GB1563635A

GB1563635A - Method of activating percompounds

Info

Publication number: GB1563635A
Application number: GB35517/77A
Authority: GB
Original assignee: Produits Chimiques Ugine Kuhlmann; Ugine Kuhlmann SA
Current assignee: Produits Chimiques Ugine Kuhlmann; Ugine Kuhlmann SA
Priority date: 1976-09-01
Filing date: 1977-08-24
Publication date: 1980-03-26
Also published as: DE2738976C3; DE2738976B2; JPS5330485A; NO146983C; LU78047A1; DE2738976A1; ES462018A1; CH626398A5; SE434960B; DK383677A; NL7709591A; FR2363629A1; IE45372L; NO773006L; BE858048A; JPS6031879B2; CA1088954A; FR2363629B1; BR7705823A; DK145829B

Abstract

The percompounds activator used in the composition corresponds to the formula: <IMAGE> in which the symbols R1 to R6 represent hydrogen or certain alkyl, hydrocarbon or aromatic radicals according to Claim 1, it being possible for R5 and R6 additionally to represent certain acyl groups. It has the effect of causing a more rapid oxidation or bleaching at a given temperature, or an equivalent bleaching at a lower temperature.

Description

(54) METHOD OF ACTIVATING PERCOMPOUNDS (71) We, PRODUITS CHIMIQUES UGINE KUHLMANN, a French Body Corporate of 25 boulevard de l'Amiral Bruix, 75116 Paris, France, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- The present invention relates to the use of a-acyloxy-N,N'-polyacylmalonamides as activators for inorganic and organic percompounds and more particularly as activators for hydrogen peroxide, for its addition products with organic substances such as urea and dicyclohexylamine, and also of its inorganic persalts such as perborates, percarbonates and perphosphates.

The action of aqueous solutions of percompounds as oxidising and bleaching agents becomes effective only at temperatures above 70"C and usually at temperatures from 80 to 1000C.

The prior art describes numerous products which can act as activators of percompounds, i.e. which result in a more rapid oxidising or bleaching action than that which is cutomarily observed, or which result in the said action taking place under much milder temperature conditions than those which it is necessary to use in their absence. An such compounds are generally characterised by the fact that they have one or more per-hydrolysable functions.

In the bleaching field a certain number of activator compounds have begun to be developed commercially. The literature on this subject mentions especially poly-N-acetylated heterocycles such as hydantoins, glycolurils, benzimidazoles and diketopiperazines. However, this particular line of products has not been pursued because these substances display the major disadvantages of being unstable to ambient humidity and of hydrolysing spontaneously, thus rapidly losing their activating capacity. Moreover, these products require special precautions to be taken during storage and handling, or when added to other ingredients such as those used for example in the customary composition of a washing powder.Various solutions such as coating or wrapping, separate packing, or addition of desiccating products have been proposed to overcome this disadvantage but these have not been satisfactory either because putting them into practice gives rise to technical problems, or because they lead to considerable increase in the cost price of the active substance.

The present invention provides a method of activating percompounds, and compositions containing a percompound and an activator therefor, such compositions being stable for long periods in the solid state under normal conditions of storage and packing.

Accordingly, the present invention provides a method of activating a percompound, which method comprises subjecting the percompound to the influence of, as activator, an a-acyloxy-N,N'-polyacylmalonamide of the general

wherein each of Rr, R2, R3, R4, R5 and R,, which may be identical or different, is chosen from a hydrogen atom, substituted or unsubstituted straight chain alkyl radicals having from 1 to 11 carbon atoms, substituted or unsubstituted branched chain alkyl and cycloalkyl radicals having from 3 to 12 carbon atoms, substituted or unsubstituted hydrocarbon radicals having from 6 to 12 carbon atoms and including at least one aromatic nucleus; or wherein R1, R2, R3, R4 are as defined above and R5 and/or R, correspond to an acyl group COR7, wherein R7 is a hydrogen atom or a substituted or unsubstituted straight chain or branched alkyl radical having from 1 to 12 carbon atoms or a substituted or unsubstituted hydrocarbon radical having from 6 to 12 carbon atoms and including at least one aromatic nucleus. Examples of typical atoms or groups which can be substituents of the said alkyl, cycloalkyl or hydrocarbon radicals are chloro, bromo, fluoro and iodo atoms and hydroxy, nitro, alkoxy, amino, ester, amide or hydrocarbyloxy groups.

Purely by way of illustration, examples of the a-acyloxy-N,N'-poly acylmalonamides constituting activators for percompounds according to the present invention are a-acetoxy, a-methyl-N,N'-diacetyl malonamide; apropionoxy, a-ethyl-N,N'-dipropionylmalonamide; and a-acetoxy, a-methyl-N,N' dipropionylmalonamide.

A particularly advantageous method of using the activators according to the present invention is to add them to the percompound in an amount of approximately 0.33 mol per mol of percompound to be activated. However, according to requirements, it is possible to operate with a deficit or an excess of activator. Preferably the molar ratio of activator to percompound is from 0.1 to 10.

The activators according to the invention may be used in all cases where a percompound is used to obtain an oxidising or bleaching action, for example in the bleaching of textile fibres, oils, greases and waxes, hair and skin treatments in cosmetology, the passivation of metallic surfaces and in purification, disinfection and sterilisation processes.

The activators of the invention when added to the percompound or to a formula containing one or more percompounds, for example a washing powder, make it possible to obtain a more rapid bleaching or oxidising effect at a given temperature, they likewise make it possible to obtain the same bleaching effect when operating at a lower temperature than is customary with conventional bleaching agents.

For example, in the presence of sodium perborate in a wash powder medium, the activators according to the invention make it possible to obtain, at temperatures of from 30 to 500 C, a bleaching action substantially equivalent to that obtained in their absence at higher temperatures of the order of 80"C.

A method of preparing some of the a-acyloxy-N,N'-diacylmalonamides used as activators in the present invention is described in our application No. 35516/77 (Serial No. 1563634).

The following Examples illustrate the invention.

Examples 1 to 3.

Into a compartment of an AHIBA water bath heated to 400 C, there were introduced 250 ml of an aqueous solution containing 5 g per litre of a washing powder having the following composition: Constituents % by weight Na2SiO3 5.34 Na2SO4 7.25 Na2CO3 2.65 Na2HPO4 0.96 Na4P2O7 3.99 Na5P3OgO 30.41 NaPO3 11.92 H2O 18.9 Surfactants 14 Blues, various to make up composition to 100% and 1.7 g per litre of sodium perborate tetrahydrate.

Into the other compartment, the same solution was placed with the further addition of the activator to be tested, at the concentration of 1 g per litre.

Into each of the compartments there was placed a piece of "EMPA" cotton tissue impregnated with standardised wine stains, originating from the Saint-Gall (SWITZERLAND) laboratory.

After 15 minutes washing, the tissues were rinsed in a current of cold water, then dried at ambient temperature.

The bleaching power is defined by the difference between the whiteness indices (measured by means of a Carl ZEISS "ELREPHO" spectrophotometer no.

6 filter) before and after washing, reduced to a percentage of a maximum whiteness of 100.

Variation in whiteness Bleaching power (%) = x 100 100 -- initial whiteness The following results were obtained:

Activator % bleaching Example Concentration without with No. NAME g/l activator activator 1 a-acetoxy, 1 40 61.5 a-methylN,N ' diacetylmalonamide 2 a-propionoxy, 1 40 59.5 a-ethylN,N' -di- propionylmalonamide 3 a-acetoxy, 1 40 61.5 methyl-N,N ' dipropionylmalonamide Examples 4 to 6.

The same process conditions as those described in the preceding Examples were adopted, but with a washing temperature of 20"C instead of 40"C.

Activator % bleaching Example Concentration without with No. NAME g/l activator activator 4 a-acetoxy, a-methyl- 1 31.5 45.3 N,N'-diacetylmalon- amide 5 a-propionoxy, a-ethyl- 1 31.5 43.8 N,N '-dipropionylmalon amide 6 a acetoxy, a-methyl- I 3t.5 44.8 N,N '-dipropionyl- malonamide WHAT WE CLAIM IS: I.A method of activating a percompound, which method comprises subjecting the percompound to the influence of, as activator, an a-acyloxy-N,N'polyacylmalonamide of the general formula:

wherein each of R1, R2, R3, R4, R5and R6, which may be identical or different, is chosen from a hydrogen atom, substituted or unsubstituted straight chain alkyl radicals having from 1 to 11 carbon atoms, substituted or unsubstituted branched alkyl and cycloalkyl radicals having from 3 to 12 carbon atoms, substituted or unsubstituted hydrocarbon radicals having from 6 to 12 carbon atoms and including at least one aromatic nucleus; or wherein R1, R2, R3, R4 are as defined above and R5 and/or R" correspond to an acyl group COR7, wherein R7 is a hydrogen atom or a substituted or unsubstituted straight chain or branched alkyl radical having from 1 to 12 carbon atoms or a substituted or unsubstituted hydrocarbon radical having from 6 to 12 carbon atoms and including at least one aromatic nucleus.

2. A method according to claim 1, wherein the substituents on the said alkyl, cycloalkyl, or hydrocarbon radicals are chosen from chloro, bromo, fluoro and iodo atoms and hydroxy, nitro, alkoxy, amino, ester, amide or hydrocarbyloxy groups.

3. A method according to claim 1 or 2, wherein the percompound is hydrogen peroxide, or an organic addition compound thereof.

4. A method according to claim 1 or 2, wherein the percompound is a perborate, a percarbonate or a perphosphate.

5. A method according to claim 1 substantially as described in any one of the foregoing Examples 1 to 6.

6. An oxidising or bleaching composition including a percompound and an activator of general formula (I) as defined in claim 1.

7. A composition according to claim 6, wherein the molar ratio of activator to percompound is from 0.1 to 10.

**WARNING** end of DESC field may overlap start of CLMS **.

Claims

**WARNING** start of CLMS field may overlap end of DESC **.

Examples 4 to 6.

The same process conditions as those described in the preceding Examples were adopted, but with a washing temperature of 20"C instead of 40"C.

Activator % bleaching Example Concentration without with No. NAME g/l activator activator 4 a-acetoxy, a-methyl- 1 31.5 45.3 N,N'-diacetylmalon- amide 5 a-propionoxy, a-ethyl- 1 31.5 43.8 N,N '-dipropionylmalon amide 6 a acetoxy, a-methyl- I 3t.5 44.8 N,N '-dipropionyl- malonamide WHAT WE CLAIM IS: I.A method of activating a percompound, which method comprises subjecting the percompound to the influence of, as activator, an a-acyloxy-N,N'polyacylmalonamide of the general formula:

wherein each of R1, R2, R3, R4, R5and R6, which may be identical or different, is chosen from a hydrogen atom, substituted or unsubstituted straight chain alkyl radicals having from 1 to 11 carbon atoms, substituted or unsubstituted branched alkyl and cycloalkyl radicals having from 3 to 12 carbon atoms, substituted or unsubstituted hydrocarbon radicals having from 6 to 12 carbon atoms and including at least one aromatic nucleus; or wherein R1, R2, R3, R4 are as defined above and R5 and/or R" correspond to an acyl group COR7, wherein R7 is a hydrogen atom or a substituted or unsubstituted straight chain or branched alkyl radical having from 1 to 12 carbon atoms or a substituted or unsubstituted hydrocarbon radical having from 6 to 12 carbon atoms and including at least one aromatic nucleus.
2. A method according to claim 1, wherein the substituents on the said alkyl, cycloalkyl, or hydrocarbon radicals are chosen from chloro, bromo, fluoro and iodo atoms and hydroxy, nitro, alkoxy, amino, ester, amide or hydrocarbyloxy groups.
3. A method according to claim 1 or 2, wherein the percompound is hydrogen peroxide, or an organic addition compound thereof.
4. A method according to claim 1 or 2, wherein the percompound is a perborate, a percarbonate or a perphosphate.
5. A method according to claim 1 substantially as described in any one of the foregoing Examples 1 to 6.
6. An oxidising or bleaching composition including a percompound and an activator of general formula (I) as defined in claim 1.
7. A composition according to claim 6, wherein the molar ratio of activator to percompound is from 0.1 to 10.
8. A composition according to claim 7, wherein the molar ratio of activator to

percompound is approximately 0.33.
9. A composition according to any one of claims 6 to 8, wherein the percompound is hydrogen peroxide, or an organic addition compound thereof.
10. A composition according to any one of claims 6 to 8, wherein the percompound is a perborate, a percarbonate or a perphosphate.
11. A washing powder including a composition as claimed in any one of claims 6 to 10.
12. A washing powder substantially as described in any one of the foregoing Examples 1 to 6.