WO1996025389A1

WO1996025389A1 - Low-viscosity aqueous concentrates of betaine tensides

Info

Publication number: WO1996025389A1
Application number: PCT/EP1996/000520
Authority: WO
Inventors: Massimo Armada; Ansgar Behler; Joaquim Bigorra Llosas; Hermann Hensen; Rafael Pi Subirana; Werner Seipel; Holger Tesmann; Günter Uphues; Karl-Heinz Schmid
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1995-02-16
Filing date: 1996-02-08
Publication date: 1996-08-22
Also published as: DE19505196C1

Abstract

Low-viscosity aqueous concentrates of betaine tensides of the formula (I) in which R1 is an aliphatic alkyl radical with 8 to 22 carbon atoms, R?2 and R3¿ are mutually independently an alkyl and/or hydroxyalkyl radical with 1 to 4 carbon atoms, n and m are mutually independently numbers in the 1 to 5 range and p is 0 or 1, are obtained by reacting fatty amines or fatty acid aminoamides with halogen carbonic acids or their salts in the prior art manner and adding nitrogen compounds selected from the group consisting of (a) sulphobetains, (b) amphoglycinates, (c) trimethyl glycine and/or (d) dicarbonic acid mono and/or diamides as a liquifying agent.

Description

Low viscosity aqueous concentrate of betaine surfactants

Field of the Invention

The invention relates to low-viscosity aqueous concentrates of betaine surfactants containing selected nitrogen compounds, a process for their preparation and the use of the nitrogen compounds as liquefying agents for aqueous betaine concentrates.

State of the art

Betaines or amphoteric surfactants are extremely skin-friendly and have excellent cleansing properties. They are therefore particularly suitable for the assembly of a large number of surface-active products. In the simplest case, their preparation is based on tertiary amines which are reacted with sodium chloroacetate to form alkyl betaines. The reaction of fatty acid aminoamides or imidazolines with sodium chloroacetate leads to the formation of amphoteric surfactants of the glycinate type; If acrylic acid ester is used as the alkylating agent, aminopropionates are formed. Compounds of the type mentioned are in one Plenty of reviews described, of which only Parf.Co8m.Arom. -, 67 (1986), HAPPI, 70, (Nov. 1986) and Soap Cosm.Chem.Spec. 46, (Apr. 1990).

A particular concern in the production of betaines or amphoteric surfactants is to provide products that are as pure as possible and thus dermatologically and toxicologically safe. For example, traces of free amines, chloroacetic acid and especially dichloroacetic acid in the surfactants are undesirable. Preservatives which are intended to protect betaines or amphoteric surfactants from microbial attack are also often not desired, so that there is a further need for products which are stabilized against bacterial attack even without the addition of auxiliaries. Finally, a third object of the invention is to provide as light-colored products as possible with a high solids content, preferably in the range from 40 to 60% by weight.

A number of printed publications are already known from the prior art which offer partial solutions for the cumulative task.

For example, DE-Al 39 39 264 (Henkel) proposes to reduce the chloroacetic acid content in amphoteric surfactants by subsequently treating the aqueous solutions with ammonia, amino acids or oligopeptides. A process is known from DE-0S 29 26 479 (Th.Goldschmidt) in which the quaternization is carried out in the pH range from 7.5 to 10.5 and the residual content is thus determined free alkylating agent minimized. The teaching of DE-A 20 63 424 (Rewo), which describes the pH regulation for the alkylation of imidazolines, points in the same direction. Furthermore, DE-C 37 26 322 (Th.Goldschmidt) describes a process for the aftertreatment of betaines, in which mineral acids are added to the substances in amounts such that the pH of the solution is 1 to 4.5. However, these processes have no influence on the dichloroacetic acid content. In DE-Al 42 05 880 (Th.Goldschmidt) it is proposed to minimize chlorinated impurities that the betaines are carried out in aqueous solution at a temperature in the range from 115 to 180 ° C. and thus under increased pressure. Finally, DE-Cl 42 07 386 (Th.Goldschmidt) discloses betaine concentrates with solids contents above 40% by weight, which contain 1 to 3% by weight of free fatty acid and 0 to 4% by weight. % Contain glycerol, have a free amidoamine content of less than 1% by weight and have a pH in the range from 5 to 8.

Since none of these prior art methods can satisfactorily solve the cumulative problem, the object of the invention was to provide new aqueous betaines which are flowable and pumpable, even when stored for a long time gel, have a solids content of at least 40% by weight and a minimized content of undesired secondary components, in particular chlorinated substances and free amines. Raa h aibαnα of the invention

The invention relates to low-viscosity aqueous concentrates of betaine surfactants of the formula (I),

R2

IR ¹ [CONH (CH2) _n ] pN ⁺ - (CR ₂ ) _m C∞- (I)

I R3

in which R ^{1 is} an aliphatic alkyl radical with 8 to 22 carbon atoms, R ^ and R ^ independently of one another for an alkyl and / or hydroxyalkyl radical with 1 to 4 carbon atoms, n and m independently of one another for numbers in the range from 1 to 5 and p stands for 0 or 1, obtainable by condensation of fatty amines or fatty acid aminoamides with halogenated carboxylic acid salts, which are characterized in that they contain a nitrogen compound selected from the group formed by

(a) sulfobetaines,

(b) amphoglycinates,

(c) trimethylglycine and / or

(d) Dicarboxylic acid mono- and / or diamides

have as a liquefier.

Surprisingly, it was found that the addition of the nitrogen compounds mentioned reduces the viscosity of the concentration to such an extent that flowable and pumpable products Products with a solids content in the range of 40 to 55 wt .-% can be made available, which show no tendency to gelation even after prolonged storage. The concentrates according to the invention are also light colored and have a minimized content of chlorinated compounds. A free aminoamide content is not necessary to ensure a sufficiently low viscosity. In addition, the concentrates are sufficiently protected against antimicrobial attack without the addition of preservatives.

Betaine

Betaines, more precisely fatty alkyl betaines and fatty acid amido betaines, are both known groups of substances. The invention preferably relates to

*** Fatty alkyl betaines of the formula (I) in which R ^{1 is} an alkyl radical having 8 to 18 carbon atoms, R2 and R3 are each a methyl group, n and m independently of one another are 1, 2 or 3 and p is 0, respectively.

*** Fatty acid amidobetaines of the formula (I) in which R ¹ for an alkyl radical having 7 to 17 carbon atoms, R2 and R3 for each methyl group, n and m independently of one another for 1, 2 or 3 and p for 1 stands. Sulfobetaines

Sulfobetaines are known amphoteric surfactants which can be obtained by quaternizing fatty amines or fatty acid aminoamides, preferably with chloroalkanesulfonates such as, for example, chlorohydroxypropanesulfonic acid; the latter in turn is accessible by reacting epichlorohydrin with sodium bisulfite. An overview of this topic can be found, for example, in Tens.Surf.Det., .28, 235, 337 (1991).

Sulfobetaines which are suitable as liquefying agents of group (a) follow, for example, the formula (II),

R5

I.

R [CONH (CH ₂ ) nl] plN ⁺ - [A] -S0 ₃ - (II)

I R6

in which R ^ represents an aliphatic alkyl radical with 8 to 22, preferably 8 to 18 carbon atoms, R ^ and R *> independently of one another for an alkyl and / or hydroxyalkyl radical having 1 to 4 carbon atoms, nl for numbers in the range from 1 to 5, pl is 0 or 1 and A is an optionally hydroxy-substituted alkylene group having 1 to 5 carbon atoms. Typical examples are quaternization products from coconut dimethylamine or coconut fatty acid amidopropylamine with chlorohydroxy propane sulfonic acid or its sodium salt. Amphoolvcinate

Amphoglycinates which can be used as liquefying agents in group (b) follow the formulas (purple) and (Illb),

CH2CH2OH

1 ⁺

R7 [CONH (CH2) _n 2] p2NH- (CH2) _m 2COO- (purple)

CH2CH2OH (CH2) _m 2COOX

I 1+

R ⁷ [CON (CH ₂ ) n2] p2N ^H - ( ^CH 2) - ιι2COO- (Illb)

in which R ^{7 stands} for an aliphatic alkyl radical having 8 to 22, preferably 8 to 18 carbon atoms, n2 and m2 independently of one another for numbers in the range from 1 to 5, p2 for 0 or 1 and X for an alkali metal. Particularly suitable amphoglycinates are derived from coconut ethanolamine or coconut fatty acid ethyl ethanol amide. In addition to the amphoglycinates, the corresponding imidazoline precursors can also be added to the betaines according to the invention before or during the quaternization. In the course of this embodiment, the amphoglycinates are generated in situ and liquefy the product.

Dicarboxamides

Dicarboxylic acid mono- and / or diamides are suitable as fluidizing agents in group (c). These are preferably reaction products of dicarboxylic acids of the formula (IV) HOOC- [A] -COOH (IV)

in which A represents a linear or branched, aliphatic, cycloaliphatic or aromatic alkylene group having 1 to 36 carbon atoms, with amines of the formula (V)

R ⁸ -NH-R ⁹ (V)

in which R ^ represents a linear or branched, aliphatic, cycloaliphatic, optionally hydroxy-substituted and / or amino-substituted alkyl radical having 1 to 18, preferably 2 to 4 carbon atoms and R ^ represents hydrogen or R ⁸ .

Typical examples are reaction products of succinic acid, maleic acid, adipic acid, phthalic acid and / or dimer fatty acid with ethylamine, ethanolamine, propanolamine, diethanolamine and especially dimethylaminopropylamine. The latter is preferably added before or during quaternization and betainized in situ. Reaction products of dimer fatty acid with dimethylaminopropylamine or adipic acid with diethylenetriamine are particularly preferred.

Betaine concentrates

The betaine concentrates according to the invention have a solids content of at least 40, preferably from 40 to 60 and in particular from 42 to 48% by weight, based on the concentrates. The active substance content, ie the content of betaines, is generally 8 to 12% by weight lower. The nitrogen compounds in the concentrates can be 1 to 40, preferably 2 to 25 and in particular 4 to 8% by weight, based on the concentrates. The proportion of inorganic salts, for example sodium chloride, can make up 5 to 10% by weight.

In view of the storage stability of the products, it has proven advantageous to adjust the concentrates to a pH in the range from 5 to 8.

The content of free fatty acid amino amide and soap is usually less than 1 and in particular less than 0.8% by weight, the content of mono- and dichloroacetic acid in each case less than 5 ppm - based on the concentrates. In a special embodiment of the method according to the invention, the betaine concentrates can contain 0.1 to 0.8% by weight of free C 1 -C 2 -fatty acid and / or 0.1 to 3% by weight of a polyol, preferably glycerin, sorbitol or butyl glucoside can be added.

Condensation reaction

The invention further relates to a process for the preparation of low-viscosity aqueous concentrates of betaine surfactants, in which fatty amines or fatty acid aminoamides are reacted with halocarboxylic acids or their salts in a manner known per se, and nitrogen compounds selected from the group which is formed of

(a) sulfobetaines,

(b) amphoglycinates, (c) trimethylglycine and / or

(d) Dicarboxylic acid mono- and / or diamides

as a liquefier in particular before, also during or after the quaternization.

The condensation reaction is carried out in a manner known per se, the fatty amine or fatty acid amino amide, preferably Ci2 / 18 ~ or C8 / i8 ^co * k ^{os: ett} --- ^un i ^ne or fatty acid amino amides, and the halocarboxylic acids or their salts, preferably sodium chloroacetate, are heated in compliance with a pH in the range from 7 to 8 and, after the free aminoamide content has dropped below 0.5% by weight, the reaction mixture is passed through a pressure vessel Subsequent treatment of 1 to 2 hours at a temperature of 100 to 140 ° C and a pH = 10 to 14 - measured in 10 wt .-% product solution. After completing the post-reaction, it is advisable to adjust the concentrate to a neutral pH again. Products with a particularly low viscosity are obtained when the nitrogen compounds are prepared. or, during the quaternization reaction.

Industrial applicability

The aqueous betaines according to the invention are also highly concentrated, liquid, stable in storage and have a minimized proportion of undesirable secondary constituents. They are suitable for the production of surface-active agents, especially cleaning products as well as hair treatment and care products. agents in which they can be present in amounts of 1 to 30, preferably 2 to 10% by weight, based on the agents.

Another object of the invention therefore relates to the use of the nitrogen compounds mentioned as a liquefier for the preparation of low-viscosity aqueous concentrates of betaine surfactants.

The following examples are intended to explain the subject matter of the invention in more detail without restricting it.

Examples

Example 1:

227.2 g (1.91 mol) of sodium chloroacetate were combined with 190 g of sulfobetaine Dehyton ( ^R ) F512 (Henkel KGaA, betaine content 36% by weight), 6.2 g lauric acid (0.08% by weight) and 40 g (5 wt .-% - each based on the betaine to be formed) glycerol dissolved in about 780 ml of water. 497.5 g (1.63 mol) of a fatty acid aminoamide which had been prepared by amidating a hardened coconut fatty acid with 3-N, N-dimethylaminopropylamine and had a content of 4.6% by weight were then stirred in at 40.degree. had titratable nitrogen. After the mixture had been heated to 90 ° C. and a clear, thin solution had formed, a further 55.3 g (0.18 mol) of the fatty acid amide were added. While maintaining a pH between 7.5 and 9.0, the reaction was continued until after about 2 hours the content of free amine functions was below 0.5 mmol / 100 g, ie <0.15% fatty acid aminoamide (determined by HPLC Analysis) had dropped. 43.2 g of 37% by weight sodium hydroxide solution were then added to the batch, corresponding to a pH of 12.5 in 10% by weight product solution, and the product was stirred in a pressure apparatus at 120 ° C. for 1 hour. After cooling, the product pH was adjusted to 7.0 with 53.8 g of 24% by weight hydrochloric acid. The characteristics of the low-viscosity product are summarized in Table 1. Example 2

Example 1 was repeated in place of the sulfobetaine using 200 g of an amphoglycinate based on coconut fatty acid aminoethylamide (40% by weight AS). The characteristics of the low-viscosity product are summarized in Table 1.

Example 3

Example 1 was repeated in place of the sulfobetaine using 40 g trimethylglycine (100 wt% AS). The characteristics of the low-viscosity product are summarized in Table 1.

Example 4;

Example 1 was repeated instead of the sulfobetaine using 40 g of a monoamide of a technical dimer fatty acid with dimethylaminopropylamine (100% by weight AS). The characteristics of the low-viscosity product are summarized in Table 1.

Comparative Example VI

Example 1 was repeated without adding a nitrogen compound. The characteristics of the product are summarized in Table 1.

All percentages are% by weight. Table 1 Characteristics of the test products

E.g. BET NVb. FFS Ss∑ NaCl H _? Q Vis.

%%%%%% mPa-s

1 33.2 4.0 0.6 2.3, 8 48.8 210

2 32.2 4.5 0.8 2.3 ⁷ , 9 48.9 230

3 36.9 2.3 0.6 2.3 ⁷ , 9 48.6 230

4 36.5 2.7 0.6 2.3 ⁷ , 9 48.6 200

VI 37.1 - 0.6 2.4 ⁷ , 7 48.8 fixed

Legend: BET = betaine

NVb. = Nitrogen compound

FFS = free fatty acid

GLY = glycerin

Vis = Brookfield viscosity; 20 ° C, 50 rpm, spindle 3

Claims

1. Low-viscosity aqueous concentrates of betaine surfactants of the formula (I),

R

I.

Rl [CONH (CH2) _n ] pN ⁺ - (CH2) _1B COO- (I)

I R3

in which R ^{1 represents} an aliphatic alkyl radical with 8 to 22 carbon atoms, R ² and R ³ independently of one another for an alkyl and / or hydroxyalkyl radical having 1 to 4 carbon atoms, n and m independently of one another for numbers in the range from 1 to 5 and p is 0 or 1, obtainable by condensation of fatty amines or fatty acid aminoamides with halocarboxylic acid salts, characterized in that they contain nitrogen compounds selected from the group formed by

(a) sulfobetaines,

(b) amphoglycinates,

(c) trimethylglycine and / or

(d) Dicarboxylic acid mono- and / or diamides

have as a liquefier.

2. Concentrates according to claim 1, characterized in that the betaine surfactants of the formula (I) follow, in which R ¹ for an alkyl radical with 8 to 18 carbon atoms, R2 and R3 each represent a methyl group, n and m independently of one another are 1, 2 or 3 and p is 0.

3. Concentrates according to claim 1, characterized in that the betaine surfactants follow the formula (I) in which R ¹ for an alkyl radical having 7 to 17 carbon atoms, R2 and R3 for each methyl group, n and m independently of one another for 1, 2 or 3 and p represents 1.

4. concentrates according to claims 1 to 3, characterized gekenn¬ characterized in that they contain sulfobetaines of formula (II),

R5

I R4 [CONH (CH2) nl] plN ⁺ - [A] -Sθ3- (II)

IR ^β

R ⁴ for an aliphatic alkyl radical with 8 to 22 carbon atoms, R ^ and R *> independently of one another for an alkyl and / or hydroxyalkyl radical with 1 to 4 carbon atoms, nl for numbers in the range from 1 to 5, pl for 0 or 1 and A represents an optionally hydroxyl-substituted alkylene group having 1 to 5 carbon atoms. 5. concentrates according to claims 1 to 4, characterized gekenn¬ characterized in that they contain amphoglycinates of the formula (purple) or (Illb),

CH2CH2OH

1+

R ⁷ [CONH (CH ₂ ) n2] p2NH- (CH2) _m 2COO- (purple)

CH2CH2OH (CH ₂ ) _m 2COOX

I 1+

R [CON (CH ₂ ) _n 2] p2NH- (CH2) ₁ α2COO- (Illb)

in which R ^{7 stands} for an aliphatic alkyl radical with 8 to 22 carbon atoms, n2 and m2 independently of one another for numbers in the range from 1 to 5, p2 for 0 or 1 and X for an alkali metal.

Concentrates according to Claims 1 to 5, characterized in that they contain reaction products of dicarboxylic acids of the formula (IV)

HOOC- [A] -COOH (IV)

in which A represents a linear or branched, aliphatic, cycloaliphatic or aromatic alkylene group having 1 to 36 carbon atoms, with amines of the formula

(V)

R8_UH-R9 (V) in which R ^{Ö represents} a linear or branched, aliphatic, cycloaliphatic, optionally hydroxysubstituted and / or amino-substituted alkyl radical having 1 to 18 carbon atoms and R ^ is hydrogen or R ⁸ .

7. Concentrates according to claims 1 to 6, characterized in that the content of nitrogen compounds is in the range from 1 to 40% by weight, based on the concentrates.

8. concentrates according to claims 1 to 7, characterized gekenn¬ characterized in that the solids content in the range of 40 to 55 wt .-% - based on the concentrates - is.

9. concentrates according to claims 1 to 8, characterized gekenn¬ characterized in that the pH is in the range of 5 to 8.

10. Concentrates according to claims 1 to 9, characterized gekenn¬ characterized in that the free fatty acid aminoamide content is below 1 wt .-% - based on the concentrates.

11. Concentrates according to claims 1 to 10, characterized in that the soap content is below 1% by weight, based on the concentrates.

12. Concentrates according to claims 1 to 11, characterized ge indicates that the content of mono- or dichloroacetic acid is in each case below 5 ppm - based on the concentrate. 13. A process for the preparation of low-viscosity aqueous concentrates of betaine surfactants according to claim 1, in which fatty amines or fatty acid aminoamides are reacted with halogen carboxylic acids or their salts in a manner known per se, characterized in that nitrogen compounds are selected from the group that is formed by

(a) sulfobetaines,

(b) amphoglycinates,

(c) trimethylglycine and / or

(d) Dicarboxylic acid mono- and / or diamides

as a liquefier before, during or after the quaternization.

14. Use of nitrogen compounds according to claim 1 as a liquefier for the preparation of low-viscosity aqueous concentrates of betaine surfactants.