EP1628912A2 - Use of pulverulent mixtures containing hydrogen peroxide and hydrophobed silicon dioxide for the controlled release of hydrogen peroxide or oxygen - Google Patents

Use of pulverulent mixtures containing hydrogen peroxide and hydrophobed silicon dioxide for the controlled release of hydrogen peroxide or oxygen

Info

Publication number
EP1628912A2
EP1628912A2 EP04731928A EP04731928A EP1628912A2 EP 1628912 A2 EP1628912 A2 EP 1628912A2 EP 04731928 A EP04731928 A EP 04731928A EP 04731928 A EP04731928 A EP 04731928A EP 1628912 A2 EP1628912 A2 EP 1628912A2
Authority
EP
European Patent Office
Prior art keywords
hydrogen peroxide
silicon dioxide
released
use according
oxygen
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP04731928A
Other languages
German (de)
French (fr)
Inventor
Egon Walzer
Corinna Schmidt
Friedhelm Brandner
Steffen Hasenzahl
Mario Scholz
Birgit Del Grosso
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Evonik Operations GmbH
Original Assignee
Degussa GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from DE102004002356A external-priority patent/DE102004002356A1/en
Application filed by Degussa GmbH filed Critical Degussa GmbH
Publication of EP1628912A2 publication Critical patent/EP1628912A2/en
Withdrawn legal-status Critical Current

Links

Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K33/00—Medicinal preparations containing inorganic active ingredients
    • A61K33/40—Peroxides
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0216—Solid or semisolid forms
    • A61K8/022—Powders; Compacted Powders
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/11—Encapsulated compositions
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/22—Peroxides; Oxygen; Ozone
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/25—Silicon; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/58—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing atoms other than carbon, hydrogen, halogen, oxygen, nitrogen, sulfur or phosphorus
    • A61K8/585—Organosilicon compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/18—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing inorganic materials
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42—Use of materials characterised by their function or physical properties
    • A61L15/46—Deodorants or malodour counteractants, e.g. to inhibit the formation of ammonia or bacteria
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P17/00—Drugs for dermatological disorders
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/08—Preparations for bleaching the hair
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/10—Preparations for permanently dyeing the hair
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/02—Preparation of oxygen
    • C01B13/0203—Preparation of oxygen from inorganic compounds
    • C01B13/0211—Peroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
    • C01B15/01—Hydrogen peroxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
    • C01B15/055—Peroxyhydrates; Peroxyacids or salts thereof
    • C01B15/14—Peroxyhydrates; Peroxyacids or salts thereof containing silicon
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • 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
    • C11D3/3942—Inorganic per-compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/41—Particular ingredients further characterized by their size
    • A61K2800/412—Microsized, i.e. having sizes between 0.1 and 100 microns
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/10—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing inorganic materials
    • A61L2300/11—Peroxy compounds, peroxides, e.g. hydrogen peroxide
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
    • A61L2300/404—Biocides, antimicrobial agents, antiseptic agents
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/60—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a special physical form
    • A61L2300/602—Type of release, e.g. controlled, sustained, slow

Definitions

  • Hydrogen peroxide and hydrophobicized silicon dioxide for the controlled release of hydrogen peroxide or
  • the invention relates to the use of powdery mixtures containing hydrogen peroxide and hydrophobized silicon dioxide for the controlled release of hydrogen peroxide and / or oxygen.
  • Hydrogen peroxide is produced in the form of aqueous solutions and put on the market. For numerous applications it is advantageous to use a fixed storage form of hydrogen peroxide instead of the aqueous solutions.
  • Commercial solid storage forms for hydrogen peroxide are sodium carbonate perhydrate, sodium perborate and the adduct of urea with hydrogen peroxide.
  • these forms of storage have the disadvantage that, together with hydrogen peroxide, other water-soluble constituents are introduced, which are undesirable in many applications because, for example, they lead to changes in the pH value in aqueous solutions and increase the salt content or the content of organic substances can.
  • Powdery products are known from German published patent application DE 20 137 63 which contain hydrogen peroxide and at least 9% by weight of a finely divided hydrophobicized silica which do not have the disadvantage mentioned above.
  • DE 20 137 63 uses bleaching, in particular products containing oils, fats and cellulose, as well as the addition of these products
  • the invention thus relates to the use of powdered mixtures containing hydrogen peroxide and hydrophobized silicon dioxide for the controlled release of hydrogen peroxide and / or oxygen.
  • Powdery mixtures are preferably used in which hydrogen peroxide is present in the form of drops of an aqueous solution of hydrogen peroxide, which are enveloped by hydrophobized silicon dioxide.
  • Such powdery mixtures can be prepared in a simple manner by intensively mixing an aqueous hydrogen peroxide solution with the hydrophobized silicon dioxide.
  • Hydrophobicized silicon dioxide has non-polar organic residues on the surface and is therefore not wetted by pure water.
  • a pyrogenically prepared, hydrophobized silicon dioxide with a methanol wettability of at least 40 is preferably used as the hydrophobicized silicon dioxide.
  • the methanol wettability is a measure of the hydrophobicity of the silicon dioxide and is determined as the methanol content in percent by volume of a methanol-water mixture at which 50% of the hydrophobized silicon dioxide introduced into the methanol-water mixture sediment. If the methanol content is lower, there is no wetting and the hydrophobicized silicon dioxide largely floats. With a higher methanol content, extensive wetting occurs and most of the silicon dioxide sediments.
  • hydrophobized silicon dioxide with a wettability by methanol of at least 40 results in particularly storable powdery mixtures which are present as free-flowing powders even when the content of hydrophobicized silicon dioxide is less than 9% by weight.
  • Powdery mixtures are preferably used which contain hydrogen peroxide in the form of an aqueous solution with a content in the range from 5 to 70% by weight of hydrogen peroxide and particularly preferably in the range from 10 to 50% by weight of hydrogen peroxide.
  • Hydrogen peroxide solution preferably contains one or more stabilizers which stabilize the solution against decomposition to water and oxygen.
  • stabilizers are, for example, stannates, phosphates, pyrophosphates, polyphosphates, organic phosphonic acids and aminophosphonic acids and also their salts, nitrates and magnesium salts. The choice of type and amount of stabilizers can be used to determine whether predominantly when using the powdery mixtures Hydrogen peroxide is released or whether predominantly oxygen is released.
  • the powdery mixtures containing hydrogen peroxide and hydrophobized silicon dioxide are used for the time-delayed release of hydrogen peroxide.
  • the powdery mixtures are preferably exposed to only slight pressure and shear forces.
  • oxygen can also be released with a time delay.
  • hydrogen peroxide and oxygen can also be released with a time delay.
  • the powdery mixtures are preferably used for the time-delayed release of hydrogen peroxide in an aqueous medium.
  • the powdery mixtures are brought into contact with the aqueous medium and, if appropriate, dispersed therein, the dispersing preferably being carried out with low shear forces.
  • the powdery mixture is brought into contact with the aqueous medium in a container which is permeable to water and hydrogen peroxide and impermeable to the hydrophobized silicon dioxide.
  • the containers used for this purpose preferably consist wholly or partly of a filter medium whose pore size is smaller than the average particle size of the particles of hydrophobized silicon dioxide used to produce the powdery mixture.
  • the container containing the powdery mixture is immersed in the aqueous medium, so that the transport of hydrogen peroxide from the container into the medium takes place predominantly by diffusion.
  • the container is flowed through by the aqueous medium.
  • the containers can be one have any shape and, for example, the shape of a filter bag, a filter cartridge or a cartridge.
  • the powdery mixtures containing hydrogen peroxide and hydrophobized silicon dioxide are used in order to release hydrogen peroxide by the action of pressure.
  • the pressure can be applied mechanically, for example by a plunger, hydraulically by liquid pressure or pneumatically by gas pressure.
  • Hydraulic pressure is preferably used to release hydrogen peroxide into an aqueous medium.
  • the powdery mixture is preferably used in a container which is permeable to water and hydrogen peroxide and impermeable to the hydrophobized silicon dioxide.
  • the container used is preferably flowed through by the aqueous medium, the pressure being exerted by the dynamic pressure of the flowing aqueous medium.
  • hydrogen peroxide can be released into a flowing aqueous medium, the amount of hydrogen peroxide released being adapted to the amount of the flowing medium without the need for measuring or control devices.
  • the powdery mixtures containing hydrogen peroxide and hydrophobized silicon dioxide can moreover also be used to release hydrogen peroxide in a controlled manner in a powdery medium.
  • the mixtures are mixed with the powdery medium, an amount of the mixture containing hydrogen peroxide and silicon dioxide in the range from 0.1 to 10% by weight of the total amount being preferably used.
  • the mixtures containing hydrogen peroxide and hydrophobized silicon dioxide can be used in order to release hydrogen peroxide in the powdery medium with a time delay and thus to maintain a low hydrogen peroxide concentration over a longer period of time.
  • the mixtures containing hydrogen peroxide and hydrophobized silicon dioxide can also be used in addition to in a powdery medium release hydrogen peroxide at a defined point in time.
  • the release of hydrogen peroxide by the action of pressure can be used, for example, to initiate a chemical reaction in the powdery medium, for example to cure the powdery medium.
  • the powdery mixtures containing hydrogen peroxide and hydrophobized silicon dioxide can moreover also be added to emulsions, gels, creams or pastes in order in the preparations thus obtained
  • the powdery mixtures can be used for the delayed release of hydrogen peroxide in order to maintain a low concentration of hydrogen peroxide in the preparation over a longer period of time.
  • the powdery mixtures can also be used to release hydrogen peroxide in the preparation at a defined point in time by the action of pressure or by the action of shear forces.
  • the powdery mixtures can be used for the delayed release of hydrogen peroxide in order to maintain a low concentration of hydrogen peroxide in the preparation over a longer period of time.
  • the powdery mixtures can also be used to release hydrogen peroxide in the preparation at a defined point in time by the action of pressure or by the action of shear forces.
  • Mixtures used in cosmetic preparations to release hydrogen peroxide under pressure when rubbed on the skin can also be used to trigger a chemical reaction in the preparation and thus to change the composition and properties of the preparation.
  • Such preparations can be used, for example, as adhesives which crosslink and harden under the action of pressure.
  • Hydroperoxide can be released over an extended period of time in an amount that inhibits the multiplication of microorganisms and thus preserves the medium into which hydrogen peroxide is released.
  • hydrogen peroxide can be released in a targeted manner at a certain point in time by the action of pressure in an amount effective to kill microorganisms, and a preparation can be given a disinfecting effect in a targeted manner at a certain point in time.
  • the pulverulent mixtures containing hydrogen peroxide and hydrophobized silicon dioxide are used for the production of wound treatment agents which, when used, release a hydrogen growth inhibiting and possibly also disinfecting effect by releasing hydrogen peroxide under pressure.
  • wound treatment agents can be implemented as wound plasters or as creams, ointments or gels for wound treatment.
  • the powdery mixtures containing hydrogen peroxide and hydrophobized silicon dioxide can also be used for the controlled release of oxygen into a gaseous medium.
  • the release of oxygen is preferably delayed, so that a certain oxygen concentration is maintained in the gaseous medium over a longer period of time. Due to the release of oxygen over a longer period of time, a sufficient oxygen concentration can be maintained in the gaseous medium even when oxygen is removed from the gaseous medium, for example by
  • Oxygen concentration can inhibit the growth of anaerobic microorganisms and thus also the formation of volatile metabolic products by such anaerobic
  • the time-delayed release of oxygen from hydrogen peroxide and powdery mixtures containing hydrophobicized silicon dioxide can thus also be used to avoid the formation of an odor, the cause of which is the formation of volatile
  • Metabolic products from anaerobic microorganisms are the use in hygiene products which are worn on the body, in food packaging, in storage containers for rotting waste and in air filters.
  • Example 1 93 g of a 10% by weight hydrogen peroxide solution were mixed with 7 g of Aerosil® R812S in a multimixer (Braun, Model MX32) at the highest level for 45 s. The high shear forces of the mixer break up the liquid into small droplets, which are enclosed by the hydrophobic aerosil. The mixture obtained is a free flowing powder.
  • Hydrogen peroxide and quantities and types of hydrophobic Aerosil performed and also gave free flowing powders.
  • Example 5 4 g of the product obtained in Example 1 were placed in a commercially available tea bag and the tea bag was closed. The tea bag was completely immersed in 1 liter of deionized water in a stirred vessel and the solution was slowly stirred at room temperature. Samples were taken at regular intervals and the hydrogen peroxide content of the solution was determined by cerimetric titration.
  • Example 6 was carried out analogously with the product obtained in Example 2.
  • Example 2 10 g of the product obtained in Example 1 were pressurized with 4 bar compressed air in a pressure filter (pore size 1.2 ⁇ m). The hydrogen peroxide released by the action of pressure was collected in a reservoir. Within 15 minutes, 33% of the hydrogen peroxide obtained in the product was collected in the form of an aqueous solution, and within 30 minutes a total of 50% of the amount used.
  • Example 2 10 g of the product obtained in Example 1 were placed on a glass frit (G2) and a water jet vacuum was applied to the frit. The hydrogen peroxide released in the form of an aqueous solution by atmospheric pressure was collected in a receiver.
  • Example 1 165 g of a commercially available cornstarch were mixed with 1.8 g of the product obtained in Example 1.
  • the so Treated starch was stored in an open vessel at 20 to 23 ° C and a humidity of 50-60% for 13 weeks. No infestation by mold or other microorganisms was discernible during storage.
  • the treated starch had unchanged good flow properties after storage.
  • Example 3 The product obtained in Example 3 was stored at room temperature over a period of 60 days.

Abstract

The invention relates to pulverulent mixtures containing hydrogen peroxide and hydrophobed silicon dioxide, used to control the release of hydrogen peroxide and/or oxygen. The controlled release can be time-delayed or activated by the application of pressure. The invention permits hydrogen peroxide to be released in aqueous or pulverulent media and in emulsions, gels, creams or pastes.

Description

Verwendung von pυlverförmigen Mischungen, enthaltend Use of powder-form mixtures containing
Wasserstoffperoxid und hydrophobiertes Siliciuxαdioxid zur kontrollierten Freisetzung von Wasserstoffperoxid oderHydrogen peroxide and hydrophobicized silicon dioxide for the controlled release of hydrogen peroxide or
Sauerstoffoxygen
Gegenstand der Erfindung ist die Verwendung von pulverförmigen Mischungen, enthaltend Wasserstoffperoxid und hydrophobiertes Siliciumdioxid zur kontrollierten Freisetzung von Wasserstoffperoxid und/oder Sauerstoff.The invention relates to the use of powdery mixtures containing hydrogen peroxide and hydrophobized silicon dioxide for the controlled release of hydrogen peroxide and / or oxygen.
Wasserstoffperoxid wird in Form von wässrigen Lösungen hergestellt und in den Handel gebracht. Für zahlreiche Anwendungen ist es vorteilhaft, an Stelle der wässrigen Lösungen eine feste Lagerform von Wasserstoffperoxid einzusetzen. Handelsübliche feste Lagerformen für Wasserstoffperoxid sind Natriumcarbonatperhydrat, Natriumperborat und das Addukt von Harnstoff mit Wasserstoffperoxid. Diese Lagerformen haben jedoch den Nachteil, dass zusammen mit Wasserstoffperoxid weitere wasserlösliche Bestandteile eingebracht werden, die in vielen Anwendungen unerwünscht sind, weil sie zum Beispiel in wässrigen Lösungen zu Veränderungen des pH-Wertes führen und den Salzgehalt, bzw. den Gehalt an organischen Stoffen erhöhen können.Hydrogen peroxide is produced in the form of aqueous solutions and put on the market. For numerous applications it is advantageous to use a fixed storage form of hydrogen peroxide instead of the aqueous solutions. Commercial solid storage forms for hydrogen peroxide are sodium carbonate perhydrate, sodium perborate and the adduct of urea with hydrogen peroxide. However, these forms of storage have the disadvantage that, together with hydrogen peroxide, other water-soluble constituents are introduced, which are undesirable in many applications because, for example, they lead to changes in the pH value in aqueous solutions and increase the salt content or the content of organic substances can.
Aus der deutschen Offenlegungsschrift DE 20 137 63 sind pulverförmige Produkte bekannt, die Wasserstoffperoxid und mindestens 9 Gew.-% einer fein verteilten hydrophobierten Kieselsäure enthalten, welche den zuvor genannten Nachteil nicht aufweisen. In DE 20 137 63 werden als Anwendungen dieser Produkte die Bleiche, insbesondere von Ölen, Fetten und Zellulose enthaltenden Produkten und der Zusatz zuPowdery products are known from German published patent application DE 20 137 63 which contain hydrogen peroxide and at least 9% by weight of a finely divided hydrophobicized silica which do not have the disadvantage mentioned above. DE 20 137 63 uses bleaching, in particular products containing oils, fats and cellulose, as well as the addition of these products
Reinigungsmitteln und kosmetischen Produkten genannt. Neben der Eigenschaft, dass trockene Pulver mit guter Stabilität vorliegen, sind in DE 20 137 63 keine weiteren Anwendungseigenschaften genannt. Bei zahlreichen Anwendungen, bei denen Wasserstoffperoxid in Form einer festen Lagerform eingesetzt wird, ist es darüber hinaus erwünscht, dass Wasserstoffperoxid aus der festen Lagerform kontrolliert freigesetzt wird, z.B. indem die Freisetzung verzögert über einen längeren Zeitraum erfolgt oder indem die Freisetzung in Reaktion auf die Änderung einer physikalischen Größe erfolgt.Detergents and cosmetic products called. In addition to the property that dry powders are present with good stability, no further application properties are mentioned in DE 20 137 63. In numerous applications in which hydrogen peroxide is used in the form of a solid storage form, it is also desirable for hydrogen peroxide to be released from the solid storage form in a controlled manner, for example by delaying the release over a longer period of time or by the release in response to the change a physical quantity.
Es wurde nun überraschend gefunden, dass sich durch die Verwendung von pulverförmigen Mischungen, enthaltend Wasserstoffperoxid und hydrophobiertes Siliciumdioxid in einfacher Weise eine kontrollierte Freisetzung von Wasserstoffperoxid erreichen lässt, ohne dass weitere wasserlösliche Stoffe freigesetzt werden. An Stelle von Wasserstoffperoxid oder zusammen mit Wasserstoffperoxid kann durch die Verwendung dieser pulverförmigen Mischungen auch molekularer Sauerstoff freigesetzt werden.It has now surprisingly been found that the use of pulverulent mixtures containing hydrogen peroxide and hydrophobized silicon dioxide enables controlled release of hydrogen peroxide to be achieved in a simple manner without further water-soluble substances being released. Instead of hydrogen peroxide or together with hydrogen peroxide, molecular oxygen can also be released by using these powdery mixtures.
Gegenstand der Erfindung ist somit die Verwendung von pulverförmigen Mischungen, enthaltend Wasserstoffperoxid und hydrophobiertes Siliciumdioxid zur kontrollierten Freisetzung von Wasserstoffperoxid und/oder Sauerstoff.The invention thus relates to the use of powdered mixtures containing hydrogen peroxide and hydrophobized silicon dioxide for the controlled release of hydrogen peroxide and / or oxygen.
Vorzugsweise werden pulverförmige Mischungen verwendet, in denen Wasserstoffperoxid in Form von Tropfen einer wässrigen Lösung von Wasserstoffperoxid vorliegt, die von hydrophobiertem Siliciumdioxid umhüllt sind. Solche pulverförmigen Mischungen lassen sich in einfacher Weise durch intensives Vermischen einer wässrigen Wasserstoffperoxidlösung mit dem hydrophobierten Siliciumdioxid herstellen.Powdery mixtures are preferably used in which hydrogen peroxide is present in the form of drops of an aqueous solution of hydrogen peroxide, which are enveloped by hydrophobized silicon dioxide. Such powdery mixtures can be prepared in a simple manner by intensively mixing an aqueous hydrogen peroxide solution with the hydrophobized silicon dioxide.
Hydrophobierte Siliciumdioxide weisen an der Oberfläche unpolare organische Reste auf und werden deshalb von reinem Wasser nicht benetzt. Für die erfindungsgemäße Verwendung werden vorzugsweise hydrophobierte Siliciumdioxide eingesetzt, die durch Umsetzung von Siliciumdioxidpulver mit Dimethyldichlorsilan, Octamethylcyclotetrasiloxan, Polydimethylsiloxan, Octylsilan oder Hexamethyldisilazan hergestellt wurden.Hydrophobicized silicon dioxide has non-polar organic residues on the surface and is therefore not wetted by pure water. For the use according to the invention, preference is given to using hydrophobized silicas which, by reacting silicon dioxide powder with dimethyldichlorosilane, octamethylcyclotetrasiloxane, Polydimethylsiloxane, octylsilane or hexamethyldisilazane were produced.
Als hydrophobiertes Siliciumdioxid wird vorzugsweise ein pyrogen hergestelltes, hydrophobiertes Siliciumdioxid mit einer Methanolbenetzbarkeit von mindestens 40 verwendet. Die Methanolbenetzbarkeit ist ein Maß für die Hydrophobie des Siliciumdioxids und wird bestimmt als der Methanolgehalt einer Methanol-Wasser-Mischung in Volumenprozent, bei dem 50 % des in die Methanol-Wasser- Mischung eingebrachten hydrophobierten Silicumdioxids sedimentieren. Bei einem geringeren Methanolgehalt erfolgt keine Benetzung und das hydrophobierte Silicumdioxid schwimmt größtenteils auf. Bei einem höheren Methanolgehalt erfolgt weitgehende Benetzung und der größte Teil des Siliciumdioxids sedimentiert . Durch die Verwendung von pyrogen hergestelltem, hydrophobierten Siliciumdioxid mit einer Methanolbenetzbarkeit von mindestens 40 werden besonders lagerfähige pulverförmige Mischungen erhalten, die auch bei Gehalten an hydrophobiertem Siliciumdioxid von weniger als 9 Gew.-% als frei fließfähige Pulver vorliegen.A pyrogenically prepared, hydrophobized silicon dioxide with a methanol wettability of at least 40 is preferably used as the hydrophobicized silicon dioxide. The methanol wettability is a measure of the hydrophobicity of the silicon dioxide and is determined as the methanol content in percent by volume of a methanol-water mixture at which 50% of the hydrophobized silicon dioxide introduced into the methanol-water mixture sediment. If the methanol content is lower, there is no wetting and the hydrophobicized silicon dioxide largely floats. With a higher methanol content, extensive wetting occurs and most of the silicon dioxide sediments. The use of pyrogenically prepared, hydrophobized silicon dioxide with a wettability by methanol of at least 40 results in particularly storable powdery mixtures which are present as free-flowing powders even when the content of hydrophobicized silicon dioxide is less than 9% by weight.
Vorzugsweise werden pulverförmige Mischungen verwendet, die Wasserstoffperoxid in Form einer wässrigen Lösung mit einem Gehalt im Bereich von 5 bis 70 Gew.-% Wasserstoffperoxid und besonders bevorzugt im Bereich von 10 bis 50 Gew.-% Wasserstoffperoxid enthalten. Die wässrigePowdery mixtures are preferably used which contain hydrogen peroxide in the form of an aqueous solution with a content in the range from 5 to 70% by weight of hydrogen peroxide and particularly preferably in the range from 10 to 50% by weight of hydrogen peroxide. The watery
Wasserstoffperoxidlösung enthält vorzugsweise einen oder mehrere Stabilisatoren, die die Lösung gegen Zersetzung zu Wasser und Sauerstoff stabilisieren. Geeignete Stabilisatoren sind zum Beispiel Stannate, Phosphate, Pyrophosphate, Polyphosphate, organische Phosphonsäuren und Aminophosphonsäuren sowie deren Salze, Nitrate und Magnesiumsalze. Durch die Wahl von Art und Menge der Stabilisatoren lässt sich beeinflussen, ob bei der Verwendung der pulverförmigen Mischungen überwiegend Wasserstoffperoxid freigesetzt wird oder ob überwiegend Sauerstoff freigesetzt wird.Hydrogen peroxide solution preferably contains one or more stabilizers which stabilize the solution against decomposition to water and oxygen. Suitable stabilizers are, for example, stannates, phosphates, pyrophosphates, polyphosphates, organic phosphonic acids and aminophosphonic acids and also their salts, nitrates and magnesium salts. The choice of type and amount of stabilizers can be used to determine whether predominantly when using the powdery mixtures Hydrogen peroxide is released or whether predominantly oxygen is released.
In einer bevorzugten Ausführungsform der Erfindung werden die Wasserstoffperoxid und hydrophobiertes Siliciumdioxid enthaltenden pulverförmigen Mischungen zur zeitverzögerten Freisetzung von Wasserstoffperoxid verwendet. Zur zeitverzögerten Freisetzung von Wasserstoffperoxid werden die pulverförmigen Mischungen vorzugsweise nur geringen Druck- und Scherkräften ausgesetzt. An Stelle von Wasserstoffperoxid kann zeitverzögert auch Sauerstoff freigesetzt werden. Ebenso können gleichzeitig auch Wasserstoffperoxid und Sauerstoff zeitverzögert freigesetzt werden.In a preferred embodiment of the invention, the powdery mixtures containing hydrogen peroxide and hydrophobized silicon dioxide are used for the time-delayed release of hydrogen peroxide. For the time-delayed release of hydrogen peroxide, the powdery mixtures are preferably exposed to only slight pressure and shear forces. Instead of hydrogen peroxide, oxygen can also be released with a time delay. Likewise, hydrogen peroxide and oxygen can also be released with a time delay.
Die pulverförmigen Mischungen werden vorzugsweise zur zeitverzögerten Freisetzung von Wasserstoffperoxid in ein wässriges Medium verwendet. Die pulverförmigen Mischungen werden dazu mit dem wässrigen Medium in Kontakt gebracht und gegebenenfalls darin dispergiert, wobei das Dispergieren vorzugsweise mit geringen Scherkräften durchgeführt wird. In einer bevorzugten Ausführungsform wird die pulverförmige Mischung in einem für Wasser und Wasserstoffperoxid durchlässigen und für das hydrophobierte Siliciumdioxid undurchlässigen Behälter mit dem wässrigen Medium in Kontakt gebracht. Die dazu verwendeten Behälter bestehen vorzugsweise ganz oder teilweise aus einem Filtermedium, dessen Porengröße kleiner ist als die mittlere Partikelgröße der zur Herstellung der pulverförmigen Mischung eingesetzten Partikel aus hydrophobierten Siliciumdioxid. In einer Ausführungsform der Erfindung wird der die pulverförmige Mischung enthaltende Behälter in das wässrige Medium eingetaucht, sodass der Transport von Wasserstoffperoxid aus dem Behälter in das Medium überwiegend durch Diffusion erfolgt. In einer anderen Ausführungsform wird der Behälter von dem wässrigen Medium durchströmt. Die Behälter können eine beliebige Form aufweisen und beispielsweise die Form eines Filterbeutels, einer Filterpatrone oder einer Kartusche aufweisen. Durch die Verwendung solcher Behälter kann Wasserstoffperoxid zeitverzögert in ein wässriges Medium freigesetzt werden und gleichzeitig das zurückbleibende hydrophobierte Siliciumdioxid im Behälter zurückgehalten werden.The powdery mixtures are preferably used for the time-delayed release of hydrogen peroxide in an aqueous medium. For this purpose, the powdery mixtures are brought into contact with the aqueous medium and, if appropriate, dispersed therein, the dispersing preferably being carried out with low shear forces. In a preferred embodiment, the powdery mixture is brought into contact with the aqueous medium in a container which is permeable to water and hydrogen peroxide and impermeable to the hydrophobized silicon dioxide. The containers used for this purpose preferably consist wholly or partly of a filter medium whose pore size is smaller than the average particle size of the particles of hydrophobized silicon dioxide used to produce the powdery mixture. In one embodiment of the invention, the container containing the powdery mixture is immersed in the aqueous medium, so that the transport of hydrogen peroxide from the container into the medium takes place predominantly by diffusion. In another embodiment, the container is flowed through by the aqueous medium. The containers can be one have any shape and, for example, the shape of a filter bag, a filter cartridge or a cartridge. By using such containers, hydrogen peroxide can be released into an aqueous medium with a time delay and at the same time the remaining hydrophobized silicon dioxide can be retained in the container.
Durch die erfindungsgemäße Verwendung von pulverförmigen Mischungen, die Wasserstoffperoxid und hydrophobiertes Siliciumdioxid enthalten, zur zeitverzögerten Freisetzung von Wasserstoffperoxid in ein wässriges Medium, lassen sich in dem wässrigen Medium über längere Zeiträume definierte Konzentrationen an Wasserstoffperoxid aufrechterhalten ohne das unerwünscht hohe Spitzen der Konzentration von Wasserstoffperoxid auftreten und ohne das dazu aufwendige Dosier- und Regeleinrichtungen notwendig werden. Eine erfindungsgemäße Verwendung der pulverförmigen Mischungen, bei der dieser Vorteil genutzt wird, ist beispielsweise die zeitverzögerte Freisetzung von Wasserstoffperoxid in Aqaurien, sowie in Behälter oder Teiche zur Fischaufzucht. Durch die erfindungsgemäße Verwendung der pulverförmigen Mischungen kann ohne Regeleinrichtungen eine Wasserstoffperoxidkonzentration aufrecht erhalten werden, die eine Vermehrung von Mikroorganismen verhindert, ohne dass für Fische und Fischlarven schädliche Wasserstoffperoxidkonzentrationen auftreten.Through the use according to the invention of pulverulent mixtures which contain hydrogen peroxide and hydrophobized silicon dioxide for the time-delayed release of hydrogen peroxide into an aqueous medium, defined concentrations of hydrogen peroxide can be maintained in the aqueous medium over long periods of time without the undesirably high peaks in the concentration of hydrogen peroxide occurring and without the need for expensive dosing and control devices. A use of the powdery mixtures according to the invention, in which this advantage is used, is, for example, the time-delayed release of hydrogen peroxide in aquaria, and in containers or ponds for fish farming. By using the powdery mixtures according to the invention, a hydrogen peroxide concentration can be maintained without regulating devices, which prevents an increase of microorganisms without causing harmful hydrogen peroxide concentrations for fish and fish larvae.
In einer weiteren Ausführungsform der Erfindung werden die Wasserstoffperoxid und hydrophobiertes Siliciumdioxid enthaltenden pulverförmigen Mischungen verwendet, um Wasserstoffperoxid durch Druckeinwirkung freizusetzen. Die Druckeinwirkung kann dabei mechanisch, zum Beispiel durch einen Stempel, hydraulisch durch Flüssigkeitsdruck oder pneumatisch durch Gasdruck erfolgen. Durch mechanische oder pneumatische Druckeinwirkung wird Wasserstoffperoxid in Form einer wässrigen Lösung freigesetzt, die im wesentlichen die gleiche Konzentration aufweist, wie die zur Herstellung der pulverförmigen Mischung eingesetzte Wasserstoffperoxidlösung. Eine hydraulische Druckeinwirkung wird vorzugsweise eingesetzt um Wasserstoffperoxid in ein wässriges Medium freizusetzen. Die pulverförmige Mischung wird bei dieser Ausführungsform vorzugsweise in einem für Wasser und Wasserstoffperoxid durchlässigen und für das hydrophobierte Siliciumdioxid undurchlässigen Behälter eingesetzt. Der eingesetzte Behälter wird vorzugsweise von dem wässrigen Medium durchströmt, wobei die Druckeinwirkung durch den Staudruck des strömenden wässrigen Mediums erfolgt. Mit dieser Ausführungsform kann Wasserstoffperoxid in ein strömendes wässriges Medium freigesetzt werden, wobei die freigesetzte Wasserstoffperoxidmenge der Menge des strömenden Mediums angepasst wird, ohne dass dazu Messoder Regeleinrichtungen erforderlich wären.In a further embodiment of the invention, the powdery mixtures containing hydrogen peroxide and hydrophobized silicon dioxide are used in order to release hydrogen peroxide by the action of pressure. The pressure can be applied mechanically, for example by a plunger, hydraulically by liquid pressure or pneumatically by gas pressure. By mechanical or pneumatic pressure, hydrogen peroxide is released in the form of an aqueous solution has essentially the same concentration as the hydrogen peroxide solution used to prepare the powdery mixture. Hydraulic pressure is preferably used to release hydrogen peroxide into an aqueous medium. In this embodiment, the powdery mixture is preferably used in a container which is permeable to water and hydrogen peroxide and impermeable to the hydrophobized silicon dioxide. The container used is preferably flowed through by the aqueous medium, the pressure being exerted by the dynamic pressure of the flowing aqueous medium. With this embodiment, hydrogen peroxide can be released into a flowing aqueous medium, the amount of hydrogen peroxide released being adapted to the amount of the flowing medium without the need for measuring or control devices.
Die Wasserstoffperoxid und hydrophobiertes Siliciumdioxid enthaltenen pulverförmigen Mischungen können darüber hinaus auch verwendet werden, um Wasserstoffperoxid kontrolliert in einem pulverförmigen Medium freizusetzen. Die Mischungen werden dazu mit dem pulverförmigen Medium gemischt, wobei vorzugsweise eine Menge der Wasserstoffperoxid und Siliciumdioxid enthaltenden Mischung im Bereich von 0,1 bis 10 Gew.-% der Gesamtmenge verwendet wird. Die Wasserstoffperoxid und hydrophobiertes Siliciumdioxid enthaltenden Mischungen können verwendet werden, um in dem pulverförmigen Medium Wasserstoffperoxid zeitverzögert freizusetzen und so über einen längeren Zeitraum eine geringe Wasserstoffperoxidkonzentration aufrecht zu erhalten. Durch den Zusatz der Wasserstoffperoxid und hydrophobiertes Siliciumdioxid enthaltenden pulverförmigen Mischung kann zusätzlich auch die Rieselfähigkeit des pulverförmigen Mediums verbessert werden. Die Wasserstoffperoxid und hydrophobiertes Siliciumdioxid enthaltenden Mischungen können darüber hinaus auch verwendet werden, um in einem pulverförmigen Medium zu einem definierten Zeitpunkt durch Druckeinwirkung Wasserstoffperoxid freizusetzen. Die Freisetzung von Wasserstoffperoxid durch Druckeinwirkung kann zum Beispiel verwendet werden, um im pulverförmigen Medium eine chemische Reaktion einzuleiten, zum Beispiel um das pulverförmige Medium auszuhärten.The powdery mixtures containing hydrogen peroxide and hydrophobized silicon dioxide can moreover also be used to release hydrogen peroxide in a controlled manner in a powdery medium. For this purpose, the mixtures are mixed with the powdery medium, an amount of the mixture containing hydrogen peroxide and silicon dioxide in the range from 0.1 to 10% by weight of the total amount being preferably used. The mixtures containing hydrogen peroxide and hydrophobized silicon dioxide can be used in order to release hydrogen peroxide in the powdery medium with a time delay and thus to maintain a low hydrogen peroxide concentration over a longer period of time. By adding the powdery mixture containing hydrogen peroxide and hydrophobized silicon dioxide, the flowability of the powdery medium can also be improved. The mixtures containing hydrogen peroxide and hydrophobized silicon dioxide can also be used in addition to in a powdery medium release hydrogen peroxide at a defined point in time. The release of hydrogen peroxide by the action of pressure can be used, for example, to initiate a chemical reaction in the powdery medium, for example to cure the powdery medium.
Die Wasserstoffperoxid und hydrophobiertes Siliciumdioxid enthaltenden pulverförmigen Mischungen können darüber hinaus auch Emulsionen, Gels, Cremes oder Pasten zugesetzt werden, um in den so erhaltenen ZubereitungenThe powdery mixtures containing hydrogen peroxide and hydrophobized silicon dioxide can moreover also be added to emulsions, gels, creams or pastes in order in the preparations thus obtained
Wasserstoffperoxid und/oder Sauerstoff kontrolliert freizusetzen. Die pulverförmigen Mischungen können dabei zur zeitverzögerten Freisetzung von Wasserstoffperoxid verwendet werden, um in der Zubereitung über einen längeren Zeitraum eine niedrige Konzentration an Wasserstoffperoxid aufrecht zu erhalten. Die pulverförmigen Mischungen können darüber hinaus auch verwendet werden, um in der Zubereitung zu einem definierten Zeitpunkt durch Druckeinwirkung oder durch die Einwirkung von Scherkräften Wasserstoffperoxid freizusetzen. Vorzugsweise werden die pulverförmigenRelease hydrogen peroxide and / or oxygen in a controlled manner. The powdery mixtures can be used for the delayed release of hydrogen peroxide in order to maintain a low concentration of hydrogen peroxide in the preparation over a longer period of time. The powdery mixtures can also be used to release hydrogen peroxide in the preparation at a defined point in time by the action of pressure or by the action of shear forces. Preferably the powder
Mischungen in kosmetischen Zubereitungen verwendet, um unter Druckeinwirkung beim Verreiben auf der Haut Wasserstoffperoxid freizusetzen. Die Freisetzung von Wasserstoffperoxid durch Druckeinwirkung oder die Einwirkung von Schwerkräften kann außerdem verwendet werden, um in der Zubereitung eine chemische Reaktion auszulösen und so die Zusammensetzung und die Eigenschaften der Zubereitung zu verändern. Solche Zubereitungen können beispielsweise als Klebstoffe verwendet werden, die unter Druckeinwirkung vernetzen und aushärten.Mixtures used in cosmetic preparations to release hydrogen peroxide under pressure when rubbed on the skin. The release of hydrogen peroxide by the action of pressure or the action of gravity can also be used to trigger a chemical reaction in the preparation and thus to change the composition and properties of the preparation. Such preparations can be used, for example, as adhesives which crosslink and harden under the action of pressure.
Durch die Verwendung von Wasserstoffperoxid und hydrophobiertes Siliciumdioxid enthaltenden pulverförmigen Mischungen zur kontrollierten Freisetzung von Wasserstoffperoxid, insbesondere in ein wässriges Medium, ein pulverförmiges Medium, eine Emulsion, ein Gel, eine Creme oder eine Paste lässt sich in dem Medium, in das Wasserstoffperoxid freigesetzt wird, die Vermehrung von Mikroorganismen hemmen und bei Freisetzung einer dazu wirksamen Menge auch eine Abtötung von Mikroorganismen erreichen. Bei einer Verwendung mit zeitverzögerterBy using hydrogen peroxide and hydrophobicized silicon dioxide-containing powdery mixtures for the controlled release of hydrogen peroxide, in particular in an aqueous medium, a powdery medium, an emulsion, a gel, a Cream or a paste can be inhibited in the medium into which hydrogen peroxide is released, the multiplication of microorganisms and, if an amount effective for this purpose is released, microorganisms can also be killed. When using with a time delay
Freisetzung von Wasserstoffperoxid kann Wasserstoffperoxid über einen längeren Zeitraum in einer Menge freisetzt werden, die die Vermehrung von Mikroorganismen hemmt und so eine Konservierung des Mediums bewirkt, in das Wasserstoffperoxid freigesetzt wird. Bei einer Verwendung zur Freisetzung von Wasserstoffperoxid durch Druckeinwirkung kann durch die Druckeinwirkung zu einem bestimmten Zeitpunkt gezielt Wasserstoffperoxid in einer zur Abtötung von Mikroorganismen wirksamen Menge freigesetzt werden und so einer Zubereitung gezielt zu einem bestimmten Zeitpunkt eine desinfizierende Wirkung gegeben werden.Release of hydrogen peroxide can be released over an extended period of time in an amount that inhibits the multiplication of microorganisms and thus preserves the medium into which hydrogen peroxide is released. When used to release hydrogen peroxide by the action of pressure, hydrogen peroxide can be released in a targeted manner at a certain point in time by the action of pressure in an amount effective to kill microorganisms, and a preparation can be given a disinfecting effect in a targeted manner at a certain point in time.
In einer Ausführungsform der Erfindung werden die Wasserstoffperoxid und hydrophobiertes Siliciumdioxid enthaltenden pulverförmigen Mischungen zur Herstellung von Wundbehandlungsmitteln verwendet, die bei der Anwendung durch Freisetzung von Wasserstoffperoxid unter Druckeinwirkung eine das Keimwachstum hemmende und gegebenenfalls auch desinfizierende Wirkung entwickeln. Solche Wundbehandlungsmittel können als Wundpflaster oder als Cremes, Salben oder Gele zur Wundbehandlung ausgeführt werden.In one embodiment of the invention, the pulverulent mixtures containing hydrogen peroxide and hydrophobized silicon dioxide are used for the production of wound treatment agents which, when used, release a hydrogen growth inhibiting and possibly also disinfecting effect by releasing hydrogen peroxide under pressure. Such wound treatment agents can be implemented as wound plasters or as creams, ointments or gels for wound treatment.
In einer weiteren Ausführungsform der Erfindung können die Wasserstoffperoxid und hydrophobiertes Siliciumdioxid enthaltenden pulverförmigen Mischungen auch zur kontrollierten Freisetzung von Sauerstoff in ein gasförmiges Medium verwendet werden. Vorzugsweise erfolgt die Freisetzung von Sauerstoff zeitverzögert, so dass in dem gasförmigen Medium über einen längeren Zeitraum eine bestimmte Sauerstoffkonzentration aufrechterhalten wird. Durch die über einen längeren Zeitraum erfolgende Freisetzung von Sauerstoff kann in dem gasförmigen Medium auch dann eine ausreichende Sauerstoffkonzentration aufrecht erhalten werden, wenn dem gasförmigen Medium Sauerstoff entzogen wird, zum Beispiel durchIn a further embodiment of the invention, the powdery mixtures containing hydrogen peroxide and hydrophobized silicon dioxide can also be used for the controlled release of oxygen into a gaseous medium. The release of oxygen is preferably delayed, so that a certain oxygen concentration is maintained in the gaseous medium over a longer period of time. Due to the release of oxygen over a longer period of time, a sufficient oxygen concentration can be maintained in the gaseous medium even when oxygen is removed from the gaseous medium, for example by
StoffWechselreaktionen von Mikroorganismen. Durch das Aufrechterhalten einer ausreichendenMetabolism reactions of microorganisms. By maintaining adequate
Sauerstoffkonzentration lässt sich das Wachstum anaerober Mikroorganismen hemmen und damit auch die Bildung von flüchtigen Stoffwechselprodukten durch solche anaerobenOxygen concentration can inhibit the growth of anaerobic microorganisms and thus also the formation of volatile metabolic products by such anaerobic
Mikroorganismen hemmen. Die zeitverzögerte Freisetzung von Sauerstoff aus Wasserstoffperoxid und hydrophobiertes Siliciumdioxid enthaltenden pulverförmigen Mischungen lässt sich damit auch zur Vermeidung einer Geruchsbildung verwenden, deren Ursache die Bildung von flüchtigenInhibit microorganisms. The time-delayed release of oxygen from hydrogen peroxide and powdery mixtures containing hydrophobicized silicon dioxide can thus also be used to avoid the formation of an odor, the cause of which is the formation of volatile
Stoffwechselprodukten durch anaerobe Mikroorganismen ist. Beispiele für eine solche erfindungsgemäße Verwendung zur Vermeidung einer Geruchsbildung sind die Verwendung in Hygieneprodukten, die am Körper getragen werden, in Lebensmittelverpackungen, in Lagerbehältern für verrottende Abfälle und in Luftfiltern. Metabolic products from anaerobic microorganisms. Examples of such a use according to the invention for avoiding odor formation are the use in hygiene products which are worn on the body, in food packaging, in storage containers for rotting waste and in air filters.
Beispiele:Examples:
Herstellung von Wasserstoffperoxid und hydrophobiertes Siliciumdioxid enthaltenden pulverförmigen MischungenProduction of powdery mixtures containing hydrogen peroxide and hydrophobized silicon dioxide
In Beispiel 1 wurden 93 g einer 10 Gew.-% Wasserstoffperoxidlösung mit 7 g Aerosil® R812S in einem Multimixer (Fa. Braun, Modell MX32) bei höchster Stufe 45 s gemischt. Die hohen Scherkräfte des Mixers zerteilen die Flüssigkeit in kleine Tröpfchen, die vom hydrophoben Aerosil umschlossen werden. Die erhaltene Mischung ist ein frei fließendes Pulver.In Example 1, 93 g of a 10% by weight hydrogen peroxide solution were mixed with 7 g of Aerosil® R812S in a multimixer (Braun, Model MX32) at the highest level for 45 s. The high shear forces of the mixer break up the liquid into small droplets, which are enclosed by the hydrophobic aerosil. The mixture obtained is a free flowing powder.
Die Beispiele 2 bis 4 wurden analog mit den in Tabelle 1 angeführten Mengen und Konzentrationen anExamples 2 to 4 were prepared analogously with the amounts and concentrations listed in Table 1
Wasserstoffperoxid und Mengen und Typen an hydrophobiertem Aerosil durchgeführt und ergaben ebenfalls frei fließende Pulver.Hydrogen peroxide and quantities and types of hydrophobic Aerosil performed and also gave free flowing powders.
Tabelle 1:Table 1:
Herstellung von pulverförmigen Mischungen enthaltendProduction of powdery mixtures containing
Wasserstoffperoxid und hydrophobiertes SiliciumdioxidHydrogen peroxide and hydrophobicized silicon dioxide
Zeitverzögerte Freisetzung von Wasserstoffperoxid in ein wässriges Medium Delayed release of hydrogen peroxide in an aqueous medium
In Beispiel 5 wurden 4 g des in Beispiel 1 erhaltenen Produkts in einen handelsüblichen Teebeutel gefüllt und der Teebeutel verschlossen. Der Teebeutel wurde in einem Rührgefäß in 1 Liter vollentsalztem Wasser vollständig untergetaucht und die Lösung wurde bei Raumtemperatur langsam gerührt. In regelmäßigen Abständen wurden Proben entnommen und der Wasserstoffperoxidgehalt der Lösung durch cerimetrische Titration bestimmt.In Example 5, 4 g of the product obtained in Example 1 were placed in a commercially available tea bag and the tea bag was closed. The tea bag was completely immersed in 1 liter of deionized water in a stirred vessel and the solution was slowly stirred at room temperature. Samples were taken at regular intervals and the hydrogen peroxide content of the solution was determined by cerimetric titration.
Beispiel 6 wurde analog mit dem in Beispiel 2 erhaltenen Produkt durchgeführt.Example 6 was carried out analogously with the product obtained in Example 2.
Tabelle 2 Zeitverzögerte Freisetzung von H202 in ein wässriges MediumDelayed release of H 2 0 2 in an aqueous medium
Die in Tabelle 2 zusammengefassten Resultate zeigen, dass Wasserstoffperoxid zeitverzögert über einen Zeitraum von mehr als 48 h aus den Teebeuteln in das umgebende wässrige Medium freigesetzt wurde .The results summarized in Table 2 show that hydrogen peroxide is delayed over a period of was released from the tea bags into the surrounding aqueous medium for more than 48 h.
Freisetzung von Wasserstoffperoxid durch DruckeinwirkungRelease of hydrogen peroxide by pressure
Beispiel 7Example 7
10 g des in Beispiel 1 erhaltenen Produkts wurden in einem Druckfilter (Porengröße 1,2 μm) mit einem Überdruck von 4 bar Pressluft beaufschlagt. Das durch Druckeinwirkung freigesetzte Wasserstoffperoxid wurde in einem Reservoir aufgefangen. Innerhalb 15 min wurden 33 % des im Produkt erhaltenen Wasserstoffperoxids in Form einer wässrigen Lösung aufgefangen, innerhalb von 30 min insgesamt 50 % der eingesetzten Menge.10 g of the product obtained in Example 1 were pressurized with 4 bar compressed air in a pressure filter (pore size 1.2 μm). The hydrogen peroxide released by the action of pressure was collected in a reservoir. Within 15 minutes, 33% of the hydrogen peroxide obtained in the product was collected in the form of an aqueous solution, and within 30 minutes a total of 50% of the amount used.
Beispiel 8Example 8
10 g des in Beispiel 1 erhaltenen Produkts wurden auf einer Glasfritte (G2) vorgelegt und an die Fritte wurde Wasserstrahlvakuum angelegt. Das durch den Atmosphärendruck in Form einer wässrigen Lösung freigesetzte Wasserstoffperoxid wurde in einer Vorlage aufgefangen.10 g of the product obtained in Example 1 were placed on a glass frit (G2) and a water jet vacuum was applied to the frit. The hydrogen peroxide released in the form of an aqueous solution by atmospheric pressure was collected in a receiver.
Innerhalb 15 min wurden 33 % des im eingesetzten Materials enthaltenen Wasserstoffperoxids freigesetzt, innerhalb von 60 min insgesamt 50 %.33% of the hydrogen peroxide contained in the material used was released within 15 minutes, and a total of 50% within 60 minutes.
Zeitverzögerte Freisetzung von Wasserstoffperoxid in ein pulverförmiges MediumDelayed release of hydrogen peroxide in a powdery medium
Beispiel 9Example 9
165 g einer handelsüblichen Speisestärke wurden mit 1,8 g des in Beispiel 1 erhaltenen Produkts vermischt. Die so behandelte Stärke wurde in einem offenen Gefäß bei 20 bis 23°C und einer Luftfeuchtigkeit von 50 - 60% für 13 Wochen gelagert. Während der Lagerung war kein Befall durch Schimmelpilze oder andere Mikroorganismen erkennbar. Die behandelte Stärke wies nach der Lagerung eine unverändert gute Rieselfähigkeit auf.165 g of a commercially available cornstarch were mixed with 1.8 g of the product obtained in Example 1. The so Treated starch was stored in an open vessel at 20 to 23 ° C and a humidity of 50-60% for 13 weeks. No infestation by mold or other microorganisms was discernible during storage. The treated starch had unchanged good flow properties after storage.
Eine unbehandelte Probe der gleichen Stärke zeigte nach vergleichbarer Lagerung Verklumpungen und erste Anzeichen von Schimmelbefall.An untreated sample of the same strength showed clumping and the first signs of mold after comparable storage.
Zeitverzögerte Freisetzung von SauerstoffDelayed release of oxygen
Beispiel 10Example 10
Das in Beispiel 3 erhaltene Produkt wurde bei Raumtemperatur über einen Zeitraum von 60 Tagen gelagert. Der Wassersto fperoxidgehalt des Pulvers nahm dabei von anfangs 50,1 Gew.-% auf 45,6 Gew.-% nach 30 Tagen und 40,5 Gew.-% nach 60 Tagen ab. Durch die Zersetzung von Wasserstoffperoxid bei der Lagerung wurde Sauerstoff an die Umgebungsluft abgegeben, wobei sich die freigesetzte Sauerstoffmenge zu 15 Nl/kg nach 30 Tagen und zu 32 Nl/kg nach 60 Tagen berechnet (Nl = Normliter) . Über einen Zeitraum von 60 Tagen erfolgte demnach eine gleichmäßige Freisetzung von Sauerstoff an die Umgebungsluft mit einer Rate von ca. 0,5 Nl/kg-d. The product obtained in Example 3 was stored at room temperature over a period of 60 days. The hydrogen peroxide content of the powder decreased from initially 50.1% by weight to 45.6% by weight after 30 days and 40.5% by weight after 60 days. Due to the decomposition of hydrogen peroxide during storage, oxygen was released into the ambient air, with the amount of oxygen released being 15 Nl / kg after 30 days and 32 Nl / kg after 60 days (Nl = standard liter). Accordingly, there was a uniform release of oxygen into the ambient air over a period of 60 days at a rate of approximately 0.5 Nl / kg-d.

Claims

Patentansprüche : Claims:
1. Verwendung von pulverförmigen Mischungen, enthaltend Wasserstoffperoxid und hydrophobiertes Siliciumdioxid, zur kontrollierten Freisetzung von Wasserstoffperoxid und/oder Sauerstoff.1. Use of powdery mixtures containing hydrogen peroxide and hydrophobized silicon dioxide for the controlled release of hydrogen peroxide and / or oxygen.
2. Verwendung nach Anspruch 1, dadurch gekennzeichnet, dass in der pulverförmigen Mischung Wasserstoffperoxid in Form von mit hydrophobiertem Siliciumdioxid umhüllten Tropfen einer wässrigen Lösung von Wasserstoffperoxid vorliegt.2. Use according to claim 1, characterized in that hydrogen peroxide is present in the powdery mixture in the form of drops of an aqueous solution of hydrogen peroxide coated with hydrophobicized silicon dioxide.
3. Verwendung nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass als hydrophobiertes Siliciumdioxid ein pyrogen hergestelltes, hydrophobiertes Siliciumdioxid mit einer Methanolbenetzbarkeit von mindestens 40 verwendet wird.3. Use according to claim 1 or 2, characterized in that a pyrogenically prepared, hydrophobized silicon dioxide with a methanol wettability of at least 40 is used as the hydrophobized silicon dioxide.
4. Verwendung nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass die Freisetzung von Wasserstoffperoxid und/oder Sauerstoff zeitverzögert erfolgt.4. Use according to one of claims 1 to 3, characterized in that the release of hydrogen peroxide and / or oxygen is delayed.
5. Verwendung nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass Wasserstoffperoxid durch Druckeinwirkung freigesetzt wird.5. Use according to one of claims 1 to 3, characterized in that hydrogen peroxide is released by the action of pressure.
6. Verwendung nach einem der voranstehenden Ansprüche, dadurch gekennzeichnet, dass Wasserstoffperoxid in ein wässriges Medium freigesetzt wird.6. Use according to one of the preceding claims, characterized in that hydrogen peroxide is released into an aqueous medium.
7. Verwendung nach Anspruch 6, dadurch gekennzeichnet, dass die pulverförmige Mischung in einem für Wasser und Wasserstoffperoxid durchlässigen und für das hydrophobierte Siliciumdioxid undurchlässigen Behälter eingesetzt wird.7. Use according to claim 6, characterized in that the powdery mixture in a permeable for water and hydrogen peroxide and for hydrophobized silica impermeable container is used.
8. Verwendung nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass Wasserstoffperoxid in ein pulverförmiges Medium freigesetzt wird.8. Use according to one of claims 1 to 5, characterized in that hydrogen peroxide is released into a powdery medium.
9. Verwendung nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass die pulverförmige Mischung einer Emulsion, einem Gel, einer Creme oder einer Paste zugesetzt wird.9. Use according to one of claims 1 to 5, characterized in that the powdery mixture of an emulsion, a gel, a cream or a paste is added.
10. Verwendung nach einem der voranstehenden Ansprüche, dadurch gekennzeichnet, dass Wasserstoffperoxid in einer Menge freigesetzt wird, die die Vermehrung von Mikroorganismen hemmt.10. Use according to one of the preceding claims, characterized in that hydrogen peroxide is released in an amount which inhibits the multiplication of microorganisms.
11. Verwendung nach einem der voranstehenden Ansprüche, dadurch gekennzeichnet, dass Wasserstoffperoxid in einer zur Abtötung von Mikroorganismen wirksamen Menge freigesetzt wird.11. Use according to any one of the preceding claims, characterized in that hydrogen peroxide is released in an amount effective to kill microorganisms.
12. Verwendung nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass Sauerstoff in ein gasförmiges Medium freigesetzt wird.12. Use according to one of claims 1 to 4, characterized in that oxygen is released into a gaseous medium.
13. Verwendung nach Anspruch 1, dadurch gekennzeichnet, dass Sauerstoff in einer Menge freigesetzt wird, die die Bildung von flüchtigen Stoffwechselprodukten durch anaerobe Mikroorganismen hemmt.13. Use according to claim 1, characterized in that oxygen is released in an amount which inhibits the formation of volatile metabolic products by anaerobic microorganisms.
14. Verwendung von pulverförmigen Mischungen, enthaltend Wasserstoffperoxid und hydrophobiertes Siliciumdioxid, zur Herstellung von Wundbehandlungsmitteln, aus denen bei der Anwendung durch Druckeinwirkung Wasserstoffperoxid in einer Menge freigesetzt wird, die die Vermehrung von Mikroorganismen hemmt. 14. Use of powdery mixtures containing hydrogen peroxide and hydrophobized silicon dioxide for the production of wound treatment agents, from which, when applied by pressure Hydrogen peroxide is released in an amount that inhibits the multiplication of microorganisms.
EP04731928A 2003-05-23 2004-05-10 Use of pulverulent mixtures containing hydrogen peroxide and hydrophobed silicon dioxide for the controlled release of hydrogen peroxide or oxygen Withdrawn EP1628912A2 (en)

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DE102004002356A DE102004002356A1 (en) 2003-05-23 2004-01-15 Use of powdery mixtures containing hydrogen peroxide and hydrophobized silicon dioxide for the controlled release of hydrogen peroxide or oxygen
PCT/EP2004/004954 WO2004103508A2 (en) 2003-05-23 2004-05-10 Use of pulverulent mixtures containing hydrogen peroxide and hydrophobed silicon dioxide for the controlled release of hydrogen peroxide or oxygen

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