DD144073A1 - PROCESS FOR PRODUCING STABILIZED PEROXIDE-CONTAINING SOLUTIONS - Google Patents

Abstract

Peroxide-containing solutions, preferably aqueous, in particular Bleaching and cleaning agents are made by adding long chain Alkyl or aralkyl aminoalkylidene phosphonic acid compounds stabilized. The compounds used are hydrolysis-stable, non-hygroscopic and have a good stabilizing effect. The Use of the long-chain am-inoalkylidenphosphonsäurederivate has the favorable side effect, that at the same time the surface tension lowered in the aqueous system and improves the builder effect becomes. The stabilized solutions can be used as bleaching, and Cleaning agents, in particular for the fiber-sparing bleaching of Textiles.

Description

- </ - 213 276

Title of the invention

Process for the preparation of stabilized peroxide-containing solutions

C '\

Field of application of the invention

The invention relates to a stabilization of peroxide-containing, preferably aqueous solutions, in particular of bleaching and cleaning agents, by adding long-chain alkyl or aralkyl-Aminoalkylidendiphosphonsäuren or derivatives thereof.

The stabilized solutions can be used as bleaching and cleaning agents, in particular for the fiber-sparing bleaching of textiles.

Characteristic of the known technical solutions

There are already a number of stabilizers available for the Re-. It is known to use water-insoluble stabilizers based on basic alumina silicates, such as, for example, water-soluble stabilizers. Sodium or magnesium silicate used in detergent formulations. In addition, there are other water-insoluble stabilizers for per compounds, e.g. hydrous tin oxides (W. Machu: 'The hydrogen peroxide and the per compounds, Vienna (1951) p. 195 ff.) ·

A disadvantage of these water-insoluble stabilizers is that they enter into washing and cleaning agent formulations as additional fiber in the formulation

and show no further beneficial effects for purification other than the stabilizing effect.

Furthermore, water-soluble stabilizers are described which are also compatible with other detergent components. Thus, in addition pyrophosphates such as derivatives of amino tri (methylenephosphonic acid) (in US-PS 3,234,140 and DE-OS 2,405,214), the ethane-l-hydroxy-1,1-diphosphonic acid ((in GB-PS 927 617), of ethylenediaminetetra methylenephosphonic acid) (in CH-PS, 577 552) as well as derivatives of amino acids (eg imidodiacetic acid or imidodisuccinic acid) of phenol, thiophenol, phenylurea, etc. (in Machu: the hydrogen peroxide and the per compounds).

j

The mostfen of said stabilizers have not found any technical application, since the production costs are too large in relation to the effect achieved.

Although good stabilization is achieved with a number of compounds, such as aminotrimethylenephosphonic acid or ethylenediamine tetramethylene phosphonic acid, the use of these substances in detergent formulations is disadvantageous in that they have no beneficial effect on the washing effect itself. It is also disadvantageous in the abovementioned short-chain aissinoalkylidenephosphonic acids or derivatives that some of the compounds are hygroscopic and therefore unsuitable for detergent formulations.

For detergent formulations were already organophosphorus compounds of the formula II,

ORRRO XO Ii i i''1,0X

^N p - C'-N - G - Ρ 'II

xc / 'l ox

XU _RR UX

in which R denotes H, alkyl or aryl and may be identical or different, and X represents cations, hydrogen, alkyl or aryl radicals, as hydrolysis-stable, borderline

213276

chenaktiven Builder proposed (U.S. Patent 3,344,077) "long-chain alkyl or Arylaminoalkylidenphosphonsäuren have not been used as stabilizers for peroxide-containing solutions,

Object of the invention

It is the object of the invention to develop a process for the preparation of stabilized peroxide-containing, preferably aqueous solutions, in particular of bleaching and cleaning agent mixtures, wherein the stabilizer, in addition to the stabilizing effect further, for the bleaching • and cleaning process beneficial properties, such as eg (J lowering of the surface tension of the aqueous phase and / or improved builder effect, should have.

Explanation of the essence of the invention

This goal is achieved by a method for manufacturing ·? ment of stabilized peroxide-containing solutions, preferably of bleaching and cleaning agents, by using Aminoalkylidenphosphonsäuren or their derivatives, by according to the invention the peroxygen compounds containing solution, preferably the aqueous solution, at a pH between 5 and 12 and a temperature of 5 to 100 ° C. 10.1 to 20% by weight, aminoalkylidenephosphonic acid compounds of the general formula I,

^x "i

RN [C-P (O) (OZ) ₂ II

in which R is alkyl of C ₃ H ₁₇ to C ₃₀ H ₆₁ , straight-chain or branched, or benzyl, X and Y are hydrogen or alkyl of CH to CH _Q and may be identical or different, and Z is hydrogen, alkyl of CH ₃ to C ₃₀ H ₂₁ , metal or ammonium, or mixtures of different compounds of the formula I are added. +) related to the peroxygen compound,

, * 21 3 27 6

The preparation of Aminoalkylidenphosphonsäuren takes place. In a known manner by reacting primary aliphatic or aromatic branched or straight-chain amines with formaldehyde and phosphorous acid. The reaction is carried out in sow ~ rer solution at 100 to 125 ⁰ C and using a top excess of formaldehyde ,, is advantageous to use a 20% xgen excess of phosphorous acid and a solvent "which contains a water-soluble alcohol or a ketone.

The salts, preferably the trisodium salts, the aminoalkylidenephosphonic acids are obtained in a known manner by appropriate reaction with the metal hydroxides, preferably with NaOH.

As salts of the aminoalkylidenephosphonic acids, it is possible to use those such as those of ammonium, sodium, potassium, lithium, magnesium or calcium. Preferably, the trisodium salt is used which has good water solubility.

The esters of Aminoalkylidenphosphonsäuren can serve as stabilizers.

To remove interfering impurities from the aminoalkylidene phosphonic acids, which can influence the peroxide decomposition in the solution to be stabilized in an uncontrolled manner, they are purified. For this they are recrystallized from hydrochloric acid, washed out halogen impurities and then extracted to remove unreacted amine with an alcohol-water mixture.

It has been shown that a particularly good stabilization of the solutions is achieved by using the purified aminoalkylidenephosphonic.

The stabilization of the peroxide-containing aqueous solutions, preferably the bleaching and cleaning agents, by adding the Aminoalkylidenphosphonsäuren or their derivatives of the above general formula, preferably in a purified state, to Peroxidvsrbinüung and / or H _p o » The aminoalkylidenphosphonsäureverbindung either in water + } produced.

213276

dissolved or added as a solid to the peroxide compound.

For the stabilizing effect, it is immaterial whether to be stabilized peroxide from an H ₂ O ₂ comes donating compound or one © H ₂ 0 ₂ -containing solution. The stabilizers according to the invention are to be used both in the acidic, neutral and preferably in the alkaline medium.

The stabilizers according to the invention can be combined well with other detergent and cleansing agent components.

In addition to the bleach, these generally consist of one or more surfactants and builders or builder salts for the cleaning power. Furthermore, alkaline components, fillers and the usual auxiliary agents, such as optical brighteners, soil suspending agents, sequestering agents, fragrances, dyes, etc., may be present. Also, enzymes, especially proteolytic enzymes, can be included in the formulation. The surfactants present in this composition can be selected from the group of anionic, nonionic or amphoteric surfactants and mixtures thereof.

To determine the stabilizing effect of the aminoalkylidenephosphonic acid salts, the decrease in the active oxygen content of an aqueous perborate solution is measured as a function of time. For this purpose, from a heated to 70 C aqueous solution containing 15 g / l NaBO ₂ * H ₂ O ₃ · 3H ₂ O, 1 ppm CuSO ₄ and 2 · 10 ~ ³ ^ mol / 17 soda / borax buffer, in At intervals, samples were taken (10 g each), quenched, and the active oxygen content therein determined by iodometry. From the decay curve of the sodium perborate, the half-life is graphically determined. The comparison of the half-lives without and in the presence of Aminoalkylidsnphosphonsäureverbindungen invention shows a slowing of peroxide decomposition, which is a measure of the stabilizing effect for the latter case under otherwise identical experimental conditions. In a homologous series of compounds of formula I hangs under the same experimental conditions

Stabilizing effect of the salts of Aminoalkylidenphosphonsäuren of their concentration and on the length of the hydrophobic radical from »öer addition of the stabilizer can be either dissolved or carried out in solid form. It has been found that the stabilizing effect in the case of the relatively long-chain aminoalkylidenephosphonic acid salts (R greater than C ₁₂ H _{2) is} surprisingly particularly pronounced, with a simultaneous decrease in the surface tension of the aqueous system.

Assuming that the S.tsbilisierungseffekt for peroxide-containing solutions depends on the particular structure of the functional group of Aminoalkylidenphosphonsäureverbindungen, one should actually expect the increase of the hydrophobic radical R, a decrease in the Stabili-.sierungswirkung.

The results of studies on salts of the formula I in which R = C ₀ H., C, HL · ^{υηα <^} n ^H · 17 ^is show in the order listed, the expected decrease in the stabilizing effect "

When salts of the formula I having a chain length greater than R ^c j2 ^H 25 ^3tei 9, however, the stabilizing effect of ^t at comparable concentrations surprisingly again.

The advantages of using the longer chain aminoalkylidene phosphonic acid compounds as stabilizers for peroxide containing solutions, preferably bleaching and cleaning agents, is that

the stabilizing effect is substantially improved in comparison to short-chain aminoalkylidenephosphoic acid compounds.

- The compounds are hydrolysis-stable and non-hygroscopic V. -

- The fiber damage during the bleaching process is lower than when using unstabilized bleaching agents and also

the surface tension of the aqueous system is lowered by the aminoalkylidene phosphonic acid compounds.

₇ 213 27 6

embodiments

General rule

The stabilized peroxide-containing aqueous solutions are prepared by mixing the peroxide-containing compound and / or H ₂ O with the aminoalkylidenephosphonic acid compound at a temperature between 5 and 100 C and at a pH between 5 and 12 and dissolving in water it is immaterial whether the aminoalkyl phosphonic acid compound is dissolved in water or added as a solid to peroxide-containing aqueous solution. "

Then, according to the method described below, the disintegration times of the stabilized peroxides are determined iodometrically. The half-life of the unstabilized peroxide-containing solution is compared with a concentration series of stabilized peroxide-containing solutions.

Example 1 (comparative example)

A standard solution is prepared as follows: 3.75 g of NaBO ₂ · H ₂ O · 3H ₂ O are mixed with ₄ and 2 x 10 mol / i of soda / borax buffer with 1 ppm CuSO and in 250 ml of doubly distilled H ₂ O. "

In a sample of this solution, the active oxygen content is determined iodometrically «

Subsequently, the solution is heated to 70 C in a thermostatted vessel and at intervals (of a few minutes) samples of 10 g each are taken, quenched and the active oxygen content is determined there as well. "

The obtained values are evaluated graphically. "From the decay curve a half-life of t /" = 22.8 min, · - results

Example 2:

To the standard solution prepared according to Example 1 are added different amounts of purified ethylamine bis (ethylene phosphonic acid trisodium salt) (C compound).

213 2 7 6

added and the solutions of different concentrations (see * concentration range) at predetermined Zeitabständsn the active oxygen content, as described in Example 1, determined · the half-lives are determined · The increase aer half-lives as a function of aer concentration of C ₂ ~ compound shows from the decay curves following Concentration series:

Concentration / _ / i / η η οκ η n λ o a

Ο, compound Λί / V ° 0.25 0.5 12 4

Half-life / min / 22.75 34.5 480 56.5 83 142.5

Example 3 ;:

To the standard solution prepared according to Example 1 are different amounts of purified butylamine ~ bis (methylenephosph

acid trisodium salt) (C compound)

and in the solutions of different concentration (cf. concentration series) at fixed time intervals the active oxygen content, as described in Example 1,

The half-lives are determined from the decay curves. The influence of different concentrations of C. compound and the dea hydrocarbon radical is shown by the following concentration series in comparison with Example 2:

Concentration / "/ -, / _{n n oc} - _{n κ} ι o α C ₄ compound" / g / V O 0.25 0.5 1 2 4

Half-life / min / 22.75 31.6 45.3 54.3 75.2 97 ₉ 0

Example 4s. ,

To the standard solution prepared according to Example 1, different amounts of purified Octylamin ~ biö (tnefhy · lenphosphonsäuretrinatfiiirasalz) (C compound) are added and in the solutions of different concentration (see · Concentration series) at fixed intervals the active oxygen content, as in Example 1 described, determined · The half-life times are determined from decay curves. The influence of different concentrations of compound and of the hydrocarbon radical is shown in the following.

⁹ 213276

series of tests in comparison with examples 2 to 3:

Concentration _{/ / χ / G O5} ι ₂ 4

C compound ' ^{a /} ' - · ···

Half-word time / min / 22.75 37.8 47 53, y3 55

Example 5,

become/

To the standard solution prepared according to Example X, different amounts of purified dodecylamine-bis (methylenephosphonic acid trisodium salt) (C ₂ "* compound) and in the solutions of different concentration (see * concentration series) at fixed intervals of the active oxygen content, as described in Example 1, determined · from the decay curves, the half-lives are determined · the influence of different concentrations of ₍₂ ^-Ve: r * bond, and the hydrocarbon residue shows the following series of concentrations in comparison with examples 2 to ^4:;? '...

Concentration / "/ λ / η η" η * ι ο λ C ₁₂ bond / 9 / V ° 0.25 0.5 1 2 4

Half-life / min / 22.75 21.5 34 _β Ο 58.5 79.5

Example 6:

To the standard solution prepared according to Example 1, different amounts of purified hexadecylamine-bis (methylenphosphonsäuretrinatriuinsalz) (C ^ compound) and given in the solutions of different concentration (see · concentration series) at fixed intervals of the active oxygen content, as described in Example 1, determined , The half-lives are determined from the decay curves. The influence of different concentrations of C., .-

ib

tion and that of the hydrocarbon radical shows the following concentration series in comparison with Examples 2 to 5:

concentration _{/ n} / i / _n ηιι ' η οκ η κ λ C ^ compound / 9 / V. O 0.125 0.25 0.5 1

Half-time / min / 22.75 39 56 105.5 240

Example 7a:

To the standard solution prepared according to Example 1, different amounts of purified octadecylbis (methylenphosphonsäuretriatriumsalz) (C ^ ₈ compound) gageben and in the solutions of different concentration (see »concentration series) at fixed intervals of the active oxygen content, as described in Example 1, determined »The half-lives are determined from the decay curves» The influence of different concentrations of CQ compound and that of the hydrocarbon radical is shown in the following concentration series in comparison with Examples 2 to 6:

Concentration / "/% / η η -toc η ο« 'η κ

.g-connection 'v / * - t * * *

Half-life / min / 22.75 59 143 -> 300

Example 7b:

To the standard solution prepared according to Example 1 are added different amounts of not particularly purified octadecylamine bis (methylenephosphonic acid trisodium salt) (C "compound) and determined in the solutions of different concentration (see concentration series) at fixed time intervals the active oxygen content as described in Example 1 "The half iris times are determined from the decay curves." The following concentration series show the influence of different concentrations of C 1 compound and of the cleaning effect in comparison with Example 7a.

Concentration / "/ w η η i r r η o η κ

C ₁₈ -Verbindüng / ^9/1 /. O 0.125 0.25 0.5

Half-life / min / 22.75 27 29 61

213 27 6

Example 8:

To the standard solution prepared according to Example 1 are additionally 1.25 g of a detergent mixture consisting of 10 to 20 % alkylbenzenesulfonate, 40 to 50 % sodium tripolyphosphate, 5 to 10 % soap, 2 to 5 % sodium disilicate, 10 to 15 % soda, δ to 12% sodium sulfate and 1 to 3 % carboxymethylcellulose (CMC), brightener / perfume and water, which corresponds to a commercial detergent formulation (formulation A), and the influence on the half-life in the presence of different concentrations of hexadecylamine-NfN-bis (ethylenebisphosphonic acid, trisodium salt) Stabilizing effect of C _ß compound in combination with the commercial detergent formulation is illustrated by the following concentration series:

Concentration / / η / η η o * η κ ^ -compound ^ ^{/ λ /} ° ° · ²⁵ ° · ⁵

Half-life / min / 37 72 155

Example 9:

To determine the tensile strength according to TGL 29799/04, 50 washings with a concentration of cleaning agent (formulation A, cf # Example 8) of 5 g / l _{# are} carried out on a cotton test fabric and a tensile strength loss of 32 % is determined. As a damage factor, 1.85 is determined under these conditions. When the determination is carried out in the presence of 0.5 % hexadecylamine-N, N-bis (methylenephosphonic acid, trisodium salt), the tensile strength loss is reduced to 19 % and the damage factor to 1 under otherwise identical test conditions , 48,

Claims (1)

invention claim A process for the preparation of stabilized peroxide-containing solutions, preferably bleaches and cleaning compositions containing inorganic and / or organic peroxide oxygen compounds, by using Aminoalkylidenphosphonsäureverbindungen, characterized in that the peroxygen compounds containing solutions, preferably the aqueous solutions, in the pH range 5-12 and at a temperature of 5 to 100 ⁰ C: 0 _# l to 20 mass%, relative to the peroxygen compound, Aminoalkylidenphosphonsäureverbindungen of the general formula I, R - N j C - P (O) (OZ) ₂ j I in which R can be alkyl of CH ₇ to C ₃₀ H-, branched or straight-chain, or benzyl, X and Y denote identical or different substituents such as hydrogen or -alkyl of CH ₃ to C.Hg and Z = hydrogen, Alkyl of CH ₃ to C _Q H ₂₁ , metal or ammonium may be added individually or as mixtures. Process according to item 1, characterized in that salts of the aminoalkylidene phosphonic acids, such as those of ammonium, sodium, potassium, lithium, magnesium, calcium, are used * Process according to items 1 and 2, characterized in that> the aminoalkylidenephosphonic acid compound is added in solid form, Process according to items 1 and 2, characterized in that the aminoalkylidenephosphonic acid compound is added in solution 1, preferably in aqueous solution. Process according to items 1, 3 and 4, characterized in that, when using Aminoalkylidenphosphonsäureestern at the same time to peroxides inert solvents, such as ketones, are added as a solubilizer.