WO2000069937A1 - Mikrobizide copolymere - Google Patents
Mikrobizide copolymere Download PDFInfo
- Publication number
- WO2000069937A1 WO2000069937A1 PCT/EP2000/002818 EP0002818W WO0069937A1 WO 2000069937 A1 WO2000069937 A1 WO 2000069937A1 EP 0002818 W EP0002818 W EP 0002818W WO 0069937 A1 WO0069937 A1 WO 0069937A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- component
- aliphatic unsaturated
- substrate
- antimicrobial
- antimicrobial polymers
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
-
- 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
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/34—Shaped forms, e.g. sheets, not provided for in any other sub-group of this main group
-
- 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
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/12—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group, wherein Cn means a carbon skeleton not containing a ring; Thio analogues thereof
-
- 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
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
- A01N37/20—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof containing the group, wherein Cn means a carbon skeleton not containing a ring; Thio analogues thereof
-
- 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
- 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
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/54—Biologically active materials, e.g. therapeutic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
-
- 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
- A61L2300/20—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing organic materials
- A61L2300/204—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing organic materials with nitrogen-containing functional groups, e.g. aminoxides, nitriles, guanidines
-
- 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
Definitions
- the invention relates to antimicrobial polymers which are obtained by copolymerization of several aliphatic unsaturated monomers which are functionalized at least once by a primary amino group.
- the invention further relates to a process for the preparation and use of the antimicrobial polymers
- the invention relates to antimicrobial polymers which are obtained on a substrate by graft copolymerization of aliphatic unsaturated monomers which are at least simply functionalized by a primary amino group, to a process for their preparation and their use
- Bacteria must be kept away from all areas of life in which hygiene is important.This affects textiles for direct body contact, in particular for the genital area and for nursing and elderly care.In addition, bacteria must be kept away from furniture and device surfaces in care stations, particularly in the area of Intensive care and the care of small children, in hospitals, in particular in rooms for medical interventions and in isolation stations for critical infection cases and in toilets
- Tert-butylaminoethyl methacrylate is a commercially available monomer of methacrylate chemistry and is used in particular as a hydrophilic component in copolymerizations.
- EP-PS 0 290 676 describes the use of various polyacrylates and polymethacrylates as a matrix for the immobilization of bactericidal quaternary ammonium compounds
- US Pat. No. 4,532,269 discloses a terpolymer of butyl methacrylate, tributyltin methacrylate and tert-butylaminoethyl methacrylate.
- This polymer is used as an antimicrobial marine paint, the hydrophilic tert-butylaminoethyl methacrylate requiring the slow erosion of the polymer and thus the highly toxic tributyltin microbial methacrylate releases
- the copolymer made with aminomethacrylates is only a matrix or carrier substance for added microbicidal active ingredients that can diffuse or migrate from the carrier substance.
- Polymers of this type lose their effect more or less quickly if the necessary "minimal inhibitory concentration" on the surface ( MtK) is no longer achieved
- the present invention is therefore based on the object of developing novel, antimicrobial polymers which, if necessary, are intended as a coating to prevent the settlement and spread of bacteria on surfaces It has now surprisingly been found that by copolymerizing several components of aliphatic, unsaturated monomers which are functionalized at least simply by a primary amino group, or by graft copolymerizing these components on a substrate, polymers with a surface which is permanently microbicidal are obtained by solvents and physical stresses are not attacked and no migration shows, it is not necessary to use other biocidal agents
- the present invention therefore relates to antimicrobial polymers which, by copolymerizing aliphatic, unsaturated monomers which are at least simply functionalized by a primary amino group (component I), with a further aliphatic unsaturated monomer which is at least simply functionalized by a primary amino group (component II), component I and component II being different from one another, are obtained
- the present invention also relates to a process for the preparation of antimicrobial polymers which are graft copolymerized by aliphatic, unsaturated monomers which are at least simply functionalized by a primary amino group (component I), with a further aliphatic unsaturated monomer which is at least simply by a primary amino group is functionalized (component II), component I and component II being different from one another, are obtained
- Suitable comonomer building blocks of components I and II are all aliphatic unsaturated monomers which have at least one primary amino function, such as l-amino-2-propene, N-6-aminohexyl-2-propenamide, N-3-aminopropyl methacrylamide hydrochloride, Methacrylic acid 2-aminoethyl ester hydrochloride and 3-aminopropyl vinyl ether
- the aliphatic unsaturated monomers functionalized at least simply by a primary amino group in the process according to the invention can have a hydrocarbon radical of up to 50, preferably up to 30, particularly preferably up to 22 carbon atoms.
- the monomers can also be derived from keto or aldehyde groups such as acrylolyl or oxo groups or cyclic hydrocarbon radicals such as substituted or unsubstituted phenyl or cyclohexyl radicals
- the monomers of components I or II used according to the invention should have a molar mass of less than 900, preferably less than 550 g / mol
- aliphatic unsaturated monomers of the general formula which are functionalized simply by a primary amino group for components I or II are functionalized simply by a primary amino group for components I or II
- Hydrocarbon radicals with up to 50 carbon atoms which can be substituted by O, N or S atoms, are used
- the monomers of components I and II must be different. A molecular weight difference of at least 23 g / mol can exist between these monomers. Exemplary combinations of monomers of components I, II and possibly III are described in the examples
- the antimicrobial copolymers according to the invention can also be carried out by copolymerizing components I and II or I, II and III on a substrate. A physisorbed coating of the antimicrobial copolymer is obtained on the substrate All polymeric plastics, such as, for example, are suitable as substrate materials.
- polyurethanes polyamides, polyesters and ethers, polyether block amides, polystyrene, polyvinyl chloride, polycarbonates, polyorganosiloxanes, polyolefins, polysulfones, polyisoprene, polychloroprene, polytetrafluoroethylene (PTFE), corresponding copolymers and blends as well as natural and synthetic rubbers, with or without radiation-sensitive groups
- the method according to the invention can also be applied to surfaces of lacquered or otherwise plastic, metal, glass or wooden bodies
- the copolymers can be obtained by graft-polymerizing a substrate with components I and II or components I, II and III. Grafting the substrate enables the antimicrobial copolymer to be covalently bound to the substrate. All polymeric materials can be used as substrates how the plastics already mentioned are used
- the surfaces of the substrates can be activated before the graft copolymerization using a number of methods. All standard methods for activating polymeric surfaces can be used here.
- the activation of the substrate before the graft polymerization is carried out by UV radiation, plasma treatment, corona treatment, flame treatment, ozonization, electrical discharge of ⁇ -radiation, methods used
- the surfaces are expediently freed of oils, fats or other contaminants beforehand in a known manner by means of a solvent
- the substrates can be activated by UV radiation in the wavelength range 170-400 nm, preferably 170-250 nm.
- a suitable radiation source is, for example, a UV excimer device HERAEUS Noblelight, Hanau, Germany.
- mercury vapor lamps are also suitable for substrate activation if they emit significant amounts of radiation in the areas mentioned
- the exposure time is generally 0 1 seconds to 20 minutes, preferably 1 second to 10 minutes
- the activation of the standard polymers with UV radiation can also be carried out with an additional photosensitizer.
- the photosensitizer such as benzophenone
- the substrate surface is irradiated. This can also be done with a mercury vapor lamp with exposure times of 0 1 seconds to 20 minutes, preferably 1 second to 10 minutes
- the activation can also be carried out by plasma treatment using an RF or microwave plasma (Hexagon, Fa Technics Plasma, 85551 Kirchheim, Germany) in air.
- RF or microwave plasma Hexagon, Fa Technics Plasma, 85551 Kirchheim, Germany
- Nitrogen or argon atmosphere can be reached.
- the exposure times are generally 2 seconds to 30 minutes, preferably 5 seconds to 10 minutes.
- the energy input in laboratory devices is between 100 and 500 W, preferably between 200 and 300 W.
- Corona devices SOFTAL, Hamburg, Germany
- the exposure times in this case are generally 1 to 10 minutes, preferably 1 to 60 seconds
- Activation by electrical discharge, electron or ⁇ -rays (e.g. from a cobalt 60 source) and ozonization enable short exposure times, which are generally 0 1 to 60 seconds
- Flaming substrate surfaces also leads to their activation.
- Suitable devices in particular those with a barrier flame front, can be easily built or, for example, obtained from ARCOTEC, 71297 Monsheim, Germany. They can be operated with hydrocarbons or hydrogen as fuel gas In any case, damaging overheating of the substrate must be avoided, which is easily achieved by intimate contact with a cooled metal surface on the surface of the substrate facing away from the flame side. Activation by flame is accordingly limited to relatively thin, flat substrates.
- the exposure times generally amount to 0 1 second to 1 minute, preferably 0 5 to 2 seconds, all of which deal with non-luminous flames and the distances between the substrate surfaces and the outer flame front are 0 2 to 5 cm, preferably 0.5 to 2 cm
- the substrate surfaces thus activated are, according to known methods, such as dipping, spraying or brushing, with aliphatic unsaturated monomers which are at least simply functionalized by a primary amino group (component I), with one or more aliphatic unsaturated monomers, at least one of which is by a primary amino group is functionalized (component II), component I and component II being different from one another, if appropriate in solution, coated Water and water / ethanol mixtures have proven to be suitable as solvents, but other solvents can also be used, provided they have a sufficient capacity for the monomers and the substrate surfaces wet well solutions with monomer contents of 1 to 10% by weight, for example about 5% by weight, have been found to be effective in practice and generally result in coherent coats covering the substrate surface with layers thick
- the graft copolymerization of the monomers applied to the activated surfaces can expediently be initiated by radiation in the short-wave segment of the visible region or in the long-wave segment of the UV region of the electromagnetic radiation.
- radiation from a UV excimer of the wavelengths 250 to 500 nm is very suitable. preferably from 290 to 320 nm
- mercury vapor lamps are suitable, provided they emit significant amounts of radiation in the areas mentioned: n
- the exposure times are generally 10 seconds to 30 minutes, preferably 2 to 15 minutes
- a graft copolymerization of the comonomer compositions according to the invention can also be achieved by a process which is described in European patent application 0 872 512 and is based on a graft polymerization of swollen monomer and initiator molecules.
- the monomer used for swelling can be component III
- Monomers which are at least simply functionalized by a primary amino group (components I and II) and optionally a further aliphatic unsaturated monomer
- Component III component I and component II being different from one another, show microbicidal or antimicrobial behavior even without grafting onto a substrate surface
- a further embodiment of the present invention consists in that the copolymerization of components I and II or I, II and II, component I and component II being different from one another, is carried out on a substrate
- Components I, II and III can be applied to the substrate in solution.
- suitable solvents are water, ethanol, methanol, methyl ethyl ketone, diethyl ether, dioxane, hexane, heptane, benzene, toluene, chloroform, dichloromethane, tetrahydrofuran and acetonitrile
- Component III can also serve for components I and II
- component III All aliphatic unsaturated monomers which undergo copolymerization with components I and II can be used as component III. Further aliphatic unsaturated monomers which are at least simply functionalized by a primary amino group can also be used as component III, in which case components I , II and III are all different from one another.
- acrylates or methacrylates for example acrylic acid, tert-butyl methacrylate or methyl methacrylate, styrene, vinyl chloride, vinyl ethers, acrylamides, acrylonitriles, olefins (ethylene, propylene, butylene, isobutylene), allyl compounds, Vinyl ketones, vinyl acetic acid, vinyl acetate or vinyl esters are used
- antimicrobial copolymers according to the invention can also be used directly, ie not by polymerizing the components on a substrate, but rather as an antimicrobial coating. Suitable coating methods are the application of the copolymers in solution or as a melt
- the solution of the polymers according to the invention can be applied to the substrates, for example by dipping, spraying or painting If the polymers according to the invention are produced directly on the substrate surface without grafting, customary radical initiators can be added
- the initiators that can be used include azonitriles, alkyl peroxides, hydroperoxides, acyl peroxides, peroxoketones, peresters, peroxocarbonates, peroxodisulfate, persulfate and all the usual photoinitiators such as acetophenones, ⁇ -hydroxyketones, dimethyl ketals and and benzophenone
- the polymerization can also be initiated thermally or, as already stated, by electromagnetic radiation, such as UV light or ⁇ radiation
- antimicrobial polymers according to the invention can also be used as components for the formulation of paints and varnishes
- the present invention further relates to the use of the antimicrobial polymers according to the invention for the production of antimicrobially active products and the products thus produced as such.
- the products can contain or consist of modified polymer substrates according to the invention.
- modified polymer substrates according to the invention are preferably based on polyamides, polyurethanes, polyether block amides, polyester amides or imides, PVC, polyolefins, silicones, polysiloxanes, polymethacrylate or polyterephthalates, which have surfaces modified with polymers according to the invention
- Antimicrobial products of this type are, for example, and in particular machine parts for food processing, components of air conditioning systems, roofing, bathroom and toilet articles, cake articles, components of sanitary facilities, components of animal cages and dwellings, toys, components in water systems, food packaging, operating elements (touch Panel) of devices and contact lenses
- the copolymers or graft copolymers according to the invention can be used wherever bacteria-free, ie microbicidal surfaces or surfaces with non-stick properties are important.
- Examples of uses for the copolymers or graft polymers according to the invention are, in particular, paints, protective coatings or coatings in the following areas
- Heat exchangers bioreactors, membranes, medical technology, contact lenses, diapers, membranes, implants
- the present invention also relates to the use of the polymer substrates modified according to the invention with the inventive polymers or processes on the surface for the production of hygiene products or medical articles.
- hygiene products are, for example, toothbrushes, toilet seats, combs and packaging materials other objects, which may come into contact with many people, such as telephone handset, handrail of stairs, door and window handles as well as holding straps and handles in public transport
- medical technology articles are e.g. catheters, tubes, cover foils or surgical cutlery
- Example 1 0.05 g of the product from Example 1 are placed in 20 ml of a test microbial suspension of Staphylococcus aureus and shaken. After a contact of 15 minutes, 1 ml of the test microbial suspension is removed, and the number of bacteria in the test mixture is determined. After this time, no Staphylococcus germs are found aureus more detectable
- Example 2 0.05 g of the product from Example 1 are placed in 20 ml of a test microbial suspension of Pseudomonas aeruginosa and shaken. After a contact time of 60 minutes, 1 ml of the test microbial suspension is removed, and the number of bacteria in the test mixture is determined. After this time, the number of bacteria is 10 7 dropped to 10 4
- Example 2 0.05 g of the product from Example 2 are placed in 20 ml of a test microbial suspension of Staphylococcus aureus and shaken After a contact time of 15 minutes, 1 ml of the test microbial suspension is removed, and the number of bacteria in the test mixture is determined. After this time the number of bacteria is 10 7 dropped to 10 2
- Example 2 0.05 g of the product from Example 2 are placed in 20 ml of a test microbial suspension of Pseudomonas aeruginosa and shaken. After a contact time of 60 minutes, 1 ml of the test microbial suspension is removed, and the number of bacteria in the test mixture is determined. After this time, the number of bacteria is 10 7 dropped to 10 4
- Example 3 0.05 g of the product from Example 3 is placed in 20 ml of a test microbial suspension of Staphylococcus aureus and shaken. After a contact time of 15 minutes, 1 ml of the test microbial suspension is removed, and the number of bacteria in the test mixture is determined. After this time, no Staphylococcus aureus bacteria are found more detectable
- Example 3 0.05 g of the product from Example 3 are placed in 20 ml of a test microbial suspension of Pseudomonas aeruginosa and shaken. After a contact time of 60 minutes, 1 ml of the test microbial suspension is removed, and the number of bacteria in the test mixture is determined. After this time, the number of bacteria is 10 7 dropped to 10 2
- Example 4 4 g of 3-aminopropyl vinyl ether (Aldrich), 2 g of N-3-aminopropyl methacrylamide hydrochloride (Polysciences Ine), 3 g of 2-aminoethyl methacrylate hydrochloride (Aldrich), and 70 ml of ethanol are combined in one Three-necked flasks were introduced and heated to 65 ° C. under a stream of argon. 0.18 g of azobisisobutyronitrile dissolved in 4 ml of ethyl methyl ketone were then slowly added dropwise with stirring. The mixture was heated to 70 ° C. and stirred at this temperature for 72 hours.
- reaction mixture was dissolved in 0.6 l of n-hexane is stirred in, the polymeric product precipitating. After filtering off the product, the filter residue is rinsed with 140 ml of n-hexane in order to remove residual monomers still present. The product is then dried in vacuo at 50 ° C. for 24 hours
- Example 4b 0.05 g of the product from Example 4 are placed in 20 ml of a test microbial suspension of Staphylococcus aureus and shaken After a contact time of 15 minutes, 1 ml of the test microbial suspension is removed, and the number of bacteria in the test mixture is determined. After this time the number of bacteria is 10 7 dropped to 10 1 Example 4b
- 0.05 g of the product from Example 4 are placed in 20 ml of a test microbial suspension of Pseudomonas aeruginosa and shaken. After a contact time of 60 minutes, 1 ml of the test microbial suspension is removed, and the number of bacteria in the test mixture is determined. After this time, the number of bacteria is 10 7 dropped to 10 1
- reaction mixture is stirred into 0.5 1 n-hexane, during which time the polymeric product precipitates after filtering off the product, the filter residue is rinsed with 100 ml of n-hexane in order to remove any residual monomers still present.
- the product is then dried in vacuo at 50 ° C. for 24 hours
- Example 5a 0.05 g of the product from Example 5 are placed in 20 ml of a test microbial suspension of Staphylococcus aureus and shaken. After a contact time of 15 minutes, 1 ml of the test microbial suspension is removed, and the number of bacteria in the test mixture is determined 10 7 dropped to 10 3
- Example 6 0.05 g of the product from Example 5 is placed in 20 ml of a test microbial suspension of Pseudomonas aeruginosa and shaken. After a contact time of 60 minutes, 1 ml of the test microbial suspension is removed, and the number of bacteria in the test mixture is determined. After this time, the number of bacteria is 10 7 dropped to 10 4
- Example 6
- reaction mixture is stirred into 0.5 l of n-hexane, the polymeric product precipitating; after filtering off the product, the filter residue is rinsed with 100 ml of n-hexane in order to remove any residual monomers still present.
- the product is then dried in vacuo at 50 ° C. for 24 hours.
- 0.05 g of the product from Example 6 are placed in 20 ml of a test germ suspension of Staphylococcus aureus and shaken. After a contact time of 15 minutes, 1 ml of the test microbial suspension is removed and the number of microbes in the test mixture is determined. After this time the number of germs has dropped from 10 7 to 10 4 .
- 0.05 g of the product from Example 6 are placed in 20 ml of a test germ suspension of Pseudomonas aeruginosa and shaken. After a contact time of 60 minutes, 1 ml of the test microbial suspension is removed, and the number of microbes in the test mixture is determined. After this time the number of germs has dropped from 10 7 to 10 4 .
Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP00912663A EP1183288A1 (de) | 1999-05-12 | 2000-03-30 | Mikrobizide copolymere |
AU45213/00A AU4521300A (en) | 1999-05-12 | 2000-03-30 | Microbicidal copolymers |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19921902A DE19921902A1 (de) | 1999-05-12 | 1999-05-12 | Mikrobizide Copolymere |
DE19921902.8 | 1999-05-12 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2000069937A1 true WO2000069937A1 (de) | 2000-11-23 |
Family
ID=7907836
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2000/002818 WO2000069937A1 (de) | 1999-05-12 | 2000-03-30 | Mikrobizide copolymere |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP1183288A1 (de) |
AU (1) | AU4521300A (de) |
DE (1) | DE19921902A1 (de) |
WO (1) | WO2000069937A1 (de) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2002080674A1 (de) * | 2001-04-06 | 2002-10-17 | Creavis Gesellschaft Für Technologie Und Innovation Mbh | Antimikrobielle konservierungssysteme für lebensmittel |
US8222456B2 (en) | 2004-01-23 | 2012-07-17 | The Trustees Of The University Of Pennsylvania | Facially amphiphilic polyaryl and polyarylalkynyl polymers and oligomers and uses thereof |
US8236800B2 (en) | 2003-03-17 | 2012-08-07 | The Trustees Of The University Of Pennsylvania | Facially amphiphilic polymers and oligomers and uses thereof |
US8889163B2 (en) | 2001-03-08 | 2014-11-18 | The Trustees Of The University Of Pennsylvania | Facially amphiphilic polymers as anti-infective agents |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10062201A1 (de) * | 2000-12-13 | 2002-06-20 | Creavis Tech & Innovation Gmbh | Verfahren zum Einsatz antimikrobieller Polymere im Bauten- und Denkmalschutz |
DE10110885A1 (de) * | 2001-03-07 | 2002-09-12 | Creavis Tech & Innovation Gmbh | Mokrobizide Trennsysteme |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1195615A (en) * | 1967-07-14 | 1970-06-17 | Celanese Corp | Treatment of Materials and Articles made from Polyesters |
US4961954A (en) * | 1987-04-10 | 1990-10-09 | University Of Florida | Surface modified surgical instruments, devices, implants, contact lenses and the like |
EP0891708A1 (de) * | 1997-07-17 | 1999-01-20 | The Procter & Gamble Company | Antimikrobielles Mittel |
US5871823A (en) * | 1996-06-19 | 1999-02-16 | Huels Aktiengesellschaft | Hydrophilic coating of surfaces of polymeric substrates |
-
1999
- 1999-05-12 DE DE19921902A patent/DE19921902A1/de not_active Withdrawn
-
2000
- 2000-03-30 EP EP00912663A patent/EP1183288A1/de not_active Withdrawn
- 2000-03-30 WO PCT/EP2000/002818 patent/WO2000069937A1/de not_active Application Discontinuation
- 2000-03-30 AU AU45213/00A patent/AU4521300A/en not_active Abandoned
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1195615A (en) * | 1967-07-14 | 1970-06-17 | Celanese Corp | Treatment of Materials and Articles made from Polyesters |
US4961954A (en) * | 1987-04-10 | 1990-10-09 | University Of Florida | Surface modified surgical instruments, devices, implants, contact lenses and the like |
US5871823A (en) * | 1996-06-19 | 1999-02-16 | Huels Aktiengesellschaft | Hydrophilic coating of surfaces of polymeric substrates |
EP0891708A1 (de) * | 1997-07-17 | 1999-01-20 | The Procter & Gamble Company | Antimikrobielles Mittel |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8889163B2 (en) | 2001-03-08 | 2014-11-18 | The Trustees Of The University Of Pennsylvania | Facially amphiphilic polymers as anti-infective agents |
WO2002080674A1 (de) * | 2001-04-06 | 2002-10-17 | Creavis Gesellschaft Für Technologie Und Innovation Mbh | Antimikrobielle konservierungssysteme für lebensmittel |
US8236800B2 (en) | 2003-03-17 | 2012-08-07 | The Trustees Of The University Of Pennsylvania | Facially amphiphilic polymers and oligomers and uses thereof |
US8455490B2 (en) | 2003-03-17 | 2013-06-04 | The Trustees Of The University Of Pennsylvania | Facially amphiphilic polymers and oligomers and uses thereof |
US9241917B2 (en) | 2003-03-17 | 2016-01-26 | The Trustees Of The University Of Pennsylvania | Facially amphiphilic polymers and oligomers and uses thereof |
US8222456B2 (en) | 2004-01-23 | 2012-07-17 | The Trustees Of The University Of Pennsylvania | Facially amphiphilic polyaryl and polyarylalkynyl polymers and oligomers and uses thereof |
US8716530B2 (en) | 2004-01-23 | 2014-05-06 | The Trustess Of The University Of Pennsylvania | Facially amphiphilic polyaryl and polyarylalkynyl polymers and oligomers and uses thereof |
Also Published As
Publication number | Publication date |
---|---|
EP1183288A1 (de) | 2002-03-06 |
DE19921902A1 (de) | 2000-11-16 |
AU4521300A (en) | 2000-12-05 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2001085813A2 (de) | Antimikrobielle, aminofunktionalisierte copolymere | |
EP1183281A1 (de) | Verfahren zur herstellung inhärent mikrobizider polymeroberflächen | |
WO2001072859A1 (de) | Antimikrobielle beschichtungen, enthaltend polymere von acrylsubstituierten alkylsulfonsäuren | |
WO2000069925A1 (de) | Verfahren zur herstellung inhärent mikrobizider polymeroberflächen | |
WO2001016193A1 (de) | Copolymere von acryloyloxyalkylaminoverbindungen | |
WO2000069933A1 (de) | Verfahren zur herstellung inhärent mikrobizider polymeroberflächen | |
EP1228112A1 (de) | Copolymere von acryloylaminoalkylverbindungen | |
EP1293123A1 (de) | Biozide Retardierungsformulierungen | |
WO2001087998A2 (de) | Antimikrobielle polymere und polymerblends aus polymeren alkylacrylamiden | |
WO2001014435A1 (de) | Copolymere des aminopropylvinylethers | |
EP1183291A1 (de) | Antimikrobielle copolymere | |
EP1183292A1 (de) | Mikrobizide copolymere | |
WO2000069934A1 (de) | Mikrobizide copolymere | |
WO2001062810A1 (de) | Copolymere von allylphosphoniumsalzen | |
WO2000069937A1 (de) | Mikrobizide copolymere | |
WO2000069935A1 (de) | Verfahren zur herstellung inhärent mikrobizider polymeroberflächen | |
DE19940697A1 (de) | Copolymere von Acryloyloxyalkylammoniumsalzen | |
DE19943344A1 (de) | Copolymere von Dialkylaminoalkylacrylamiden | |
DE19952222A1 (de) | Copolymere von Acryloylaminoalkylammoniumsalzen | |
DE19952221A1 (de) | Copolymere von Acryloyloxyalkyldialkylaminen | |
DE10123195A1 (de) | Elutionsfreie antimikrobielle Polymere | |
DE19955992A1 (de) | Copolymere von Acryloyloxyalkylbenzophenonammoniumsalzen | |
WO2004033568A1 (de) | Antimikrobielle beschichtungen und ein verfahren zu deren herstellung |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AU BR CA CN IL JP KR NO NZ PL RU US |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE |
|
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
WWE | Wipo information: entry into national phase |
Ref document number: 2000912663 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 09926508 Country of ref document: US |
|
WWP | Wipo information: published in national office |
Ref document number: 2000912663 Country of ref document: EP |
|
WWW | Wipo information: withdrawn in national office |
Ref document number: 2000912663 Country of ref document: EP |
|
NENP | Non-entry into the national phase |
Ref country code: JP |