JPS6017787B2 - Method for producing hydroperoxide-containing mixture - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an improved process for making mixtures of alkali metal mono- or polyalkylaryl sulfonates and the corresponding hydroperoxides and to a process for making said mixtures in the dry state.

The synthesis of alkali metal aryl sulfonate compounds with a ROOH hydroperoxide functionality on the aryl nucleus has been little investigated; however, U.S. Pat.
No. 829158 describes a method for preparing compounds of this type and mixtures of alkylarylsulfonate peroxides and alkylarylsulfonates in aqueous solution.
This patent states that starting from the aqueous solution thus prepared, it may be possible to evaporate the solvent of the hydroperoxide at very low temperatures, e.g. However, no specific embodiments are disclosed. It is of interest today to have an industrial process that allows the preparation in the dry state of mixtures of alkali metal mono- or polyalkylaryl sulfonates and the corresponding hydroperoxides, the dry mixtures of which are described below. in detergent compositions or as an initiator of radical reactions, as disclosed in .

The present invention provides a method for preparing an aqueous solution of an alkali metal mono- or polyalkylaryl sulfonate containing an appropriate amount of the corresponding hydroperoxide by the action of oxygen on the alkali metal mono- or polyalkylaryl sulfonate. according to which oxygen is present at a temperature not higher than 85° C. and in the presence of cobalt as cobalt naphthenate in a ratio of 1 to 5 relative to the alkylaryl sulfonate of the alkali metal present. It is reacted with an aqueous solution of an alkali metal alkylaryl sulfonate having a multiplication value between 9 and 10.5.

The alkali metal mono- or polyalkylaryl sulfonate used as starting material is a compound of the following formula: where -M is an alkali metal, preferably sodium - RH is an alkyl group, preferably isopropyl/shi-R' is a lower alkyl group, preferably methyl,
Ethyl, n-p.

Pyl or isopropyl group -n is an integer from 0 to equal to 1, 2, 3 or 4 and preferably equal to 0 or 1.

The hydroperoxide obtained according to the method of the invention has the following general formula (when the alkali metal is sodium)
: These structures were verified by carbon-13 NMR.

The chemical setting of the central carbon of the isopropyl group -CH(CH3)2 is 83 for the hydrocarbon compound, 83 for the hydroperoxide, and 83 for the alcohol formed by the decomposition of the hydroperoxide. 72 style, which therefore has the following general formula: alkali metal mono-
The preparation of hydroperoxides of polyalkyl sulfonates with oxygen in aqueous media (as pure oxygen, as air or as oxygen-enriched air) is greatly improved if cobalt naphthenate is used as catalyst.

It was found that by using this catalyst, peroxidation was achieved at a temperature of 80-85q0 compared to 90-9yo when no catalyst was used. And this thing is 8
At temperatures higher than 5 qo, the decomposition of hydroperoxides becomes even more important as it is not negligible even in basic media. The presence of cobalt naphthenate improves oxygen utilization in this reaction and reduces the formation of significant alcohols resulting from decomposition of hydroperoxides. However, excessive amounts of cobalt naphthenate should be avoided. Applicants have indeed found that naphthenates catalyze the decomposition of hydroperoxides when more than 5 parts wind (expressed as cobalt) are used relative to the starting sulfonate. A suitable amount of cobalt naphthenate is therefore between 1 and 50 cobalt by weight based on the starting sulfonate. The peroxidation reaction takes place in a slightly basic soot and preferably at a pH value between 9 and 10.5.

It has indeed been found that at pH values higher or lower than this, the decomposition of hydroperoxides to alcohols is not negligible. The presence of peroxides and especially hydrogen peroxide promotes the initiation of peroxidation and from 10 to 2 parts by weight of hydrogen peroxide per 10 parts by weight of the starting sulfonate;
50% by weight gives good results.

When the peroxidation reaction is carried out at a temperature of 80° C., at a multiplication value of 10, in the presence of less than the IQ plate cobalt as cobalt naphthenate relative to the starting mono- or polyalkylaryl sulfonate, the resulting reaction mixture is (deliberately limiting the sulfonate conversion to a rather low value),
Drying this under reduced pressure at 20°C gives a powder containing approximately 85-90% unreacted sulfonate, 10-15% of the corresponding hydroperoxide, and which contains the alcohol produced by the decomposition of the hydroperoxide. is not detected.

It is possible to obtain powders containing higher amounts of hydroperoxides by subjecting the reaction mixture to fractional crystallization as described below and repeating this operation with monkey fluid if necessary. The applicant has found that, in order to obtain compounds of interest from an industrial point of view, it is expedient to carry out the peroxidation reaction until the resulting dry extract of the aqueous solution contains at least 25% by weight of peroxide.

On the other hand, in order to avoid excessive decomposition of peroxide to alcohol, the peroxidation should be carried out to such an extent that the total conversion of sulfonate does not exceed about 50%. Such decomposition actually reduces the selectivity of the peroxidation reaction of the starting sulfonate salt and thus reduces the yield of peroxide relative to the amount of oxygen absorbed. This yield is equal to or greater than 75% for a total conversion of the starting sulfonate salt not exceeding 50%. The sodium sulfonate used as starting material is prepared by known methods by reacting concentrated sulfuric acid with the corresponding hydrocarbon compound at elevated temperature, neutralizing with sodium hydroxide, cooling, straining and drying the precipitate. make. The peroxidation of the sodium mono- or polyalkylaryl sulfonate thus obtained is carried out in a heated tubular reactor in a closed circuit with a refluxing gas phase into which a stream of gaseous oxygen is injected.

The absorption of oxygen over time is relatively short and follows an S-shaped curve with a lag period. The rate of gas phase flowing in continuous circulation through the reaction mass is 80 to 90 cubic hours per hour. The amount of hydroperoxide in the reaction mixture and dry product is determined by chemical methods (iodometric titration). The amount of alcohol from hydroperoxide decomposition can be determined by proton NMR (
It is measured by the C ratio adjacent to the carbon with OH function).

Another object of the invention is a composition of matter comprising a solid, dry mixture of an alkali metal mono- or polyalkylaryl sulfonate and its hydroperoxide, the composition being stable at room temperature. Concerning methods of manufacturing things.

The mixture may further contain small amounts of alcohol formed by decomposition of the hydroperoxide. More particularly, such compositions may contain, by weight, the following: - 5 to 75% alkali metal mono- or polyalkylaryl sulfonate - 25 to 70% No hydroperoxide of the mono or polyalkylaryl sulfonate.
and 30% of the alcohol from the decomposition of the mono- or polyalkylaryl sulfonate.

Such dry compositions can be obtained by simple evaporation to dryness of the solutions obtained by the method described above, but due to the fact that extremely high peroxide yields cannot be obtained by peroxidation reactions. , it would be difficult in practice to obtain a dry product with significantly high peroxide content.

The industrial production of the dry composition defined above involves treating the reaction mixture obtained at the end of the peroxidation reaction in such a way as to promote partial crystallization of the mixture, straining the suspension thus obtained and vacuum It was found that this process could be carried out by drying the millet liquor at a maximum temperature of 40 oo.

It has indeed been found that the alkylaryl sulfonates used as starting materials are less soluble in water or lower alcohols than the corresponding hydroperoxides.
Such fractional crystallization can be recycled, if desired, for example on the oak liquor after partial evaporation of the water. To carry out this fractional crystallization, one of the following methods can be used: the reaction mixture is heated to 0 °C and 20 qo
or evaporate under vacuum at 40 qC and cool between 0 and 2 p.

It is also possible to dry concentrate the reaction mixture (and directly use the dry mixture obtained for its foreseen applications), dissolve it in methanol and cool the suspension to about 5 °C. and pass the precipitate. The hydroperoxide-enriched oak liquor is then concentrated to dryness under vacuum at a maximum temperature of 40°C. When applying them as detergent compositions, dry solid mixtures of alkali metal mono- or polyalkylaryl sulfonates and their corresponding hydroperoxides are used as bleaching agents and as detergent ingredients known as sodium perborate or Equivalent products may be at least partially substituted. Powdered detergents, usually used in aqueous solutions at elevated temperatures for washing textile fabrics, generally use inorganic persalts as bleaching agents.

One of the most commonly used of these is sodium perborate, which can be present up to 3% by weight of the powder detergent. It can be shown that the hydroperoxides contained in the solid dry mixtures of the invention act primarily as bleaching agents; other components in said mixtures also have less important properties of the resulting detergents (softening, , surfactant properties).

Due to the stability of the products and especially the hydroperoxides contained in these mixtures, the resulting detergents may be exposed to high temperatures (e.g. about 90°C) relative to their activity based on the presence of said hydroperoxides. ) will be used more specifically for laundry. The hydroperoxides of alkali metal mono- or polyalkylaryl sulfonates according to the invention can be used in detergent compositions.

A preferred hydroperoxide is sodium isopropylbenzenesulfonate hydroperoxide (sodium cumenesulfonate hydroperoxide).

Among the products containing hydroperoxides, 25 to 7% by weight of alkali metal alkylarylsulfonates hydroperoxides, 5 to 75% by weight of alkali metal alkylarylsulfonates and 3% by weight of blood. Stable mixtures containing alcohols from the decomposition of said hydroperoxides up to and including the decomposition of said hydroperoxides will be advantageously used.

The alkali metal alkylaryl sulfonates are most commonly constituted by the products used as starting materials for the preparation of the hydroperoxides. These mixtures can replace the same weight of sodium perborate in detergent compositions.

It is therefore possible to prepare detergents containing up to 3% by weight of said mixture. However, because of the efficacy of said mixtures as detergents and bleaching agents, the amount of said mixtures in detergents is generally limited to a value corresponding to 0.1 to 5% by weight of hydroperoxides in the laundry powder. Recommended. It is also possible to replace the customary perborates only in part by the mixtures according to the invention: it is therefore possible to simultaneously replace the mixtures according to the invention with 2 to 4% by weight of hydroperoxides on the one hand in detergent compositions. It is particularly recommended to use sodium borate per week in amounts and on the other hand in amounts of less than 5% by weight and preferably about 2% by weight.

Even with such a low bleaching agent proportion, stains and stains on textile materials are completely eliminated.

The efficacy of laundry powders is measured by the whiteness of the washed textile material.

This whiteness for the detergent composition of the invention (and this more than
the same extent for detergents with low hydroperoxide content) and low perborate content. and about 3 for detergent compositions with low hydroperoxide content.
For known detergent powders containing 0% sodium borate are substantially equivalent. It is possible to improve the results obtained with detergent compositions with low hydroperoxide content by the addition of trace amounts of cupric salts (e.g. steel sulfate), the amount of copper being 100% more effective than the detergent powder. It is lower than the ground and preferably includes between 100 and 80 squares.

This is surprising because the addition of trace amounts of cupric salts to perborate-containing detergent powders reduces the effectiveness of such powders. Thus, the compositions of the present invention allow water containing traces of steel salts, either original or as a result of the use of steel pipes, to be used without damage. However, the presence of copper salts can be used against certain types of stains [especially lmmedja].
l) Advantageous for ink dyeing, but harmful if the fabric to be washed is stained with wine.
In the latter case, it is possible to improve the whiteness of washed fabrics by adding a copper anchor forming agent to the detergent powder beforehand. Among the known cage-forming agents for copper which can be used advantageously, mention may be made of nitrilotriacetic acid (NTA) and/or one of its alkali metal salts and ethylenediaminetetraacetic acid (EDTA) and/or one of its alkali metal salts. or a mixture of these various flange-forming agents;
Considering the amount of copper that can be used, 0.1
- 5% by weight NTA, preferably 0.5-2% by weight and 0.1-2% by weight EDTA are generally used. The related powder detergent composition of the present invention therefore does not contain: There will be: - a dry solid mixture containing the mono- or polyalkylaryl sulfonate of the alkali metal, the corresponding hydroperoxide and optionally the alcohol from hydroperoxide decomposition, - if necessary the copper and tsuba mentioned above. production additives, and one or more anionic detergents such as sodium dodecylbenzene sulfonate, one or more soaps such as sodium tallow soap, sodium tripolyphosphate as a sequestering agent. and known ingredients used in detergents such as sodium silicate.

Further additions to the solid detergent compositions described above may include: - a small amount of a base (preferably between 9 and 12), such as sodium hydroxide, in order for the solutions made from these powders to have a suitable multiplication value; .

- Sodium carbonate and/or sodium sulfate used as builders, light brighteners, fragrances...
・Compounds like.

The use of the solid dry mixtures of the present invention in detergent compositions reduces or eliminates the use in the detergent of sodium dodecylbenzenesulfonate (or some equivalent compound), which is generally present in most detergent compositions. It turns out that it is even possible to do this. This reduction (or elimination) of sodium dodecylbenzenesulfonate is possible in particular in detergent compositions in which perborate is partially or completely replaced by a mixture combining hydroperoxide, sulfonate and optionally alcohol. The related detergent compositions of the present invention yield even more surprising results: the applicant claims that they have a certain softening effect, which makes it possible not to add softeners during rinsing. I discovered that. This softening effect may be due to the alcohol present in the mixture or the alcohol formed by the decomposition of hydroperoxides during use of the detergent composition. Here we will describe general washing conditions and their effects.

Detergent compositions are prepared by weighing and dissolving given amounts of the various ingredients in deionized water and working up to the hardness provided by the addition of calcium carbonate (generally 300 feet of CaC03). For washing, a laboratory apparatus was used, each bowl of which contained 6 ml of powder and 6 ml of powder.
00 water was added. The multiplication value of the solution obtained in this way was brought to the desired value by adding traces of sodium hydroxide; sodium hydroxide can also be incorporated into the powder during comminution. Preferably the washing solution is 9 and 12.
and more preferably a value of 0.5 to 0.11. It goes without saying that in all the examples below the pH of the detergent solution will be given before washing; this multiplier will be lowered by about 0.5 during the washing operation. 3 of the solution
It was then allowed to ripen to zero and held at this temperature for 18 minutes, then the basket containing the fabric was placed in the bowl and the rope commenced.

The temperature was increased from 3 to 90°C in 4 minutes and held at 90-95°C for 50 minutes. The basket was immersed in running water and the fabric sample was rinsed with deionized water and dried. Laundering was carried out on the test fabric EMPA with the following artificial contaminants: blood, red wine, and inmedial black (sulfurized black dye), hereinafter referred to as blood, wine, and black.

The washing efficiency of a given detergent is determined by the uniform chromaticity system L, a, b'
It is measured by "cube root" (19 spots), which gives an expression of color variation.

In this system, outlined in the accompanying drawing, "L" is the "pure" whiteness (between pure black (0) and pure white (100)).
``a'' is the color toward green (negative values) or toward red (positive values) according to its sign, and ``b'' is toward blue (negative values) or the yellow one (positive value)
It is a color that goes towards. The value obtained for a sample in this system with three vertical axes is represented by a single point.

The distance from this point to another point represents the total chromaticity change between the two, and is: △E=ZoteC*L2)20 a
, - also) 20 (b, -Q) 2 If we take the reference points L, a,, q (100 0, 0) representing the highest theoretical brightness of "pure", we can obtain the absolute chromaticity change for the measured sample. L. a, b are equal to the following values: ΔE=ノ(100-L)2 10a20b2 The lower this value, the better the cleaning.

The values of L, a, b are given directly by the measuring device, a reflection colorimeter.

Examples 1-5 below are examples that further illustrate the invention.

Example 1 Peroxidation of sodium diisopropyl-2,4-benzenesulfonate 160% sodium diisopropylbenzenesulfonate, 4% cobalt (relative to sulfonate) (6% cobalt as cobalt naphthenate), 480%
Evening water, 49. 20% by weight of hydrogen peroxide, and 3.0% sodium carbonate to bring the volume of the reaction medium to 9.5%.
One night was placed in the reaction vessel described above.

The gas phase was bubbled through the reaction mixture heated to 84 qo while oxygen was mixed into the gas phase.

The oxygen absorption rate, which was slow at the beginning, decreased to about 0 after 4 hours.
．． It reached 5pm/hour. The weight of hydroperoxide in the reaction mixture was 6.2% after 10 hours of reaction (yield of hydroperoxide based on arrangement: 88%).

The reaction was allowed to proceed for a further 6 hours.

The hydroperoxide content in the reaction mixture amounted to 7.5% by weight and the hydroperoxide yield based on oxygen was 76%. 7.2 evenings of oxygen was absorbed in the solstice.
A portion of the reaction mixture is evaporated to dryness under vacuum at temperatures up to 4 picC to give a dry product with the following composition:
- 59% unreacted sulfonate - 30% hydroperoxide of sodium diisopropyl-2,4-benzenesulfonate - Alcohol from separation of 9% hydroperoxide (remainder is sodium carbonate).

The total conversion of sulfonate was 37% and the conversion of hydroperoxide was 28%.

The remaining reaction mixture was heated to 2°C and filtered. The precipitate and the permeate were dried separately under vacuum. Substantially the same amount of powder thus obtained had the following composition in weight percent: Example 2 Peroxidation of sodium metacymenesulfonate (methyl-2isopropyl-4benzenesulfonate) 112 evening sodium metacymensulfonate, 3
Cobalt (for sulfonate), as naphthenate containing 6% cobalt, 665 evening water, 49.7%
20 hours of hydrogen peroxide and 3 hours of sodium carbonate to bring the pH of the soot to 9.7 were placed in the reaction vessel.

The temperature was raised to 84.90 while the oxygenated gas phase was circulated at an average rate of 0.3 M/h. After 9 hours of reaction, the hydroperoxide content of the reaction mixture was 1.9% by weight (hydroveroxide yield relative to oxygen was 92%).
).

The reaction was stopped after 21 hours.

5.06 Evening oxygen was consumed.

At this point the hydroperoxide content of the reaction mixture was 4
% by weight (yield of hydroperoxide based on oxygen: 77%). A portion of the reaction mixture was dried under vacuum.

The dry product had the following composition. 3% reaction sulfonate 27.5% corresponding hydroperoxide 8% alcohol from hydroperoxide decomposition.

The total conversion of sulfonate was 33%: the conversion to hydroperoxide was 25.5%.

The remaining reaction mixture was cooled and passed to 20q0. The resulting precipitate and monkey fluid were separately dried under vacuum at temperatures up to 40 qo. The precipitate was 1/3 of the total dry powder product. Analysis of these dry products gave the following composition (% by weight): Example 3 Para-cymenesulfonic acid (methyl-2-isopropyl-
Peroxidation of the sodium salt of benzenesulfonic acid (195)
Sodium paracymensulfonate, 6% cobalt as a naphthenate, 1% cobalt (relative to sulfonate), 565% water, 49.0% cloud cover hydrogen peroxide 20% and medium. 3 to bring the pH to 9.7
Added sodium carbonate to the reactor.

Circulation of the gas phase through the reaction mixture was started while the temperature was raised to 85°C. Oxygen was mixed into the gas stream at an average rate of 0.88 evening/hour. After 8 hours of reaction, the hydroperoxide content in the reaction mixture was 4.0% by weight (hydroveroxide yield relative to oxygen: 93%).

The reaction was stopped after 1 hour.

The hydroperoxide content in the reaction mixture was 6.3% by weight. The total acid uptake was 7.4 hours and the hydroperoxide yield relative to oxygen was 79%. A portion of the reaction mixture was dried under vacuum to give a product with the following composition (% by weight): Reacted sulfonate salt
The total conversion of 67 (%) hydroperoxide 25 alcohol 6 sulfonate was 28% and the conversion to hydroperoxide was 22%.

The remaining reaction mixture was cooled to 2°C, and then the precipitate and the liquor were separately dried at 20°C under vacuum. The powder was obtained 2/3 based on the precipitate and 1/3 based on the liquor.
The product obtained had the following composition (% by weight):

Example 4 The following was bagged into a peroxidation reactor of a mixture of sodium metacymensulfonate and sodium paracymensulfonate. Cobalt (for salt mixture), 6% cobalt naphthenate as 710 min water 20 min 49.7% hydrogen peroxide 3 min sodium carbonate, to give a multiplication value of 9.7.

The gas phase was circulated through the reaction mixture and the mixture was heated to 80°C; oxygen was introduced at an average rate of 0.84 parts/hour.

After 1 hour of reaction, the hydroperoxide content of the reaction mixture was 7. % by weight of the mother (yield based on oxygen was 9
2%). The reaction was stopped after 2 field hours.

The hydroperoxide content of the reaction mixture was 9.5% by weight. Oxygen was absorbed on December 9th.

The yield of hydroperoxide was 84.5% based on oxygen. A portion of the reaction mixture was heated to an optimum temperature of 40 pm under vacuum.
It was dried with. Its composition was as follows (wt%)
: Unreacted sulfonate 52 (%) Hydroperoxide 39 Alcohol
The total conversion of the 7-sulfonate mixture was 42% and the conversion to hydroperoxide was 36%.

The remainder of the reaction mixture was removed under vacuum to remove the 10% water present, cooled to 20 qo and filtered at this temperature although it had a gel-like appearance.

The monkey fluid and precipitate were obtained and dried separately under vacuum.

The dry product obtained (weight ratio 1/1) has the following composition (% by weight): Example 5 Cumenesulfonic acid (p-isopropylene).

Sodium cumene sulfonate, IQ style cobalt (relative to sulfonate), 6% cobalt as naphthenate, 500 min water in a peroxidation reactor of sodium pyrubenzene sulfosoate), A mixture of the hydroperoxide of sodium cumene sulfonate and sodium cumene sulfonate was prepared for 18 minutes (although this mixture was prepared from the previous operation and the precipitate obtained from the concentrated drying was then dissolved in methanol as described below). Melted, and about 30
% hydroperoxide) and then added 0.5 ml of sodium carbonate to bring the pH value to 10.

Gas phase circulation was started and the mixture was heated to 80°C.
Oxygen was added to the gas phase at an average rate of 1.29/hour. After one field hour of reaction, the hydroperoxide content of the reaction mixture was la wt%, the yield based on oxygen was 90% (86% taking into account the hydroperoxide introduced from the beginning),
The amount of oxygen absorbed was 12 o'clock.

The reaction mixture was concentrated to dryness under vacuum at a maximum temperature of 40 oo to obtain a powder with the following composition (% by weight): unreacted sulfonate 48 (%) hydroperoxide 40 (%) alcohol of decomposition.
The total conversion of 11 sulfonate was 48%: conversion to hydroperoxide was 36%.

One part by weight of this powder was mixed with two parts by weight of methanol and the mixture was heated at 40° C. for several minutes. Then 5℃
cooled and passed the precipitate. The precipitate and monkey fluid were dried separately under vacuum at 20q0. A precipitate containing 3% by weight of hydroperoxide and a powder (from the oak liquor) containing 5% by weight of hydroperoxide were obtained.

The following examples are illustrative of the use of compositions of the invention containing hydroperoxides of sodium mono- or polyalkylaryl sulfonates in the preparation of detergent compositions.

The contaminant test textile materials used in the examples below had L, a, b and ΔEqb values as follows: Table 1 The following abbreviations are used: Sodium dodecylbenzenesulfonate (approximately 50 % active substance) ODBS sodium tallow soap Soap non-ionic detergent
DNI sodium tripolyphosphate TPP sodium silicate (approximately 44%
Active substance) SiS sodium perborate tetrahydrate (
NaB034 also 0) PBS nitrilotriacetic acid
NTA sodium ethylenediaminetetraacetate EDTA sodium sulfate
SNa Example 6 This is a control example for laundering without bleach.

A powder containing the following ingredients (% by weight) was used according to the general washing conditions described above: DDBS
I0 (%) Soap 7DN1
6TPP
40SiS
IOSNa
The 27 washing solution (1 part powder to 10 eaves water) had a pH value of 10, adjusted with a small amount of sodium hydroxide.

The following results were obtained: Table □ In the case of no bleaching agent, the agricultural product is close to unwashed, whereas for blood and wine, L increases (it is sharp for blood), and the red component increases. Note that there is a clear decrease and the yellow matter remains almost unchanged.

Example 7 This is a control example using a conventional detergent containing sodium perborate.

The following powders were used for washing at a multiplication value of 10 (% by weight).

DDBS I0 (%) Soap
7DN1
6TPP
40SiS
IOEDTA
IPBS
26 Obtained the following results: Table M Compared to the perborate-free powder, it washed significantly better against wine, washed well against black, but not against blood. However, the cleaning source was slightly lower, and the yellow component increased.

It should be noted that in the case of blood, some stiffness was observed in the textile material after washing. As seen below, pH 1
It was good for black and significantly better for blood when washed at 2: 10 ■ Cape Copper was added to the W detergent composition as C 048 LO, which was less than 1 in the wash solution. Compatible with leg Cu 10.

Washing on axis 12 gave the following results: Curtain V Table Note that the effect of copper addition to detergent powder containing perborate is detrimental even if it contains EDTA.

Slightly less favorable results were obtained as shown by the table below by lowering the perforant salt content to make the active oxygen content equal to 5.3% of that of the pure hydroperoxide of the present invention. It was done.

The laundry powder contained the following ingredients: DDBS
I0 (%) Soap
7DN1 6T
PP 40S
iSIOEDTA
IPBS
3.2SNa
22.8 Table (PH1o
By removing EDTA from this formulation, △
E females were about 1 point lower in three cases.

Examples 8-22 These examples show laundering results with relevant detergent powders of the invention.

In all these examples sodium cumene sulfonate hydroperoxide was used as the bleaching agent in a mixture with sodium cumene sulfonate and the alcohol from the hydroperoxide decomposition.

This mixture of dry powders contains 50% each of these three components.
%, 40% and 10%. It is the amount of this mixture (referred to as HPC) that is shown in the skin table. Washing was carried out as described above.

The orange value of the mixture was adjusted by incorporating finely crushed bonito sodium hydroperoxide into the detergent composition. The properties of these compositions are shown in the Skin Table and the results are shown in the Skin Table.

In Example 22, the sodium sulfate in Example 19 was replaced with the same amount of sodium carbonate (Na2CQ).

Direct replacement of sodium perborate with an equivalent amount (same oxidizing power) of the "mixture" (HPC) particularly improves the cleaning of blood stains, the addition of steel sulfate even more improves the cleaning of black and N
Addition of TA improves cleaning of wine stains. The effect of feed on laundering should also be noted, especially in the case of blood and black.

Example 23 Sodium cumenesulfonate hydroperoxide was replaced by sodium metadisopropylbenzenesulfonate monohydroperoxide 1 as bleaching agent.

The product obtained by peroxidation of sodium metadisopropylbenzenesulfonate contained:
In weight %: Hydroperoxide 40 (%) Hydroperoxide starting material 50 Alcohol from hydroperoxide decomposition 1 This mixture (HPDP) was incorporated into a detergent powder which had the following composition (wt %) ):DDBS
I0 (%) Soap
7DN1 6
TPP 40
SiS IOPBS
2HPDP
IO. 7NTA
O. 5SNa
13.8 Cu l
This powder (as CuS0418LO) was dissolved in 10 parts of its weight in water and the pH of the solution was adjusted to 12 by adding a trace of sodium hydroxide.

Washing was carried out under the conditions described above.

gave the following results.

[Brief explanation of drawings]

The attached drawing outlines the cube root chromaticity system used to accurately represent the cleaning effect of detergent numerically. Skin Table Solid detergent composition used Table Laundry results

Claims (1)

[Scope of Claims] 1 Formula: ▲Mathematical formula, chemical formula, table, etc.▼ (In the formula: -M is an alkali metal such as sodium, -RH is a lower alkyl group, preferably isopropyl, -R
' is a lower alkyl group - n is an integer smaller than 5, preferably 0 or 1)) is reacted with oxygen in an aqueous solution. , at a temperature not higher than 85°C.
at pH values between 9 and 10.5 and from 1 to 50 ppm relative to the alkylaryl sulfonate as catalyst.
A process for peroxidation of alkylaryl sulfonates of alkali metals, characterized in that the reaction is carried out by using cobalt as cobalt naphthenate. 2. The method of claim 1, wherein the reaction is continued until the resulting dry extract of the solution contains at least about 25% hydroperoxide. 3. A method according to claim 1 or 2, wherein the peroxidation reaction is carried out in the presence of peroxide. 4. According to any one of claims 1 to 3, in which the peroxidation reaction is carried out in the presence of 5 to 10 parts by weight of pure hydrogen peroxide per 100 parts by weight of the alkylaryl sulfonate. Method described. 5 Formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula: -M is an alkali metal such as sodium, -RH is a lower alkyl group, preferably isopropyl, and -R
9 is a lower alkyl group and -n is an integer smaller than 5, preferably 0 or 1) in an aqueous solution at a temperature not higher than 85°C.
and 10.5 and using 1 to 50 ppm of cobalt as cobalt naphthenate to said alkylaryl sulfonate as a catalyst. After peroxidation of the salt, the resulting aqueous mixture is partially precipitated, the precipitate is separated, the filtrate is optionally crystallized at least once and the filtrate is heated to a maximum of 40°C.
A method for peroxidizing an alkylaryl sulfonate of an alkali metal, the method comprising evaporating to dryness at a temperature of . 6. The method according to claim 5, wherein the precipitation is carried out by cooling the aqueous solution to 0 to 20<0>C. 7 Concentrate under reduced pressure at temperatures up to 40°C, followed by 2
6. A process as claimed in claim 5, in which the precipitation is carried out by cooling to a temperature between and 20<0>C. 8. Process according to claim 5, in which the reaction mixture is brought into the form of a suspension by dry concentration under reduced pressure and taking up the resulting product in methanol.