WO2010010003A2

WO2010010003A2 - Catalysed peroxide bleach ("catalyst-bleach variant 3: all-in-one)

Info

Publication number: WO2010010003A2
Application number: PCT/EP2009/058958
Authority: WO
Inventors: Herbert Bachus; Christian Dörfler; Bernd Horrer
Original assignee: Cht R. Beitlich Gmbh
Priority date: 2008-07-23
Filing date: 2009-07-14
Publication date: 2010-01-28
Also published as: DE102008034231A1; EP2304012A2; WO2010010003A3

Abstract

The invention relates to solutions obtained by reacting at least one Mn-metal complex and at least one aminocarboxylic acid used as a complexing agent, and to the use thereof during the bleaching of cellulose substrates or during the treatment of waste water.

Description

Catalyzed peroxide bleaching ("catalyst bleach variant 3: all-in-one")

The invention relates to solutions obtainable from the reaction of at least one Mn metal complex and at least one aminocarboxylic acid as complexing agent and their use in the bleaching of cellulosic substrates or in the treatment of wastewater.

Hydrogen peroxide is one of the most important bleaching agents today, which decomposes when used in water and oxygen. In contrast to chlorine-containing bleaching agents, there are no toxic or carcinogenic halogen-containing substances. Thus, it continues to gain ground in many industrial areas. Typical applications for hydrogen peroxide are the paper and pulp industry, the textile finishing or household detergents, where hydrogen peroxide forms on dissolving perborates or percarbonates. 2,200,000 tonnes of hydrogen peroxide are produced each year, 50% for paper and pulp bleaching and 10% for textile bleaching.

As a disadvantage of hydrogen peroxide, the need for activation by heating or by addition of alkali as well as the running in this type of activation main reaction of decomposition to be considered pale ineffective oxygen, so that only a small part of the actual bleaching power is utilized. The patent literature describes many activators and catalysts that promise improvement here. In household detergents activators have prevailed that form peracids with hydrogen peroxide, which already act bleaching at low temperature.

Since such activators act stoichiometrically, high costs and a high additional COD load (chemical oxygen demand) for the wastewater, so that in industrial processes activators are hardly used until today.

On the other hand, catalysts are only used in small quantities. However, in the field of treatment of cellulosic fibers, as in the paper or textile industry, there are hardly any technically established catalysts for peroxide bleaching (see "Applications of Transition Metal Catalysts to Textile and Wood Pulp Bleaching", Angew Chem. Int. Ed. 2006, 45, 206-222, this review article refers to additional references (ref XX)).

The first catalyst in a commercial household detergent was a dinuclear manganese complex with one 1,4,7-trimethyl-1,4,7-triazacyclononanone ligand (L) per Mn atom, where the Mn atoms are linked by three oxygen bridges:

[LMn ^IV (μ-O) ₃ Mn ^IV L] ²⁺ Y _q (Cat. 1)

For example hexafluorophosphate can be used as the anion (Y = PF ₆ ^' , q = 2, Katl PF ₆ ). The catalyst was first used by Wieghardt et al. (Refs. 29-32), and is effective at 40 ^° C. and pH ranges of 9 to 11, but was due to Fiber damage of the cellulosic material after a short time taken back from the market.

Another catalyst with higher pH tolerance and temperature stability has also been described by Wieghardt et al. (Ref. 37), which is a dimer bridged triazacyclononanone derivative:

[Mn ^IV Mn ^πi (μ-O) 2 (μ-CH ₃ COO) (Me4dtne)] ²⁺ (cat. 2)

Me ₄ dtne = 1, 2-bis (4,7-dimethyl-l, 4,7-triazacyclonon-1-yl) ethane.

These catalysts are used to save lye, since then does not need to be neutralized. In the case of textile fiber materials, high pH values in treatment baths also result in a deterioration in the feel of the goods, which can no longer be completely compensated by subsequent plasticizer additions.

These catalysts can also lower while still providing the desired white effect treatment temperatures in the textile bleaching of 98 ⁰ C or more, for example 80 ⁰ C. The lower the treatment temperature and the pH, the lower the tendency of textiles to form creases, as an inner softness of the product is retained.

However, a major disadvantage of the catalysts are fiber damaging effects. The cause of the fiber damage of cat. 1 is believed to be that the catalyst converts to a less selective species during use, and thereby the resulting Metabolites or the end-stage manganese ions cause catalytic damage. The whitening-enhancing effect of the catalyst is partially or completely lost.

In pulp bleaching, it is common to sequester and / or remove the free manganese ions prior to bleaching with hydrogen peroxide with EDTA or DTPA. However, these two complexing agents are neither biodegradable nor are they eliminated in sewage treatment plants. In addition, as they are suspected of having toxicant heavy metal remobilizing properties and are detected in drinking water reservoirs, their use in many countries is restricted or entirely prohibited. Nevertheless, EDTA and DTPA still dominate complexing agent use in pulp bleaching. These two chelating agents also allow efficient bleaching with cat. 1, since they bind the manganese released from the catalyst during the bleaching process and thereby reduce the peroxide decomposing and cotton damaging effect.

WO 2007/042192 A1 describes bleaching compositions which comprise a defined Mn catalyst, an aminocarboxylate-based complexing agent, hydrogen peroxide and, moreover, a carbonate or borate buffer. The buffer keeps the pH constant over a certain range and thus contributes to a further stabilization of the bleaching compositions and in particular of the Mn complexes contained therein. The complexing agents used can be EDTA, HEDTA, NTA, N-hydroxyethylaminodiacetic acid, DTPA, MGDA or alanine-N, N-diacetic acid. Apart from buffers, amines are also used for stabilizing bleach compositions, as described in DE 197 02 734 A1. An indispensable component of the compositions described therein are biodegradable aliphatic or alicyclic amines having 1 to 12 C atoms; In addition, these amines, which contain only one N atom in each case, can additionally carry (also in each case several) hydroxyl groups. As complexing agents, for example, aminocarboxylates are used in these compositions, especially those which contain an N, N-diacetic acid grouping, for example EDTA, NTA, aspartic acid / glutamic acid or .beta.-alanine-N, N-diacetic acid, iminodiacetic acid.

EP 1 967 577 A1 describes mixtures which use the complexing agent iminodisuccinic acid in peroxide bleaching in order to increase the effectiveness of manganese catalysts. It is necessary here at least a 10-fold excess of complexing agent to the catalyst.

WO 2008/098921 A1 describes storage-stable mixtures of surfactants and manganese catalysts. Aminocarboxylic acids are mentioned here as complexing agents, the surfactant and the manganese catalyst being premixed, but the complexing agent must be added separately. The complexing agent must also be used here with a large excess - the 0.2 ml / l described in the examples correspond to approximately 200 mg / l, but the catalyst is used only at 2.8 mg / l. Against this background, it is an object of the present invention to improve bleaching processes of the prior art. In particular, it is an object to reduce the amounts of the components to be used, in particular the complexing agent, but nevertheless to achieve the prior art comparable, or even better bleaching results. Another object is to simplify the prior art methods.

By solving both tasks - reduction of the amounts of the starting substances and simplification of the process - a significant cost reduction should be achieved, with improved or at least the same bleaching result.

In a first embodiment, the object underlying the invention is achieved by compositions in the form of homogeneous (aqueous) solutions which are obtainable from the reaction of

(a) at least one metal complex of manganese-based of the general formula I [L _n Mn _m X p] ^z Y _q (I) wherein

L represents a ligand of an organic molecule having a number of nitrogen atoms which coordinate via its nitrogen atoms to the manganese center (centers); Mn for manganese in the oxidation state III or IV; n and m are each independently an integer of 1 to 3; X for a coordination or bridge species; p is an integer having a value of 0 to 4; z for a charge of the complex, which is a whole negative and positive

Number includes;

Y stands for a counter ion, whose type depends on the charge z of the complex, in particular for PF ₆ ^" , and q = z / [charge Y] is with

(b) at least one aminocarboxylic acid or its partially or completely neutralized salt (s), wherein the weight ratio of component (b) to component (a)

0.1: 1 to 1000: 1.

Homogeneous solutions are to be understood as meaning those which consist of only one phase. In particular, it does not already contain such solid substrates, for the bleaching of which the homogeneous solutions are later used. The term aqueous in the sense of the present invention comprises hydrophilic solutions which contain at least 1% by weight of water.

Complexes of the general formula (I) are known, for example, from WO 94/21777 A1, to which reference is made to the full extent.

In the context of the present invention, coordination species are understood in particular to be monodentate ligands. The term bridging species is taken to mean those multidentate ligands which combine at least two metal atoms (bridging) (for a more detailed explanation of these terms, see "Coordination Chemistry" by L. Gade, Wiley-VCH 1998). It has now been found that

1) aminocarboxylic acids convert these Mn catalysts, in particular as constituents of liquid ready-to-use preparations, into substantially more storage-stable species,

2) Such preparations considerably simplify the application and reduce the costs of production, storage and transport,

3) far less complexing agent has to be used for the application, and

4) while the effects achieved in terms of whiteness achieved and / or residual peroxide levels are even increased.

Shelf life in the sense of the present invention means that at storage temperatures between 3 and 50 ^° C., the solutions according to the invention lose less than 50%, in particular less than 20%, of their original bleach-activating effects over a period of 3 months.

In a preferred embodiment of the present invention, the mixtures are characterized in that the complexes are salts of the general formula II

[LMn ^IV (μ-O) ₃ Mn ^IV L] ²⁺ Y _q (II) with

L = 1, 4,7-trimethyl-l, 4,7-triazacyclononanon and / or the general formula III

[Mn ^IV Mn ^iπ (μ-O) 2 (μ-CH ₃ COO) (Me4dtne)] ²⁺ (III) with

Me ₄ dtne = l, 2-bis (4,7-dimethyl-l, 4,7-triazacyclonon-1-yl) ethane. In addition, it has been found that aminocarboxylic acids and manganese complexes can be formulated into aqueous surfactants (c) without the storage stability of the solutions obtained being reduced.

The surfactant (s) is / are preferably present in said solution (s) in an amount ranging from 20 to 90% by weight, more preferably from 40 to 70% by weight.

The at least one aminocarboxylic acid or its partially or completely neutralized salts is preferably selected from the group consisting of NTA, EDTA, DTPA, MGDA, GLDA, IDS and PEICM (definition see Tab. 2, concentration of liquid labels 30 to 40% by weight).

As a particularly preferred embodiment, it has been found that the readily biodegradable iminosuccinic acid - as a free acid or in the form of its salts - again increases the good effect already known from EP 1967577 A1. This is all the more surprising as the complexing constants are a weaker complexing agent compared to DTPA.

The above-defined components aminocarboxylic acid (b) and manganese complex (a) may be preferred in different proportions in the mixtures according to the invention. However, for the purposes of the present invention, preference is given to adjusting the weight ratio of component (b) to component (a) in the range from 0.1: 1 to 1000: 1, more preferably within a range from 0.2: 1 to 10: 1 and more preferably in the range of 0.2: 1 to 1: 1 with the advantage of higher whiteness levels. Furthermore, the above-defined solutions of aminocarboxylic acid (n) and manganese complex (s) with the surfactant component (s) may be preferred in various proportions in the mixtures according to the invention. For the purposes of the present invention, preference is given to adjusting the weight ratio of component (a) to component (c) in a ratio of 1:10 to 1: 1000, more preferably within a range of 1:50 to 1: 500 with the advantage of higher whiteness.

Preferably, the solutions according to the invention are obtained in such a way that the reaction between components (a) and (b), optionally in the presence of surfactant component (c), at elevated temperature, in particular in a temperature range of 60 to 90 ⁰ C, performs , A temperature range of 75 to 85 ⁰ C is considered to be particularly preferred. In such preparation of the solution (s), the elevated temperature is preferably maintained over a period of 30 to 300 minutes.

It is particularly preferred if the temperature in the specified ranges over a period of 60 to 180 minutes is maintained. Subsequently, it is again cooled to room temperature (which is understood in the context of the present invention, a temperature of 25 ⁰ C).

In this way, the solutions of the invention can be produced quickly, easily and reproducibly. Alternatively, the reaction between components (a) and (b), optionally in the presence of surfactant component (c), may also be carried out at room temperature for a period of 1 to 3 weeks.

The solutions according to the invention differ from the "batch solutions" in that a clear color lightening from red to yellow has taken place, and in many cases even complete decolorization occurs in the reaction.

The concentration of component (a) during the reaction is preferably set in a range from 0.02% to 0.5% by weight. The concentration of the component (b) during the reaction is alternatively or cumulatively preferably adjusted in a range of 0.05 to 0.5% by weight.

These concentrations are significantly higher than the concentrations of components (a) and (b) in the actual bleaching solution. The advantage of these increased concentrations is the faster formation of the solutions according to the invention from the components. If both components were mixed only during use, ie in the bleaching solution, a negative side reaction would be the oxidative destruction of the catalyst by hydrogen peroxide, so that the whiteness increase is reduced, see test series 1.

It is also advantageous that the solutions obtained as it were as a concentrate require less transport effort, which in turn has a significant cost savings result. The solutions according to the invention are preferably obtained by reacting the reactions between components (a) and (b), if appropriate in the presence of surfactant component (c), in a pH range <5, in particular at a pH of 4 , 5, performs. If the solutions according to the invention have a slightly acidic pH, this results in a further increase in storage stability.

In a second embodiment, the object underlying the invention is achieved by the use of the solutions according to the invention for the peroxide bleaching of cellulosic substrates. For the purposes of the present invention, cellulosic substrates are understood in particular to be cotton or shredded wood material.

The solutions can also be used in textile finishing, household washing, pulp or paper bleaching.

In a third embodiment, the object underlying the invention is achieved by the use of the solutions according to the invention for the treatment of wastewater.

In a third embodiment, the object underlying the invention is achieved by the use of the solutions according to the invention for the treatment of wastewater. Ausführunαsbeispiele:

Oxygen-bridged dimeric triazacyclonone complexes of manganese were normally intensely colored. Thus, a 0.1% solution of a complex of the formula (II) with Y = PF _{6 has} an intense red color. When only 0.3% of the iminodisuccinic acid salt (100% dry matter) was added to this solution, the solution lost its color at room temperature within 2 weeks.

Was heated, the red solution for 2 h at 8O ⁰ C, so there was a complete discoloration. Surprisingly, the catalyst thereby did not lose its activity, but rather both mixtures were superior in their effect to the original product, see Experimental Series 1, Example B2 and B3 to Comparative Example C2. Both mixtures of B2 and B3 had almost 100% of catalytic activity after 3 months, see B5 and B6; By contrast, a 0.1% catalyst solution without addition of complexing agent after only 3 months at 25 ^° C. only led to half the increase in whiteness, see V5 in comparison to V3 and V4. When all three components, complexing agent, manganese catalyst and surfactant were mixed, the maximum brightness loss after 3 months still remained below 10%, see B8 to B7. This results in a significantly increased storage stability of the mixtures according to the invention.

In the application examples, 0.3% of catalyst and 0.3% of complexing agent, based on the liquid merchandise used. This means that the catalyst was used at least in 2.5-fold excess. Here, too, arose at 2 h and 80 ⁰ C. complete decolorization of the mixture, both in the presence of surfactant agents and without.

Test series 1:

In the bleaching, a commercially available cotton tricot was used as raw material at a liquor ratio of 1: 10 in treated infrared heated Labomat bombs 20 minutes at 80 ⁰ C, then washed hot and cold and the whiteness determined.

Was an indication of the relative amounts in weight% on Felosan NFG ^®, which was used in each case with 1 g / L. In addition, 1.3 mL / L NaOH 50% and 5 mL / LH ₂ O ₂ 35% were used as further additives. All materials were added at room temperature before heating.

Table 1

a) Use of surfactant, cat. 1 (y = PF ₆ ^~ ) and IDS without premix (not according to the invention) b) surfactant and cat. 1 (y = PF ₆ ^~ ) are premixed and adjusted to pH 4.5 with acetic acid (WO 2008/098921), IDS dosed separately (not according to the invention) c) surfactant separately, cat. 1 (y = PF ₆ ^~ ) in a concentration of 0.5 to 3% and IDS premixed according to Table 1, pH of 4.5 adjusted with acetic acid and tempered according to specified temperature and time (according to the invention). By way of example, the catalyst was dissolved in water at a concentration of 0.5 to 3%, and the amount of IDS required according to Table 1 was added. d) surfactant, cat. 1 (y = PF ₆ ^~ ) and IDS premixed, pH 4.5 adjusted with acetic acid and tempered according to specified temperature and time (according to the invention)

A commercially available liquid detergent ^® NFG Felosan were, for the patterns and comparative examples and the following sodium salt solutions from complexing agents used:

Table 2:

*) TS: dry substance on neutralized complexing agent of the commodity

In the bleaching was used as raw material, a commercially available cotton tricot having a DP value of 2298 at a liquor ratio of 1: treated 10 in infrared heated Labomat bombs 20 minutes at 8O ⁰ C, thereafter washed hot and cold, and determines the residual peroxide, the whiteness and the damage factor ,

Preparation of Storage-stable Surfactant Solutions Containing a Catalyst and Complexing Agent

In this case, the catalyst and the complexing agent were stirred into the detergent and adjusted to the desired pH with acetic acid or formic acid. This mixture was then heated to 60 to 90 ⁰ C, preferably 75-85 ⁰ C and at this temperature for 30-300 minutes, preferably 60-180 minutes treated. From the original deep red solution emerged colorless to pale red-colored, clear solutions that were stable at temperatures up to 25 ⁰ C and 3 months storage time and lost less than 20% of their whiteness-enhancing potential, see test series. 1

For test series 2 Comparative Example C4 containing a phosphonate was, and examples of the invention Bl through BI l after mixing the three components of surfactant, complexing agent and catalyst for 2 hours at 8O ⁰ C tempered.

In addition to the chemicals specified in Experiment 2, 1.3 mL / L NaOH 50% and 5 mL / LH ₂ O ₂ 35% were used as further additives. All substances were at room temperature before heating added. In the bleaching another cotton tricot was used as raw material at a liquor ratio of 1: 10 in treated infrared heated Labomat bombs 20 minutes at 80 ⁰ C, then washed hot and cold and the whiteness determined.

Table 3:

*) Complexing agent based on respective liquid merchandise. a) Use of surfactant and cat. 1 (y = PF6 ^~ ) without premix (not according to the invention) b) surfactant and cat. 1 (y = PF ₆ ^~ ) premixed and adjusted to pH (WO 2008/098921), complexing agent separately dosed (not according to the invention) c) surfactant separately, cat. 1 (y = PF ₆ ^~ ) and complexing agent premixed, pH adjusted and tempered at 8O ⁰ C for 2 hours d) surfactant, cat. 1 (y = PF ₆ ^~ ) and complexing agent premixed, pH adjusted and tempered for 2 hours at 8O ⁰ C.

From Examples B8 to BI l shows that the blended catalyst and complexing agent in the surfactant had become much more effective in its effect compared to Formulation Comparison V3. All blended aminocarboxylic acids - Bl to B7 - reached at least the whiteness of separately added in the same amount IDS from V3 and gave better results than the non-inventive Phosponat DTPMP in V4.

Surprisingly, it was found that the readily biodegradable chelating iminodisuccinic acid (Baypure CX ^®) compared to the other complexing agents used in turn scored the better whiteness and this with increased residual peroxide to all other complexing agents. If you were to extend the bleaching time, you could also use this more peroxide bleaching.

Claims

claims:

1. Homogeneous solutions obtainable from the reaction of

(a) at least one manganese-based metal complex of general formula I

[L _n Mn _m Xp] ^z Y _q (I) where

L represents a ligand of an organic molecule having a number of nitrogen atoms which coordinate via its nitrogen atoms to the manganese center (centers); Mn for manganese in the oxidation state III or IV; n and m are each independently an integer of 1 to 3;

X for a coordination or bridge species; p is an integer having a value of 0 to 4; z is a charge of the complex comprising a whole negative and positive number;

Y stands for a counter ion, whose type depends on the charge z of the complex, in particular PF ₆ ^" , and q = z / [charge Y] is with

(b) at least one aminocarboxylic acid or its partially or completely neutralized salts, wherein the weight ratio of component (b) to component (a) is from 0.1: 1 to 1000: 1.

2. Solutions according to claim 1, characterized in that the complexes salts of the general formula II

[LMn ^IV (μ-O) ₃ Mn ^IV L] ²⁺ Y _q (II) with

L = 1, 4,7-trimethyl-l, 4,7-triazacyclononanon and / or the general formula III

[Mn ^IV Mn ^iπ (μ-O) 2 (μ-CH ₃ COO) (Me4dtne)] ²⁺ (III) with

Me ₄ dtne = l, 2-bis (4,7-dimethyl-l, 4,7-triazacyclonon-1-yl) ethane.

3. Solutions according to any one of claims 1 or 2, characterized in that they contain surfactants (c) preferably in an amount of 20 to 90 wt .-%, particularly preferably from 40 to 70 wt .-%, included.

4. Solutions according to any one of claims 1 to 3, characterized in that the at least one aminocarboxylic acid or its partially or completely neutralized salts, is selected from the group NTA, EDTA, DTPA, MGDA, GLDA, IDS and PEICM.

5. Solutions according to claim 4, characterized in that the at least one aminocarboxylic acid is iminodisuccinic acid (IDS).

6. Solutions according to any one of claims 1 to 5, characterized in that it is obtained from the reaction of components (a) and (b), optionally in the presence of component (c), at elevated temperature, in particular in a temperature range from 60 to 90 ⁰ C, receives.

7. Solutions according to claim 6, characterized in that one maintains the elevated temperature over a period of 30 to 300 min.

8. Solutions according to any one of claims 1 to 5, characterized in that it is obtained from the reaction of components (a) and (b), optionally in the presence of component (c), at room temperature over a period of 1 to 3 weeks ,

9. Solutions according to any one of claims 1 to 8, characterized in that one sets the concentration of component (a) during the reaction in a range of 0.02 wt.% To 0.5 wt.%.

10. Solutions according to any one of claims 1 to 9, characterized in that one sets the concentration of the components (b) during the reaction in a range of 0.02 wt.% To 1 wt.%.

11. Solutions according to any one of claims 1 to 10, characterized in that one sets the concentration of the components (c) during the reaction in a range of 20 wt.% To 35 wt.%.

12. Solutions according to any one of claims 1 to 11, characterized in that one carries out the reaction in a pH range <5, in particular at a pH of 4.5.