EP2304012A2 - Blanchiment au peroxyde catalysé (variante 3 de blanchiment par catalysateur: tout-en-un) - Google Patents

Blanchiment au peroxyde catalysé (variante 3 de blanchiment par catalysateur: tout-en-un)

Info

Publication number
EP2304012A2
EP2304012A2 EP09780540A EP09780540A EP2304012A2 EP 2304012 A2 EP2304012 A2 EP 2304012A2 EP 09780540 A EP09780540 A EP 09780540A EP 09780540 A EP09780540 A EP 09780540A EP 2304012 A2 EP2304012 A2 EP 2304012A2
Authority
EP
European Patent Office
Prior art keywords
solutions according
reaction
component
range
solutions
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP09780540A
Other languages
German (de)
English (en)
Inventor
Herbert Bachus
Christian Dörfler
Bernd Horrer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
CHT Germany GmbH
Original Assignee
CHT R Beitlich GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by CHT R Beitlich GmbH filed Critical CHT R Beitlich GmbH
Publication of EP2304012A2 publication Critical patent/EP2304012A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3947—Liquid compositions
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3932—Inorganic compounds or complexes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/10—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen
    • D06L4/12—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen combined with specific additives
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/10—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen
    • D06L4/15—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen using organic agents

Definitions

  • 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.
  • 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:
  • 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.
  • Me 4 dtne 1, 2-bis (4,7-dimethyl-l, 4,7-triazacyclonon-1-yl) ethane.
  • 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.
  • 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.
  • pulp bleaching it is common to sequester and / or remove the free manganese ions prior to bleaching with hydrogen peroxide with EDTA or DTPA.
  • these two complexing agents are neither biodegradable nor are they eliminated in sewage treatment plants.
  • 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.
  • amines are also used for stabilizing bleach compositions, as described in DE 197 02 734 A1.
  • 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.
  • 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.
  • Another object is to simplify the prior art methods.
  • the object underlying the invention is achieved by compositions in the form of homogeneous (aqueous) solutions which are obtainable from the reaction of
  • 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
  • component (b) at least one aminocarboxylic acid or its partially or completely neutralized salt (s), wherein the weight ratio of component (b) to component (a)
  • aqueous in the sense of the present invention comprises hydrophilic solutions which contain at least 1% by weight of water.
  • coordination species are understood in particular to be monodentate ligands.
  • 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
  • aminocarboxylic acids convert these Mn catalysts, in particular as constituents of liquid ready-to-use preparations, into substantially more storage-stable species
  • 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.
  • the mixtures are characterized in that the complexes are salts of the general formula II
  • Me 4 dtne l, 2-bis (4,7-dimethyl-l, 4,7-triazacyclonon-1-yl) ethane.
  • 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).
  • aminocarboxylic acid (b) and manganese complex (a) may be preferred in different proportions in the mixtures according to the invention.
  • 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.
  • 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.
  • the elevated temperature is preferably maintained over a period of 30 to 300 minutes.
  • 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).
  • 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.
  • 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.
  • 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.
  • 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.
  • the object underlying the invention is achieved by the use of the solutions according to the invention for the peroxide bleaching of cellulosic substrates.
  • 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.
  • the object underlying the invention is achieved by the use of the solutions according to the invention for the treatment of wastewater.
  • the object underlying the invention is achieved by the use of the solutions according to the invention for the treatment of wastewater.
  • 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.
  • a commercially available liquid detergent ® NFG Felosan were, for the patterns and comparative examples and the following sodium salt solutions from complexing agents used:
  • 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
  • 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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Wood Science & Technology (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Inorganic Chemistry (AREA)
  • Textile Engineering (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Detergent Compositions (AREA)
  • Paper (AREA)
  • Catalysts (AREA)

Abstract

L'invention concerne des solutions pouvant être obtenues à partir de la réaction d'au moins un complexe métallique Mn et d'au moins un acide aminocarboxylique servant d'agent complexant, ainsi que leur utilisation lors du blanchiment de substrats cellulosiques ou lors du traitement d'eaux usées.
EP09780540A 2008-07-23 2009-07-14 Blanchiment au peroxyde catalysé (variante 3 de blanchiment par catalysateur: tout-en-un) Withdrawn EP2304012A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102008034231A DE102008034231A1 (de) 2008-07-23 2008-07-23 Katalysierte Peroxidbleiche ("Katalysator-Bleiche-Variante 3: All-in-one")
PCT/EP2009/058958 WO2010010003A2 (fr) 2008-07-23 2009-07-14 Blanchiment au peroxyde catalysé (variante 3 de blanchiment par catalysateur: tout-en-un)

Publications (1)

Publication Number Publication Date
EP2304012A2 true EP2304012A2 (fr) 2011-04-06

Family

ID=41428587

Family Applications (1)

Application Number Title Priority Date Filing Date
EP09780540A Withdrawn EP2304012A2 (fr) 2008-07-23 2009-07-14 Blanchiment au peroxyde catalysé (variante 3 de blanchiment par catalysateur: tout-en-un)

Country Status (3)

Country Link
EP (1) EP2304012A2 (fr)
DE (1) DE102008034231A1 (fr)
WO (1) WO2010010003A2 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2103604A1 (fr) 2008-03-17 2009-09-23 Evonik Degussa GmbH Procédé de fabrication d'épichlorhydrine
DE102014202223A1 (de) * 2014-02-06 2015-08-06 Henkel Ag & Co. Kgaa Verwendung von Aminocarbonsäuren zur Stabilisierung von wasserarmen flüssigen Wasch- oder Reinigungsmittelkomponenten

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9305598D0 (en) 1993-03-18 1993-05-05 Unilever Plc Bleach catalyst composition
DE19702734A1 (de) 1997-01-27 1998-07-30 Basf Ag Wasch- und Reinigungsmittel-Formulierung mit einem Bleichsystem sowie einer Mischung aus Aminen und Komplexbildnern
PT1741774E (pt) * 2005-07-08 2008-11-17 Unilever Nv Composições para máquinas de lavar loiça e sua utilização
ZA200803091B (en) 2005-10-12 2009-09-30 Unilever Plc Bleaching of substrates
DE102007006908A1 (de) * 2007-02-13 2008-08-14 Cht R. Beitlich Gmbh Katalysierte Peroxidbleiche ("Katalysator-Bleiche")

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2010010003A2 *

Also Published As

Publication number Publication date
WO2010010003A2 (fr) 2010-01-28
DE102008034231A1 (de) 2010-01-28
WO2010010003A3 (fr) 2010-07-29

Similar Documents

Publication Publication Date Title
DE69125310T2 (de) Bleichmittelaktivierung
DE69216786T2 (de) Mangan enthaltender Bleichkatalysator und seine Verwendung
DE2207979C2 (de) Trockenes Bleichmittel auf der Basis von Peroxy-Bleichverbindungen
DE1519484B2 (de) Stabilisatoren fuer loesungen von peroxyverbindungen
DE2226784B2 (de) Mittel zum Stabilisieren von Peroxyverbindungen in wässerig-alkalischer Lösung und seine Verwendung
DE703604C (de) Wasch- und Reinigungsmittel
EP0713882B1 (fr) Chitosanes phosphonométhylées
DE2422691A1 (de) Stabile bleichmittel
DE2609039B2 (de) Verfahren zum Herstellen von beständigem Natriumpercarbonat
DE1792377A1 (de) Reinigungsmittel fuer Zahnprothesen
DE1617161A1 (de) Verstaerkungsmittel fuer synthetische Detergentien
DE2530539A1 (de) Addukt aus natriumsulfat, wasserstoffperoxyd und natriumchlorid und eine dieses addukt enthaltende bleichmittelzusammensetzung
EP2181186A1 (fr) Solutions d'agents tensio-actifs stables au stockage pour blanchiment au peroxyde
EP2304012A2 (fr) Blanchiment au peroxyde catalysé (variante 3 de blanchiment par catalysateur: tout-en-un)
DE2531870A1 (de) Bleichmittelzusammensetzung enthaltend ein wasserstoffperoxyd-addukt
DE2704990C2 (fr)
DE1802576A1 (de) Bleich- und Waschmittel
DE2128945A1 (de) Bleichmittel
DE10311766A1 (de) Oxidationssystem enthaltend einen makrocyclischen Metallkomplex, dessen Herstellung und Verwendung
DE3002271A1 (de) Bleichmittel
EP1174491A2 (fr) Agents de blanchissement et d' oxidation et leur utilisation
EP0510331A1 (fr) Protéine comme stabilisateur biodégradable pour le blanchiment à l'oxygène utilisé dans le lavage du linge
EP1583861B1 (fr) Procede pour le finissage de matieres fibreuses textiles
DE2152141A1 (de) Fluessigwaschmittel
DE602004005705T2 (de) Flüssige bleichmittelzusammensetzung

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20101119

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR

DAX Request for extension of the european patent (deleted)
17Q First examination report despatched

Effective date: 20151118

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN

18W Application withdrawn

Effective date: 20160518