WO1991009100A1

WO1991009100A1 - Amine oxides of amphoteric compounds, their preparation and their use

Info

Publication number: WO1991009100A1
Application number: PCT/SE1990/000813
Authority: WO
Inventors: Jadwiga Palicka; Hans Olof Lagnemo
Original assignee: Berol Nobel Ab
Priority date: 1989-12-11
Filing date: 1990-07-12
Publication date: 1991-06-27
Also published as: DE69025728D1; ATE135037T1; EP0433257A1; SE8904177D0; EP0505427A1; DE69025728T2; EP0433257B1; DK0433257T3

Abstract

Amine oxides of amphoteric compounds having general formula (I) wherein R is a hydrocarbon group having 7 to 22 carbon atoms, R1 is hydrogen or alkyl with 1 to 6 carbon atoms, x is 2 or 3, y is 0 or an integer of 1 to 4 and Q is (R2-COOM) where R2 is alkylene with 1 to 6 carbon atoms, M is H, an alkali metal, an alkaline earth metal, an ammonium or a substituted ammonium ion, and B is hydrogen or is defined according to Q, wherein at least one of the amine groups of the compounds is oxidized. The amine oxides can be prepared by reacting the amphoteric compound with a per-compound, especially with hydrogen peroxide. The amine oxides are useful in detergent and shampoo compositions and especially in detergent compositions containing perborates.

Description

Amine oxides of amphoteric compounds, their preparation and their use

The present invention relates to new compounds which are amine oxides of certain amphoteric compounds. The invention also relates to the preparation of such compounds and to the use of the compounds as surface active compounds in detergent and shampoo compositions and further also to the particular use of the compounds as surface active agents and stabilizers in detergent compositions containing perborates.

Amphoteric compounds of the type which can be charac¬ terized by the general formula

R - [N - (CHR₁)_x]_y - N - Q ^{B B} wherein R is a higher hydrocarbon group, Rτ_ is hydrogen or a lower alkyl group, x is 2 or 3, y is 0 to 4, Q is a group -R2COOM wherein R2 is an alkylene group and M is hydrogen or another cation and B is hydrogen or a group Q are per se known. Compounds of this type are disclosed for example in the European patent applications 160507, 162600, 214868 and 314648.

The present invention relates to amine oxides of amphoteric compounds of this type and more particularly to amine oxides of amphoteric compounds having the general formula (I)

R - [N - (CHR^xHy - N - Q (I)

wherein R is a hydrocarbon group having 7 to 22 carbon atoms, R_]_ is hydrogen or alkyl with 1 to 6 carbon atoms, x is 2 or 3, y is 0 or an integer of 1 to 4 and Q is (R2-COOM) where R2 is alkylene with 1 to 6 carbon atoms, M is H, an alkali metal, an alkaline earth metal, an ammonium or a substituted ammonium ion, and B is hydrogen or is defined according to Q.

In the above given formula the hydrocarbon group R can be straight or branched, saturated or unsaturated, and may contain substituents such as hydroxyl groups, ethoxy groups or carbonyl groups. R is preferably an alkyl or alkenyl group, but can also be a cycloalkyl-alkyl group, an aralkyl or aralkenyl group where the alkyl or alkenyl group contains at least 6 carbon atoms. R suitably contains 12 to 22 carbon atoms, preferably 12 to 20 carbon atoms. In par-• ticular it is preferred that R is a hydrocarbon group originating from natural fatty acids and particularly from tallow or coco fatty acid. Rτ_ is hydrogen or a lower alkyl group, suitably with 1 to 6 carbon atoms and preferably hydrogen or a methyl group, x is 2 or 3 and y is suitably 1, 2, 3 or 4 and preferably 1, 2 or 3. The group R₂ is suitably a methylene or ethylene group, preferably "a methylene group. M is hydrogen or an ion from the groups alkali metals, alkaline earth metals, ammonium or sub¬ stituted ammonium such as for example mono-, di- or trihyd- roxyethyϊammonium. M is preferably alkali metal, especially sodium. It is particularly preferred that all groups B in the compounds of the above given general formulae are groups Q.

At least one of the amine groups in the amphoteric compounds is oxidized. Useful compounds can be defined by the general formula (II)

R - [If - (CHR₁)_x)]_y - a - Q (II)

wherein R, R_]_, x, y, Q, R2. M and B have the above given definitions. However, the te^"rm amine oxide is used to include also compounds wherein only some of the amine groups have been oxidized. Preferably at least the end group nitrogen, ie the nitrogen having substituents B and Q is oxidized.

Especially preferred amine oxides are those of compounds according to formula (I) included in formula (III)

R - [N -_.(CH₂)_x]_y - N --Q (HI)

wherein Q is CH₂-COOM or CH₂CH₂-COOM, y is 1 , 2 or 3 and M, R, x and B are as earlier defined. Preferably all groups B are groups Q. In particular amine oxides of compounds according to formula (III) included in formula (IV) are preferred

R - (N - CH₂CH₂CH₂)y - N - (CH₂COONa)₂ (IV) CH₂C00Na wherein y is 1, 2 or 3 and R is as earlier defined. It is especially preferred that R originates from tallow fatty acid.

Especially preferred are amine oxides of mixtures of amphoteric compounds with above given formulae with differ¬ ent values for y, particularly mixtures of compounds wherein y is 1, 2 and 3.

The amine oxides can be prepared by reacting the amphoteric compound or the mixture of these with a per-com- pound such as a peracid or hydrogen peroxide under acid conditions. It is especially preferred to oxidize the amphoteric compounds with hydrogen peroxide and hereby the amount of hydrogen peroxide is suitably within the range of from 2 to 10 moles per mole amphoteric compound, preferably within the range of from 2 to 4 moles. The temperature at the reaction is suitably within the range from ambient temperature to 60°C and preferably from around 20 to about 40°C. It is suitable to use an aqueous solution of the amphoteric compound with a concentration of from about 25 to about 40 per cent by weight and to oxidize this with an aqueous hydrogen peroxide solution having a concentration of from 35 to 75 per cent by weight. The reaction is suitably carried out for a time of between 3 and 24 hours. The obtained product is an aqueous solution of the amine oxides of the amphoteric compounds and can be used as such without isolation of the compounds. Residual hydrogen peroxide in the solutions can be removed by per se known methods.

The amine oxides of the present invention can be used for the same purposes as the amphoteric compounds them¬ selves are used and especially as surface active agents in detergent compositions and shampoo compositions, particu¬ larly in detergent compositions. They can hereby be used in combination with per se known conventional components in such compositions. The invention also relates to detergent compositions containing the amine oxides. The amine oxides are suitably used in amounts of from 0.3 per cent by weight, based- on the total detergent composition, and amounts up to 40 per cent by weight can be used. When the^' amine oxide are used particularly as surface active agents amounts of at least 2 per cent by weight are preferably used and especially amounts within the range of from 2 to 10 per cent by weight. In detergent compositions tensides, preferably anionic and/or nonionic tensides and/or soaps are used. Anionic tensides are suitably present in amounts of from 2 to 20 per cent by weight, whereby the amounts"- depend on the amount of amine oxide and lower amounts of anionic tensides are used with higher amounts of amine oxides. The anionic tensides can for example be linear alkylbenzene sulfonate, secondary alkane sulfonate, al- cohol-ethoxy sulfate or alpha-olefin sulfonate. The non¬ ionic tensides are suitably present in an amount of from 2 to 10 per cent by weight and can for example comprise alkoxylated compounds, such as fatty alcohols, alkyl phenols and alkyl amines. The soaps are suitably present in amounts of from 2 to 4 per cent by weight and can for example comprise sodium- or potassium salts of tallow. The compositions can moreover comprise per se known components such as water glass, enzymes, builders such as phosphates, zeolites, NTA and carbonates, fillers such as sodium sulfate, carbonates and bicarbonates, bleach activators such as TAED (tetraacetylethylene diamine) or TAGU (tetra- acetylglucoluril) , diperoxy acids, foam regulators, per- fumes and colorants. The amine oxides can of course also be used together with the amphoteric compounds from which they are prepared and of course with other amphoteric compounds. The detergent compositions are suitably in powder form and can be prepared in a conventional manner, such as by dry blending, agglomeration or . spray drying a slurry of the components.

According to a particularly preferred embodiment of the present invention the amine oxides are used in deter- gent compositions containing perborates or in liquid structured bleach compositions containing perborates for stabilization. The bleaching at washing with such composi¬ tions is thereby enhanced. Commercial detergent composi- tions usually contain perborates which in alkaline aqueous solutions release hydrogen peroxide. This is decomposed into H⁺ and Hθ2^~, which has a bleaching effect at washing. However, the hydrogen peroxide is to a high degree decom¬ posed into ^' free radicals, which do not have a bleaching effect, in the presence of metal ions which are commonly present in the wash water such as copper,, iron and man¬ ganese. A common method for preventing the decomposition into free radicals is the addition of complexing agents, such as phosphonates and EDTA, to the detergent composi- tion. Despite additions of complexing agents part of the hydrogen peroxide is anyhow decomposed to free radicals at the washing. Several of these complexing agents are also doubtful with regard to environment. The amine oxides of the amphoteric compounds enhance the bleaching effect at washing in the presence of perborates. They can inhibit the decomposition of .hydrogen peroxide to free radicals at washing, which probably depends on their complexing abili- ty.

The bleaching effect of hydrogen peroxide starts at about 50 to 60°C and the full effect is reached at about 90^CC. Washing at this temperature involves both a high energy consumption and an unnecessary wear of the laundry. As a consequence of this, so-called bleach activators have been developed in later years. Bleach activators are compounds which react further with the hydrogen peroxide, or the hydrogen peroxide sources, during the wash-process and form peroxicarboxylic acids which give the bleaching at lower temperatures. One example of such a bleach activator is the commercial product TAED, tetraacetylethylene di- amine, which gives good bleaching effect at 40 to 60°C. The present amine oxides also show good effect in stabiliz¬ ing perborates when a detergent containing perborate and TAED is used for washing. The perborate in the detergent compositions can be present as mono- or tetrahydrate with an alkali metal, such as for example sodium, as positive counter ion. Perborates are usually used in detergent compositions in amounts of from 6 to 30 per cent by weight, based on total composi¬ tion. The amine oxides of the amphoteric compounds are for stabilization suitably used in a weight ratio to the_. perborate of at least 1:20 and up to 1:3. When the amine . oxides are used solely for stabilization purposes in the presence of perborates the amounts in the detergent com¬ positions are suitably from 0.3 to 2 per cent by weight based on the detergent composition. However, as will be understood the upper limit is not critical since excess of the amine oxides will have other positive effects in the compositions.

The invention is further illustrated in the following examples which, however, are not intended to limit the same. Parts and per cent relate to parts by weight and per cent by weight respectively, unless otherwise stated. Example 1

A mixture of amphoteric compounds corresponding to the given formula II where R mainly consisted of C 16 and C18 alkyl groups and the compounds had values for y of 1, 2 and 3, where the predominant part consisted of such com- pounds wherein y was 2, was used as starting material. This product is ^"commercially available under the trade name Ampholak 7Tχ(^R' . The concentration of the amphoteric compounds in aqueous solution was 30 per cent by weight. To this solution hydrogen peroxide was added as a 35% aqueous solution. The hydrogen peroxide was used in varying amounts calculated as moles of H2O2 per mole of amphoteric com¬ pound. The oxidation was carried out both at a temperature of 20°C and 40°C.

The reaction was followed by analyzing the residual amount of hydrogen peroxide, by iodometric titration. The results are given in the following table: Time lh 2h 3h lOh Temperature

4 moles of H_?Q_?

Residual amount 70 . 60 57 45 20°C

Of H₂0₂ % ^" 62 52 50 30 40°C 2 moles of H₇O_?

Residual amount 53 42 35 15 20^βC of H2O2 % Example 2

In order to investigate the stabilizing effect of the amine oxides according to the invention the following tests were carried out with a combination of this and perborate and TAED. Comparisons were made with the amphoteric parent compound instead of its amine oxide, and with a combination of solely perborate and TAED. The amphoteric compound was the same as in Example 1 and the amine oxide was the product prepared from this using 2 moles of H2O2 at 20°C after a reaction time of 20 hours. Combination A) Amine oxides 0.099 g

Perborate monohydrate 0.528 g TAED 0.240 g

Combination B) Amphoteric compounds 0.099 g

Perborate monohydrate 0.528 g TAED 0.240 g Combination C) Perborate monohydrate 0.528 g TAED 0.240 g

Solutions of the above combinations were added to water which had a temperature of 40°C, a hardness of 25°dH with regard to Ca/Mg in the ratio 3:1 was used. Further 3 ppm metal ions, 2.5 ppm Fe³⁺, 0.25 ppm Cu²⁺ and 0.25 ppm Mn²⁺, had been added. The active oxygen content was measured by titration with potassium permanganate and sodium thiosul- fate after 5, 10, 20 and 30 minutes. Combination Residual active oxygen content from H2O2 in % after 5 min 10 min 20 min 30 min A 52 41 34 31

B 46 37 32 30

C 36 ^■ 28 20 17

As can be seen from the table the amine oxides give a slightly better stabilization than, the amphoteric com¬ pounds, i- e a higher active oxygen content remains with combination A than with combination B.

The stabilization of formed peracetic acid was investigated for combinations A and C by titration with thiosulphate. Combination Residual active oxygen content from peracetic acid in % after 5 min 10 min 20 min 30 min

A 42 25 19 8 C 26 15 7 ^"5-

Claims

1. Amine oxides of amphoteric compounds, charac¬ terized in that they are amine oxides of amphoteric com¬ pounds having the general formula (I) R - [N - (CHR_)_χ)]_y - N - Q (I)

wherein R is a hydrocarbon group having 7 to 22 carbon atoms, Rτ_ is hydrogen or alkyl with l to 6 carbon atoms, x is 2 or 3, y is 0 or an integer of 1 to 4 and Q is (R2-COOM) where R₂ is alkylene with 1 to 6 carbon atoms, M is H, an alkali metal, an alkaline earth metal, an ammonium or a substituted ammonium ion, and B is hydrogen or is defined according to Q, whereby at least one of the amine 5 .groups in the compounds is oxidized.

2. Amine oxides according to claim 1, characterized in that they are the amine oxides of compounds having the general formula _Q R " [J - (CH₂)_x3_y - N - Q

wherein Q is CH₂-COOM or CH₂CH₂-COOM, y is 1 , 2 or 3 and M, R, x and B are as defined in claim 1.

3. Amine oxides according to claim 1, characterized 5 in that they are the amine oxides of compounds having the general formula

R - (N - CH₂CH₂CH₂)y - N - (CH₂COONa)₂ (IV) CH₂COONa 0 wherein y is 1, 2 or^'3 and R is as defined in claim 1.

4. Amine oxides according to any of claims 1 to 3, characterized in that R is an alkyl or alkenyl group with 12 to 22 carbon atoms.

5. Amine oxides according to any of claims 1 to 4, 5 characterized in that they are a mixture of amine oxides of amphoteric compounds having y values of 1, 2 and 3.

6. A process for the preparation of amine oxides of amphoteric compounds having the general formula (I)

R - [N - ^■(CHR₁)_x)]y - N - Q (I) 0 wherein R is a 'hydrocarbon group having 7 to 22 carbon atoms, R_ is hydrogen or alkyl with 1 to 6 carbon atoms, x is 2 or 3, y is 0 or an integer of 1 to 4 and Q is (R₂-COOM) where R₂ is alkylene with 1 to 6 carbon atoms, M is H, an alkali metal, an alkaline earth metal, an ammonium or a substituted ammonium ion, and B is hydrogen or is defined according to Q, characterized in that the defined amphoteric compounds are reacted with hydrogen peroxide to oxidize at least one of the amine groups in the compounds.

7. Use of amine oxides of amphoteric compounds having the general formula (I)

R - [w - (CHRxJxJjy - N - Q (I)

wherein R is a hydrocarbon group ha ing 7 to 22 carbon atoms, R_]_ is hydrogen or alkyl with 1 to 6 carbon atoms, x is 2 or 3, y is 0 or an integer of 1 to 4 and Q is (R₂-COOM) where R₂ is alkylene with 1 to 6 carbon atoms, M is H, an alkali metal, an alkaline earth metal, an ammonium or a substituted ammonium ion, and B is hydrogen or is defined according to Q, whereby at least one of the amine groups in the compounds is oxidized, in detergent, liquid bleach and shampoo compositions.

8. Use according to claim 7, whereby the amine oxides are the amine oxides of compounds haying the general formula

R - [N - (CH₂)_x]_y - N - Q

wherein Q is CH2-COOM or CH₂CH2-COOM, y is 1 , 2 or 3 and^' M, R, x and B are as defined in claim 7.

9. Detergent composition comprising perborates, characterized in that it further comprises at least one amine oxide of an amphoteric compounds having the general formula (I) R - [N - (CHRT xHy - N - Q (I)

wherein R is a hydrocarbon group having 7 to 22 carbon atoms, R-. is hydrogen or alkyl with 1 to 6 carbon atoms, x is 2 or 3, y is 0 or an integer of 1 to 4 and Q is

(R2-COOM) where R2 is alkylene with 1 to 6 carbon atoms, M is H, an alkali metal, an alkaline earth metal, an ammonium or a substituted ammonium ion, and B is hydrogen or is defined according to Q, whereby at least one of the amine groups in the compounds is oxidized, in an amount of at least 0.3 per cent - by weight based on the total detergent composition.

10. Detergent composition according to claim 9, characterized in that it comprises from 6 to 30 per cent by weight of perborate and from 0.3 to 2 per cent by weight of the amine oxide.