WO2007054227A1 - Resines chelatantes contenant de l’argent pour la protection de materiaux - Google Patents

Resines chelatantes contenant de l’argent pour la protection de materiaux Download PDF

Info

Publication number
WO2007054227A1
WO2007054227A1 PCT/EP2006/010456 EP2006010456W WO2007054227A1 WO 2007054227 A1 WO2007054227 A1 WO 2007054227A1 EP 2006010456 W EP2006010456 W EP 2006010456W WO 2007054227 A1 WO2007054227 A1 WO 2007054227A1
Authority
WO
WIPO (PCT)
Prior art keywords
silver
weight
copolymer
units derived
monomers
Prior art date
Application number
PCT/EP2006/010456
Other languages
German (de)
English (en)
Inventor
Johannes Kaulen
Reinhold Klipper
Martin Kugler
Erasmus Vogl
Original Assignee
Lanxess Deutschland Gmbh
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Lanxess Deutschland Gmbh filed Critical Lanxess Deutschland Gmbh
Publication of WO2007054227A1 publication Critical patent/WO2007054227A1/fr

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J45/00—Ion-exchange in which a complex or a chelate is formed; Use of material as complex or chelate forming ion-exchangers; Treatment of material for improving the complex or chelate forming ion-exchange properties
    • 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
    • A01N59/16—Heavy metals; Compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J47/00—Ion-exchange processes in general; Apparatus therefor
    • B01J47/016—Modification or after-treatment of ion-exchangers

Definitions

  • the present invention relates to novel, silver-containing macroporous chelating ion exchange resins, processes for their preparation and their use for the protection of technical materials and cosmetics.
  • zeolitic silver-containing boicidal products which, according to the manufacturer, do not lead to discoloration and which are said to release silver at an appropriate concentration.
  • silver is incorporated in ionic form in inorganic silicate frameworks.
  • the release kinetics can only be varied within narrow limits.
  • the silicate carrier materials can represent a disturbing factor in the application medium due to their hardness.
  • zeolites based on inorganic silicate scaffolds often have a higher specific gravity and therefore can not be used for many industrial applications.
  • Silver-doped ion exchangers based on organic compounds have hitherto not been used, since the silver ions responsible for the antibacterial effect were too strongly bound to the relevant ion exchangers.
  • silver or silver salts as biocidal additives when using certain ion exchangers.
  • silver is used exclusively to protect the ion exchanger itself against infestation by microorganisms.
  • the object of the present invention was therefore to synthesize new silver-containing biocides which can simultaneously perform the function of a storage for silver ions as well as the function of a metered release of silver ions.
  • Particular emphasis was placed on the requirement to find a completely organic storage medium, in contrast to mineral carriers such as inorganic zeolites.
  • special chelating resins are very well suited as storage media and delivery media for silver ions. In this case, the silver ion is bound firmly enough so as not to be washed out immediately and yet released in a controlled amount in sufficient quantity to be able to develop its biocidal activity.
  • the present invention relates to novel silver-containing macroporous chelating ion exchange resins comprising a copolymer (I) which comprises
  • (b) has a content of silver ions of 0.1 to 10 wt .-%, preferably from 0.3 to 3 wt .-%.
  • (b) has a content of silver ions of 0.1 to 10 wt .-%, preferably from 0.3 to 3 wt .-%.
  • the aromatic divinyl monomer (ii) is present in the copolymer (I) in an amount of about 5 to 6% by weight, based on the weight of the copolymer. In an alternative embodiment, the copolymer (I) still
  • novel silver-containing macroporous chelating ion exchange resins can be prepared by comprising a macroporous chelating ion exchange resin comprising a copolymer (I) which comprises
  • the inorganic silver salts are preferably water-soluble silver compounds such as silver fluoride and silver nitrate, preferably silver nitrate.
  • the silver salts are used in the form of aqueous solutions.
  • the aqueous silver salt solutions are preferably 0.001 to 2 molar of silver salts, more preferably 0.1 to 1 molar.
  • an aqueous suspension of the ion exchange resin is initially charged and the aqueous silver salt solution is metered in with stirring.
  • the metered addition is generally carried out over a period of 5 to 30 minutes, preferably 15 to 25 minutes.
  • the mixture is then stirred for 10 minutes to 10 hours, preferably for 2 hours, and then the product according to the invention is filtered off.
  • the loading of the ion exchange resin with silver salts is carried out by passing the silver salt solution over the ionic column, for example in a column. running exchange resin.
  • the solution can be filtered from above over the resin or pumped through the resin from below.
  • the loading rate is between 0.05-10 bed volumes of aqueous silver salt solution per hour per bed volume of ion exchange resin. Preferred are 1 to 3 bed volumes.
  • the process of the invention can be carried out in a wide temperature range. In general, one works at a temperature of 5 to 90 0 C, preferably at 10 0 C to 50 0 C, most preferably at room temperature.
  • the degree of loading of silver can vary within certain limits and is e.g. depending on the concentration of the silver salt solution and the loading time. Preferred is a degree of loading of 0.1 to 10 wt .-% of silver based on the ion exchange resin, more preferably a degree of loading of 0.3 to 3 wt .-% silver.
  • the macroporous chelating ion exchange resins suitable for carrying out the process according to the invention are known in some cases (cf., EP-A 0 874 004) and can be prepared analogously to the process described there by suspension polymerization of a monomer mixture comprising 86 to 96% by weight of aromatic monovinyl monomer 4 to 14% by weight of aromatic divinyl monomer and 0 to 6% by weight of oxygen-containing crosslinker monomers comprising trimethylolpropane trimethacrylate, diethyene glycol dimethacrylate and diethylene glycol divinyl ether, the percentages of the monomers being based on the weight of the monomer mixture and the polymerization being carried out in the presence of 40-48% by weight.
  • % Phase extender, and the percentage of phase extender is based on the total weight of phase extender and monomer mixture, and subsequent functionalization of the resulting copolymer with aminoalkylphosphonic or iminodiacetic acid groups.
  • the macroporous chelating ion exchange resins to be used can be ground to a suitable particle size before or after the loading according to the invention with silver.
  • a suitable particle size for example, ball mills or jet mills are suitable for this purpose.
  • the silver-containing macroporous chelating ion exchangers according to the invention are excellently suitable for use as biocides, preferably as bactericides, in the protection of materials.
  • Another object of the present invention is the use of the inventive macroporous chelating ion exchange resins for the protection of industrial products and cosmetics from attack and / or destruction by bacteria.
  • the silver-containing macroporous chelating ion exchange resins according to the invention are suitable for protecting cosmetics, toothpastes, coolants, coatings, latices or plastics against infestation and / or Destruction by bacteria and water treatment against bacterial infestation.
  • the silver-containing macroporous chelating ion exchange resins can be used alone or in combination with biocides commonly used in the protection of materials.
  • the silver-containing macroporous chelating ion exchange resins according to the invention are distinguished by a number of advantages. So they are able to release the silver ions over a fairly long period in an even amount. It is also favorable that hardly
  • the material to be protected may e.g. be cyclically transferred via the silver-containing ion exchange resins according to the invention. There is still no danger that silver ions are released in too high an amount.
  • the resin was washed with 5 column volumes of deionized water. A small amount was dried in a drying oven under vacuum at 80 0 C to constant mass. The dried resin was analyzed elementally by atomic absorption spectroscopy on silver. A content of silver of 0.75 wt .-% was found.
  • a chemically defined nutrient medium was adjusted to a viable count of approximately 10 7 germs / ml.
  • the inventive silver-containing chelate resin according to Example 1 and the silver-containing reference substance Lewatit TP 214 were, according to the concentration information, each filled in Erlenmeyer flasks and mixed with the inoculated nutrient medium.
  • the cultures thus prepared were then incubated together with a comparison culture without addition of silver-containing chelate resin (zero control) for 24 hours at 29 ° C. in a shaker (100 rpm).
  • the inventive silver-containing macroporous chelating ion exchange resin according to Example 1 shows, as can be seen from the nuclei densities according to Table 1, even in the lowest concentration a significant antibacterial effect.
  • the silver-loaded ion exchanger Lewatit ® TP 214 has no antibacterial effect even at a very high use concentration of 10%.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Agronomy & Crop Science (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Cosmetics (AREA)

Abstract

L’invention concerne de nouvelles résines échangeuses d'ions chélatantes macroporeuses et contenant de l’argent, lesdites résines comprenant un copolymère (I) contenant (i) de 86 à 96 % en poids d’unités dérivées de monomères monovinyle aromatiques et (ii) de 4 à 14 % en poids d’unités dérivées de monomères divinyle aromatiques, ledit copolymère (I) (a) étant fonctionnalisé avec des groupements d’aminoalkylphosphone ou avec des groupements d’acide iminodiacétique et (b) présentant une teneur en ions argent comprise entre 0,1 et 10 % en poids. Ces résines sont utilisées notamment pour la protection de matériaux techniques et de produits cosmétiques.
PCT/EP2006/010456 2005-11-11 2006-10-31 Resines chelatantes contenant de l’argent pour la protection de materiaux WO2007054227A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005053888A DE102005053888A1 (de) 2005-11-11 2005-11-11 Silberhaltige Chelatharze für den Materialschutz
DE102005053888.6 2005-11-11

Publications (1)

Publication Number Publication Date
WO2007054227A1 true WO2007054227A1 (fr) 2007-05-18

Family

ID=37560899

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2006/010456 WO2007054227A1 (fr) 2005-11-11 2006-10-31 Resines chelatantes contenant de l’argent pour la protection de materiaux

Country Status (2)

Country Link
DE (1) DE102005053888A1 (fr)
WO (1) WO2007054227A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE212015000056U1 (de) 2014-01-29 2016-09-07 Unilever N.V. Reinigungszusammensetzungen enthaltend oligodynamisches Metall und Wirksamkeitsverstärker
DE102021123449A1 (de) 2021-09-10 2023-03-16 Uwe Michael Schlitt Vorrichtung und Verfahren zum Dosieren und Konservieren flüssiger Medien

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102015221750B4 (de) * 2015-11-05 2019-10-31 WM aquatec GmbH & Co.KG Beschichtetes, partikuläres Polymermaterial, Verfahren zur Herstellung des beschichteten, partikulären Polymermaterials sowie Verwendung des beschichteten, partikulären Polymermaterials

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2656465A1 (de) * 1976-12-14 1978-06-15 Gehrig Joseph Dr Verfahren zur entkeimung von fluessigkeiten
US5464559A (en) * 1994-03-18 1995-11-07 Kansas State University Research Foundation Composition for treating water with resin bound ionic silver
EP0874004A1 (fr) * 1997-04-21 1998-10-28 Rohm And Haas Company Résines chélatantes améliorées
EP1652864A1 (fr) * 2004-10-30 2006-05-03 Lanxess Deutschland GmbH Procédé de préparation de polymères en forme de perles contenant de l'argent

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2656465A1 (de) * 1976-12-14 1978-06-15 Gehrig Joseph Dr Verfahren zur entkeimung von fluessigkeiten
US5464559A (en) * 1994-03-18 1995-11-07 Kansas State University Research Foundation Composition for treating water with resin bound ionic silver
EP0874004A1 (fr) * 1997-04-21 1998-10-28 Rohm And Haas Company Résines chélatantes améliorées
EP1652864A1 (fr) * 2004-10-30 2006-05-03 Lanxess Deutschland GmbH Procédé de préparation de polymères en forme de perles contenant de l'argent

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE212015000056U1 (de) 2014-01-29 2016-09-07 Unilever N.V. Reinigungszusammensetzungen enthaltend oligodynamisches Metall und Wirksamkeitsverstärker
DE102021123449A1 (de) 2021-09-10 2023-03-16 Uwe Michael Schlitt Vorrichtung und Verfahren zum Dosieren und Konservieren flüssiger Medien

Also Published As

Publication number Publication date
DE102005053888A1 (de) 2007-05-16

Similar Documents

Publication Publication Date Title
DE69109351T2 (de) Antimikrobielle Zusammensetzung.
DE3751056T2 (de) Amorphe Aluminiumsilikatteilchen enthaltendes Polymer und Verfahren zu seiner Herstellung.
EP1969017B1 (fr) Production d'une resine absorbant l'eau par incorporation d'un additif particulaire
EP3661364B1 (fr) Elimination de bactéries de l'eau potable par filtration
DE4000978A1 (de) Verfahren zur entfernung von schwermetallionen aus wein und weinaehnlichen getraenken
WO2008077265A1 (fr) Stérilisation et conservation de fluides
DE2728106A1 (de) Mikrobiozides produkt
EP3186001A1 (fr) Agent de sorption pour la liaison de métaux et fabrication de l'agent de sorption
EP0296441A2 (fr) Utilisation de composés polyfonctionnels insolubles de l'ammonium quaternaire pour le liage adsorptif de micro-organismes
DE69606200T2 (de) Ionenpolymere in tablettenform
WO2007054227A1 (fr) Resines chelatantes contenant de l’argent pour la protection de materiaux
DE102011114952A1 (de) Adsorbens zur Abtrennung fluorierter organischer Verbindungen aus kontaminierten Fluiden, Verfahren zu dessen Herstellung und Verwendung desselben
DE69126520T2 (de) Antimikrobielle Zusammensetzung mit einer Hitze- und Witterungsbeständigkeit
DE102019108803B4 (de) Verwendung eines Komplexierungsmittels zur Rückgewinnung von Metallionen aus Industrieabwasser sowie ein Verfahren dazu
DE4404404A1 (de) Acroleinpolymer
WO2018158334A1 (fr) Procédé de préparation d'acide sulfosuccinique et utilisation d'acide sulfosuccinique
RU2424797C1 (ru) Нанокомпозиционный полимерный материал, способ его получения и дезинфицирующее средство на его основе
JP3159485B2 (ja) 無機質抗菌剤、その製造方法及び抗菌性樹脂組成物
AT511235B1 (de) Antimikrobielle ausrüstung von kunststoffen und textilen oberflächen
WO2018158333A2 (fr) Absorbeur et fabrication d'un absorbeur
DE2533159C2 (fr)
CN113736200A (zh) 一种抗菌高吸水树脂复合材料及其制备方法
DE102010016485A1 (de) Verfahren zum Herstellen eines Stoffs mit einstellbaren biologisch aktiven Gradienteneigenschaften und Verwendung des Verfahrens
DE102007042615A1 (de) Erhöhung der bioziden Wirkung von Wasserstoffperoxid in Abwässern durch Übergangsmetallkatalysatoren
WO2002068518A1 (fr) Dispersions polymeres et solutions polymeres antibacteriennes et fongicides

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application
NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 06806627

Country of ref document: EP

Kind code of ref document: A1