WO2005019101A2 - Chlorine dioxide releasing composite article - Google Patents

Chlorine dioxide releasing composite article Download PDF

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Publication number
WO2005019101A2
WO2005019101A2 PCT/US2004/024865 US2004024865W WO2005019101A2 WO 2005019101 A2 WO2005019101 A2 WO 2005019101A2 US 2004024865 W US2004024865 W US 2004024865W WO 2005019101 A2 WO2005019101 A2 WO 2005019101A2
Authority
WO
WIPO (PCT)
Prior art keywords
composite article
activating stimulus
organic matrix
chlorine dioxide
article
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.)
Ceased
Application number
PCT/US2004/024865
Other languages
French (fr)
Other versions
WO2005019101A3 (en
WO2005019101A8 (en
Inventor
Barry K. Speronello
Linda Hratko
Michael S. Cochran
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.)
BASF Catalysts LLC
Original Assignee
Engelhard Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Engelhard Corp filed Critical Engelhard Corp
Priority to AU2004267046A priority Critical patent/AU2004267046B2/en
Priority to CA2535002A priority patent/CA2535002C/en
Priority to DE602004026480T priority patent/DE602004026480D1/en
Priority to CN2004800221920A priority patent/CN1902125B/en
Priority to AT04786156T priority patent/ATE463464T1/en
Priority to EP04786156A priority patent/EP1708962B1/en
Publication of WO2005019101A2 publication Critical patent/WO2005019101A2/en
Publication of WO2005019101A8 publication Critical patent/WO2005019101A8/en
Anticipated expiration legal-status Critical
Publication of WO2005019101A3 publication Critical patent/WO2005019101A3/en
Ceased legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B11/00—Oxides or oxyacids of halogens; Salts thereof
    • C01B11/02—Oxides of chlorine
    • C01B11/022—Chlorine dioxide (ClO2)
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B11/00—Oxides or oxyacids of halogens; Salts thereof
    • C01B11/02—Oxides of chlorine
    • C01B11/022—Chlorine dioxide (ClO2)
    • C01B11/023—Preparation from chlorites or chlorates
    • C01B11/024—Preparation from chlorites or chlorates from chlorites

Definitions

  • This invention relates to a device which will produce chlorine dioxide gas when exposed to an activating stimulus such as ambient humidity or light, and methods of using the same.
  • the prior art discloses a variety of powdered compositions that produce C10 2 gas under a variety of conditions, included in these are materials for the controlled sustained release of C102 (CSR materials), which release C10 2 when exposed to water vapor. Also included are materials disclosed by which produce C10 2 when exposed to light.
  • Extruded polymer sheet material can be relatively less expensive to produce in small sizes, because the sheet may be produced in a large economical size, and then smaller size pieces may be inexpensively cut from the larger sheet.
  • the extrusion temperature of C10 2 -releasing polymer sheet must be no higher than about 150-160°C. If the temperature is above that, then the amount of chlorite that is lost by decomposition during extrusion can be unacceptably high. This has limited the choice of polymer matrices to those comprising a substantial amount of relatively low melting, low density polyethylene.
  • polyethylene is an undesirable matrix material because it is not highly permeable to water vapor used to initiate the release of chlorine dioxide from most chlorine dioxide-releasing materials. Plus the extrusion temperature of polyethylene is about 150 degrees C, so it is right on the borderline where decomposition of chlorite anion can occur. Since chlorite decomposition can lead to explosive oxidation of the polyethylene, such extruded sheet materials typically contain lower concentrations of chlorite anion than many powdered versions. Lower chlorite content, in turn, limits their maximum yield of C10 2 .
  • the invention relates to composite articles comprising a material capable of producing C10 2 upon exposure to an activating stimulus that is integrated into an organic matrix, and methods of using the article.
  • the organic matrix is formable at a temperature below about 150°C, preferably below about 135°C, and most preferably below about 110°C.
  • an activating stimulus such as water or light
  • the organic matrix permits at least some contact between the Outproducing material and the activating stimulus, which in turn causes the material to generate C10 2 .
  • the organic matrix is also permeable to C10 2 so as to allow at least a portion of C10 2 generated by the ClCVproducing material to escape the composite article.
  • the article is stable during storage prior to exposure to the stimulus.
  • the invention relates to a composite article comprising a C10 2 -producing material integrated into an organic matrix, and methods of using the same.
  • the ClCVproducing material is any material or combination of materials that is capable of generating C10 2 upon exposure to some activating stimulus.
  • the activating stimulus may be water vapor, electromagnetic energy, or any other trigger that effects the formation of C10 2 by the Outproducing material.
  • C10 2 - producing materials comprise a chlorite-containing compound, such as sodium chlorite, and an acidifying agent. Examples of Ou t producing materials are described in U.S. Patent Nos. 6,294,108 and WO 03/056951 A2, both incorporated herein by reference.
  • the organic matrix contains at least one organic material and: a) is formable at temperatures below about 150°C, preferably below about 135°C, more preferably below about 110°C; b) permits at least some contact between an activating stimulus and the CKVproducing material when the composite article is exposed to the activating stimulus so as to enable generation of C10 2 ; and c) is permeable to C10 2 .
  • the low temperature formability of the organic matrix is compatible with temperature-sensitive CKVproducing materials. When exposed to an activating stimulus, the organic matrix allows the activating stimulus to contact an integrated Ou t producing material, and permits the resulting C10 2 to escape into the space surrounding the article.
  • low melting molecular solids In particular, low melting hydrophilic molecular solids.
  • low melting molecular solids are polyethylene glycol wax (such as that sold under the trade name CARBOWAX by the Dow Chemical Co.), mixtures of polyethylene glycol wax with paraffin wax, stearic acid, and mixtures of polyethylene glycol wax with stearic acid.
  • An organic matrix comprising only paraffin wax as the organic material is preferably used with a humidity-activated O0 2 -releasing material and with a pore former incorporated into the formulation to facilitate humidity intrusion.
  • thermoformable or thermosetting functionalized polymers such as EVA (ethylene vinyl acetate) . These are commonly used in the formulation of hot melt glue products that soften and flow (i.e. can be extruded) at relatively low temperatures. Other hot melt glue type formulations are also satisfactory for this purpose. If O0 2 release is to be initiated by exposure to light, it is preferred that the matrix material be effectively transparent to the light.
  • the composite article may be formed by combining the C10 2 -releasing material(s) with the organic matrix material(s), heating to a temperature that is below 150°C to soften or melt the matrix material(s), and extruding the mixture into rods, sheet, pellets, or the like.
  • the matrix material(s) may be heated to a temperature below 150°C and softened/melted prior to combination with the C10 2 - producing material.
  • the composite article may be formed by casting a mixture into a mold and cooling; by coating a mixture on a flat surface to form a thin sheet (such as by the doctor blade process); or by passing a mixture through the nip space between two rollers to form a sheet.
  • any of several other methods known to those in the art may be used to form an article.
  • the composite article may contain other constituents that provide desired characteristics.
  • fibrous material may be added to the composite to increase stiffness and strength, or plasticizers may be added to increase flexibility.
  • Pore formers such as silica gel and diatomaceous earth, may be added to increase the porosity of the article. Increased porosity could facilitate the passage of water vapor into, and/or O0 2 out of, the article.
  • Coloring and fragrances may be added to enhance aesthetics.
  • Desiccants may be added to limit water exposure during storage.
  • the composite article may be used wherever O0 2 would be desired and exposure to an activating stimulus would occur.
  • Some specific applications include: food shelf-life extension, microbial deterioration protection of good (e.g., shoes) during transportation and/or storage, microbial-resistant packaging, deodorizing devices, and deodorizing coatings.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Geology (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Epidemiology (AREA)
  • Agronomy & Crop Science (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Medicinal Chemistry (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Plant Pathology (AREA)
  • Animal Behavior & Ethology (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Pest Control & Pesticides (AREA)
  • Dentistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Wrappers (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Thermotherapy And Cooling Therapy Devices (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Saccharide Compounds (AREA)
  • Compounds Of Unknown Constitution (AREA)
  • Food Preservation Except Freezing, Refrigeration, And Drying (AREA)

Abstract

A composite article that includes a C1O2-producing material integrated into an organic matrix and methods of using the same are described. The organic matrix of the composite article is formable at a temperature under about 150 °C, permits contact between an activating stimulus (e.g., water vapor and/or electromagnetic energy) and the C1O2-producing material when the composite article is exposed to the activating stimulus, and is permeable to C1O2.

Description

CHLORINE DIOXIDE RELEASING COMPOSITE ARTICLE
Field of the invention This invention relates to a device which will produce chlorine dioxide gas when exposed to an activating stimulus such as ambient humidity or light, and methods of using the same.
Background of the Invention
The prior art discloses a variety of powdered compositions that produce C102 gas under a variety of conditions, included in these are materials for the controlled sustained release of C102 (CSR materials), which release C102 when exposed to water vapor. Also included are materials disclosed by which produce C102 when exposed to light.
It is desirable for ease of use and disposal for such materials to be contained or packaged in a manner that contains the powder in a porous pouch (i.e., a sachet) or for it to be extruded into a polymer matrix film, such as polyethylene. In this manner the user is protected from direct contact with the powder, and spent powder may be more readily removed from the area that was treated.
Unfortunately, sachets are relatively bulky and expensive to fabricate, and in small sizes are very light and difficult to handle. As a result, the cost of packaging powders in small sachets (less than about 2 grams in size) is often impractically high.
Extruded polymer sheet material can be relatively less expensive to produce in small sizes, because the sheet may be produced in a large economical size, and then smaller size pieces may be inexpensively cut from the larger sheet. However, due to the low decomposition temperature of the chlorite anion that is incorporated into all C102 producing materials, the extrusion temperature of C102-releasing polymer sheet must be no higher than about 150-160°C. If the temperature is above that, then the amount of chlorite that is lost by decomposition during extrusion can be unacceptably high. This has limited the choice of polymer matrices to those comprising a substantial amount of relatively low melting, low density polyethylene. But polyethylene is an undesirable matrix material because it is not highly permeable to water vapor used to initiate the release of chlorine dioxide from most chlorine dioxide-releasing materials. Plus the extrusion temperature of polyethylene is about 150 degrees C, so it is right on the borderline where decomposition of chlorite anion can occur. Since chlorite decomposition can lead to explosive oxidation of the polyethylene, such extruded sheet materials typically contain lower concentrations of chlorite anion than many powdered versions. Lower chlorite content, in turn, limits their maximum yield of C102.
Summary of the Invention
Generally, the invention relates to composite articles comprising a material capable of producing C102 upon exposure to an activating stimulus that is integrated into an organic matrix, and methods of using the article. The organic matrix is formable at a temperature below about 150°C, preferably below about 135°C, and most preferably below about 110°C. When the composite article is exposed to an activating stimulus, such as water or light, the organic matrix permits at least some contact between the Outproducing material and the activating stimulus, which in turn causes the material to generate C102. The organic matrix is also permeable to C102 so as to allow at least a portion of C102 generated by the ClCVproducing material to escape the composite article. Preferably the article is stable during storage prior to exposure to the stimulus.
Detailed Description of the Preferred Embodiments
The invention relates to a composite article comprising a C102-producing material integrated into an organic matrix, and methods of using the same.
The ClCVproducing material is any material or combination of materials that is capable of generating C102 upon exposure to some activating stimulus. The activating stimulus may be water vapor, electromagnetic energy, or any other trigger that effects the formation of C102 by the Outproducing material. Typically, C102- producing materials comprise a chlorite-containing compound, such as sodium chlorite, and an acidifying agent. Examples of Outproducing materials are described in U.S. Patent Nos. 6,294,108 and WO 03/056951 A2, both incorporated herein by reference.
The organic matrix contains at least one organic material and: a) is formable at temperatures below about 150°C, preferably below about 135°C, more preferably below about 110°C; b) permits at least some contact between an activating stimulus and the CKVproducing material when the composite article is exposed to the activating stimulus so as to enable generation of C102; and c) is permeable to C102. The low temperature formability of the organic matrix is compatible with temperature-sensitive CKVproducing materials. When exposed to an activating stimulus, the organic matrix allows the activating stimulus to contact an integrated Outproducing material, and permits the resulting C102 to escape into the space surrounding the article.
One class of materials that may be suitable for the organic matrix is low melting molecular solids. In particular, low melting hydrophilic molecular solids. Examples of low melting molecular solid materials are polyethylene glycol wax (such as that sold under the trade name CARBOWAX by the Dow Chemical Co.), mixtures of polyethylene glycol wax with paraffin wax, stearic acid, and mixtures of polyethylene glycol wax with stearic acid. An organic matrix comprising only paraffin wax as the organic material is preferably used with a humidity-activated O02-releasing material and with a pore former incorporated into the formulation to facilitate humidity intrusion.
Another class of materials suitable for the organic matrix are low melting thermoformable or thermosetting functionalized polymers, such as EVA (ethylene vinyl acetate) . These are commonly used in the formulation of hot melt glue products that soften and flow (i.e. can be extruded) at relatively low temperatures. Other hot melt glue type formulations are also satisfactory for this purpose. If O02 release is to be initiated by exposure to light, it is preferred that the matrix material be effectively transparent to the light.
The composite article may be formed by combining the C102-releasing material(s) with the organic matrix material(s), heating to a temperature that is below 150°C to soften or melt the matrix material(s), and extruding the mixture into rods, sheet, pellets, or the like. Alternatively, the matrix material(s) may be heated to a temperature below 150°C and softened/melted prior to combination with the C102- producing material.
Alternatively, the composite article may be formed by casting a mixture into a mold and cooling; by coating a mixture on a flat surface to form a thin sheet (such as by the doctor blade process); or by passing a mixture through the nip space between two rollers to form a sheet. Likewise, any of several other methods known to those in the art may be used to form an article.
The composite article may contain other constituents that provide desired characteristics. For example, fibrous material may be added to the composite to increase stiffness and strength, or plasticizers may be added to increase flexibility. Pore formers, such as silica gel and diatomaceous earth, may be added to increase the porosity of the article. Increased porosity could facilitate the passage of water vapor into, and/or O02 out of, the article. Coloring and fragrances may be added to enhance aesthetics. Desiccants may be added to limit water exposure during storage. The composite article may be used wherever O02 would be desired and exposure to an activating stimulus would occur. Some specific applications include: food shelf-life extension, microbial deterioration protection of good (e.g., shoes) during transportation and/or storage, microbial-resistant packaging, deodorizing devices, and deodorizing coatings.
A non-limiting example of a preferred embodiment will now be described. Example
Thirteen point three (13.3) grams of chlorine dioxide releasing powder similar to that described in example 7 of US Patent 6,294,108 was mixed into 20 grams of melted polyethylene glycol wax (CARBOWAX 4000 brand) at a temperature below 100°C. Five point three (5.3) grams of that mixture was poured into a small aluminum dish to produce a disk approximately 2 inches in diameter and 1/8 inch thick. This disk was tested for the release of chlorine dioxide at 80% relative humidity using the test method described in US Patent 6,294,108, and it produced 5 ppm of O0 at about 20 hours.

Claims

What is claimed is:
1. A composite article comprising a Outproducing material integrated into an organic matrix, wherein the Outproducing material releases C102 when contacted by an activating stimulus, and wherein the organic matrix: a) is formable at a temperature below about 150°C; b) permits at least some contact between the activating stimulus and the Outproducing material when the composite article is exposed to the activating stimulus; and c) is permeable to O02.
2. The composite article of claim 1, wherein the organic matrix is formable at a temperature below about 135°C.
3. The composite article of claim 1, wherein the organic matrix is formable at a temperature below about 110°C.
4. The composite article of claim 1, wherein the activating stimulus is water vapor.
5. The composite article of claim 1, wherein the activating stimulus is electromagnetic energy.
6. A method of producing chlorine dioxide, comprising exposing the composite article of claim 1 to an activating stimulus.
7. The method of claim 6, wherein the activating stimulus is water vapor.
8. The method of claim 7, wherein the activating stimulus is electromagnetic energy.
PCT/US2004/024865 2003-08-04 2004-07-30 Chlorine dioxide releasing composite article Ceased WO2005019101A2 (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
AU2004267046A AU2004267046B2 (en) 2003-08-04 2004-07-30 Chlorine dioxide releasing composite article
CA2535002A CA2535002C (en) 2003-08-04 2004-07-30 Chlorine dioxide releasing composite article
DE602004026480T DE602004026480D1 (en) 2003-08-04 2004-07-30 CHLORDIOXID RELEASED OBJECT
CN2004800221920A CN1902125B (en) 2003-08-04 2004-07-30 Chlorine dioxide releasing composite article
AT04786156T ATE463464T1 (en) 2003-08-04 2004-07-30 CHLORINE DIOXIDE RELEASING COMPOSITE ARTICLE
EP04786156A EP1708962B1 (en) 2003-08-04 2004-07-30 Chlorine dioxide releasing composite article

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US49243103P 2003-08-04 2003-08-04
US60/492,431 2003-08-04
US10/902,735 2004-07-29
US10/902,735 US8137581B2 (en) 2003-08-04 2004-07-29 Chlorine dioxide releasing composite article

Publications (3)

Publication Number Publication Date
WO2005019101A2 true WO2005019101A2 (en) 2005-03-03
WO2005019101A8 WO2005019101A8 (en) 2005-06-02
WO2005019101A3 WO2005019101A3 (en) 2006-08-31

Family

ID=34622787

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Application Number Title Priority Date Filing Date
PCT/US2004/024865 Ceased WO2005019101A2 (en) 2003-08-04 2004-07-30 Chlorine dioxide releasing composite article

Country Status (10)

Country Link
US (1) US8137581B2 (en)
EP (1) EP1708962B1 (en)
CN (1) CN1902125B (en)
AT (1) ATE463464T1 (en)
AU (1) AU2004267046B2 (en)
CA (1) CA2535002C (en)
DE (1) DE602004026480D1 (en)
ES (1) ES2341251T3 (en)
PT (1) PT1708962E (en)
WO (1) WO2005019101A2 (en)

Families Citing this family (8)

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Publication number Priority date Publication date Assignee Title
JP2011528361A (en) * 2008-07-15 2011-11-17 ビーエーエスエフ、カタリスツ、エルエルシー Methods, systems and equipment for administration of chlorine dioxide
WO2010009064A2 (en) * 2008-07-15 2010-01-21 Basf Corporation Non-cytotoxic chlorine dioxide fluids
EP2313062A2 (en) * 2008-07-15 2011-04-27 BASF Corporation Tooth polishing compositions and methods of tooth polishing without mechanical abrasion
US8311625B2 (en) * 2009-02-04 2012-11-13 Basf Corporation Chlorine dioxide treatment for biological tissue
US20100209332A1 (en) * 2009-02-19 2010-08-19 Basf Catalysts Llc Nonaqueous Chlorine Dioxide-Generating Compositions and Methods Related Thereto
WO2011094657A2 (en) 2010-01-31 2011-08-04 Basf Corporation Additives for chlorine dioxide-containing compositions
US20140311094A1 (en) * 2013-04-17 2014-10-23 Cryovac, Inc. Methods of Increasing the Generation of a Gas Within a Package
CN119498347A (en) * 2024-11-19 2025-02-25 苏州卓煊环保科技有限公司 A chlorine dioxide sustained-release product and its preparation method and application

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US5719100A (en) * 1992-03-20 1998-02-17 Zahradnik; Rudolf Water treatment compositions
US5545450A (en) * 1992-08-11 1996-08-13 E. Khashoggi Industries Molded articles having an inorganically filled organic polymer matrix
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Also Published As

Publication number Publication date
AU2004267046B2 (en) 2010-03-25
AU2004267046A1 (en) 2005-03-03
ES2341251T3 (en) 2010-06-17
PT1708962E (en) 2010-04-29
DE602004026480D1 (en) 2010-05-20
WO2005019101A3 (en) 2006-08-31
EP1708962B1 (en) 2010-04-07
US20060024369A1 (en) 2006-02-02
US20090238872A9 (en) 2009-09-24
CN1902125A (en) 2007-01-24
EP1708962A2 (en) 2006-10-11
CA2535002A1 (en) 2005-03-03
US8137581B2 (en) 2012-03-20
WO2005019101A8 (en) 2005-06-02
CA2535002C (en) 2013-10-29
ATE463464T1 (en) 2010-04-15
CN1902125B (en) 2011-06-22

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