DE2336108A1 - OXYDATING AGENTS WITH COMPLEXING PROPERTIES AND DETERGENT COMPOSITIONS CONTAINING THESE COMPOUNDS - Google Patents

Description

Oxidizing agents with complexing properties and detergent compositions containing these compounds

The invention relates to oxidizing agents with complexing (sequestering) properties which are used as bleaching agents and detergent compositions containing these substances.

The invention represents a further step against environmental pollution and especially in relation to combating the eutrophication of standing and flowing water.

The elements that contribute most to the eutrophication of water are phosphorus and nitrogen. These elements are in particular released into the aquatic environment through detergent compositions introduced, in particular by the "builders" used in these compositions, namely sodium tripolyphosphate and sodium nitrilotriacetate. In order to avoid this pollution, attempts have recently been made to use the traditional "builder" fabrics to be replaced by a range of phosphorus- and nitrogen-free substances.

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So it was proposed by the applicant in BE-PS 776 705, as a complexing agent (sequestering agent) and "builder" the alkali metal or ammonium salts of poly-oc-hydroxyacrylic acids to use. These polymers, which have considerable complexing properties, are obtained starting from polychloroacrylic acid by the action of water and an alkali metal or ammonium hydroxide, or using any known method.

The invention relates to new oxidizing agents that additionally complexing properties towards metal ions, in particular against calcium and magnesium ions, these agents do not contain any elements that cause pollution contribute to the waters. The new oxidizing agents according to the invention are suitable for all those cases in which the usual oxidizing agents are used, in particular as bleaching agents. For this reason and because of their complexing Properties can be used to advantage for this be, at the same time sodium perborate or other bleaching agents and sodium tripolyphosphate and / or other "builders" completely or partially to replace in detergent compositions.

The new oxidizing agents according to the invention, which also develop complexing properties, comprise active oxygen containing poly-a-hydroxyacrylic acid and / or an alkyl derivative this acid and / or one or more salts of these compounds.

Although the complexing oxidizing agents according to the invention can be prepared using any suitable method, it is preferred to make them by action a peroxide compound on the poly-a-hydroxyacrylic acid and / or an alkyl derivative of this acid and / or one or more salts of these compounds or a polymeric precursor thereof Acid, such as poly-a-chloroacrylic acid or a lactone of poly-hydroxyacrylic acid here.

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You can also, in particular, by one-stage or two-stage treatment of the poly-α-chloroacrylic acid or the alkyl derivative .this "compound with water, hydrogen peroxide and a Alkali metal or ammonium hydroxide can be obtained. This acid can also initially be mixed with an alkali metal hydroxide solution and then treat with hydrogen peroxide.

The complexing oxidizing agents according to the invention can also by the action of hydrogen peroxide and an alkali metal hydroxide to a lactone of poly-a-hydroxyacrylic acid or a derivative of this acid can be prepared.

The complexing bleaching agents according to the invention can be used also by binding active oxygen to a poly-ahydroxyacrylic acid molecule or a derivative or a salt of this compound, as described in BE-PS 776 705 of Applicant is described. This binding of active oxygen can, for example, be caused by the action of hydrogen peroxide a poly-α-hydroxyacrylate suspended in a non-solvent liquid or by action from hydrogen peroxide to a poly (hydroxy acrylate) dissolved in water, followed by precipitation of the compound containing the active oxygen. Another possible one Variant of the process is to use a poly-a-hydroxyacrylate to treat with the oxygen-containing organic phase, obtained in the synthesis of hydrogen peroxide by the alkyl anthraquinone process. The bond of active Oxygen on the PoΙγ-α-hydroxyacrylic acid or a derivative this compound can also be produced by the action of hydrogen peroxide using a fluidized bed process Acid.

The new oxidizing agents according to the invention can be used everywhere with advantage where oxidizing agents are usually used, ie as epoxidizing agents _? As a bleaching agent for cellulose materials (Textilit,., paper pulp, wood, etc.), for bleaching oils and fats, as an oxidizing agent for vat dyes, etc. g Q988 5/1326

An advantageous use of the bleaching agents according to the invention is in detergent compositions. As stated above, these compounds have in addition to the bleaching effect resulting from the presence of active oxygen the remarkable property of complexing (sequestering) metal ions, especially calcium ions and magnesium ions j '. Furthermore, the polymer obtained after the release of the active oxygen contained in the compound is a poly-a-hydroxyacrylate of the type described in BE-PS 776 705 is described, which has very good complexing properties and is a very good "builder".

The simultaneous presence of bleaching and "builder" properties makes it possible at the same time sodium perborate and optionally other bleaching agents and sodium tripolyphosphate and optionally other "builders" or complexing agents entirely or partially by the complexing oxidizing agents according to the invention to replace. The replacement of perborate in the detergent or detergent compositions allows in particular to significantly reduce the amount of additional "builder" substances required in the composition.

It can be seen that, in addition to the bleaching agents and surface-active agents according to the invention, all of the compositions conventionally used therein can be used in the detergent compositions. In addition to the usual additives, all "builders" such as phosphates and polyphosphates, silicates and polysilicates, carbonates, salts of nitrilotriacetic acid, ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid and homologous polyaminocarboxylic acids, all polymers and copolymers with complexing effects, such as acrylic and maleic acids, can be used -, fumaric acid and itaconic acid polymers and copolymers of these acids with ethylene, propylene, isobutylene and styrene and / or with vinyl alcohol, allyl alcohol, methyl vinyl ether, acrolein, vinyl acetate , acrylic acid amide etc., - and in particular hydroxycarboxylate polymers such as poly-polymers -hyciroxyacrylate, etc. In con. Detergent compositions which the inventive granular

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Contain plexing oxidizing agents, others may also

Bleach and optical brighteners may be included. < ■

As surface-active agents, in particular, those of I.P. Sisley and P.J. Wood in "Encyclopedia of Surface Active Agents ", Chemical Publishing Co., New York, Volume I, 1961 and Volume II, 1964 and in PR-PS 1,589,887 and in DT-PS 1 594 865 insert the connections described.

The active content of the oxidizing agents according to the invention Oxygen can range from 1 to 20% by weight, depending on the intended use and method of manufacture. The products used in detergent compositions preferably contain more than 2% by weight, in particular 5 to 18% by weight active oxygen.

The oxidizing agents according to the invention can, if desired, also be provided with a coating.

The following Examples 1 to 7 are intended to illustrate the preparation of the active Oxygen-containing poly-ct-hydroxy acrylic acids and . explain their salts, but without thereby restricting the invention.

example 1

For the preparation of a complexing bleaching agent according to the invention proceed as follows.

To 50 ecm of a 30 percent by weight hydrogen peroxide solution, containing 10 g of sodium hydroxide, 5.4 g of poly-a-chloroacrylic acid are added. The temperature of the reaction mixture rises to 55.degree

—2

on, and 5-10 moles of chlorine are released in the course of 2 hours. The complexing oxidant is with methanol precipitated, washed with methanol and then dried at room temperature under reduced pressure (20 mm Hg). The iodometric certain active oxygen content of the bleaching agent obtained in this way is 8.2% by weight.

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Example 2

Hydrolyzed to produce an oxidizing agent according to the invention add 3 g of poly-a-chloroacrylic acid completely with water, add 30 ml of a 30 percent strength by weight hydrogen peroxide solution containing 5 g of sodium hydroxide to the lactone obtained, and keeps the solution at a temperature of 5 C. Then the oxidizing agent is used in the same way as in Example 1 isolated. The active oxygen content of the oxidizing agent obtained is 17.3% by weight.

Example 3

2.50 g of poly-a-chloroacrylic acid and 10 ecm of a 1On sodium hydroxide solution are placed in a flask with a capacity of 100 ecm. Then, after the material has dissolved, 1.0 g of 67 percent by weight hydrogen peroxide is added. The complexing Bleach is precipitated with methanol, washed with benzene and dried in vacuo (1 mm Hg) for 16 hours. The solid obtained contains 5.0% by weight of active oxygen.

Example 4

For the production of a complexing bleaching agent, one gives in a 500 ml flask fitted with a Dean-Starck trap is, 10 g of sodium poly-a-hydroxyacrylate, which one according to the received the procedure described in BE-PS 786 464, and 130 ecm benzene. The suspension is then subjected to an azeotropic distillation, with stirring, until the water is completely removed away. The suspension is then cooled and, with vigorous stirring, slowly to remove an excessively large aqueous Avoid phase, mixed with 3.69 g of 67 percent by weight hydrogen peroxide. Then the one obtained is filtered Solid off and dry it for 16 hours in vacuo (1 mm Hg) to remove the solvent and excess water remove. The product obtained has an active oxygen content of 7.0% by weight.

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Example 5

The procedure is the same as that described in Example 3, but using that according to the DT-OS as the starting material 2 061 584 described method produced sodium poly-ochydroxyacrylat begins. The complexing bleach obtained has an active oxygen content of 7.5% by weight.

Example 6

2.39 g of sodium poly-a-hydroxyacrylate (obtained according to the procedure described in BE-PS 786 464), 1 g of 67 percent by weight hydrogen peroxide and 19 g of water in a 100 ml flask. By adding 10n sodium hydroxide solution the p "value is brought to 7. The complexing oxidizing agent is in the same way as described in Example 2, precipitated and dried. The material contains 5.0% by weight active oxygen.

Example 7

10 g of sodium poly-a-hydroxyacrylate, obtained according to the procedure described in BE-PS 786 464, and 170 ecm of benzene are placed in a 2 liter flask equipped with a Dean-Starck trap. The suspension obtained is subjected to an azeotropic distillation until the water is removed in full. The suspension in benzene is then cooled and unit 1 1 of a solution containing 200 g of a mixture of tert-amyltetrahydrbanthraquinone and sec-amyltetrahydroanthraquinone per kg, which was previously hydrogenated to 50% and according to the in BE-PS 769 6 75 The method described had been oxidized, added. A mixture of 50% by weight diisobutylcarbinol and a petroleum fraction which mainly contains aromatic ^ hydrocarbons ("Solvesso IGC") is used as the solvent. The suspension is stirred for 64 hours and then filtered. The solid obtained is washed with benzene and dried in vacuo for 4 hours and 30 minutes. The product obtained has an active acid content of 5.7% by weight.

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Example 8

This example serves to demonstrate the bleaching power of various Detergent compositions containing the oxidizing agent of the invention to compare with that of powders containing sodium perborate as a bleach.

These washing tests were carried out with different washing powders, which had a common basic composition given in Table I below. The only ingredients which have been varied are the bleaching agent (sodium perborate and the complexing agent obtained according to Examples 1 to 7 Oxidizing agents or a mixture of these products) and the "builder" (sodium tripolyphosphate, sodium poly-a-hydroxyacrylate or a mixture of these substances).

Table Ί

Basic composition g / lOO g washing powder Linear alkyl benzene sulfonate
(LAS DOBANE JN) 2.5 Hydrogenated sebum soap 3.0 Ethoxylated fatty alcohol
(ALFOL C16 Cl8 50 OE) 6.0 'Ethoxylated fatty alcohol
(ALFOL ClO C12 5 OE) 0.5 Na ₂ SiO ₃ * 9H ₂ O 10.5

An amount of anhydrous sodium sulfate is added to the material to make a total of 100 grams of washing powder.

The tests given below were carried out by washing of cotton samples that had been artificially soiled. The soiling was done by impregnating the fabric with a concentrated solution of the polluting substance (Tea, wine, coffee and currant juice) followed by one Padding treatment and air drying. This cycle was repeated three times. The soiled fabric was

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then artificially for 4 hours in a ventilated oven aged at 1O5 ° C.

Washing was done with a laboratory washing machine (LINITEST from ORIGINAL HANAU G.m.b.H.).

The conditions used in the washing process were as follows:

Temperature: 80 ° C

Washing time: 30 minutes

water used: 250 ml with a hardness of 18 HF

Detergent powder: 2 g / l

Samples: two samples with one surface

of 100 cm
about 0.6 g

2
of 100 cm and a weight of

The effect of the washing treatment is due to the change in the reflection of the samples measured. The measurement is carried out with the aid of a reflectometer (ELREPHO from ZEISS) by determination of diffuse reflected light. The reflected light is filtered through a trichromatic filter with a green color (FMY / c) analyzed. The values observed are given as a percentage based on magnesium oxide. The degree of dirt removal in percent is calculated using the following formula:

Degree of whiteness after washing - Degree of whiteness before washing

S.E.- = 100 χ =

Initial degree of whiteness (before artificial soiling) - Degree of whiteness before washing

Investigations 1 to 9 were carried out with the same type of pollution (tea). Tests 1 and 2 are comparative tests that were carried out with sodium perborate (PBS) as the bleaching agent and sodium tripolyphosphate (TPP) or sodium poly-a-hydroxyacrylate (PHAS) as "builder ^11. Tests 3 to 9 show the effectiveness of the washing powder which contain the active oxygen-containing sodium poly-a-hydroxyacrylates according to the invention, obtained according to Examples 1 to 7. In these various investigations, the content was determined

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of the powder in active oxygen is kept at a constant value of 2% by weight, which is also the case for the percentage by weight of the "Builder" applies (40%). In doing so, sodium poly-α-hydroxyacrylate (PHASO) containing active oxygen became accurate Like sodium poly-a-hydroxyacrylate (PHAS), calculated as a "builder", taking the active oxygen content into account became.

Studies 10 and 11 compare the effectiveness a washing powder according to the invention, the active oxygen-containing sodium poly-a-hydroxyacrylate (PHASO) as Contains bleach and sodium tripolyphosphate (TPP) as "builders" (test 10) with that of a comparative washing powder represents the bleaching agent sodium perborate (PBS) and a mixture of sodium poly-a-hydroxyacrylate (PHAS) and sodium tripolyphosphate (TPP) contains as "builder", the contents of active oxygen and "builder" being the same, opposite three types of pollution (wine, coffee and currant juice) "

Investigations 12 to 14 show the effectiveness of one according to the invention Washing powder containing sodium poly-a-hydroxyacrylate (PHASO) containing active oxygen as a bleaching agent and sodium poly-a-hydroxyacrylate (PHAS) as an additional "builder", the powder having variable contents of active Oxygen compared to tea stains.

Investigations 15 and 16 relate to washing powder according to the invention, which is a mixture of sodium perborate (PBS) and sodium poly-a-hydroxyacrylate (PHASO) containing active oxygen as bleach and either sodium poly-a-hydroxyacrylate (PHAS) (investigation 15) or sodium tripolyphosphate (TPP) (investigation 16) included as a "builder". These powders contain 2% by weight of active oxygen and 40% by weight of "builder", where the active oxygen-containing sodium poly-a-hydroxyacrylate (PHASO) was calculated as a "builder", the content of active Oxygen was taken into account. The results of this

various studies are given in Table II below summarized.

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Table II

Investigations 1 CVl 3 U 5 6th 7th 8th - ■ 1 2 3 U 5 6th 9 10a 11a 10b 11b 10c 11c 12th 13th 1U 15th 16 U - U - U - U U U U U This figure includes the amount of PHAS formed in situ from PHASO,
ie the amount of PHASO minus the content of active oxygen.
⁺ The active oxygen contained in this washing powder becomes half
supplied by PBS and half by PHASO. Anhydrous soda
sulphate (g / 100 σ 17.5 17.5 35.5 35.5 35.5 35.5 35.5 35.5 ~ 8.2 17.3 5.0 7.0 7.5 5.0 35.5 33.5 15.5 33.5 15.5 33.5 15.5 36.16 35.0 3U, O5 26.5 26.5 6.9 - 6.9 - 6.9 - 7.0 ' 7.0 7.0 7.0 7.0 PBS "
PHASO "
PHAS "
TPP " 2QO
Uo, 0 20.0
Uo, 0 2U, U
17.6 11.5
30.5 UO, 0
2.0 28.6
13, U 26.7
15.3 Uo, o
2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 35.1
6.9 29.0
15.0 20.0
27.0
15.0 29.0
15.0 20.0
27.0
15.0 29.0
15.0 20.0
27.0
15.0 21, ie
19.92 35.72
6.78 U2 _; 8U
0.61 10.0
1U, 28
26.72 10.0
1U.2S
26.72 2.0 2.0 2.0 2.0 2.0 2.0 1.5 2.5 3.0. ++)
2.0 -H-)
2.0 Total quantity +)
"Builder"" Uo, 0 Uo, 0 uo, o Uo, 0 Uo, o uo, o U0, o Uo, o tea tea tea tea tea tea tea Uo, ο U2.0 U2.0 U2.0 U2.0 U2.0 U2.0 39.8U UO, 0 Uo, 0 UO, 0 Wine Wine Coffee
fairy Cat
fairy Jon.
berry Jen,
B. tea tea tea tea tea total quantity
Washing powder". " *in 59 3 50.2 5ö, 5 50.3 50.1 50.3 57.9 0.0. U33 U6 £ 66, U 6c46 59.6 61.6 56.0 5Ö, U 59.2 59, U 60.0 PHASQ manufactured
qetnail example 0.6 0.2 0.6 0.5 0.5 0.2 0.6 7th 1.1 1.0 0.6 0.2 0.5 0.3 1.7 0.9 1.1 0.7 0.6 Content of the PHASO
ac t. Sour. (Wt. % ) - 5.7 Pick up the washing powder
current acidic (Wt%) - 2.0 pollution 2.0 tea SE. % (Means off
6 investigations) tea 56.00 1/2 error limit
(at 95%),% 59.9 0.3 0.7

It can be seen from these results that the effectiveness of the active oxygen containing sodium poly-a-hydroxy-

acrylate remains constant regardless of the method of manufacture. The effectiveness of containing an oxidizing agent according to the invention Washing powder is in all cases comparable to that of the comparative washing powder containing sodium perborate. she have the additional advantage that the additional "builder" amount, which is required for the powder to retain its effectiveness can be reduced significantly. This is from an ecological point of view Particularly interesting, as the content of the washing powder in phosphorus and / or nitrogen is much lower, when using sodium triphosphate as a "builder". If you use a "builder" who is free from eutrophication evoking elements, such as sodium poly-a-hydroxyacrylate, if you have a washing powder that does not cause eutrophication, that has a detergent effect that is comparable to that of washing powders, the sodium perborate and sodium tripolyphosphate contain.

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Claims (11)

- 13 claims 1.) Oxidizing agents with complexing properties, thereby characterized in that they contain active oxygen poly-a-hydroxyacrylic acid and / or an alkyl derivative of this acid and / or one or more salts of this compound. 2.) Oxidizing agent according to claim 1, obtainable by action a peroxide compound on poly-α-hydroxyacrylic acid and / or an alkyl derivative of this acid and / or one or more salts of this compound or a polymeric precursor this acid. 3.) oxidizing agent according to claim 2, characterized in that the polymeric precursor of poly-ahydroxyacrylic acid Poly-α-chloroacrylic acid or a lactone which is poly-α-hydroxyacrylic acid. 4.) Oxidizing agent according to Claims 1, 2 and 3, obtainable by treating a poly-a-chloroacrylic acid and / or one Alkyl derivative of this compound with water, hydrogen peroxide and an alkali metal or ammonium hydroxide. 5.) Oxidizing agents according to claims 1, 2 and 3, available by treating a lactone of a poly-α-hydroxyacrylic acid with hydrogen peroxide and an alkali metal or ammonium hydroxide. 6.) Oxidizing agent according to Claims 1 and 2, obtainable by the action of hydrogen peroxide on poly-a-hydroxyacryl acid and / or an alkyl derivative of this acid and / or one or more salts that are in the form of a suspension in a organic liquid that does not act as a solvent is present. 309885/1326 7.) Oxidizing agent according to claims 1 and 2, obtainable by the action of hydrogen peroxide on a poly-hydroxyacrylic acid and / or an alkyl derivative of this acid and / or one or more salts of these compounds which be in the form of a solution in water. 8.) Oxidizing agent according to claims 1 and 2, obtainable by the action of hydrogen peroxide, in the form of a Solution of previously hydrogenated and oxidized tert-amyl tetrahydroanthraquinone and sec-amyltetrahydroanthraquinone is present, on poly-α-hydroxyacrylic acid and / or an alkyl derivative this acid and / or one or more salts of this compound. 9.) Detergent compositions based on one or more surface-active compounds, one or more Bleaching agents, one or more "builders" and optionally further additives, characterized in that at least one of the used Bleach is a complexing oxidizing agent according to is any one of claims 1 to 8. 10.) Detergent compositions that are free of phosphorus, nitrogen and boron-containing substances, thereby characterized in that they contain one or more surface-active substances, one or more "builders", which contain neither phosphorus nor nitrogen, a complexing oxidizing agent according to any one of claims 1 to 8 and possibly others, no pollution inducing compounds commonly used in detergent compositions. 11.) detergent compositions according to claim 10, characterized in that they contain one or more surfactants, as no "phosphorus and nitrogen "Builder" containing a sodium poly-a-hydroxyacrylate, a complexing oxidizing agent according to one 309885/1326 of claims 1 to 8 and optionally no environmental pollution inducing, usually in detergent compositions used compounds included. 309835/1326