described betaine compounds correspond to the following formula (See Formula), in which RCO is an aliphatic acyl radical having from 6 to 22 carbon atoms, z is a linear polyhydroxyhydrocarbon radical having at least 3 optionally oxyalkylated hydroxyl groups , m is an integer from 1 to 4, n is an integer from 1 to 4, R1 is C1 to C4 alkyl or C2 to C4 hydroxyalkyl, and R2 is C1 to C4 alkyl or C2 to C4 hydroxyalkyl; of betaine and the aqueous, alcoholic or aqueous-alcoholic solutions or dispersions thereof are prepared by betainization of a corresponding tertiary amine compound with a halogenocarboxylic acid or a halogenocarboxylic acid salt, the novel betaine compounds and their solutions are suitable, in particular , for the preparation of surfactant compositions for hair and body care

Description

POLYHYDROXYALAMYLAMIDOBETAINAS FIELD OF THE INVENTION The invention relates to polyhydroxyalkylamidobetaines, to aqueous, alcoholic or aqueous-alcoholic solutions thereof, to a process for the preparation of these betaines and their solutions, and to the use of the novel betaine compounds and their solutions.

BACKGROUND OF THE INVENTION Betaines are valuable compounds from the group of zwitterionic surfactants. As a result of their good cleansing power and their other advantageous properties, in particular with respect to foam properties and skin tolerance, they are used in the form of liquid formulations to clean the hair and the body above all. In general, the solvents or dispersing agents are water, lower alkanols, such as methanol, ethanol and / or isopropanol, or a mixture thereof. Concentrated to highly concentrated formulations (which comprise as little solvent as possible) and at the same time low viscosity, are convenient with regard to storage and transportation costs, after-treatment and use at the point of application. Commercially available betaine solutions, in general, have a betaine content (active compound content) of less than 30% by weight. Reference is made to concentrated betaine solutions when the content of active compound is approximately 30 to 35% by weight, and to highly concentrated betaine solutions when the content of active compound is even higher. Betaines are generally prepared by betainization of tertiary amine compounds with an omega-halogenocarboxylic acid or an omega-halogenocarboxylic acid salt in an aqueous or aqueous-alcoholic medium. In the prior art, two variants are described to achieve concentrated or highly concentrated solutions or dispersions of betaine. In one variant, organic solubilizing agents are added to the reaction mixture, see US-A-5, 464, 565. The other variant is based on the search for betaine compounds which have a good solubility in water or water / mixtures. alcohol. These betaines can also be used advantageously directly for the preparation of the above-mentioned highly concentrated concentrate formulations. Such a route is described in DE-A-43 07 475. The compounds are betainized aminopolyols which have an improved water solubility compared to other betaine compounds. There may also be mentioned DE-A-42 38 207 and DE-A-42 38 211, which describe quaternized water-soluble fatty acid polyhydroxyalkylamides, ie, quaternary ammonium compounds. We have now found a novel class of betaines, which are distinguished by a good solubility in water and also give low viscosity formulations with a high concentration of betaine. The betaine compounds according to the invention of the group of betainized polyhydroxyalkylamidoamines correspond to the following formula 1: Rl RCO-N- (CH2) a- + - (CH2) n -COO- (1) Z R wherein RCO is an aliphatic acyl radical having from 6 to 22 carbon atoms, Z is a linear polyhydroxyhydrocarbon radical having at least 3 optionally oxyalkylated hydroxyl groups, m is an integer from 1 to 4, n is an integer from 1 to 4, R1 is Ci to C &sub3; > or hydroxyalkyl of C2 to G-,, and R2 is Ci to C alkyl < or hydroxyalkyl of C2 to d.

Preferred compounds of formula 1 according to the invention are those in which RCO is a fatty acyl radical having from 8 to 18 carbon atoms, Z is a radical of a sugar alcohol which is derived from a mono- or reducing disaccharide, in particular glucose, m is number 3, n is number 1 and R1 and R2 (identical or different) are methyl, ethyl or propyl.

The following may also be indicated with respect to RCO and Z: the aliphatic acyl radical RCO, which is preferably the aforementioned fatty acyl radical, may be saturated or unsaturated (preferably mono- to tri-unsaturated). Examples that may be mentioned are caprylic acid acrylic radicals, capric, lauric, palmitic, stearic and oleic, as well as cocoacil, seboacil, preferably hydrogenated seboacil, and the like. The fatty acid radical is often a mixture of two or more acyl groups, for example, C12 and C14 acyl (C12 / 1-, acyl of Cie and Cie (Cid / iß) or acyl of C12 to Cie. mentioned above, the linear polyhydroxyhydrocarbon radical is preferably derived from sugar alcohols derived from the group consisting of reducing sugars or reducing sugar derivatives.The preferred reducing sugars are the monosaccharides, preferably pentoses and hexoses, and the oligosaccharides, preferably disaccharides, and, where appropriate, also trisaccharides Examples of monosaccharides are glucose, galactose, mannose and talose such as hexoses, and arabinose, ribose and xylose as pentoses .. Of the monosaccharides hexoses are preferred Examples of oligosaccharides (polysaccharides) are lactose, maltose, maltotriose and the like Particularly preferred polyhydroxyalkyl radicals originate from reducing hexoses, in particular glucose (sorbitol radical). The betaine compounds of formula 1 according to the invention are prepared by betainization of a tertiary amine compound of formula 2 wherein R, R1, R2, Z and m have the meanings mentioned, with a halogenocarboxylic acid of the formula (3) X- (CH2) n-C00H (3) in which X is a halogen, preferably chlorine or bromine, and n has the meaning cited, or with a salt thereof, preferably an alkali metal salt, in water, a lower alcohol or a mixture of water and a lower alcohol as a solvent (the betaine compound being formed according to formula 1) . The reaction of the tertiary amine compound, for example fatty N, N-dimethylaminopropyl alkylglucamide, and the halogenocarboxylic acid or alkali metal salt of halogenocarboxylic acid, is specifically carried out in such a way that the tertiary amine and the betainising agent are used in a molar ratio of 1: 1 to 1.2, preferably 1: 1 to 1.05. The solvent may be water, a lower alcohol preferably methanol, ethanol and / or isopropanol, or a mixture of water and the alcohols mentioned. The amount of solvent (which is introduced into the reaction mixture as such or in the form of solutions of the starting compounds) is generally chosen so that the betaine solution obtained after the reaction has a betaine content ( active compound content) approximately 30 to 65% by weight, and preferably 30 to 60% by weight, the percentages by weight being based on the solution or dispersion. The reaction temperature in general is 60 to 110 ° C, preferably 70 to 100 ° C. The betainization reaction, which proceeds under atmospheric pressure, is maintained until the desired conversion is achieved. The reaction mixture is maintained at a pH of 7 to 12, preferably 7 to 10, from the beginning to the end of the reaction. Preferably an alkali metal hydroxide is used, which is added to the reaction mixture if it no longer has the pH mentioned, such as, for example, if the sodium salt of monochloroacetic acid is used, to adjust and maintain the aforementioned pH. According to a preferred process, the tertiary amine and the solvent are initially introduced into the reaction vessel. The mixture is heated from 70 to 100 ° C. 1 to 1.2 moles, preferably 1 to 1.05 moles, of halogenocarboxylic acid are introduced per mole of amine compound in the form of an aqueous solution of 60 to 80% concentration and an alkali metal hydroxide in the form of an aqueous solution of 30 to 50% by weight concentration, to adjust the pH of the solution or reaction mixture from 7 to 12, preferably 7 to 10, in the hot amine solution, while maintaining the aforementioned temperature. The halocarboxylic acid solution and the alkali metal hydroxide solution are added alternately and in portions (in each case in about 3 to 4 portions), starting with the halogenocarboxylic acid. After introducing each portion of the halocarboxylic acid solution and alkali metal hydroxide solution into the reaction mixture, the mixture is allowed to react subsequently until the halogenocarboxylic acid has reacted or until a uniform pH has been established. At the end of these additions, the reaction mixture is maintained at 70 to 100 ° C under atmospheric pressure until the required solution of betaine is present. In addition to the solvent and a little alkali metal salt, the resulting betaine solutions comprise the betaine compound according to the invention in a high concentration. It can be isolated by removing the solvent and salt. Generally this is unnecessary because the betaines according to the invention are used mainly in solutions. The solutions according to the invention of betainized polyhydroxyalkylamidoamines essentially comprise A) from 30 to 65% by weight, preferably from 30 to 60% by weight of at least one betaine compound of the formula (1), and B) water , an inferior alcohol or a mixture of water and a lower alcohol, like the rest to make up to 100% by weight; the percentages are by weight based on the solution. The solutions according to the invention are prepared as described above. The amine compounds of the mentioned formula 2 which are required for the preparation of the betaines according to the invention and their solutions are advantageously obtained by a) reaction of a polyhydroxyhydrocarbon compound from which the radical Z is derived in the formula 1 or formula 2, with an amide of formula 4 wherein m, Ri and R2 have the meanings cited, in an aqueous or aqueous-alcoholic medium and in the presence of a hydrogenation catalyst to give the polyhydroxyalkylamine of the formula wherein Z, R1 and R2 have the meanings cited and b) reaction of the product obtained in step a), which essentially comprises the polyhydroxyalkylamine of the formula 5, with an alkyl ester of fatty acid of the formula wherein R has the meaning cited and R3 is an alkyl group of Ci to C3, to give the polyhydroxyalkylamidoamine of the formula 2 cited. Steps a) and b) are described in more detail below: Step a) is a reductive amination of a polyhydroxy compound of the aforementioned type, such as mono- or disaccharide compounds, preferably hexoses, such as glucose, with an amine of the formula 4. The sugar compound and the amine compound are used in a molar ratio of approximately 1: 1 to 1.2. The solvent, which is preferably water or a mixture of water and a lower alcohol, such as methanol, ethanol and / or isopropanol, is employed in an amount of about 30 to 50% by weight, based on the polyhydroxyalkylamine formed. The catalysts that can be used are the usual hydrogenation catalysts such as palladium on active carbon, copper chromite and in particular Raney nickel, in a general amount of 0.01 to 3% by weight, preferably 0.1 to 1% by weight, in base to the sugar compound by aminating. The reductive amination reaction is carried out at a temperature of 40 to 150 ° C, preferably 50 to 120 ° C, and under a hydrogen pressure of 10 to 200 bar, preferably 20 to 100 bar. The indo-sugar compound according to formula 5 is obtained in practically quantitative yields. In step b), the reaction product obtained in step a) (if appropriate, after removing the catalyst by filtration) is subjected to acylation with about 1 mole of a fatty acid ester of formula 6 per mole of amino-sugar compound, in the presence of a basic catalyst, preferably an alkali metal ethylate. This is preferably carried out at a temperature of about 60 to 130 ° C, for example by boiling the reaction mixture under reflux, and leads to the acylated sugar sugar of formula 2. The betaine compounds according to the invention have properties unexpectedly good. They are soluble in water, in lower alcohols or in mixtures thereof at room temperature (20 to 25 ° C) up to high concentrations. Concentrated to highly concentrated solutions are surprisingly low in viscosity at room temperature, ie they are sufficiently fluid, easily pourable, pumpable and the like. Low viscosity also exists if the betaine solutions comprise salts such as sodium chloride or sodium bromide. The aqueous, alcoholic or aqueous-alcoholic solutions of betaine according to the invention, furthermore, are distinguished by high clarity (they are seen as clear water for the human eye) and storage stability. The betaines according to the invention are based on the regeneration of raw materials and are biologically degradable, which is a further advantage of these surfactant compounds with outstanding surface-active properties. Based on this property profile, the betaines and the betaine solutions according to the invention are advantageously used for the preparation of surfactant compositions for hair and body care. The invention will now be illustrated in greater detail by means of examples.

EXAMPLE 1 Initially, 113.6 g (0.25 mol) of N, N-dimethylaminopropyl-Ci2 / i4-gluca ida and 233.1 g of distilled water are introduced into a 5-neck flask equipped with a reflux condenser, stirrer, thermometer and two dropping funnels, and the mixture is heated from 80 to 85 ° C, stirring at the same time. Then, at this temperature, 10.2 g (87 mmol) of an 80% concentration aqueous monochloroacetic acid solution are added over the course of 15 minutes; the mixture is stirred for 30 minutes, then 7.3 g (91 mmol) of a 50% strength aqueous NaOH solution are added over the course of 10 minutes, and the mixture is subsequently stirred for 5 minutes. This procedure is repeated twice more, after which a subsequent 180 minute reaction follows. For an even more complete reaction, the reaction temperature increases from 90 to 95 ° C, 1.1 g (14 mmoles) more of the NaOH solution are added to maintain a pH of 8 to 9 and the stirring is continued for 8 hours . The resulting clear solution comprises essentially 32% by weight of a betaine of the formula 1 - in which RCO is a fatty acyl radical of C12 / 14, m is 3, n is 1, z is a sorbityl radical and Ri and R2 are CH3-, NaCl and water to make 100% by weight. The solution is of low viscosity and therefore is easily pourable.

EXAMPLE 2 Lot size: 113.6 g (0.250 moles) of N, N-dimethylaminopropyl-Ci2 / i4-glucamide 117.5 g of distilled water 30.6 g (0.263 moles) of 80% concentration of monochloroacetic acid aqueous solution 23.0 g (0.285 moles) of aqueous solution of NaOH at 50% concentration. The reaction is carried out analogously to example 1. The resulting clear solution comprises essentially 45% by weight of a betaine of the formula 1-in which RCO is a fatty acyl radical of C 12/14, m is 3, n is 1, z is a sorbityl radical and R1 and R2 are CH3-, NaCl and water to make 100% by weight. Despite its high betaine content, the solution is highly liquid (easily pourable) at room temperature and stable in storage, and does not show haze or precipitation even after a relatively long storage time.

Claims

NOVELTY OF THE INVENTION CLAIMS

1. - A polyhydroxyalkylamidobetaine of the following formula 1 Rl RCO-N- (CH2) a-N + - (CH2) n-COO '(1) Z R2 wherein, RCO is an aliphatic acyl radical having from 6 to 22 carbon atoms, Z is a linear polyhydroxyhydrocarbon radical having at least 3 optionally oxyalkylated hydroxyl groups, m is an integer from 1 to 4, n is a integer from 1 to 4, R1 is C to C alkyl or hydroxy alkyl from C2 to CA, and R2 is Ci to CA alkyl or C2 to C20 hydroxyalkyl.

2.- A betaine in accordance with the claim 1, characterized in that in formula 1, RCO is a fatty acyl radical having from 8 to 18 carbon atoms, Z is a radical of a sugar-alcohol which is derived from a mono- or disaccharide, m is the number 3, n is the number 1 and R1 and R2 are methyl, ethyl or propyl.

3. A betaine according to claim 1, characterized in that in formula 1, RCO is a fatty acyl radical having 8 to 18 carbon atoms, Z is a sorbityl radical, m is the number 3, n is the number 1 and R1 and RJ are methyl, ethyl or propyl.

4. A process for the preparation of a polyhydroxyalkylamidobetaine according to claim 1, comprising betainization of a tertiary amine compound of formula 2 wherein R, R1, R2, Z and m have the meanings mentioned, with a halogenocarboxylic acid of the formula (3), X- (CH2) n -COOH (3), in which X is a halogen, and n has the cited meaning, or with a salt thereof, in water, an inferior alcohol or a mixture of water and a lower alcohol as a solvent.

5. The process according to claim 4, characterized in that 1 to 1.2 moles of halogenocarboxylic acid or halocarboxylic acid salt are used per mole of tertiary amine compound and an amount of solvent such that the betaine solution obtained after the The reaction has a betaine content of 30 to 65% by weight, based on the weight of the solution, and the betainization reaction is carried out at a temperature of 60 to 110 ° C and at a pH of the reaction mixture of 7%. to 12.

The process according to claim 4, characterized in that: 1) a mixture of the solvent and the tertiary amine compound is prepared and this mixture is heated from 70 to 100 ° C; 2) 1 to 1.2 ml of halogenocarboxylic acid in the form of an aqueous solution at 80% concentration by weight, per mole of amine, and an alkali metal hydroxide in the form of a mixture are introduced into the hot mixture in portions and in alternating sequence. of an aqueous solution of 30 to 50% concentration by weight, to maintain a pH of the mixture of 7 to 12, while maintaining the aforementioned temperature of 70 to 100 ° C, starting with the halogenocarboxylic acid and maintaining a time of Subsequent reaction for the reaction after each portion of halocarboxylic acid solution and alkali metal hydroxide solution, and 3) The reaction mixture obtained in step 2 is maintained at a temperature of 70 to 100 ° C until the content of betaine required

7. An aqueous, alcoholic or aqueous-alcoholic solution of a polyhydroxyalkyl idobetaine comprising essentially a) from 30 to 65% by weight of at least one compound of the formula 1 in claim 1, and b) water, a lower alcohol or a mixture of water and a lower alcohol, like the rest to make 100% by weight, the percentages by weight based on the solution.

8. - A solution according to claim 7, characterized in that the component of a) is present in an amount of 30 to 60% by weight.

9. The use of a polyhydroxyalkylamidobetaine according to claim 1, for the preparation of surfactant compositions for hair and body care.

10. The use of an aqueous, alcoholic or aqueous-alcoholic solution according to claim 7, for the preparation of surfactant compositions for hair and skin care.