EP0682695B1 - Oxydationsmittel - Google Patents

Oxydationsmittel Download PDF

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Publication number
EP0682695B1
EP0682695B1 EP94905802A EP94905802A EP0682695B1 EP 0682695 B1 EP0682695 B1 EP 0682695B1 EP 94905802 A EP94905802 A EP 94905802A EP 94905802 A EP94905802 A EP 94905802A EP 0682695 B1 EP0682695 B1 EP 0682695B1
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Prior art keywords
product
peroxygen source
bleaching
solution
activator
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EP94905802A
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French (fr)
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EP0682695A1 (de
EP0682695A4 (de
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Vincent Brian Croud
Stephen James Tompsett
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Warwick International Group Ltd
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Warwick International Group Ltd
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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/10—Bleaching ; Apparatus therefor
    • D21C9/16—Bleaching ; Apparatus therefor with per compounds
    • D21C9/163—Bleaching ; Apparatus therefor with per compounds with peroxides
    • 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
    • C11D3/3907—Organic compounds
    • C11D3/3917—Nitrogen-containing compounds
    • 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
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/10—Bleaching ; Apparatus therefor
    • D21C9/1026—Other features in bleaching processes
    • D21C9/1036—Use of compounds accelerating or improving the efficiency of the processes
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/10—Bleaching ; Apparatus therefor
    • D21C9/16—Bleaching ; Apparatus therefor with per compounds
    • D21C9/166—Bleaching ; Apparatus therefor with per compounds with peracids

Definitions

  • the present invention relates to the in situ production of peroxygen-based oxidising species from a peroxygen source and an activator followed by the use of the product as an oxidising agent, for instance as a bleach or a biocide.
  • peroxygen bleach precursor or peroxygen source
  • bleach activator is acyl donors.
  • the bleach precursor and activator when added to the aqueous laundry liquor react together in a reaction involving attack by peroxide anion on the activator to form a peroxygen bleaching species usually the peroxy acid anion.
  • the conditions of laundry liquors are invariably alkaline, usually having a pH of at least 9.
  • the activator and peroxygen source do not react together during storage and are themselves stable under storage conditions.
  • Organic peroxy acids are well known as useful oxidising agents for a wide range of specific oxidation reactions that they perform in high-to-quantitative yield.
  • a review of the various methods known for the preparation of peroxy acids is available in "Organic Peroxides", volume 1, D. Swern Ed, Wiley Interscience (1970) 313-335.
  • Most of the reactions described use the corresponding carboxylic acid, the acid anhydride, the acid chloride or the aldehyde as the starting materials for instance for a perhydrolysis reaction using hydrogen peroxide.
  • One of the reactions uses the alkaline perhydrolysis of imidazolides of carboxylic acids to form the peroxy carboxylic acids (Folli, U et al (1968) Bollettino, 26, 61-69).
  • peracetic acid a strong oxidising agent
  • peracids are however unstable and can be dangerous to transport in bulk.
  • the problem with the in situ reaction of acetic acid and hydrogen peroxide is that water must be removed to drive the reaction or else a large excess of one of the reactants must be used, necessitating complex separation and recycling steps.
  • Acetic anhydride has also been used in place of acetic acid as starting material for this in situ reaction. The conditions during the in situ reaction step and subsequent oxidation reaction will be acidic.
  • Acetic acid and acetic anhydrides as starting materials for an in situ reaction require special precautions on handling and so are not suitable for use in a domestic environment.
  • Acetic anhydride is water sensitive and so requires special storage conditions.
  • tooth whitening compositions which contain peroxy acetic acid as the bleaching agent.
  • Compositions into which peroxy acetic acid itself is incorporated are acidic. It is suggested that the peroxy acetic acid can be generated in situ by the reaction in aqueous solution of tetraacetyl ethylene diamine and sodium perborate. In the specific examples of that embodiment of the invention the aqueous solution formed when the perborate and activator are dissolved is alkaline.
  • a peroxygen source is reacted with an activator compound which is an N-acyl compound in which the acyl moiety has at least 2 carbon atoms in a first step in aqueous solution under acidic conditions to form an oxidising product.
  • the oxidising product is found to be a stronger oxidising agent than the peroxygen source.
  • the peroxygen source is reacted with an activator compound of the formula I in which R 1 is an alkyl, alkenyl, aralkyl, alkaryl or aryl group, any of which groups has up to 24 carbon atoms and may be substituted or unsubstituted, and -NR 2 R 3 is a leaving group in which R 2 and R 3 are independently selected from H, C 1-24 -alkyl, -alkenyl, -aralkyl, alkaryl or -aryl groups, and carbonyl-containing groups having at least 2 carbon atoms in which the carbonyl group is joined to the nitrogen atom in the formula I, in a first step in aqueous solution under acidic conditions to form an oxidising species which is a stronger oxidising agent than the peroxygen source itself.
  • the present inventors believe that the mechanism of reaction is that the N-acyl activator is perhydrolysed, the N-containing part of the molecule acting as leaving group, to form the respective percarboxylic acid of the acyl group.
  • the product containing the stronger oxidising species is subsequently used as a bleaching agent in an aqueous environment at a pH of less than 7.
  • the product of the first step (hereinafter sometimes called the perhydrolysis step for convenience) is subsequently used as an oxidising agent in an oxidising step which is carried out without removal of any by-products from the first perhydrolysis step.
  • R 1 is an aliphatic group preferably a C 1-18 -alkyl or -alkenyl group, or an aryl group.
  • alkyl and alkenyl groups may be straight, branched or cyclic.
  • R 2 and R 3 may be joined to form a cyclic group.
  • R 1 may further or alternatively be joined to either R 2 or R 3 to form a cyclic group.
  • These cyclic groups may include heteroatoms, for instance oxygen or optionally substituted nitrogen atoms, carboxyl groups as well as -CH 2 - groups or substituted derivatives thereof. They may be saturated or unsaturated.
  • the compound of the formula I is preferably any N-acyl compound which has been described as a bleach activator for use in laundry detergents.
  • the compound of the formula is preferably an amide derivative such as an acyl imidazolide as described by Folli et al (op cit) and N,N-diacyl amides, for instance, triacetyl ethanolamine or, most preferably tetraacetyl ethylenediamine (TAED).
  • TAED tetraacetyl ethylenediamine
  • the precursor peroxygen source may be hydrogen peroxide itself, but is alternatively an inorganic persalt, for instance a percarbonate or a perborate, for instance sodium perborate, or an organic peroxide such as benzoyl peroxide or urea peroxide.
  • the pH in the perhydrolysis step is preferably less than 6.5 throughout the entire reaction. Since the pH tends to drop during the reaction due to the formation of the percarboxylic acid, this means that the pH should be acidic and preferably less than 6.5 at the beginning of the reaction. Preferably the pH is less than about 6.0, at the start of the reaction. The pH is usually more than 2.0, at the start of the reaction and preferably throughout the reaction, preferably more than 5.0.
  • the amount of water present is preferably at least as much as (in terms of moles) as the peroxgyen source.
  • the concentration of hydrogen peroxide is preferably less than 70% weight/volume (that is weight of hydrogen peroxide based on volume of water plus hydrogen peroxide plus other components in the mixture concerned).
  • the concentration is less than 60% weight by volume and more preferably less than 30% w/v.
  • the concentration is preferred for the concentration to be less than 15 or even 10% w/v for instance 5% w/v or less.
  • the concentration is usually at least 0.2%, preferably at least 1% w/v, more preferably at least 2% w/v.
  • the concentration is preferably such as to give the equivalent available oxygen as the quoted concentrations of hydrogen peroxide.
  • the concentration of hydrogen peroxide or perborate or percarbonate is suitably in the range 0.01M to 10M, preferably in the range 0.05 or 0.1M to 5M, more preferably in the range 0.2M to 2M often less than 1M, in the perhydrolysis reaction mixture.
  • the temperature is preferably in the range 0 to 95°C, more preferably in the range 10 to 80°C.
  • the invention is most useful when the temperature is less than 60°C, or even less than 50°C, for instance less than 40°C or even around room temperature.
  • the temperature is often above 20°C.
  • the temperature in any subsequent oxidising step is preferably in the same ranges as the temperature during the perhydrolysis step and is preferably substantially the same temperature especially where the product solution is immediately used for instance as a bleach or disinfectant.
  • a particular advantage of using activators for the peroxygen source is that the oxidising product tends to be formed at a relatively low temperature, for instance less than hand hot which is advantageous from a safety point of view.
  • the activator compound is generally used in an amount such that it is capable of providing in the range 0.1 to 5.0 equivalents of acyl groups based on the moles of peroxygen source, preferably in the range 0.2 to 1.0.
  • the amount is often less than stoichiometric, for instance up to 0.9 or 0.8 of the stoichiometric amount.
  • tetraacetyl ethylenediamine reacts as an activator to donate one acyl group from each nitrogen atom and so to provide 0.2 equivalents acyl groups per mole of peroxide, 0.1 mole of TAED is needed for total reaction. Often less than this is used, although the optimum amount depends upon the degree of increase in oxidising performance compared to the costs of the peroxygen source and activator.
  • the present invention provides also use of a composite product comprising all the starting materials for the perhydrolysis reaction.
  • the product can simply be added to water to provide the entire reaction mixture.
  • the product therefore comprises a peroxygen source, an N-acyl activator compound preferably of the formula I, as well as components for rendering the pH of an aqueous solution to which the components of the product are added acidic if necessary, though in some circumstances the peroxygen source itself may be sufficiently acidic that no extra acidifying component is needed.
  • An acidifying component may comprise an acid and/or buffering material.
  • the component may comprise a polybasic organic acid, such as a polybasic carboxylic acid such as citric, succinic, or adipic acid or sulphamic acid.
  • the component may react with a by-product of the perhydrolysis reaction to make an acid.
  • perborate is used, borate is a by-product and so any component known to react with borate to drop the pH, eg cis-1,2-diols, eg glycols and polyols, boric acid or sodium dihydrogen phosphate, can be used.
  • Such acidifying components are also suitable for use with other inorganic persalts.
  • the composite product may contain the individual components in two or more separate compositions, for instance one of which contains the peroxygen source (for instance an aqueous solution of hydrogen peroxide as a concentrate for dilution or ready for use without further dilution) and another of which contains the activator, for instance of the formula I, it is preferred for a mixture of at least two of the components to be provided in a single composition, in which the components do not react, and which is preferably substantially waterfree. It is preferred to provide at least the activator and acidifying component, if any, as a mixture in a single composition in a form in which they are stable.
  • the peroxygen source for instance an aqueous solution of hydrogen peroxide as a concentrate for dilution or ready for use without further dilution
  • the activator for instance of the formula I
  • Such a product which does not contain peroxygen source may for instance, be added to an aqueous solution of peroxygen source, such as hydrogen peroxide, which is readily commercially available, in the form of 60%, 20% 10% or, preferably 5% w/v, or less, solution. It is most preferred for the activator, peroxygen source and any acidifying component to be present in a single composition.
  • peroxygen source such as hydrogen peroxide
  • the products may be in liquid form, for instance in a non-aqueous liquid medium, in which the components may be dissolved or dispersed.
  • particles of activator with protective coatings for instance produced by microencapsulation techniques or spray coating of solid activator, may be suspended in an aqueous, or non aqueous, solution of peroxygen source.
  • particles of solid peroxygen source optionally being coated with a protective coating. Coated particles of either peroxygen source or activator may be disrupted simply by being diluted into water or physically disrupted by applying abrasion.
  • the product is in solid form, for instance as a mixture of particles of the individual components or, more preferably, comprising particles each of which comprise all of the components.
  • Such particles may be provided by techniques similar to those used in the laundry detergent industry, for instance including particles produced by spray drying liquid slurries, by granulation techniques using binders for instance synthetic or natural polymers (or derivatives) or by melt blending followed by extrusion or other techniques.
  • the composite product may include other additives, for instance stabilisers which stabilise the product before use, as well as stabilisers for the stronger oxidising species formed in the reaction, especially heavy metal sequestrants.
  • the new product may also include surfactants to act as wetting agents and inorganic salts, for instance which affect the physical properties of the solid form or act as diluent or to increase the rate of disintegration or dissolution of the product.
  • Other ingredients may be included depending on the form of the product and the final application of the reaction product, for instance perfumes, abrasives.
  • the product contains the active ingredients in appropriate relative quantities so that when the composition is diluted (or the compositions are mixed) with water the first step of the reaction proceeds at the optimal rate and at the desired pH.
  • the activator and peroxygen source are for instance present in relative amounts such that 5% to 150% of the stoichiometric amount of activator (for complete reaction with the peroxygen source) is provided.
  • the amount of activator is 10 to 100%, more preferably 20 to 80% of the stoichiometric amount.
  • the reaction product of the perhydrolysis reaction is preferably used immediately, without removal of any by-products or addition of other materials, in a second step in which it is used as an oxidising agent, bleaching or disinfecting agent.
  • additional ingredients for the second step such as pH-adjusters, and surfactants/wetting agents which may cationic, anionic, amphoteric or non-ionic.
  • Other additives which may improve the second step of the process are for instance disinfectants, biocides, slimicides, enzymes, inhibitors or radical scavengers, abrasives etc. Cobiocides are particularly valuable where the primary objective of the second step is disinfection/sterilisation.
  • the second step of the process of the present invention may be used as a bleaching/disinfection process, by which we mean any process in which unwanted colour is reduced or removed, non-coloured stains are reduced or removed and/or a substrate is disinfected.
  • the second step may include processes in which hard surfaces in domestic, industrial or institutional applications are cleansed, fabrics (for instance during fabric manufacture and dyeing) or the solution is used in water, effluent or sewage treatment as a biocide, in pulp and paper bleaching, paper deinking, wood bleaching, in fibre and fabric manufacture, a biocide, fungicide, bacteriocide, sporicide and/or viricide, as a contact lens disinfectant or general disinfectant for use inter alia in general environmental clean up.
  • the second step may be used in food production for instance to bleach flour, beverages, or edible oils in the food and brewing industries, for instance to clean pipes used for beverages, or, in cosmetic uses such as hair bleaching or tooth or denture whitening and disinfecting.
  • the product of the first step may alternatively be used as an oxidising agent in organic synthesis eg for use in epoxidation reactions of alkenes or as a catalyst. It can be used as a curing agent for certain adhesives.
  • reaction can be carried out at a relatively low concentration it can be carried out without special precautions, for instance in a domestic or institutional environment.
  • compositions which are suitable to be diluted direct into water to allow the first and second steps of the reaction to proceed without further additions may be categorised in four convenient categories.
  • the first category comprises liquid formulations which include a surfactant.
  • These compositions will be suitable for use as hard surface cleaners and other uses where surface active disinfection and/or bleaching is required, for instance floor cleaning compositions, domestic and institutional hard surface cleaners, toilet disinfectants, general toiletries disinfectant, sanitising bottles, including glass and plastic bottles, and pipe cleaning compositions.
  • floor cleaning compositions for instance floor cleaning compositions, domestic and institutional hard surface cleaners, toilet disinfectants, general toiletries disinfectant, sanitising bottles, including glass and plastic bottles, and pipe cleaning compositions.
  • the composition will be relatively low foaming, although for some, for instance toilet disinfecting and general toiletries disinfectant, it may be desirable for the composition to have a relatively high foam.
  • suitable surfactants which will foam is well known in the art.
  • anti-foaming agents for instance soap or silicone anti-foams.
  • Liquid formulations including surfactants may be useful in other applications such as for use to bleach fibres or fabrics, such as nappies or in
  • a second category of composition comprises liquid formulations but which contain no surfactants. These may be useful where no surface activity is necessary, for instance in effluent and water treatment, in toilet disinfectants, for use as a swimming pool treatment, for colour removal from chemicals, from pulp during paper making or recycling, in general industrial sterilisation and in some domestic sterilisation situations, for instance as a general toiletry disinfectant, in denture cleaning compositions, in sanitising glass and plastic bottles or other containers, as well as in certain environmental clean-up operations. Furthermore, where the composition is to be used as a general industrial oxidation reaction, it may be undesirable to include a surfactant.
  • liquid formulations mentioned above may be pourable liquids, which are aqueous or non-aqueous, or may be in gel or paste form. Furthermore the compositions may be two-phase, for instance a cream form. Alternatively the compositions could be in the form of a mousse (where the composition contains surfactant) by the injection of a gas, especially for domestic hard surface cleaning operations.
  • a further category of composition is in solid form and includes a surfactant.
  • the general uses of these compositions are similar to those for which the liquid formulations including a surfactant are useful, as mentioned above.
  • a further category of formulation comprises a solid composition but without surfactant. These compositions are useful in the same categories of uses as the liquid formulations without surfactant.
  • the compositions may, in solid form, be more storage stable, since it is in general easier to keep the bleach activator and peroxygen donor compound in separate particles and prevent them coming into contact with one another during storage. It is furthermore easier to isolate other components of the composition from one another and from the bleach components, especially where storage sensitive compounds such as enzymes, other biocides or perfumes are present.
  • Solid compositions may be in the form of particulate mixtures or may be tabletted.
  • Tabletted formulations, or even granular formulations may include agents to increase the dissolution rate of the compositions upon addition to water.
  • suitable components incorporating into tablets aid disintegration of the tablet.
  • Such ingredients may create effervescence, for instance; a suitable component is sodium bicarbonate, or other alkali metal bicarbonate.
  • compositions may also contain ingredients to assist in their application or stability or which improve their appearance, for instance thickeners, dispersants, opacifiers, hydrotropes, dyes, perfumes etc.
  • concentration of the peroxygen source is reported in terms of the starting concentration of aqueous hydrogen peroxide, to which other reactants are added.
  • the molar concentration of the mixtures can be calculated.
  • TAED and DADHT as activators for peroxygen bleaches at acidic pH, for stains in solution and on fabrics
  • the swatches were left in solution for 75 minutes.
  • the brightness was compared to an unbleached chlorophyll stained swatch after rinsing with deionised water and drying as in the previous examples.
  • Acetic anhydride is a widely used source of peracids under laboratory conditions. This material is however water sensitive, corrosive and therefore not easy to handle. The following experiments were designed to see how effective acetic anhydride was as a peracid generator under dilute aqueous conditions.
  • Chlorophyll stained swatches were added to these solutions and left to bleach for 75 mins. After this time the swatches were removed and washed in water to remove any remaining active species.
  • Chlorophyll stained swatches were added to the solutions used above and left to bleach overnight for 17 hours. The swatches were rinsed. The pH of the bleaching solution was measured after the cloths had been removed.
  • Fresh solutions using the first three compositions were prepared and allowed to stand overnight before chlorophyll stained swatches were added. The cloths were left to bleach for 75 mins and then removed and rinsed.
  • the relative concentration of oxidising agent was determined at time intervals using an iodometric titration on ice.
  • the solutions studied were those used in experiments 5.2.1 and 5.2.2 Comp Experiment E as 5.3.1 and 5.3.2, respectively.
  • the iodometric titration carried out was that used for calibrating peracetic acid.
  • the solution to be assayed is added to a flask containing potassium iodide, acetic acid and ice.
  • the iodine liberated is titrated with sodium thiosulphate.
  • the TAED activated solution gives a lower initial concentration of strong oxidising agent.
  • the TAED solution increases in strong oxidising agent concentration while the acetic anhydride solution loses peracid.
  • the levels of strong oxidising agent acid are higher in the TAED containing solution.
  • the bleaching performance of some of the solutions was determined on un-glazed, tea-stained tiles.
  • the bleaching solution is applied to one half of the tile and the difference in whiteness, as determined using a Hunter-Lab apparatus between the two halves is determined. The value is given as ⁇ W.
  • the Hunter-Lab apparatus is set to CIE tristimulus XYZ scale.
  • the W reading is the Z% brightness.
  • Granule 1 is Mykon ATC (available from the applicant company) formed from 90-94% TAED carboxymethyl cellulose binder and no more than 2% water and has particle size 95% in the range 0.2 to 1.6 mm.
  • Granule 2 is Mykon ASD formed from 83 TO 87% TAED, CMC binder and 2.5 to 3.5% methylene phosphonic acid sequestrant and no more than 2.5% water having particle size 95% in the range 0.2 to 1.6 mm.
  • the solutions were applied with a brush to half a stained tile and then either dipped in water or wiped with a cloth to remove the liquid. The whiteness was then recorded as described above.
  • the ⁇ W values for Flash alone, removed by wiping and dipping, were 4.0 and 9.7, respectively.
  • the ⁇ W values for the boosted Flash were 4.8 and 13.5 respectively.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
  • Catching Or Destruction (AREA)
  • Epoxy Compounds (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Claims (20)

  1. Verfahren, worin eine Persauerstoff-Quelle mit einer Aktivator-Verbindung, bei der es sich um eine N-Acylverbindung mit mindestens zwei Kohlenstoffatomen in der Acylgruppe handelt, in einem ersten Schritt in wäßriger Lösung unter sauren Bedingungen umgesetzt wird, um ein oxidierendes Produkt zu bilden, welches ein stärkeres Oxidationsmittel ist als die Persauerstoff-Quelle.
  2. Verfahren nach Anspruch 1, worin die Aktivator-Verbindung die Formel I aufweist
    Figure imgb0008
     worin R1 eine Alkyl-, Alkenyl-, Aralkyl-, Alkaryl- oder Arylgruppe ist, jede dieser Gruppen bis zu 24 Kohlenstoffatome aufweist und substituiert oder unsubstituiert sein kann, und -NR2R3 eine Abgangsgruppe ist, worin R2 und R3 unabhängig aus H, C1-24-Alkyl-, -Alkenyl-, -Aralkyl-, -Alkaryl- oder -Arylgruppen und Carbonyl-haltigen Resten mit mindestens 2 Kohlenstoffatomen, worin die Carbonylgruppe an das Stickstoffatom in Formel I gebunden ist, ausgewählt sind, wobei R2 und R3 als cyclische Gruppe miteinander verbunden sein können und/oder R1 entweder an R2 oder R3 gebunden sein kann, um eine cyclische Gruppe zu bilden.
  3. Verfahren nach Anspruch 2, worin R1 eine aliphatische Gruppe, vorzugsweise eine C1-18-Alkyl- oder -Alkenylgruppe, ist oder eine Arylgruppe ist.
  4. Verfahren nach irgendeinem vorhergehenden Anspruch, worin das Produkt, das stärkere Bleich-Spezies enthält, anschließend als Bleich- und/oder Desinfektionsmittel in einer wäßrigen Umgebung bei einem pH von weniger als 7 verwendet wird.
  5. Verfahren nach irgendeinem vorhergehenden Anspruch, worin das Produkt des ersten Schritts anschließend als Oxidationsmittel in einem Oxidationsschritt verwendet wird, der ohne Entfernung irgendwelcher Nebenprodukte aus dem ersten Schritt durchgeführt wird.
  6. Verfahren nach irgendeinem vorhergehenden Anspruch, worin die Persauerstoff-Quelle aus Wasserstoffperoxid, organischen Peroxiden und anorganischen Persalzen ausgewählt ist.
  7. Verfahren nach irgendeinem vorhergehenden Anspruch, worin der pH in dem ersten Schritt zu Beginn der Reaktion weniger als 6,5 beträgt und vorzugsweise mehr als 2, 0, bevorzugter mehr als 5,0, beträgt.
  8. Verfahren nach irgendeinem vorhergehenden Anspruch, worin die Konzentration der Persauerstoff-Quelle in der Reaktionsmischung des ersten Schritts weniger als 10 M, vorzugsweise weniger als 5 M, bevorzugter weniger als 2 M, beträgt und vorzugsweise mindestens 0,01 M, noch mehr bevorzugt weniger als 1 M und mindestens 0,05 M, insbesondere mindestens 0,1 M, beträgt.
  9. Verfahren nach irgendeinem vorhergehenden Anspruch, worin die Temperatur in dem ersten Schritt der Reaktion im Bereich von 0 bis 95°C, vorzugsweise mindestens 20°C und bis zu 80°C, bevorzugter bis zu 60°C, beträgt.
  10. Verwendung eines Kompositprodukts, welches eine Persauerstoff-Quelle und eine N-Acyl-Aktivatorverbindung mit mindestens zwei Kohlenstoffatomen in der Acylgruppe und, falls erforderlich, eine ansäuernde Komponente, die in der Lage ist, eine wäßrige Lösung der Persauerstoff-Quelle und der Aktivator-Verbindung sauer zu machen, umfaßt, zur Bildung der Reaktantenmischung für den ersten Schritt eines Verfahrens nach irgendeinem vorhergehenden Anspruch durch Zugabe des Produkts zu Wasser, um die Persauerstoff-Quelle, den Aktivator und die ansäuernde Komponente unter Bildung einer sauren Lösung zu lösen.
  11. Verwendung nach Anspruch 10, worin die Aktivator-Verbindung in dem Produkt in einer Menge vorhanden ist, die ausreicht, um 0,1 bis 5 Äquivalente Acylgruppen pro Mol Persauerstoff-Quelle, vorzugsweise bis zu 1,0 Äquivalente, bereitzustellen.
  12. Verwendung nach Anspruch 10 oder 11, worin die ansäuernde Komponente in dem Produkt in einer solchen Menge vorhanden ist, daß der pH weniger als 6,5 beträgt, wenn die Komponenten des Produkts in wäßriger Lösung gelöst werden, wobei die Persauerstoff-Quelle in einer Konzentration im Bereich von 0,01 bis 10 M (vorzugsweise im Bereich von 0,1 bis 1,0 M) vorliegt.
  13. Verwendung nach irgendeinem der Ansprüche 10 bis 12, worin die Aktivator-Verbindung wie in Anspruch 2 oder Anspruch 3 definiert ist.
  14. Verwendung nach irgendeinem der Ansprüche 10 bis 13, worin die Persauerstoff-Quelle aus Wasserstoffperoxid, organischen Peroxiden und anorganischen Persalzen ausgewählt ist.
  15. Verwendung nach irgendeinem der Ansprüche 11 bis 14, worin das Kompositprodukt ein Tensid beinhaltet.
  16. Verwendung nach irgendeinem der Ansprüche 10 bis 15, worin das wäßrige Produkt als Oxidationsmittel, vorzugsweise als Bleich- und/oder Desinfektionsmittel, verwendet wird.
  17. Wäßrige saure Lösung, umfassend eine Persauerstoff-Quelle, eine N-Acyl-Aktivatorverbindung mit mindestens 2 Kohlenstoffatomen in der N-Acylgruppe, ein Tensid und, falls erforderlich, eine ansäuernde Komponente.
  18. Verwendung der Lösung eines Produkts nach Anspruch 17 als Oxidationsmittel, vorzugsweise als Bleich- und/oder Desinfektionsmittel.
  19. Verfahren, worin ein Kompositprodukt wie in irgendeinem der Ansprüche 10 bis 16 definiert mit Wasser verdünnt wird, um eine saure Lösung zu bilden.
  20. Verfahren nach Anspruch 19, worin die dadurch gebildete wäßrige saure Lösung als Bleichmittel, Desinfektionsmittel, Sterilisationsmittel oder Biozid verwendet wird, wobei der pH während der Verwendung der Lösung bei weniger als 7 bleibt.
EP94905802A 1993-02-08 1994-02-07 Oxydationsmittel Expired - Lifetime EP0682695B1 (de)

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Application Number Priority Date Filing Date Title
GB939302443A GB9302443D0 (en) 1993-02-08 1993-02-08 Oxidising agents
GB9302443 1993-02-08
PCT/GB1994/000229 WO1994018298A1 (en) 1993-02-08 1994-02-07 Oxidising agents

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EP0682695A4 EP0682695A4 (de) 1994-10-05
EP0682695A1 EP0682695A1 (de) 1995-11-22
EP0682695B1 true EP0682695B1 (de) 1997-10-29

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JP (1) JPH08509695A (de)
CN (1) CN1050380C (de)
AT (1) ATE159755T1 (de)
AU (1) AU5976494A (de)
CA (1) CA2155633A1 (de)
DE (1) DE69406531T2 (de)
ES (1) ES2110220T3 (de)
FI (1) FI953742A (de)
GB (1) GB9302443D0 (de)
IL (1) IL108598A0 (de)
IN (1) IN180646B (de)
TR (1) TR27789A (de)
WO (1) WO1994018298A1 (de)
ZA (1) ZA94863B (de)

Cited By (3)

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EP3983340B1 (de) * 2019-06-12 2023-08-02 Nouryon Chemicals International B.V. Verfahren zur isolierung von carbonsäure aus einem wässrigen seitenstrom
US11976034B2 (en) 2019-06-12 2024-05-07 Nouryon Chemicals International B.V. Process for the production of diacyl peroxides
US11976035B2 (en) 2019-06-12 2024-05-07 Nouryon Chemicals International B.V. Process for the production of diacyl peroxides

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5753138A (en) * 1993-06-24 1998-05-19 The Procter & Gamble Company Bleaching detergent compositions comprising bleach activators effective at low perhydroxyl concentrations
ES2113176T3 (es) * 1993-11-25 1998-04-16 Warwick Int Group Activadores de blanqueo.
WO1995021290A1 (en) * 1994-02-07 1995-08-10 Warwick International Group Limited Pulp bleaching
GB9414625D0 (en) * 1994-02-07 1994-09-07 Warwick Int Group Oxidising compositions
GB9600159D0 (en) * 1996-01-05 1996-03-06 Warwick Int Group Process for bleaching or disinfecting a substrate
US5879409A (en) * 1996-02-23 1999-03-09 The Procter & Gamble Company Bleach additive and bleaching compositions having glycine anhydride activators
CN1185329C (zh) * 1996-07-29 2005-01-19 普罗格特-甘布尔公司 不对称的无环酰亚胺漂白活化剂和使用它们的组合物
JP2001522866A (ja) 1997-11-10 2001-11-20 ザ、プロクター、エンド、ギャンブル、カンパニー Ｏ‐置換ｎ，ｎ‐ジアシルヒドロキシルアミンブリーチアクチベーターおよびそれを用いた組成物
US6569286B1 (en) * 1998-09-30 2003-05-27 Warwick International Group Limited Method for the alkaline bleaching of pulp with a peroxyacid based oxygen bleaching species using an agglomerated bleach activator
US8007636B2 (en) * 2004-11-05 2011-08-30 Akzo Nobel N.V. Method of treating cellulose fibres with chlorine dioxide and an alkyl cellulose derivative
JP2007197416A (ja) * 2005-12-28 2007-08-09 Fujifilm Corp 殺菌用水性組成物の製造方法
DE102006028029A1 (de) * 2006-06-14 2007-12-20 Henkel Kgaa Aufhell- und/oder Färbemittel mit Azoliden
US8969283B2 (en) * 2009-02-05 2015-03-03 American Sterilizer Company Low odor, hard surface sporicides and chemical decontaminants
CN103205883B (zh) * 2012-01-13 2016-05-11 山西彩佳印染有限公司 一种棉织物双氧水室温间歇式练漂方法
CN103205884B (zh) * 2012-01-13 2016-05-04 山西彩佳印染有限公司 一种棉织物双氧水快速连续冷堆练漂方法
CN110790692B (zh) * 2019-10-30 2021-06-22 陕西铭锐石油科技有限公司 一种温度触发释氧型油膜剥离表面活性剂及其制备方法和应用

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1010048B (de) * 1953-05-20 1957-06-13 Degussa Verfahren zum Waschen von Faserstoffen oder Textilwaren
DE1469609A1 (de) * 1964-07-10 1969-03-27 Basf Ag Verfahren zum gleichzeitigen Faerben und Bleichen von proteinhaltigem Fasergut
EP0396287A3 (de) * 1989-05-04 1991-10-02 The Clorox Company Verfahren und Erzeugnis für ein verbessertes Bleichen unter in situ Bildung von Persäure

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3983340B1 (de) * 2019-06-12 2023-08-02 Nouryon Chemicals International B.V. Verfahren zur isolierung von carbonsäure aus einem wässrigen seitenstrom
US11976034B2 (en) 2019-06-12 2024-05-07 Nouryon Chemicals International B.V. Process for the production of diacyl peroxides
US11976035B2 (en) 2019-06-12 2024-05-07 Nouryon Chemicals International B.V. Process for the production of diacyl peroxides

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DE69406531T2 (de) 1998-02-26
EP0682695A1 (de) 1995-11-22
GB9302443D0 (en) 1993-03-24
ZA94863B (en) 1995-02-08
CA2155633A1 (en) 1994-08-18
TR27789A (tr) 1995-08-29
AU5976494A (en) 1994-08-29
IL108598A0 (en) 1994-05-30
CN1050380C (zh) 2000-03-15
ES2110220T3 (es) 1998-02-01
DE69406531D1 (de) 1997-12-04
ATE159755T1 (de) 1997-11-15
FI953742A0 (fi) 1995-08-07
FI953742A (fi) 1995-09-12
IN180646B (de) 1998-02-28
EP0682695A4 (de) 1994-10-05
WO1994018298A1 (en) 1994-08-18
CN1119025A (zh) 1996-03-20
JPH08509695A (ja) 1996-10-15

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