EP0783035B1 - Bleaching system containing Bis-and-Tris-(mu-oxo)-di-manganese complex salts - Google Patents

Bleaching system containing Bis-and-Tris-(mu-oxo)-di-manganese complex salts Download PDF

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EP0783035B1
EP0783035B1 EP96120743A EP96120743A EP0783035B1 EP 0783035 B1 EP0783035 B1 EP 0783035B1 EP 96120743 A EP96120743 A EP 96120743A EP 96120743 A EP96120743 A EP 96120743A EP 0783035 B1 EP0783035 B1 EP 0783035B1
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Prior art keywords
bis
bleach
formula
bleach system
oxo
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EP0783035A3 (en
EP0783035A2 (en
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Ahmed Dr. Tafesh
Matthias Prof. Dr. Beller
Vera Friderichs
Gerd Dr. Reinhardt
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Clariant Produkte Deutschland GmbH
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Clariant GmbH
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    • 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

Definitions

  • Bleaches that release active oxygen are an essential ingredient modern washing and cleaning agents. Your main job is distance stubborn stains such as tea, coffee, red wine or fruit juices from textile fibers or solid surfaces. This is done by oxidative destruction of the chromophoric system; adhering microorganisms are killed at the same time and neutralizes odors.
  • Hydrogen peroxide organic or inorganic peracid used.
  • powdered products is used as a source for active oxygen mostly used a persalt.
  • Typical examples are Sodium perborates or percarbonates or urea adducts.
  • bleach activators are often added.
  • examples for this are Tetraacetylethylenediamine (TAED), diacetyldioxohexahydrotriazine (DADHT), Pentaacetylglycose (PAG), benzoyloxybenzenesulfonate (BOBS) and Nonanoyloxybenzenesulfonate (NOBS).
  • TAED Tetraacetylethylenediamine
  • DADHT diacetyldioxohexahydrotriazine
  • PAG Pentaacetylglycose
  • BBS benzoyloxybenzenesulfonate
  • NOBS Nonanoyloxybenzenesulfonate
  • transition metals are free or complex Form catalyze the decomposition of hydrogen peroxides.
  • the effectiveness of is unsatisfactory in most cases.
  • the addition of metal salts leads to catalytic decomposition of hydrogen peroxide, however, no bleaching effect is observed. Most is this is associated with damage to the textile fabric.
  • the appearance of free Transition metals during the washing and cleaning process is therefore undesirable. If, on the other hand, the metal salt is used in a complex form, the corresponding complex during storage and under Conditions of use to be stable to hydrolysis and oxidation Suppress side effects.
  • EP A 458 397 and 458 398 describes the use of macrocyclic Polyamines as complex ligands in multinuclear, oxygen-bridged Manganese complexes. In combination with oxidizing agents, these complexes show especially on tea stains, good bleaching properties. As a disadvantage however, the difficult to access complex ligand of the triazacyclononane type has an effect out. It is only in a multi-stage, by-product-rich manufacturing process accessible. Similar complexes are described in EP 544 519, again the Synthesis of the complex ligand is very complex and difficult on an industrial scale realize.
  • anion A are Cl - , Br - , J - , NO 3 - , ClO 4 - , NCS - , PF 6 - , RSO 3 - , RSO 4 - , SO 4 2- , BPh 4 - , OAc - .
  • Preferred anions are PF 6 - , ClO 4 - , tosylate.
  • the ligands of the formula II contained in these manganese complex salts are prepared by reacting 2- (chloromethyl) pyridinium chloride with an alkylenediamine in the presence of a phase transfer catalyst (see Synthesis, June 1992, p. 539-540) or in an analogous manner for the substituted other ligands of the formula II.
  • the manganese complex salts of the formula I are prepared in accordance with the information in Inorg. Chem. 1989, 28, 3606-3608, by oxidizing an aqueous solution containing MnCl 2 and the ligand with H 2 O 2 or analogously to that in Inorg. Chem. 1994, 33, 4105-4111 described method, in which the oxidation is carried out with ammonium peroxodisulfate.
  • the metal complexes can be either pre-washed and Detergent added or ligand and during the washing process Transition metal can be generated in situ.
  • These complex salts have catalytic properties and are capable of Bleaching performance of peracids, persalts or hydrogen peroxide in washing and To significantly increase the cleaning process.
  • the bleaching catalysts are in Combination with an oxidizing agent used.
  • Oxidizing agents that can be used are hydrogen peroxide, Alkali metal perborates, percarbonates, perphosphates or persulfates.
  • the catalysts are used in powdered products be, sodium perborate mono- or tetrahydrate, caroate in the form of the triple salt and sodium percarbonate, the latter in particular in coated form.
  • This Compounds can either with the catalysts alone or according to one preferred embodiment, additionally together with a bleach activator be used. This extends the range of applications and the germicidal properties of the formulation enhanced.
  • Bleach activators are known from numerous patent applications. Examples for this are reactive esters and amides as in GB 836,988, 864,798, 907,356, 1,003,310 and 1,519,351; EP 284,292, 331,229, 303,520, 185,522, 174,132, 120,591 and US 1,246,339, 3,332,882, 4,128,494, 4,412,934, 4,675,393, 4,751,015 and 4,397,757.
  • Tetraacetylethylenediamine is particularly preferred, Nonanoyloxibenzenesulfonate, benzoyloxibenzenesulfonate, nonanoyl and Benzoylcaprolactam, isatoic, maleic, succinic and citric anhydrides and acylated sugar or sugar derivatives, in addition alkyl or aryl nitriles.
  • peroxibenzoic acid and substituted derivatives Typical representatives are peroxibenzoic acid and substituted derivatives, aliphatic mono- and dicarboxylic acids such as pemonanoic acid, perlauric acid, 1,9-diperoxiazeldic acid and 1,12-dodecanediperic acid.
  • N, N'-phthaloylaminoperoxycarboxylic acids such as N, N'-phthaloylaminoperoxyhexanoic acid (PAP), 6-octylamino-6-oxoperoxihexanoic acid, monoperoxiphthalic acid and their Salts, 2-alkylperoxy-1,4-butanedioic acids or 4,4'-sulphonylbisperoxybenzoic acid.
  • composition of the bleach system according to the invention can vary widely Limits fluctuate and are generally between 0.0005 and 2% by weight, preferably 0.001 to 0.5% by weight of the bleaching catalyst described and 1 to 99.9995%, preferably 5 to 99.999% of an oxidizing agent from the group inorganic or organic peracids or salts, and optionally 0 to 70%, preferably 10 to 60% of a bleach activator.
  • the bleaching systems according to the invention are used in heavy-duty detergents, Multi-component detergents (modular systems), stain salts, Stain pretreatment agents, dishwasher detergents, cleaning agents for hard surfaces, disinfectants, and denture cleaners. Beside the bleach the catalysts also take on the function of dye transfer inhibitors. Usually the catalysts are in granular form for washing and Detergent added. Inorganic pelletizers can be used Salts such as sodium sulfate, chloride, phosphate or silicates can be used. In a preferred application form, they are incorporated into the activator granules.
  • granulation can be inorganic or organic auxiliaries are used, film-forming materials are preferred such as surfactants, fatty acids, celulose derivatives, or polymers.
  • the granules can additionally be provided with a coating, which on the one hand ensures their storage stability increases and interactions with other detergent ingredients during the Storage can be prevented, but also their release kinetics can be influenced.
  • the bleach system according to the invention can be used in detergents and cleaning agents in the form of a powder or as granules.
  • the detergents and cleaning agents contain usually still surface-active compounds such as anionic, non-ionic, zwitterionic, amphoteric or cationic surfactants, builders, Enzymes and additives.
  • Surfactants can be of natural or synthetic origin and are e.g. in "Surface Active Agents and Detergents" Volume and II by Schwanz, Perry and Berch described. Examples are alkyl sulfates, alkyl sulfonates, alkylarylsulfonates, alpha-sulfofatty acid methyl esters, soaps and alkyl ether sulfonates. nonionic Surfactants such as alkyl polyglycol ethers, alkyl polyglucosides, glucamides, sugar esters and Amine oxides can also be used.
  • Important builder and cobuilder substances which in combination with the bleach systems according to the invention can be used Phosphates such as sodium tripolyphosphate, type A, X and P zeolites, Alkali metal carbonates and bicarbonates, amorphous and crystalline silicates, especially layered silicates such as SKS-6, 7, 9 or 10 from Hoechst AG or disilicates as sold by Akzo under the trade name Britesil7.
  • a co-builder can include organic carboxylic acids such as citric acid or amino acids are used, but also polymers of the type of polyacrylic acid or Copolymers of acrylic acid and maleic acid or their derivatives. Farther phosphonate or other complexing agents can be added.
  • Amylase, proteases, lipases, cellulases and peroxidases can be used as enzymes other additives cellulose ethers, silicones, bentonites, optical brighteners and perfume be used.
  • N, N, N ', N'-tetrakis (2-pyridylmethyl) -1,2-ethylenediamine were dissolved in 30 ml of a mixture of ethanol and water (5: 1) and then Mn (acetate) 3 . 2H 2 O (0.96 g; 3.6 mmol) was added. Then 2.2 g (20 mmol) sodium butyrate was added and then 2 ml HClO 4 (70%). A pH of 7.5 was established. Then 3 g (24.48 mmol) NaClO 4 were added and this mixture was stirred for 4 hours at room temperature.
  • Manganese (II) sulfate and the 4-dentate were used as comparative compounds
  • Example 3 Washing tests in a Linitest device
  • Example 4 Washing tests in a Linitest device
  • Example 3 The tests were carried out as described in Example 3. Instead of the test soil tea (BC-1), beetroot and curry on cotton (manufacturer laundry research Krefeld) were used. catalyst Beetroot ⁇ RE Curry ⁇ RE without 0 0 K1 + 2.0 + 0.6 K2 + 4.0 + 0.9
  • the washing tests were carried out in the Linitest réelle at 40 ° C; Washing time 30 min. 1.5 g / l WMP were pre-dissolved in 200 ml water (15 ° dH) and 0.5 g / l sodium perborate monohydrate was added. Before the start of the washing tests, 0; 1.5; 3; 6; 12; 25 mg / l of the catalysts added. The washing tests were carried out analogously to Example 3.
  • the table shows the reflectance differences ⁇ RE of the washes with and without a catalyst.
  • Catalyst concentration [mg / l] catalyst 0 1.5 3 6 12 25 K1 0 + 2.0 + 2.0 + 3.2 + 2.6 + 2.7 K2 0 + 1.6 + 2.3 + 3.2 + 4.8 +5.1
  • Example 7 Influence of various oxidizing agents on the bleaching result

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
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Abstract

Bleach systems contain bis- and tris-( mu -oxo)-di-manganese complex salts of formula (I) ÄLMn( mu -O)a( mu -OAc)bMnLÜ (x+) Ay; in which Ac = 2-8C acyl; a = 1-3; b = 0 if a = 2 or 3 or b = 2 if a = 1; x = 2 or 3; A = a mono- or di-valent anion; y = the equivalent amount of anion A to balance the positive charges; L = a ligand of formula R-N(Q)2 (II) or (Q)2N-(C(R<1>)2)g-N(Q)2 (III); Q = a group of formula (i); R = 1-12C alkyl, 5-10C cycloalkyl, phenyl, NH2, NHR<2>, N(R<2>)2, OH, OR<2> or COOH; R<1> = H, 1-12C alkyl, 5-10C cycloalkyl, NH2, NHR<2>, N(R<2>)2, OH, OR<2>, COOH, COOR<2>, Cl, Br, F or CN; R<2> = 1-12C alkyl or 5-10C cycloalkyl; g = 2 or 3; m, n = 0-4. Also claimed are washing agents and cleaning agents containing this bleach system.

Description

Bleichmittel, die aktiven Sauerstoff freisetzen, sind ein wesentlicher Bestandteil moderner Wasch- und Reinigungsmittel. Ihre Hauptaufgabe ist die Entfernung hartnäckiger Anschmutzungen wie Tee, Kaffee, Rotwein oder Fruchtsäften von textilen Fasern oder festen Oberflächen. Dies erfolgt durch oxidative Zerstörung des chromophoren Systems; gleichzeitig werden anhaftende Mikroorganismen abgetötet und Geruchsstoffe neutralisiert.Bleaches that release active oxygen are an essential ingredient modern washing and cleaning agents. Your main job is distance stubborn stains such as tea, coffee, red wine or fruit juices from textile fibers or solid surfaces. This is done by oxidative destruction of the chromophoric system; adhering microorganisms are killed at the same time and neutralizes odors.

Als bleichendes Agens werden meist Wasserstoffperoxid, organische oder anorganische Persäure verwendet. In pulverförmigen Produkten wird als Quelle für aktiven Sauerstoff meist ein Persalz eingesetzt. Typische Beispiele dafür sind Natriumperborate oder -percarbonate oder Hamstoffaddukte.Hydrogen peroxide, organic or inorganic peracid used. In powdered products is used as a source for active oxygen mostly used a persalt. Typical examples are Sodium perborates or percarbonates or urea adducts.

Um die Wirksamkeit dieser Perverbindungen im Temperaturbereich von 40 bis 60°C zu steigern, werden vielfach Bleichaktivatoren zugesetzt. Beispiele hierfür sind Tetraacetylethylendiamin (TAED), Diacetyldioxohexahydrotriazin (DADHT), Pentaacetylglycose (PAG), Benzoyloxibenzolsulfonat (BOBS) und Nonanoyloxibenzolsulfonat (NOBS). In Gegenwart des Aktivators werden aus den Persalzen die entsprechenden Persäuren freigesetzt, die meist ein breiteres Wirkspektrum aufweisen als Wasserstoffperoxid.To the effectiveness of these per compounds in the temperature range of 40 to 60 ° C. to increase, bleach activators are often added. examples for this are Tetraacetylethylenediamine (TAED), diacetyldioxohexahydrotriazine (DADHT), Pentaacetylglycose (PAG), benzoyloxybenzenesulfonate (BOBS) and Nonanoyloxybenzenesulfonate (NOBS). In the presence of the activator, the Persalts released the corresponding peracids, usually a broader one Show spectrum of activity as hydrogen peroxide.

In vielen Fällen führt aber auch die Kombination eines Persalzes mit einem Aktivator noch nicht zu den optimalen Bleicheigenschaften. Problematisch ist insbesondere die eingeschränkte Wirksamkeit solcher Bleichsysteme bei niederen Anwendungstemperaturen und ihre fehlende Reaktivität gegenüber bestimmten Anschmutzungen. In many cases, however, the combination of a persalt with an activator leads not yet the optimal bleaching properties. It is particularly problematic the limited effectiveness of such bleaching systems at low Application temperatures and their lack of reactivity to certain Soils.

Wünschenswert sind daher Systeme mit weiter gesteigerter Leistung. Aus ökonomischen und ökologischen Gründen werden katalytisch wirkende Additive bevorzugt. Daneben besteht aber auch ein Bedarf an Katalysatoren, die direkt mit Wasserstoffperoxid oder Caroaten reagieren und durch die die Aktivatorkonzentration deutlich reduziert oder überflüssig wird.Systems with further increased performance are therefore desirable. Out economic and ecological reasons become catalytically active additives prefers. In addition, there is also a need for catalysts that work directly with Hydrogen peroxide or caroates react and through which the Activator concentration is significantly reduced or becomes unnecessary.

Es ist seit vielen Jahren bekannt, daß Übergangsmetalle in freier oder komplexierter Form die Zersetzung von Wasserstoffperoxiden katalysieren. Die Wirksamkeit der bisher beschriebenen Verbindungen ist aber in den meisten Fällen unbefriedigend. Vielfach führt der Zusatz von Metallsalzen zwar zu einer katalytischen Zersetzung des Wasserstoffperoxids, ein Bleicheffekt wird jedoch nicht beobachtet. Meist ist dies mit einer Schädigung des textilen Gewebes verbunden. Das Auftreten freier Übergangsmetalle während des Wasch- und Reinigungsprozesses ist daher unerwünscht. Wird dagegen das Metallsalz in komplexierter Form verwendet, muß der entsprechende Komplex während der Lagerung und unter Anwendungsbedingungen hydrolyse- und oxidationsstabil sein, um diese Nebenwirkungen zu unterdrücken.It has been known for many years that transition metals are free or complex Form catalyze the decomposition of hydrogen peroxides. The effectiveness of However, the connections described so far are unsatisfactory in most cases. In many cases, the addition of metal salts leads to catalytic decomposition of hydrogen peroxide, however, no bleaching effect is observed. Most is this is associated with damage to the textile fabric. The appearance of free Transition metals during the washing and cleaning process is therefore undesirable. If, on the other hand, the metal salt is used in a complex form, the corresponding complex during storage and under Conditions of use to be stable to hydrolysis and oxidation Suppress side effects.

Komplexe des Kupfers oder Cobalts mit Pyridincarbonsäure oder -dicarbonsäure sind in US 3,156,654 beschrieben. US 3,532,634 lehrt die Verwendung von Picolinsäuren, Pyrrolidincarbonsäuren oder Phenanthrolin. In US 4,430,243 werden EDTA und EDTMP-Komplexe von Kupfer, Eisen und Mangan als Bleichkatalysatoren beansprucht, nach US 4,478,733 können Mangansalze in Waschmittelformulierungen auf Basis Zeolith/Ortophosphat erfolgreich verwendet werden. Als effektive Komplexierungsmittel für Übergangsmetalle wurden zudem Hydroxicarbonsäuren (EP A 237 111), Porphinsysteme (EP A 306 089), 2,2'-Bispyridylamine (EP A 392 592), Salen-Derivate (EP A 408 131), makrocyclische Polyamine (EP A 439 387) oder Polyole wie Sorbitol (EP A 443 651) beschrieben. Aus ökologischen Gründen wird meist Mangan als Zentralatom gewählt, daneben sind aber auch Komplexe von Eisen, Kupfer und Cobalt bekannt. Complexes of copper or cobalt with pyridinecarboxylic acid or dicarboxylic acid are described in US 3,156,654. US 3,532,634 teaches the use of Picolinic acids, pyrrolidine carboxylic acids or phenanthroline. In US 4,430,243 EDTA and EDTMP complexes of copper, iron and manganese as Bleaching catalysts claimed, according to US 4,478,733, manganese salts in Detergent formulations based on zeolite / ortophosphate successfully used become. They have also been shown to be effective complexing agents for transition metals Hydroxyarboxylic acids (EP A 237 111), porphine systems (EP A 306 089), 2,2'-bispyridylamines (EP A 392 592), salen derivatives (EP A 408 131), macrocyclic Polyamines (EP A 439 387) or polyols such as sorbitol (EP A 443 651) are described. For ecological reasons, manganese is usually chosen as the central atom, next to it complexes of iron, copper and cobalt are also known.

EP A 458 397 und 458 398 beschreibt die Verwendung von macrocyclischen Polyaminen als Komplexliganden in mehrkemigen, sauerstoffverbrückten Mangankomplexen. Diese Komplexe zeigen in Kombination mit Oxidationsmitteln, insbesondere an Tee-Anschmutzungen, gute Bleicheigenschaften. Als nachteilig wirkt sich allerdings der schwer zugängliche Komplexligand vom Triazacyclononan-Typ aus. Er ist nur in einem mehrstufigen, nebenproduktreichen Herstellprozeß zugänglich. In EP 544 519 sind ähnliche Komplexe beschrieben, wiederum ist die Synthese des Komplexliganden sehr aufwendig und großtechnisch schwer zu realisieren.EP A 458 397 and 458 398 describes the use of macrocyclic Polyamines as complex ligands in multinuclear, oxygen-bridged Manganese complexes. In combination with oxidizing agents, these complexes show especially on tea stains, good bleaching properties. As a disadvantage however, the difficult to access complex ligand of the triazacyclononane type has an effect out. It is only in a multi-stage, by-product-rich manufacturing process accessible. Similar complexes are described in EP 544 519, again the Synthesis of the complex ligand is very complex and difficult on an industrial scale realize.

Es besteht daher auch weiterhin ein Bedarf an einfach herzustellenden, effektiven Bleichkatalysatoren mit breiten Wirkspektren zum Einsatz in Wasch- und Reinigungsmitteln.There is therefore still a need for effective, easy-to-manufacture Bleaching catalysts with a broad spectrum of activity for use in washing and Detergents.

Überraschenderweise wurde nun gefunden, daß sich die im folgenden beschriebenen Mangankomplexsalze ausgezeichnet zum Einsatz in Wasch- und Reinigungsmitteln eignen und bereits in katalytischen Mengen die Wirksamkeit von Wasserstoffperoxid, Peressigsäure und anderen Bleichsystemen um ein Mehrfaches steigern. Von besonderem Vorteil gegenüber dem Stand der Technik erweist sich die leichte Zugänglichkeit dieser Katalysatoren.Surprisingly, it has now been found that those described below Manganese complex salts excellent for use in detergents and cleaning agents are suitable and already in catalytic amounts the effectiveness of Hydrogen peroxide, peracetic acid and other bleaching systems around a Increase multiple. Of particular advantage compared to the state of the art the easy accessibility of these catalysts proves.

Gegenstand der Erfindung sind Bleichmittelsysteme enthaltend Bis- und Tris-(µoxo)-di-Mangan-Komplexsalze der Formel I [LMn(µ-O)a(µ-OAc)bMnL]xAy worin

Ac
eine C2-C8-Acylgruppe ist,
a i
st 1, 2 oder 3,
b
ist 0, wenn a 2 oder 3 ist oder b ist 2, wenn a 1 ist,
x
bezeichnet die Anzahl der positiven Ladungen und ist 2 oder 3,
A
ist ein ein- oder zweifach negativ geladenes Anion,
y
bedeutet die für den Ausgleich der positiven Ladungen erforderliche equivalente Menge an Anion A und
L
bedeutet einen Liganden der Formel II
Figure 00040001
Figure 00040002
worin R1 Wasserstoff, C1-C12-Alkyl, C5-C10-Cycloalkyl, NH2, NHR2, N(R2)2, OH, OR2, COOH, COOR2, Cl, Br, F oder CN, R2 C1-C12-Alkyl oder C5-C10-Cycloalkyl bedeuten, g 2 oder 3 und m und n Null oder eine ganze Zahl von 1 bis 4 ist.The invention relates to bleaching systems containing bis- and tris (μoxo) -di-manganese complex salts of the formula I. [LMn (µ-O) a (µ-OAc) b MnL] x A y wherein
Ac
is a C 2 -C 8 acyl group,
ai
st 1, 2 or 3,
b
is 0 if a is 2 or 3, or b is 2 if a is 1,
x
denotes the number of positive charges and is 2 or 3,
A
is a single or double negatively charged anion,
y
means the equivalent amount of anion A and required to balance the positive charges
L
means a ligand of formula II
Figure 00040001
Figure 00040002
wherein R 1 is hydrogen, C 1 -C 12 alkyl, C 5 -C 10 cycloalkyl, NH 2 , NHR 2 , N (R 2 ) 2 , OH, OR 2 , COOH, COOR 2 , Cl, Br, F or CN, R 2 are C 1 -C 12 alkyl or C 5 -C 10 cycloalkyl, g is 2 or 3 and m and n is zero or an integer from 1 to 4.

Bevorzugt sind Liganden bei denen alle Substituenten R1 in den Liganden L Wasserstoff bedeuten und n = 1 ist. Als Anion A kommen in Frage Cl-, Br-, J-, NO3 -, ClO4 -, NCS-, PF6 -, RSO3 -, RSO4 -, SO4 2-, BPh4 -, OAc-. Bevorzugte Anionen sind PF6 -, ClO4 -, Tosylat.Ligands in which all the substituents R 1 in the ligands L are hydrogen and n = 1 are preferred. As anion A are Cl - , Br - , J - , NO 3 - , ClO 4 - , NCS - , PF 6 - , RSO 3 - , RSO 4 - , SO 4 2- , BPh 4 - , OAc - . Preferred anions are PF 6 - , ClO 4 - , tosylate.

Die Herstellung der in diesen Mangan-Komplexsalzen enthaltenen Liganden der Formel IIerfolgt durch Umsetzung von 2-(Chlormethyl)pyridiniumchlorid mit einem Alkylendiamin in Gegenwart eines Phasentransferkatalysators (s. Synthesis, June 1992, p. 539-540) bzw. in analoger Weise für die substituierten anderen Liganden der Formel II. Die Herstellung der Mangan-Komplexsalze der Formel I erfolgt entsprechend den Angaben in Inorg. Chem. 1989, 28, 3606-3608, indem man eine wäßrige Lösung, die MnCl2 und den Liganden enthält, mit H2O2 oxidiert oder analog zu dem in Inorg. Chem. 1994, 33, 4105-4111 beschriebenen Verfahren, bei dem die Oxidation mit Ammoniumperoxodisulfat vorgenommen wird.The ligands of the formula II contained in these manganese complex salts are prepared by reacting 2- (chloromethyl) pyridinium chloride with an alkylenediamine in the presence of a phase transfer catalyst (see Synthesis, June 1992, p. 539-540) or in an analogous manner for the substituted other ligands of the formula II. The manganese complex salts of the formula I are prepared in accordance with the information in Inorg. Chem. 1989, 28, 3606-3608, by oxidizing an aqueous solution containing MnCl 2 and the ligand with H 2 O 2 or analogously to that in Inorg. Chem. 1994, 33, 4105-4111 described method, in which the oxidation is carried out with ammonium peroxodisulfate.

Beispiele für besonders bevorzugte Komplexliganden sind:

  • N,N,N',N'-Tetrakis(2-pyridylmethyl)-1,2-ethylendiamin
  • N,N,N',N'-Tetrakis(2-pyridylmethyl)-1,3-propylendiamin
  • N,N,N',N'-Tetrakis(2-pyridylethyl)-1,3-propylendiamin
  • N,N,N',N'-Tetrakis(2-pyridylethyl)-1,4-butylendiamin
    • Examples of particularly preferred complex ligands are:
  • N, N, N ', N'-tetrakis (2-pyridylmethyl) -1,2-ethylenediamine
  • N, N, N ', N'-tetrakis (2-pyridylmethyl) -1,3-propylenediamine
  • N, N, N ', N'-tetrakis (2-pyridylethyl) -1,3-propylenediamine
  • N, N, N ', N'-tetrakis (2-pyridylethyl) -1,4-butylenediamine

    • Die Metallkomplexe können entweder in vorgefertigter Form dem Wasch- und Reinigungsmittel zugegeben oder während des Waschprozesses aus Ligand und Übergangsmetall insitu generiert werden.The metal complexes can be either pre-washed and Detergent added or ligand and during the washing process Transition metal can be generated in situ.

    Beispiele für erfindungsgemäß zu verwendende Komplexsalze sind:

  • Bis(µ-oxo)bis[N,N,N',N'-tetrakis(2-pyridylmethyl)-1,2-ethylendiamin]-dimangan(III,IV)Perchlorat
  • Tris(µ-oxo)bis[N,N,N',N'-tetrakis(2-pyridylmethyl)-1,2-ethylendiamin]-dimangan(IV,IV)Hexafluorophosphat
  • (µ-Oxo)bis(µ-OAc)bis[N,N,N',N'-tetrakis(2-pyridylmethyl)-1,2-ethylendiamin]-dimangan(III,III)Perchlorat
  • (µ-Oxo)bis(µ-OBu)bis[N,N,N',N'-tetrakis(2-pyridylmethyl)-1,2-ethylendiamin]-dimangan(III,III)Perchlorat
  • Tris(µ-oxo)bis[N,N,N',N'-tetrakis(2-pyridylmethyl)-1,3-propylendiamin]-dimangan(IV,IV)Hexafluorophosphat
    • Examples of complex salts to be used according to the invention are:
  • Bis (μ-oxo) bis [N, N, N ', N'-tetrakis (2-pyridylmethyl) -1,2-ethylenediamine] -dimangan (III, IV) perchlorate
  • Tris (μ-oxo) bis [N, N, N ', N'-tetrakis (2-pyridylmethyl) -1,2-ethylenediamine] -dimangan (IV, IV) hexafluorophosphate
  • (Μ-oxo) bis (μ-OAc) bis [N, N, N ', N'-tetrakis (2-pyridylmethyl) -1,2-ethylenediamine] -dimangan (III, III) perchlorate
  • (Μ-oxo) bis (μ-OBu) bis [N, N, N ', N'-tetrakis (2-pyridylmethyl) -1,2-ethylenediamine] -dimangan (III, III) perchlorate
  • Tris (μ-oxo) bis [N, N, N ', N'-tetrakis (2-pyridylmethyl) -1,3-propylenediamine] -dimangan (IV, IV) hexafluorophosphate

    • Diese Komplexsalze besitzen katalytische Eigenschaften und sind in der Lage die Bleichleistung von Persäuren, Persalzen oder Wasserstoffperoxid im Wasch- und Reinigungsprozeß beträchtlich zu steigern.These complex salts have catalytic properties and are capable of Bleaching performance of peracids, persalts or hydrogen peroxide in washing and To significantly increase the cleaning process.

    In den erfindungsgemäßen Bleichmittelsystemen werden die Bleichkatalysatoren in Kombination mit einem Oxidationsmittel eingesetzt. Beispiele solcher Oxidationsmittel, die Verwendung finden können, sind Wasserstoffperoxid, Alkalimetallperborate, -percarbonate, -perphosphate oder -persulfate. Besonders bevorzugt werden, wenn die Katalysatoren in pulverförmigen Produkten eingesetzt werden, Natriumperborat Mono- oder Tetrahydrat, Caroat in Form des Tripelsalzes und Natriumpercarbonat, letzteres insbesondere in gecoateter Form. Diese Verbindungen können entweder mit den Katalysatoren allein oder gemäß einer bevorzugten Ausführungsform, zusätzlich zusammen mit einem Bleichaktivator verwendet werden. Hierdurch wird das Anwendungsspektrum erweitert und die keimabtötenden Eigenschaften der Formulierung verstärkt.In the bleaching agent systems according to the invention, the bleaching catalysts are in Combination with an oxidizing agent used. Examples of such Oxidizing agents that can be used are hydrogen peroxide, Alkali metal perborates, percarbonates, perphosphates or persulfates. Especially are preferred if the catalysts are used in powdered products be, sodium perborate mono- or tetrahydrate, caroate in the form of the triple salt and sodium percarbonate, the latter in particular in coated form. This Compounds can either with the catalysts alone or according to one preferred embodiment, additionally together with a bleach activator be used. This extends the range of applications and the germicidal properties of the formulation enhanced.

    Bleichaktivatoren sind aus zahlreichen Patentanmeldungen bekannt. Beispiele hierfür sind reaktive Ester und Amide wie in GB 836,988, 864,798, 907,356, 1,003,310 und 1,519,351; EP 284,292, 331,229, 303,520, 185,522, 174,132, 120,591 und US 1,246,339, 3,332,882, 4,128,494, 4,412,934, 4,675,393, 4,751,015 und 4,397,757 beschrieben. Besonders bevorzugt sind Tetraacetylethylendiamin, Nonanoyloxibenzolsulfonat, Benzoyloxibenzolsulfonat, Nonanoyl- und Benzoylcaprolactam, Isatosäure-, Malein-, Bernstein- und Zitronensäureanhydride sowie acylierte Zucker oder Zuckerderivate, daneben Alkyl- oder Arylnitrile. Bleach activators are known from numerous patent applications. Examples for this are reactive esters and amides as in GB 836,988, 864,798, 907,356, 1,003,310 and 1,519,351; EP 284,292, 331,229, 303,520, 185,522, 174,132, 120,591 and US 1,246,339, 3,332,882, 4,128,494, 4,412,934, 4,675,393, 4,751,015 and 4,397,757. Tetraacetylethylenediamine is particularly preferred, Nonanoyloxibenzenesulfonate, benzoyloxibenzenesulfonate, nonanoyl and Benzoylcaprolactam, isatoic, maleic, succinic and citric anhydrides and acylated sugar or sugar derivatives, in addition alkyl or aryl nitriles.

    An Stelle des Aktivatorsystems (Persalz plus Bleichaktivator) können auch bestimmte organische Peroxicarbonsäuren als Oxidationsmittel direkt Verwendung finden. Typische Vertreter sind Peroxibenzoesäure und substituierte Derivate, aliphatische Mono- und Dicarbonsäuren wie Pemonansäure, Perlaurinsäure, 1,9-Diperoxiazeldinsäure und 1,12-Dodecandipersäure. Weitere Beispiele sind N,N'-Phthaloylaminoperoxicarbonsäuren wie N,N'-Phthaloylaminoperoxihexansäure (PAP), 6-Octylamino-6-oxoperoxihexansäure, Monoperoxiphthalsäure und ihre Salze, 2-Alkylperoxi-1,4-butandisäuren oder 4,4'-Sulphonylbisperoxibenzoesäure.Instead of the activator system (persalt plus bleach activator) you can also certain organic peroxycarboxylic acids are used directly as oxidizing agents Find. Typical representatives are peroxibenzoic acid and substituted derivatives, aliphatic mono- and dicarboxylic acids such as pemonanoic acid, perlauric acid, 1,9-diperoxiazeldic acid and 1,12-dodecanediperic acid. Other examples are N, N'-phthaloylaminoperoxycarboxylic acids such as N, N'-phthaloylaminoperoxyhexanoic acid (PAP), 6-octylamino-6-oxoperoxihexanoic acid, monoperoxiphthalic acid and their Salts, 2-alkylperoxy-1,4-butanedioic acids or 4,4'-sulphonylbisperoxybenzoic acid.

    Die Zusammensetzung des erfindungsgemäßen Bleichmittelsystems kann in weiten Grenzen schwanken und liegt im allgemeinen zwischen 0,0005 bis 2 Gew.-%, vorzugsweise 0,001 bis 0,5 Gew.-% des beschriebenen Bleichkatalysators und 1 bis 99,9995 %, vorzugsweise 5 bis 99,999 % eines Oxidationsmittels aus der Gruppe der anorganischen oder organischen Persäuren oder Persalze, und gegebenenfalls 0 bis 70 %, vorzugsweise 10 bis 60 % eines Bleichmittelaktivators.The composition of the bleach system according to the invention can vary widely Limits fluctuate and are generally between 0.0005 and 2% by weight, preferably 0.001 to 0.5% by weight of the bleaching catalyst described and 1 to 99.9995%, preferably 5 to 99.999% of an oxidizing agent from the group inorganic or organic peracids or salts, and optionally 0 to 70%, preferably 10 to 60% of a bleach activator.

    Die erfindungsgemäßen Bleichsysteme finden Verwendung in Vollwaschmitteln, Mehrkomponentenwaschmitteln (Baukastensysteme), Fleckensalzen, Fleckenvorbehandlungsmitteln, Maschinengeschirrspülmitteln, Reinigungsmitteln für harte Oberflächen, Desinfektionsmitteln, und Gebißreinigern. Neben der Bleiche übernehmen die Katalysatoren auch die Funktion von Dye-Transfer- Inhibitoren. Normalerweise werden die Katalysatoren in granulierter Form dem Wasch- und Reinigungsmittel zugesetzt. Als Granulierhilfsmittel können dabei anorganische Salze wie Natriumsulfat, -chlorid, -phosphat oder Silikate verwendet werden. In einer bevorzugten Anwendungsform werden sie in das Aktivatorgranulat eingearbeitet. Zur Granulierung können dem Stand der Technik entsprechend anorganische oder organische Hilfsstoffe verwendet werden, bevorzugt sind filmbildende Materialien wie Tenside, Fettsäuren, Celulosederivate, oder Polymere. Die Granulate können zusätzlich mit einem Coating versehen sein, wodurch zum einen ihre Lagerstabilität erhöht und Wechselwirkungen mit anderen Waschmittelinhaltsstoffen während der Lagerung unterbunden werden können, zum anderen aber auch ihre Auslösekinetik beeinflußt werden kann. The bleaching systems according to the invention are used in heavy-duty detergents, Multi-component detergents (modular systems), stain salts, Stain pretreatment agents, dishwasher detergents, cleaning agents for hard surfaces, disinfectants, and denture cleaners. Beside the bleach the catalysts also take on the function of dye transfer inhibitors. Usually the catalysts are in granular form for washing and Detergent added. Inorganic pelletizers can be used Salts such as sodium sulfate, chloride, phosphate or silicates can be used. In a preferred application form, they are incorporated into the activator granules. to According to the state of the art, granulation can be inorganic or organic auxiliaries are used, film-forming materials are preferred such as surfactants, fatty acids, celulose derivatives, or polymers. The granules can additionally be provided with a coating, which on the one hand ensures their storage stability increases and interactions with other detergent ingredients during the Storage can be prevented, but also their release kinetics can be influenced.

    Üblicherweise werden die erfindungsgemäßen Bleichmittelsysteme, bestehend aus Katalysator und Oxidationsmittel und gegebenenfalls Aktivator, in den Wasch- und Reinigungsmitteln in folgenden Konzentrationen eingesetzt:

  • Vollwaschmittel: 2 bis 40 Gew.-%
  • Fleckensalze und Wäschevorbehandlungsmittel: 20 bis 100 Gew.-%
  • Maschinengeschirrspülmittel: 1 bis 30 Gew.-%
  • Reinigungsmittel für harte Oberflächen und Desinfektionsreiniger: 2 bis 50 Gew.-%
  • Gebißreiniger: 2 bis 20 Gew.-%
    • The bleaching agent systems according to the invention, consisting of catalyst and oxidizing agent and optionally activator, are usually used in the washing and cleaning agents in the following concentrations:
  • Heavy duty detergent: 2 to 40% by weight
  • Stain salts and laundry pretreatment agents: 20 to 100% by weight
  • Dishwasher detergent: 1 to 30% by weight
  • Hard surface cleaner and disinfectant cleaner: 2 to 50% by weight
  • Denture cleaner: 2 to 20% by weight

    • Das erfindungsgemäße Bleichmittelsystem kann den Wasch- und Reinigungsmitteln in Form eines Pulvers oder als Granulat zugesetzt werden.The bleach system according to the invention can be used in detergents and cleaning agents in the form of a powder or as granules.

    Neben dem Bleichmittelsystem enthalten die Wasch- und Reinigungsmittel normalerweise noch oberflächenaktive Verbindungen wie anionischen, nichtionische, zwitterionische, amphoterische oder kationische Tenside, Builder, Enzyme und Additive.In addition to the bleach system, the detergents and cleaning agents contain usually still surface-active compounds such as anionic, non-ionic, zwitterionic, amphoteric or cationic surfactants, builders, Enzymes and additives.

    Tenside können natürlichen oder synthetischen Ursprungs sein und sind z.B. in "Surface Active Agents and Detergents" Band und II von Schwanz, Perry und Berch beschrieben. Beispiele sind Alkylsulfate, Alkylsulfonate, Alkylarylsulfonate, alpha-Sulfofettsäuremethylester, Seifen und Alkylethersulfonate. Nichtionische Tenside wie Alkylpolyglykolether, Alkylpolyglucoside, Glucamide, Zuckerester und Aminoxide können ebenfalls verwendet werden.Surfactants can be of natural or synthetic origin and are e.g. in "Surface Active Agents and Detergents" Volume and II by Schwanz, Perry and Berch described. Examples are alkyl sulfates, alkyl sulfonates, alkylarylsulfonates, alpha-sulfofatty acid methyl esters, soaps and alkyl ether sulfonates. nonionic Surfactants such as alkyl polyglycol ethers, alkyl polyglucosides, glucamides, sugar esters and Amine oxides can also be used.

    Wichtige Builder- und Cobuildersubstanzen, die in Kombination mit den erfindungsgemäßen Bleichmittelsystemen verwendet werden können, sind Phosphate wie Natriumtripolyphosphat, Zeolithe vom Typ A, X und P, Alkalimetallcarbonate und -hydrogencarbonate, amorphe und kristalline Silikate, insbesondere Schichtsilikate wie SKS-6, 7, 9 oder 10 der Hoechst AG oder Disilikate wie sie von Akzo unter dem Handelsnamen Britesil7 vertrieben werden. Als Co-Builder können u.a. organische Carbonsäuren wie Zitronensäure oder Aminosäuren verwendet werden, daneben aber auch Polymere vom Typ der Polyacrylsäure oder Mischpolymerisate aus Acrylsäure und Maleinsäure oder deren Derivate. Weiterhin können Phosphonat oder andere Komplexbildner zugesetzt werden.Important builder and cobuilder substances, which in combination with the bleach systems according to the invention can be used Phosphates such as sodium tripolyphosphate, type A, X and P zeolites, Alkali metal carbonates and bicarbonates, amorphous and crystalline silicates, especially layered silicates such as SKS-6, 7, 9 or 10 from Hoechst AG or disilicates as sold by Akzo under the trade name Britesil7. As a co-builder can include organic carboxylic acids such as citric acid or amino acids are used, but also polymers of the type of polyacrylic acid or Copolymers of acrylic acid and maleic acid or their derivatives. Farther phosphonate or other complexing agents can be added.

    Als Enzyme können Amylase, Proteasen, Lipasen, Cellulasen und Peroxidasen, als weitere Additive Celluloseether, Silikone, Bentonite, optische Aufheller und Parfum verwendet werden. Amylase, proteases, lipases, cellulases and peroxidases can be used as enzymes other additives cellulose ethers, silicones, bentonites, optical brighteners and perfume be used.

    Beispiele für die Herstellung der Katalysatoren.Examples of the preparation of the catalysts.

    Beispiel 1example 1 (µ-Oxo)bis(µ-acetato)bis[N,N,N',N'-tetrakis(2-pyridylmethyl-)1,2-ethylendiamin]-dimangan IV,IV-perchlorat (Katalysator K1)(Μ-oxo) bis (μ-acetato) bis [N, N, N ', N'-tetrakis (2-pyridylmethyl) -1,2-ethylenediamine] -dimangan IV, IV perchlorate (catalyst K1)

    Eine Mischung aus 25,5 ml Ethanol und 4,5 ml Wasser wurde durch dreimaliges Anlegen eines Vakuums entgast und mit Argon behandelt, um alle Reste an Sauerstoff zu entfernen, die sonst eine Oxidation von Mnll zu MnIV bewirken würden. Zu dieser Mischung wurden 2,47 g (5,82 mmol) N,N,N',N'-Tetrakis(2-pyridylmethyl)-ethylendiamin gegeben. Man erhielt eine gelbe Lösung mit einem pH-Wert von 8,8. Dann wurden 0,96 g (3,6 mmol) Mangantriacetat (Mn(OAc)3·2H2O) zugegeben. Die Lösung wurde braun und wies einen pH-Wert von 6,2 auf. Anschließend wurden 2 g (14,58 mmol) Natriumacetat zugegeben (pH 6,5), dann Perchlorsäure (55 Tropfen) bis zu einem pH-Wert von 5. Nach Zugabe von 3 g (24,48 mmol) Natriumperchlorat fiel bei pH 6,1 ein Niederschlag aus. Die Reaktionsmischung wurde 4 Stunden lang gerührt. Die ausgefallenen Kristalle wurden abgefiltert und unter Stickstoff getrocknet. Man erhielt 3,08 g Rohprodukt der Verbindung (µ-Oxo) bis (µ-acetato)bis[N,N,N',N'-tetrakis-(2-pyridylmethyl-)1,2-ethylendiamin-]di-mangan-IV,IV-perchlorat. Analyse ber. Mn 8,39 % C 51,35 % H 4,92 % N 12,83 % O 17,1 % gef. Mn 8,4 % C 48,0 % H 4,9 % N 12,7 % O 17,9 % A mixture of 25.5 ml of ethanol and 4.5 ml of water was degassed by applying a vacuum three times and treated with argon to remove any residual oxygen which would otherwise cause oxidation of MnII to MnIV. 2.47 g (5.82 mmol) of N, N, N ', N'-tetrakis (2-pyridylmethyl) ethylenediamine were added to this mixture. A yellow solution with a pH of 8.8 was obtained. Then 0.96 g (3.6 mmol) of manganese triacetate (Mn (OAc) 3 · 2H 2 O) was added. The solution turned brown and had a pH of 6.2. Then 2 g (14.58 mmol) of sodium acetate were added (pH 6.5), then perchloric acid (55 drops) to a pH of 5. After addition of 3 g (24.48 mmol) of sodium perchlorate, the pH dropped to 6 , 1 a precipitation. The reaction mixture was stirred for 4 hours. The precipitated crystals were filtered off and dried under nitrogen. 3.08 g of crude product of the compound (μ-oxo) bis (μ-acetato) to [N, N, N ', N'-tetrakis (2-pyridylmethyl-) 1,2-ethylenediamine] di-manganese were obtained -IV, IV perchlorate. analysis calc. Mn 8.39% C 51.35% H 4.92% N 12.83% O 17.1% gef. Mn 8.4% C 48.0% H 4.9% N 12.7% O 17.9%

    Beispiel 2Example 2 (µ-Oxo)bis(µ-butyrato)bis[N,N,N',N'-tetrakis(2-pyridylmethyl-)1,2-ethylen-diamin]dimangan III,IV perchlorat (Katalysator K2)(Μ-oxo) bis (μ-butyrato) bis [N, N, N ', N'-tetrakis (2-pyridylmethyl) 1,2-ethylene-diamine] dimanganese III, IV perchlorate (catalyst K2)

    2,47 (5,82 mmol) N,N,N',N'-Tetrakis-(2-pyridylmethyl)-1,2-ethylendiamin wurden in 30 ml einer Mischung aus Ethanol und Wasser (5:1) gelöst und anschließend Mn(Acetat)3 .2H2O (0,96 g; 3,6 mmol) hinzugegeben. Dann wurde 2,2 g (20 mmol) Natriumbutyrat zugegeben und anschließend 2 ml HClO4 (70 %ig). Es stellte sich ein pH-Wert von 7,5 ein. Dann wurden 3 g (24,48 mmol) NaClO4 zugegeben und diese Mischung wurde 4 Stunden bei Raumtemperatur gerührt. Es bildete sich ein Niederschlag, der abfiltriert, mit einer Ethanol/Wasser-Mischung (85 % EtOH/15 % H2O) gewaschen und getrocknet wurde. Rohausbeute 2,3 g. Der Feststoff wurde mit 70 ml Aceton behandelt und die Aceton-Lösung von den unlöslichen anorganischen Salzen abfiltriert. Nach Abdestillation des Acetons und Umkristallisation mit Ethanol/Wasser 5:1 erhielt man das oben genannte Komplexsalz. Analyse ber. Mn 7,5 % C 49,17 % H 4,95 % N 11,47 % gef. Mn 8,0 % C 44,8 % H 4,5 % N 12,1 % 2.47 (5.82 mmol) N, N, N ', N'-tetrakis (2-pyridylmethyl) -1,2-ethylenediamine were dissolved in 30 ml of a mixture of ethanol and water (5: 1) and then Mn (acetate) 3 . 2H 2 O (0.96 g; 3.6 mmol) was added. Then 2.2 g (20 mmol) sodium butyrate was added and then 2 ml HClO 4 (70%). A pH of 7.5 was established. Then 3 g (24.48 mmol) NaClO 4 were added and this mixture was stirred for 4 hours at room temperature. A precipitate formed which was filtered off, washed with an ethanol / water mixture (85% EtOH / 15% H 2 O) and dried. Crude yield 2.3 g. The solid was treated with 70 ml of acetone and the acetone solution was filtered off from the insoluble inorganic salts. After distilling off the acetone and recrystallization with ethanol / water 5: 1, the above-mentioned complex salt was obtained. analysis calc. Mn 7.5% C 49.17% H 4.95% N 11.47% gef. Mn 8.0% C 44.8% H 4.5% N 12.1%

    Beispiel 3Example 3 Tris(µ-oxo)bis[N,N,N',N'-tetrakis(2-pyridylmethyl-]1,3-diaminopropan-di-mangan-IV,IV-Hexafluorphosphat (Katalysator K3)Tris (μ-oxo) bis [N, N, N ', N'-tetrakis (2-pyridylmethyl] 1,3-diaminopropane-di-manganese-IV, IV-hexafluorophosphate (Catalyst K3)

    3,5 g (19 mmol) KPF6 und 3,86 g (8,8 mmol) N,N,N',N'-tetrakis-(2-pyridylmethyl-)1,3-diaminopropan wurden bei 5°C zu 120 ml einer Äthanol/-Wasser-Mischung (5:1) zugegeben und gerührt. Die Lösung verfärbte sich gelb und es wurden 3,48 g (17,6 mmol) MnCl2 ·4H2O zugegeben. Zu der schwach gelben Lösung wurden dann 20 ml H2O2 (3 %ig) und 5,2 ml NaOH (20 %ig) zugegeben. Die Temperatur stieg auf 12°C und das Reaktionsgemisch verfärbte sich braun. Die Reaktionsmischung wurde dann 1 Stunde lang auf 5°C gekühlt und dann 2 Stunden bei Raumtemperatur gehalten. Die Lösemittel wurden im Vakuum abdestilliert und das angefallene Rohprodukt wurde mit Aceton behandelt um überschüssiges Mangandioxid zu entfernen. Analyse ber. C 35,86 % H 3,75 % N 9,29 % gef. C 33,8 % H 3,2 % N 8,3 % 3.5 g (19 mmol) of KPF 6 and 3.86 g (8.8 mmol) of N, N, N ', N'-tetrakis (2-pyridylmethyl-) 1,3-diaminopropane were added at 5 ° C 120 ml of an ethanol / water mixture (5: 1) added and stirred. The solution turned yellow and there were 3.48 g (17.6 mmol) of MnCl 2 · 4H 2 O was added. 20 ml of H 2 O 2 (3%) and 5.2 ml of NaOH (20%) were then added to the pale yellow solution. The temperature rose to 12 ° C and the reaction mixture turned brown. The reaction mixture was then cooled to 5 ° C for 1 hour and then kept at room temperature for 2 hours. The solvents were distilled off in vacuo and the resulting crude product was treated with acetone to remove excess manganese dioxide. analysis calc. C 35.86% H 3.75% N 9.29% gef. C 33.8% H 3.2% N 8.3%

    Als Vergleichsverbindungen wurden Mangan(II)sulfat und der 4-zähnige Mangankomplex Bis(µ-oxo)bis[N,N'-bis(2-pyridylmethyl)-N,N'-dimethyl-1,2-ethylendiamin]-dimangan(III,IV) Perchlorat (Katalysator V1) verwendet.Manganese (II) sulfate and the 4-dentate were used as comparative compounds Manganese complex bis (µ-oxo) bis [N, N'-bis (2-pyridylmethyl) -N, N'-dimethyl-1,2-ethylenediamine] -dimangane (III, IV) Perchlorate (catalyst V1) used.

    Anwendungstechnische BeispieleApplication engineering examples Beispiel 1: Stabilität von Wasserstoffperoxid in Gegenwart der KatalysatorenExample 1: Stability of hydrogen peroxide in the presence of the catalysts

    0,5 g Natriumperborat-Monohydrat wurden in 1 I Wasser (15°dH) gelöst und auf 20°C temperiert. Nach Zugabe von 4 mg einer Manganverbindung wurde die Wasserstoffperoxidkonzentration in Abhängigkeit von der Zeit durch jodometrische Titration verfolgt. Gehalt an Wasserstoffperoxid in der Lösung Zeit Katalysator 0 min 10 min 20 min 30 min ohne Zusatz 100 % 100 % 99 % 99 % Mn2SO4 100 % 75 % 42 % 23 % K1 100 % 99 % 100 % 99 % K2 100 % 100 % 99 % 98 % 0.5 g of sodium perborate monohydrate was dissolved in 1 liter of water (15 ° dH) and temperature-controlled at 20 ° C. After adding 4 mg of a manganese compound, the hydrogen peroxide concentration was monitored as a function of time by iodometric titration. Hydrogen peroxide content in the solution Time catalyst 0 min 10 min 20 min 30 min without addition 100% 100% 99% 99% Mn 2 SO 4 100% 75% 42% 23% K1 100% 99% 100% 99% K2 100% 100% 99% 98%

    Die Ergebnisse zeigen, daß die erfindungsgemäßen Katalysatoren im Gegensatz zu freien Manganionen Wasserstoffperoxid nicht unkontrolliert zersetzen.The results show that the catalysts according to the invention are in contrast to Do not decompose free manganese ions hydrogen peroxide in an uncontrolled manner.

    Beispiel 2: Stabilität von Peressigsäure in Gegenwart der KatalysatorenExample 2: Stability of peracetic acid in the presence of the catalysts

    1 g Natriumpercarbonat und 0,5 g TAED-Pulver (TAED: Tetraacetylethylendiamin) werden zusammen mit 0,01 g der Manganverbindung in 1 I Wasser (15°dH) gegeben, das auf 40°C temperiert ist. Die freigesetzte Menge an Peressigsäure wird in Abhängigkeit von der Zeit durch jodometrische Titration bestimmt. Gehalt an Peressigsäure in der Lösung Zeit Katalysator 0 min 10 min 20 min 30 min ohne Zusatz 0 % 88 % 77 % 70 % Mn2SO4 0 % 66 % 37 % 27 % K1 0% 88 % 70% 59% 1 g of sodium percarbonate and 0.5 g of TAED powder (TAED: tetraacetylethylene diamine) are added together with 0.01 g of the manganese compound in 1 liter of water (15 ° dH), which is heated to 40 ° C. The amount of peracetic acid released is determined as a function of time by iodometric titration. Peracetic acid content in the solution Time catalyst 0 min 10 min 20 min 30 min without addition 0% 88% 77% 70% Mn 2 SO 4 0% 66% 37% 27% K1 0% 88% 70% 59%

    Die Ergebnisse zeigen, daß weder die Freisetzung der Persäure noch ihre Stabilität in wäßriger Lösung durch die erfindungsgemäßen Katalysatoren wesentlich beeinflußt werden. Eine unkontrollierte Zersetzung durch Metallspuren findet nicht statt.The results show that neither the release of the peracid nor its stability in aqueous solution by the catalysts of the invention essential to be influenced. An uncontrolled decomposition by metal traces does not take place instead of.

    Beispiel 3: Waschversuche im LinitestgerätExample 3: Washing tests in a Linitest device

    2 g/l Testwaschmittel (P-frei, WMP, Wäschereiforschung Krefeld) wurden in 200 ml Wasser (15°dH) gelöst. Anschließend wurden 1 g/L Natriumpercarbonat und 0,5 g/L TAED und jeweils 4 Lappen einer Testanschmutzung (Tee auf Baumwolle, BC-1, Wäschereiforschung Krefeld) hinzugegeben. Die Waschversuche wurden bei 40°C in einem Linitest-Gerät der Fa. Haraeus, Hanau, durchgeführt, Waschdauer 30 min. Der Weißgrad der Wäsche wurde anschließend mit einem Elrepho-Gerät (Fa. Datacolor) bestimmt. In einer zweiten Versuchsreihe wurden die Versuche unter Zugabe von 10 mg/L eines Katalysators durchgeführt. In den Ergebnistabelle sind die Remissionsdifferenzen (Wäsche mit Katalysator) - (Wäsche ohne Katalysator) aufgeführt. Katalysator ΔRE ohne 0 K1 + 5,9 K2 + 6,5 K3 + 5,5 Mn2SO4 + 4,3 V1 + 5,0 2 g / l test detergent (P-free, WMP, laundry research Krefeld) was dissolved in 200 ml water (15 ° dH). Then 1 g / L sodium percarbonate and 0.5 g / L TAED and 4 rags each of a test soil (tea on cotton, BC-1, laundry research Krefeld) were added. The washing tests were carried out at 40 ° C. in a Linitest device from Haraeus, Hanau, washing time 30 minutes. The whiteness of the laundry was then determined using an Elrepho device (from Datacolor). In a second series of experiments, the experiments were carried out with the addition of 10 mg / L of a catalyst. The remission differences (washing with catalyst) - (washing without catalyst) are listed in the results table. catalyst ΔRE without 0 K1 + 5.9 K2 + 6.5 K3 + 5.5 Mn 2 SO 4 + 4.3 V1 + 5.0

    Die Ergebnisse zeigen die Überlegenheit der erfindungsgemäßen Katalysatoren auf Basis 3- und 6-zähniger Komplexliganden gegenüber freien Manganionen und dem nicht erfindungsgemäßen Katalysator V1.The results show the superiority of the catalysts according to the invention Base of 3- and 6-toothed complex ligands against free manganese ions and the Catalyst V1 not according to the invention.

    Beispiel 4: Waschversuche im LinitestgerätExample 4: Washing tests in a Linitest device

    Die Versuche wurden wie in Beispiel 3 beschrieben durchgeführt. Anstelle der Testanschmutzung Tee (BC-1) wurden Rote Bete und Curry auf Baumwolle (Hersteller Wäschereiforschung Krefeld) verwendet. Katalysator Rote Bete ΔRE Curry ΔRE ohne 0 0 K1 + 2,0 + 0,6 K2 + 4,0 + 0,9 The tests were carried out as described in Example 3. Instead of the test soil tea (BC-1), beetroot and curry on cotton (manufacturer laundry research Krefeld) were used. catalyst Beetroot ΔRE Curry ΔRE without 0 0 K1 + 2.0 + 0.6 K2 + 4.0 + 0.9

    Durch den Einsatz der erfindungsgemäßen Katalysatoren lassen sich auch die Bleichergebnisse an den Testanschmutzungen Rote Bete und Curry deutlich steigern.By using the catalysts of the invention, the Bleaching results on the test soils beetroot and curry clearly increase.

    Beispiel 5: Konzentrationsabhängigkeit der katalysierten Wasserstoffperoxid-BleicheExample 5: Concentration dependence of the catalyzed hydrogen peroxide bleach

    Die Waschversuche wurden im Linitestgerät bei 40°C durchgeführt; Waschzeit 30 min. 1,5 g/l WMP wurden in 200 ml Wasser (15°dH) vorgelöst und 0,5 g/l Natriumperborat-Monohydrat hinzugegeben. Vor Beginn der Waschversuche wurden 0; 1,5; 3; 6; 12; 25 mg/l der Katalysatoren hinzugefügt. Die Waschversuche wurden analog Beispiel 3 durchgeführt. In der Tabelle aufgeführt sind die Remissionsdifferenzen ΔRE der Wäschen mit und ohne Katalysator. Katalysator-Konzentration [mg/l] Katalysator 0 1,5 3 6 12 25 K1 0 + 2,0 + 2,0 + 3,2 + 2,6 + 2,7 K2 0 + 1,6 + 2,3 + 3,2 + 4,8 +5,1 The washing tests were carried out in the Linitestgerät at 40 ° C; Washing time 30 min. 1.5 g / l WMP were pre-dissolved in 200 ml water (15 ° dH) and 0.5 g / l sodium perborate monohydrate was added. Before the start of the washing tests, 0; 1.5; 3; 6; 12; 25 mg / l of the catalysts added. The washing tests were carried out analogously to Example 3. The table shows the reflectance differences ΔRE of the washes with and without a catalyst. Catalyst concentration [mg / l] catalyst 0 1.5 3 6 12 25 K1 0 + 2.0 + 2.0 + 3.2 + 2.6 + 2.7 K2 0 + 1.6 + 2.3 + 3.2 + 4.8 +5.1

    Die Ergebnisse zeigen, daß die erfindungsgemäßen Katalysatoren bereits in geringsten Konzentrationen eine deutliche Verstärkung der Bleichleistung von Wasserstoffperoxid bewirken.The results show that the catalysts of the invention are already in lowest concentrations a significant increase in the bleaching performance of Cause hydrogen peroxide.

    Beispiel 6: Konzentrationsabhängigkeit der katalysierten Peressigsäure-BleicheExample 6: Concentration dependence of the catalyzed peracetic acid bleach

    Die Versuche wurden analog Beispiel 5 durchgeführt. Zusätzlich wurden jeweils 0,25 g/l TAED zur Waschlauge hinzugegeben. In der folgenden Tabelle sind die jeweiligen Remissionsdifferenzen ΔRE der Wäschen mit und ohne Katalysator aufgeführt. Katalysator Katalysator-Konzentration [mg/l] 0 1,5 3 6 12 K1 0 + 1,6 + 2,2 + 3,0 + 3,3 K2 0 + 2,4 + 2,8 + 4,5 + 5,4 The tests were carried out analogously to Example 5. In addition, 0.25 g / l TAED was added to the wash liquor. The table below shows the respective reflectance differences ΔRE of the washes with and without a catalyst. catalyst Catalyst concentration [mg / l] 0 1.5 3 6 12 K1 0 + 1.6 + 2.2 + 3.0 + 3.3 K2 0 + 2.4 + 2.8 + 4.5 + 5.4

    Die Ergebnisse zeigen, daß die erfindungsgemäßen Katalysatoren bereits in geringsten Konzentrationen eine deutliche Verstärkung der Bleichleistung von Peressigsäure bewirken. The results show that the catalysts of the invention are already in lowest concentrations a significant increase in the bleaching performance of Effect peracetic acid.

    Beispiel 7: Einfluß verschiedener Oxidationsmittel auf das BleichergebnisExample 7: Influence of various oxidizing agents on the bleaching result

    Die Waschversuche wurden im Linitestgerät bei 20°C durchgeführt.

    Wasserhärte:
    15°dH
    Waschzeit:
    30 min
    Anschmutzung:
    Tee auf Baumwolle (BC-1)
    Waschmittel:
    1,5 g/l WMP-Waschmittel
    Oxidationssysteme: PAP:
    Phthalimidoperoxicapronsäure (0,5 g/l)
    BOBS:
    Benzoyloxybenzolsulfonat-Natrium (0,25 g/l) in Kombiantion mit 0,5 g/l Natriumperborat-Monohydrat
    Caroat:
    Kaliumperoxomonosulfat (0,5 g/l)
    The washing tests were carried out in the Linitest at 20 ° C.
    Water hardness:
    15 ° dH
    Washing time:
    30 min
    soiling:
    Tea on cotton (BC-1)
    Laundry detergent:
    1.5 g / l WMP detergent
    Oxidation systems: PAP:
    Phthalimidoperoxicaproic acid (0.5 g / l)
    BOBS:
    Benzoyloxybenzenesulfonate sodium (0.25 g / l) in combination with 0.5 g / l sodium perborate monohydrate
    Caroat®:
    Potassium peroxomonosulfate (0.5 g / l)

    In der folgenden Tabelle sind die jeweiligen Remissionsdifferenzen ΔRE der Wäschen mit und ohne Katalysator aufgeführt. Katalysator Oxidationsmittel PAP BOBS Caroat K1 ohne +7,1 + 6,0 + 3,2 mit + 9,2 + 6,5 + 5,8 K2 ohne + 7,0 + 5,9 + 3,1 mit + 9,0 + 8,8 + 6,7 The table below shows the respective reflectance differences ΔRE of the washes with and without a catalyst. catalyst oxidant PAP BOBS Caroat® K1 without +7.1 + 6.0 + 3.2 With + 9.2 + 6.5 + 5.8 K2 without + 7.0 + 5.9 + 3.1 With + 9.0 + 8.8 + 6.7

    Die Ergebnisse zeigen, daß die Katalysatoren bereits in geringsten Konzentrationen in der Lage sind, die Bleichleistung verschiedenartiger Oxidationsmittel bei 20°C zu steigern.The results show that the catalysts are even in the lowest concentrations are able to increase the bleaching performance of various oxidizing agents at 20 ° C increase.

    Claims (8)

    1. A bleach system comprising bis- and tris(µ-oxo)dimanganese complex salts of the formula I [LMn(µ-O)a(µ-OAc)bMnL]xAy in which
      Ac
      is a C2-C8-acyl group,
      a
      is 1, 2 or 3,
      b
      is 0 if a is 2 or 3 or is 2 if a is 1,
      x
      denotes the number of positive charges and is 2 or 3,
      A
      is an anion with a negative charge of one or two,
      y
      is the equivalent amount of anion A required to compensate the positive charges, and
      L
      is a ligand of the formula II
      Figure 00200001
      in which R1 is hydrogen, C1-C12-alkyl, C5-C10-cycloalkyl, NH2, NHR2, N(R2)2, OH, OR2, COOH, COOR2, Cl, Br, F or CN, R2 is C1-C12-alkyl or C5-C10-cycloalkyl, g is 2 or 3, and m and n are zero or an integer from 1 to 4.
    2. A bleach system as claimed in claim 1, which comprises compounds of the formula I in which all substituents R1 in the ligands L are hydrogen and n = 1.
    3. A bleach system as claimed in claim 1, which comprises compounds of the formula I in which A is Cl-, Br-, I-, NO3 -, ClO4 -, NCS-, PF6 -, RSO3 -, RSO4 -, SO4 2-, BPh4 -, or OAc-.
    4. A bleach system as claimed in claim 1, which comprises an inorganic peroxide from the group consisting of percarbonates, perborates, perphosphates, persilicates and peroxymono- or -disulfates.
    5. A bleach system as claimed in claim 1, which additionally comprises a bleach activator from the group consisting of reactive esters, amides, imides, anhydrides and nitriles.
    6. A bleach system as claimed in claim 1, which comprises the bleaching catalyst in granulated form.
    7. A bleach system as claimed in claim 1, which comprises the bleaching catalyst as a constituent of bleach activator granules.
    8. A detergent or cleaner comprising a bleach system as claimed in claim 1.
    EP96120743A 1996-01-04 1996-12-23 Bleaching system containing Bis-and-Tris-(mu-oxo)-di-manganese complex salts Expired - Lifetime EP0783035B1 (en)

    Applications Claiming Priority (2)

    Application Number Priority Date Filing Date Title
    DE19600159A DE19600159A1 (en) 1996-01-04 1996-01-04 Bleaching agent systems containing bis- and tris (mu-oxo) -di-manganese complex salts
    DE19600159 1996-01-04

    Publications (3)

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    EP0783035A2 EP0783035A2 (en) 1997-07-09
    EP0783035A3 EP0783035A3 (en) 1998-02-25
    EP0783035B1 true EP0783035B1 (en) 2003-09-24

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    AT (1) ATE250660T1 (en)
    CA (1) CA2194342A1 (en)
    DE (2) DE19600159A1 (en)
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    Families Citing this family (17)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    CA2248476A1 (en) * 1997-10-01 1999-04-01 Unilever Plc Bleach activation
    US6274122B1 (en) 1999-01-07 2001-08-14 Mclaughlin Gerald Device and method using dry mixtures for whitening teeth
    WO2002071968A2 (en) * 2001-03-14 2002-09-19 Gerald Mclaughlin Strips for treating teeth
    GB2386616A (en) * 2002-03-21 2003-09-24 Unilever Plc Bleaching composition
    JP2005194244A (en) * 2004-01-09 2005-07-21 Shigenobu Yano Zinc ion fluorescence sensor
    JP4929153B2 (en) 2004-03-05 2012-05-09 ジェン−プロウブ インコーポレイテッド Reagents, methods, and kits for use in inactivating nucleic acids
    KR100647976B1 (en) * 2004-05-03 2006-11-23 애경산업(주) Bleach and detergent compositions containing macrocyclic manganese complex
    MX2010010961A (en) 2008-04-09 2010-11-05 Basf Se Use of metal hydrazide complex compounds as oxidation catalysts.
    WO2009141258A1 (en) * 2008-05-23 2009-11-26 Henkel Ag & Co. Kgaa Washing agent that is gentle on textiles
    WO2010131231A2 (en) * 2009-05-14 2010-11-18 Ecolab Usa Inc. Peroxygen catalyst-containing fabric and use for in situ generation of alkalinity
    WO2012000846A1 (en) 2010-06-28 2012-01-05 Basf Se Metal free bleaching composition
    US9371504B2 (en) 2011-10-25 2016-06-21 Basf Se Use of acrylate copolymers as soil antiredeposition agents and soil release agents in laundry processes
    RU2014120925A (en) 2011-10-25 2015-12-10 Басф Се APPLICATION OF COMBINED OR BLOCK COPOLYMERS AS MEANS AGAINST REPEAT DEPOSITION OF POLLUTION AND DIRT-RESISTANT MEANS IN THE WASHING PROCESSES
    US10837949B1 (en) * 2012-03-22 2020-11-17 Piers Richard Warburton Peracetic acid sensor with filter to remove hydrogen peroxide
    AU2014243274B2 (en) 2013-03-27 2017-10-12 Henkel Ag & Co. Kgaa Block copolymers as soil release agents in laundry processes
    KR20160105790A (en) 2013-11-27 2016-09-07 바스프 에스이 Random copolymers as soil release agents in laundry processes
    WO2017186480A1 (en) 2016-04-26 2017-11-02 Basf Se Metal free bleaching composition

    Family Cites Families (35)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    US1246339A (en) 1916-08-21 1917-11-13 Isaac J Smit Self-illuminating depresser for dental and surgical work.
    BE549817A (en) 1955-07-27
    GB864798A (en) 1958-03-20 1961-04-06 Unilever Ltd Bleaching processes and compositions
    BE591624A (en) 1959-06-19
    US3156654A (en) 1961-06-19 1964-11-10 Shell Oil Co Bleaching
    GB1003310A (en) 1963-01-15 1965-09-02 Unilever Ltd Bleaching processes and compositions
    US3332882A (en) 1964-12-18 1967-07-25 Fmc Corp Peroxygen compositions
    GB1182143A (en) 1966-03-01 1970-02-25 United States Borax Chem Bleaching Compositions and Methods.
    GB1519351A (en) 1975-01-29 1978-07-26 Unilever Ltd Preparation of acetoxy arylene sulphonates
    US4128494A (en) 1976-09-01 1978-12-05 Produits Chimiques Ugine Kuhlmann Activators for percompounds
    US4397757A (en) 1979-11-16 1983-08-09 Lever Brothers Company Bleaching compositions having quarternary ammonium activators
    GR76237B (en) 1981-08-08 1984-08-04 Procter & Gamble
    DE3360762D1 (en) 1982-04-02 1985-10-17 Unilever Nv Process for preparing sugar acetates
    US4412934A (en) 1982-06-30 1983-11-01 The Procter & Gamble Company Bleaching compositions
    US4478733A (en) 1982-12-17 1984-10-23 Lever Brothers Company Detergent compositions
    GB8304990D0 (en) 1983-02-23 1983-03-30 Procter & Gamble Detergent ingredients
    GB8422158D0 (en) 1984-09-01 1984-10-03 Procter & Gamble Ltd Bleach compositions
    TR22733A (en) 1984-12-14 1988-05-24 Clorox Co MONTHED AND DIESTER PERASIT IPTIDAI SUBSTANCES
    US4728455A (en) 1986-03-07 1988-03-01 Lever Brothers Company Detergent bleach compositions, bleaching agents and bleach activators
    US4751015A (en) 1987-03-17 1988-06-14 Lever Brothers Company Quaternary ammonium or phosphonium substituted peroxy carbonic acid precursors and their use in detergent bleach compositions
    US4933103A (en) 1987-03-23 1990-06-12 Kao Corporation Bleaching composition
    US4915863A (en) 1987-08-14 1990-04-10 Kao Corporation Bleaching composition
    GB8720863D0 (en) 1987-09-04 1987-10-14 Unilever Plc Metalloporphyrins
    DE68908439T2 (en) 1988-03-01 1993-12-23 Unilever Nv Quatenary ammonium compounds for use in bleaching systems.
    GB8908416D0 (en) 1989-04-13 1989-06-01 Unilever Plc Bleach activation
    GB8915781D0 (en) 1989-07-10 1989-08-31 Unilever Plc Bleach activation
    US5114688A (en) 1990-01-23 1992-05-19 L'air Liquide, Societe Anonyme Pour L'etude Et Exploitation Des Procedes Georges Claude Binuclear metal macrocyclic and macrobicyclic complexes for oxygen separation and transport
    GB9003741D0 (en) 1990-02-19 1990-04-18 Unilever Plc Bleach activation
    EP0458398B1 (en) * 1990-05-21 1997-03-26 Unilever N.V. Bleach activation
    US5194416A (en) 1991-11-26 1993-03-16 Lever Brothers Company, Division Of Conopco, Inc. Manganese catalyst for activating hydrogen peroxide bleaching
    US5256779A (en) * 1992-06-18 1993-10-26 Lever Brothers Company, Division Of Conopco, Inc. Synthesis of manganese oxidation catalyst
    US5686014A (en) * 1994-04-07 1997-11-11 The Procter & Gamble Company Bleach compositions comprising manganese-containing bleach catalysts
    CN1066194C (en) * 1994-04-07 2001-05-23 普罗格特-甘布尔公司 Bleach compositions comprising bleach activators and bleach catalysts
    GB9407533D0 (en) * 1994-04-13 1994-06-08 Procter & Gamble Detergent compositions
    US5720897A (en) * 1995-01-25 1998-02-24 University Of Florida Transition metal bleach activators for bleaching agents and detergent-bleach compositions

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    DE59610733D1 (en) 2003-10-30
    EP0783035A3 (en) 1998-02-25
    CA2194342A1 (en) 1997-07-05
    US5942152A (en) 1999-08-24
    ES2207663T3 (en) 2004-06-01
    EP0783035A2 (en) 1997-07-09
    DE19600159A1 (en) 1997-07-10
    JPH09194886A (en) 1997-07-29

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