WO1995014075A1

WO1995014075A1 - Activators for inorganic peroxy compounds

Info

Publication number: WO1995014075A1
Application number: PCT/EP1994/002569
Authority: WO
Inventors: Georg Thiele; Michael Del Grosso
Original assignee: Degussa Aktiengesellschaft
Priority date: 1993-11-15
Filing date: 1994-08-03
Publication date: 1995-05-26
Also published as: DE4338922A1; EP0729503A1

Abstract

The invention concerns the use of N-acylated pyroglutamic acid derivatives of the formula (I ou II), in which R1 is preferably H or Na and R2 is an optionally substituted aliphatic or aromatic hydrocarbon group, preferably a straight-chain alkyl group, as activators for inorganic peroxy compounds in aqueous systems, in particular for low-temperature bleaches. The invention also concerns bleaching, washing, cleaning and disinfecting agents containing such activators. The bleaching power of the compounds identified as activators is at least equivalent to that of tetraacetylethylenediamine (TAED) and exceeds it in some cases.

Description

Activators for inorganic peroxygen compounds

description

The invention is directed to the use of N-acylated pyroglutamic acid derivatives as activators for inorganic peroxygen compounds, such as, in particular, hydrogen peroxide and compounds releasing hydrogen peroxide. The invention is also directed to bleaching, washing, cleaning and disinfecting agents which contain these activators.

Inorganic peroxygen compounds are used as oxidizing agents in bleaching, washing, cleaning and disinfecting agents in order to improve the action of such agents. In particular, hydrogen peroxide and those substances which release hydrogen peroxide in aqueous solution, such as perborates and percarbonates, are used as peroxygen compounds. The effect of the inorganic peroxygen compounds depends not only on the pH value, but also on the temperature. While at

Temperatures above about 80 ° C a good effect is achieved, the use of so-called activators is required when using the inorganic peroxygen compounds mentioned at lower temperatures, in particular at 60 ° C or 40 ° C or below. The activators are predominantly N-acyl or O-acyl compounds. In the aqueous phase, the inorganic peroxygen compounds and the activators form percarboxylic acids, which have a higher oxidation potential than H2O2 and these releasing compounds and therefore also have a good washing, cleaning, bleaching and disinfecting effect in the low temperature range. Numerous classes of substances have been proposed as activators among the N-acyl compounds, including: N, N, N ', N'-tetraacetylethylene diamine in (TAED), N, N, N', N'-tetraacetylglycoluril (TAGU), N, N'-di (alkoxycarbonyl) hydantoins (US 3,928,223), N-mono- and N, N * -Di (-C * - to C ^ alkanoyl-hydantoins (DE-A 14 67 582 and DE-C 19 49 561), N- (Cι ~ to C4) alkyloxycarbonylsucciniird.de (US 3,928,223) and N, N'-diacyl-2,5-diketopiperazines (DE-A 20 38 106) -Acyl compounds essentially only enforce TAED Both in the TAED and in several other N-acyl compounds not all acyl groups are converted into the corresponding percarboxylic acids - from TAED a maximum of 2 moles of peracetic acid are formed.

In view of the growing need for washing, bleaching, cleaning and disinfecting agents for the

There is also an interest in the low-temperature range in further activators based on N-acyl compounds which essentially approach the property profile of the TAED and / or exceed it in one or the other point. If possible, the activators should be accessible from readily available and biodegradable raw materials.

It was found that N-acylated pyroglutamic acid derivatives of the formula (I)

Formula (I)

or general formula (II)

Formula (II)

in which mean:

R ^{1 is} hydrogen, C ¹ -C 4 -alkyl, alkali metal or ammonium, R ^{2 is a} linear or branched saturated or olefinically unsaturated hydrocarbon radical having 1 to 11 C atoms, the longest chain of which can be interrupted by one or more ether bridges and one or two in addition Substituents from the series carboxy, Cι ~ to C _ß -alkoxy, -N ((Ci-C ^) alkyl) 3 ⁺ Cl ^~ ,

Can have phenyl or mono- or disubstituted phenyl,

or phenyl or mono- or disubstituted phenyl, where the substituents C] - to C4 ~ alkyl,

Can be carboxy, -S0 ₃ H, -CN, -N ((^ -03) alkyl) ₃ ⁺ Cl ^_ or -N0 ₂ ,

or a radical of the general formula (IIi;

Formula (III)

where R ^{1 has} the abovementioned meaning and n represents an integer between 2 and 12,

well used as activators for inorganic peroxygen compounds in aqueous systems, especially in bleaching, cleaning, washing and disinfecting liquors.

The preferred compound of the formula (I), which can be in the form of its diastereomers, is cyclo- [pyroglutamyl-pyroglutamyl], which is also known as tetrahydro-dipyrrolo [1,2-a; 1 ', 2'-d] pyrazine-3, 5, 8, 10-tetraon. The compound of formula (I) is known - GB 1 068 814 and J. Amer. Chem. Soc. (1952), Vol. 74, 2859-2864 - but was not previously known as an activator. The compound (I), which can be obtained in a simple manner from racemic or optically active pyroglutamic acid and acetic anhydride, can be regarded both as N-acylated pyrrolidone and as N-acylated diketopiperazine. The optically active starting compound L-pyroglutamic acid is easily accessible from L-glutamic acid obtained by fermentation.

Surprisingly, the N-acylated pyroglutamic acid derivative of the formula (I) proved to be a very effective activator: on average over six test stains on cotton (stained with tea, coffee, red wine, curry, tomato ketchup and clay), the bleaching effectiveness of this activator comes close to that of the TAED and clearly exceeds this for soiling like tomato.

N-acylated racemic or optically active pyroglutamic acid derivatives of the general formulas (II) and (III) which can be used as activators can be obtained in a manner known per se by acylation of DL-, L- or D-pyroglutamic acid with an acyl halide or carboxylic anhydride. Some of the N-acylpyroglutamic acids that can be used as activators according to the invention, such as N-acetylpyroglutamic acid, were known. Chem. Pharm. Bull 29 (9), 2699-2701

(1981) - but not their usability as activators. Compounds of the formula (II) which have not yet been described, such as N-hexanoyl-, N-heptanoyl, N-octanoyl and N-nonanoylpyroglutamic acid, and compounds falling under the formula (III), such as N, N'-dodecane-l, 12- dioyl-di-2-pyrrolidone-5-carboxylic acid, from which in the presence of hydrogen peroxide the diperoxydodecanedioic acid known to be particularly effective in bleaching is formed in situ, can be prepared in an analogous manner to the previously known substances from pyroglutamic acid and the acid halides of Produce monocarboxylic acids (for activators according to formula (II)) or α, ω-dicarboxylic acids (for activators according to formula (III)). Activators according to formula (II) have proven to be surprisingly effective, although only one mole of peracid can be formed per mole: when used at the same weight, the bleaching effect of these activators when washing at 60 ° C. is comparable to that of TAED.

In the activators of the formula (II) or (III), the radical R ^{1 is} H, methyl, ethyl, propyl or butyl or in the form of the cation Li, Na, K or NH4. Substances with R ¹ equal to H or alkali metal, in particular Na, are preferred. In principle, R * - * - can also stand for an equivalent of an alkaline earth metal, but such substances are not preferred because of the undesirable content of

Alkaline earth ions in the washing and bleaching liquors should not be increased. Starting from pyroglutamic acid or pyroglutamates for the production of the activators, substances with the preferred meaning for R ^{1 are} obtained directly. The solubility of compounds of the formula (II) can be increased by converting R * ^* * - H to R ¹ to Na, which is particularly expedient if R ^{2 is} a longer hydrocarbon radical, benzyl or phenyl.

As already stated, the meaning for R ² can be very different. R ^{2 is} particularly advantageously a linear alkyl group having 1 to 11 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, undecyl. Olefinic hydrocarbon residues such as vinyl, allyl, propen-2-yl are possible, but are less preferred. The number and size of the substituents on the hydrocarbon residue is generally kept low to limit the molecular weight of the resulting percarboxylic acid. In addition to phenyl, the aromatic radical R ² is substituted phenyl with preferably one or two carboxy or sulfo groups is preferred.

Compounds of formula type (III) are new. N is particularly advantageously 2, 3, 4 and 10. The dicarboxylic acids required for the preparation of these compounds, namely succinic acid, glutaric acid, adipic acid and dodecanedioic acid, their dichlorides with 2 mol

Pyroglutamic acid to form (III) are readily available. R * - * - is also preferably hydrogen or sodium in the case of the substances of the formula (III).

The use according to the invention relates to the activation of inorganic peroxygen compounds, in particular H2O2, and those compounds which release hydrogen peroxide in the aqueous phase. Of particular note are perborates, especially sodium perborate monohydrate, sodium perborate tetrahydrate, super-oxidized sodium perborate, and sodium percarbonate (2 Na2CO3-3 H2O2). Perphosphates, persilicates and persulfates can also be used. Several inorganic per-compounds can also be present during activation.

When used, inorganic peroxygen compounds and activators are used in a ratio of 1 mol of active oxygen to 0.05 to 1 mol, preferably 1 to 0.1 to 0.5 mol, of activator.

The activators to be used according to the invention can be used for activation in pure form or with auxiliaries, such as granulation aids, stabilizers, pH-regulating substances; Suitable forms of addition are powders, pastes, tablets, granules or coated granules.

Depending on the intended use, the activators and inorganic peroxygen compounds can also be used in the aqueous-organic phase in addition to the purely aqueous phase come. The usual washing, bleaching and cleaning liquors have a purely aqueous environment. An aqueous-organic environment can be useful in disinfection applications and in technical oxidation processes.

The pH of the reaction medium can be between about 4 and 13, but is preferably carried out in the alkaline range, usually at pH 8 to 11, since in this range both the in situ formation of the organic peracid proceeds well and the stability of the Perconnections is satisfactory.

Another object of the invention is directed to bleaching, washing, cleaning and disinfecting agents which contain an inorganic peroxygen compound and an activator from the series of the N-acylated compounds which can be used according to the invention and described above

Pyroglutamic acids of formula (I), (II) or (III) contain.

The agent can contain one or more inorganic peroxygen compounds and one or more activators, including at least one activator according to the invention and, if required, commercially available or other known activators.

Activators and inorganic peroxygen compounds to be used according to the invention can be combined with all the usual constituents of detergents and bleaches in order to obtain detergents and bleaches which are used for textile treatment in low and high temperatures

Medium temperature range, but are also suitable for hot laundry.

The main constituents of such detergents and bleaches are, in addition to the per-compounds and activators mentioned, builders and surfactants. Among the builders are in particular sodium aluminum silicates (zeolites), condensed phosphates, alkali silicates, alkali carbonates, complexing aminocarboxylic acids, polyphosphonic acids, polyvalent hydroxycarboxylic acids and polycarboxylic acids and salts of the acids mentioned. Among the surfactants, non-ionic surfactants such as fatty alcohol and alkylphenol polyethylene glycol ethers and long-chain alkyl glycosides, and anionic surfactants such as alkyl benzene sulfonates and sulfates of fatty alcohols and polyethylene glycol monoethers are particularly noteworthy. Other substances in the detergents and bleaches are electrolytes, pH regulators, stabilizers, foam regulators, graying inhibitors, optical brighteners, enzymes, softeners. The substances and amounts to be used in such agents are known to the person skilled in the art - an overview, together with literature, is provided by HG Hauthal in "Chemistry in Our Time" 26 (1992) No. 6, 293-303).

The detergents and bleaches according to the invention are usually composed as follows:

5 to 30 wt .-%, preferably 10 to 25 wt .-% anionic and / or nonionic

Surfactants, 5 to 60% by weight, preferably 20 to 40% by weight

Builders from the group sodium aluminum silicates, condensed phosphates, alkali silicates,

Alkali carbonates, and mixtures thereof, 0 to 20% by weight, preferably 1 to 8% by weight

Builders from the group of complexing aminocarboxylic acids,

Polyphosphonic acids, polycarboxylic acids or their salts and their mixtures, 2 to 35% by weight, preferably 10 to 25% by weight, of inorganic peroxygen compounds from the group sodium perborates and

Sodium percarbonate, 0.3 to 20% by weight, preferably 1 to 10% by weight, of N-acylated to be used according to the invention

Pyroglutamic acid derivatives as

Activators ad 100% usual additives and water

Pure bleaching agents, as they can be used as additives for bleach-free detergents, are generally composed as follows:

5 to 50% by weight, in particular 15 to 35% by weight, inorganic peroxygen compounds, in particular Na perborate onohydrate or tetrahydrate or / and

Sodium percarbonate,

2 to 50% by weight, in particular 5 to 25% by weight, of N-acylated pyroglutamic acid derivatives to be used as activators,

0 to 5 wt .-% peroxide stabilizers, such as

Water glass and complexing agent,

0 to 40% by weight of pH regulating agents and 100% by weight of other customary auxiliaries.

Cleaning agents according to the invention generally contain surfactants, builders, peroxygen compounds and activators to be used according to the invention; Abrasives also contain abrasive components.

Disinfectants according to the invention are generally based on a combination of inorganic per-compounds and activators to be used according to the invention and auxiliaries from the series of stabilizers, surfactants, pH-regulating substances and, if desired, organic solvents and others microbiocidal substances as the peracids resulting from the activators and per-compounds.

example 1

Cyclo- [pyroglutamyl-pyroglutamyl] (I)

280 g (2.2 mol) of L-pyroglutamic acid and 568 g (5.6 mol) of acetic anhydride were stirred under reflux for 4 h. Excess solvent was removed in a rotary evaporator, the remaining residue was mixed with 300 ml of H2O and stirred vigorously. After filtration and drying, 79 g were obtained as a colorless solid. The - ^ H NMR spectroscopic data are consistent with the structure.

Example 2

N-acetyl-2-pyrrolidone-5-carboxylic acid

77.6 g (0.6 mol) of DL-pyroglutanic acid and 121.6 g (1.2 mol) of triethylamine were placed in 800 ml of acetonitrile and, while stirring at an ice bath temperature, a solution of 67.2 g (0.6 mol) Acetyl chloride in 400 ml of acetonitrile was added dropwise within 15 min. The mixture was then stirred for 1 h at room temperature, the reaction mixture was filtered, the solvent was removed on a rotary evaporator, the residue was taken up in 2 l of H2O and the pH was brought to 6 with KOH solution. The mixture was washed with ethyl acetate and the pH was Value of the aqueous solution set to 2. Subsequent extraction with ethyl acetate and drying of the organic phase (MgSC> 4) gave 20 g as a colorless oil after removal of the solvent and Kugelrohr distillation. The iH NMR spectroscopic data are consistent with the structure. Example 3

N-nonanoyl-2-pyrrolidone-5-carboxylic acid

19.4 g (0.15 mol) of L-pyroglutamic acid were initially charged with 30.4 g (0.3 mol) of triethylamine in 100 ml of acetonitrile and 26.5 g (0.15 mol) of nonanoyl chloride at 20 ° within 20 minutes C. added dropwise. The mixture was then stirred at 50 ° C. for 4 h, the reaction mixture was filtered, the solvent of the filtrate was removed on a rotary evaporator, the residue was taken up in H2O and the weakly acidic solution was neutralized with potassium hydroxide. The aqueous phase was washed with acetic ester, adjusted to pH 2, extracted with ethyl acetate, dried (MgSC> 4) and the solvent was removed on a rotary evaporator. 26.3 g were obtained as a colorless solid. The * - * - H NMR spectroscopic data are consistent with the structure.

Example 4

N-Nonanoyl-2-pyrrolidone-5-carboxylic acid sodium salt The product prepared according to Example 3 was dissolved in 100 ml of ethanol, and the solution was mixed with an amount of ethanolic NaOH (1 molar) equivalent to the carboxylic acid; then the solvent was removed.

Example 5

Peracid formation from activators according to Examples 1 to 4 and their stability:

8 g of a bleach-free zeolite-containing detergent tower powder, 1.5 g of sodium perborate monohydrate (Pbmh) and 0.5 g of activator were added to 1 liter of water at a temperature of 40 ° C. At certain intervals 100 ml samples were taken, these were immediately added to a mixture of 250 g of ice and 15 ml of glacial acetic acid and then titrated with 0.1N sodium thiosulfate solution and starch as an indicator after the addition of potassium iodide. Only the peracids formed in situ were recorded under the specified conditions. The results - content of equivalent peracid as a function of time - follow from Table 1.

Table 1: Peracid formation and stability

Activator according to 1 2 3 4 example

Time (min) peracid - equivalents (measured)

2 1.23 0.17 0.15 0.25

10 0.76 0.54 0.42 0.52

20 0.46 0.59 0.57 0.58

30 0.21 0.53 0.59 0.56

40 0.50 0.59 0.52

50 0.45 0.55 0.46

From the course of the peracid formation and its degradation it can be seen that the activator according to Example 1 is readily soluble under the test conditions and after a short time about 62% of the theoretically possible amount of peracid is available. The activators of Examples 2 to 4 show a higher stability of the formed Peracid. Peracid formation is accelerated by using an activator in the salt form over that in the acid form. Example 6

Bleaching performance of the activators on fabrics (cotton; WFK tomato ketchup) with test soiling in a laboratory washing machine at 40 ° C.

The test is carried out in a launderometer (type Atlas) using a bleach and activator-free commercial detergent from the US market (TIDE-Ultra®).

Wash liquor: 200 ml water hardness: 5 ° d

Temperature: 40 ° C

Rinse: tap water 3 * 30 s

Fleet ratio: 1:20 Ca: Mg = 2.7: 1

Washing time: 15 minutes

The amounts used (g per wash liquor) and test results follow from Table 2. The increase in reflectance was determined at 460 nm (Datacolor Elrepho 2000, xenon lamp, UV blocking filter 420 nm, BaSO4 ^as standard (100%)).

Table 2

Test No. a b c d e f g

Composition:

Detergent 0.27 0.27 0.27 0.27 0.27 0.27 0.27

Pbmh 0.015 0.015 0.015 0.015 0.015 0.015 0.015

Activator from 0.015 0.023 Example 1

Activator from 0.015 0.037 Example 2

Activator from 0.015 0.019 Example 4

Activator TAED 0.016 (for comparison)

Test soil: tomato ketchup

% Remissions 19.0 20.9 16.2 16.6 16.4 17.1 1.7.6 increase

Example 7

The bleaching action of the activator according to Example 4 was tested on six test soils on cotton (bandy black clay; WFK-BW: tea, curry, red wine, coffee, tomato ketchup) in comparison with TAED in the launderometer (Atlas).

Temperature: 60 ° C

Amounts to be added: Detergent *) 3.8 g / 1 pbmh 0.71 g / 1

Activator 0.24 g / 1 liquor ratio: 1:20 wash liquor: 200 ml

Washing time: 15 minutes (laboratory washing machine)

Water hardness: 14 ° d

Rinse: 3 x 30 s

The (arithmetic mean) bleaching effect determined from six test stains, expressed as% increase in reflectance (measurement conditions analogous to Example 6), was

Activator 4: 18.1% TAED: 18.2%

*) Detergent ingredients in g / 1 liquor

Alkylbenzenesulfonates 0.52

Fatty alcohol ethoxylates 0.35

Soap 0.10 Zeolite A 1.52

Polycarboxylates 0.18

Soda 0.76

Na and Mg silicates 0.24

CMC 0.06 excipients (total) 0.07

Claims

1. Use of N-acylated pyroglutamic acid derivatives of the formula (I)

Formula (I)

or general formula (II)

Formula (II)

in which: R ^{1 is} hydrogen, C ¹ -C 4 -alkyl, alkali metal or ammonium, R ^{2 is a} linear or branched saturated or olefinically unsaturated hydrocarbon radical having 1 to 11 C atoms, the longest chain of which may be interrupted by one or more ether bridges, and the additional can have one or two substituents from the series carboxy, C] _- to C3 ~ alkoxy, -N ((C1-C3) alkyl) 3 ⁺ Cl ^~ , phenyl or mono- or disubstituted phenyl, or phenyl or mono- or doubly substituted phenyl, where the substituents can be C 1 -C 4 -alkyl, carboxy, -SO3H, -CN, -N ((Cι ~ C ₃ ) alkyl) 3 ⁺ Cl ^_ or -N0 ₂ , or a radical of the general formula (III)

Formula (III)

where Rl has the abovementioned meaning and n stands for an integer between 2 and 12,

as activators for inorganic

Peroxygen compounds in aqueous systems, especially in bleaching, cleaning, washing and disinfecting liquors.

2. Use according to claim 1, characterized in that the compound of formula (I), ie cyclo- [pyroglutamyl-pyroglutamyl], is used for activation.

3. Use according to claim 1, characterized in that N-acetyl-pyroglutamic acid or N-nonanoyl-pyroglutamic acid or an alkali salt of the acids mentioned is used for activation.

4. Use according to one of claims 1 to 3, characterized in that hydrogen peroxide, a perborate or percarbonate is used as the peroxygen compound.

5. Use according to one of claims 1 to 4, characterized in that 0.05 to 1 mol of activator is used to activate 1 mol of active oxygen. Bleaching, washing, cleaning or disinfecting agents containing an inorganic peroxygen compound and an activator, characterized in that it is an N-acetylated activator

Pyroglutamic acid derivative of the formula (I)

Formula (I)

or general formula (II)

Formula (II)

in which mean:

R ^{1 is} hydrogen,

to C4 ~ alkyl, alkali metal or

Ammonium, R ² linear or branched saturated or olefinically unsaturated hydrocarbon radical with 1 to 11 carbon atoms, the longest chain of which can be interrupted by one or more ether bridges and which additionally contains one or two substituents from the series carboxy, C 1 -C 3 -alkoxy, -N ((C1-C3) alkyl) 3 ⁺ Cl ^" , phenyl or mono- or disubstituted phenyl, or phenyl or mono- or disubstituted phenyl, where the substituents Zy- to C4 ~ alkyl, carboxy, -SO3H , -CN, -N ((C! -C3) alkyl) ₃ ⁺ Cl ^" or -N0 ₂ , or a radical of the general formula (III)

Formula (III)

where R has the abovementioned meaning and n stands for an integer between 2 and 12,

0 contains.

7. Composition according to claim 6, characterized in that it contains cyclo- [pyroglutamyl-pyroglutamyl] as activator.

5 8. Composition according to claim 6, characterized in that it contains N-nonanoyl-pyroglutamic acid or an alkali salt of the acid as activator.

9. Agent according to one of claims 6 to 8, 0 characterized in that it contains a perborate or percarbonate as the inorganic peroxygen compound and 0.05 to 1 mol of activator per mole of active oxygen.

10. N-nonanoyl-pyroglutamic acid and its alkali salts.