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WO2001087998A2 - Polymeres et melanges d'alkylacrylamides polymeriques antimicrobiens - Google Patents

Polymeres et melanges d'alkylacrylamides polymeriques antimicrobiens Download PDF

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Publication number
WO2001087998A2
WO2001087998A2 PCT/EP2001/004640 EP0104640W WO0187998A2 WO 2001087998 A2 WO2001087998 A2 WO 2001087998A2 EP 0104640 W EP0104640 W EP 0104640W WO 0187998 A2 WO0187998 A2 WO 0187998A2
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Prior art keywords
antimicrobial
polymer
polymers
polymerization
formula
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PCT/EP2001/004640
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German (de)
English (en)
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WO2001087998A3 (fr
Inventor
Peter Ottersbach
Friedrich Sosna
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Creavis Gesellschaft Für Technologie Und Innovation Mbh
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Application filed by Creavis Gesellschaft Für Technologie Und Innovation Mbh filed Critical Creavis Gesellschaft Für Technologie Und Innovation Mbh
Priority to AU2001256322A priority Critical patent/AU2001256322A1/en
Publication of WO2001087998A2 publication Critical patent/WO2001087998A2/fr
Publication of WO2001087998A3 publication Critical patent/WO2001087998A3/fr

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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
    • 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
    • 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
    • C08F20/00—Homopolymers and 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
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/52—Amides or imides
    • C08F20/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F20/56—Acrylamide; Methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides

Definitions

  • Antimicrobial polymers and polymer blends made from polymers of alkyl acrylamides made from polymers of alkyl acrylamides
  • the invention relates to antimicrobial polymers made from alkyl acrylamides.
  • the invention further relates to a method for producing and using these antimicrobial polymers, in particular in polymer blends.
  • Mucus layers often form, which cause microbial populations to rise extremely, which have a lasting impact on the quality of water, beverages and food, and can even lead to product spoilage and consumer health damage.
  • Bacteria must be kept away from all areas of life where hygiene is important. This affects textiles for direct body contact, especially for the intimate area and for nursing and elderly care. In addition, bacteria must be kept away from furniture and device surfaces in care stations, in particular 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 infections and in toilets.
  • Another way of preventing surface bacteria from spreading is to incorporate antimicrobial substances into a matrix.
  • the copolymer produced with aminomethacrylates is only a matrix or carrier substance for added microbicidal active substances which can diffuse or migrate from the carrier substance. Polymers of this type lose theirs more or less quickly
  • the present invention is therefore based on the object, novel, antimicrobially active polymers, for. B. to develop as coatings. These are intended to effectively prevent the settlement and spread of bacteria, algae and fungi on surfaces.
  • coatings which contain antimil ⁇ obielle polymers, surfaces can be equipped so that an antimicrobial effect of these surfaces can be generated permanently, and resistant to solvents and physical stresses. These coatings do not contain low molecular weight biocides, which effectively rules out the migration of ecologically problematic substances over the entire period of use.
  • the present invention therefore relates to antimicrobial polymers which can be obtained by polymerizing a monomer of the formula I:
  • R 1 -H or -CH 3
  • R 2 branched or unbranched aliphatic hydrocarbon radical with 1 to 10
  • Carbon atoms or -HR 3 branched or unbranched aliphatic hydrocarbon radical with 1 to 10
  • Acrylic acid amide, methacrylic acid amide, methacrylic acid isopropylamide, acrylic acid tert-butylamide, N, N-dimethylacrylamide or N-isopropylacrylamide are preferably used as monomers of the formula I.
  • the invention therefore also relates to a process for the preparation of these antimil ⁇ -objective polymers by chemically, thermally or radiation-chemically induced radical polymerization of monomers of the formula I, optionally with at least one further aliphatic unsaturated monomer.
  • acrylic acid or methacrylic acid compounds such as.
  • methyl methacrylate, methyl acrylate, tert-butyl methacrylate, tert-butyl acrylate, butyl methacrylate, butyl acrylate, ethyl methacrylate, ethyl acrylate, propyl methacrylate, isopropyl methacrylate, propyl methacrylate, propyl acrylate and acrylic acid propyl ester are used.
  • the process can be carried out to produce the various embodiments of the polymers or copolymers according to the invention which will be described below.
  • the present invention further relates to antimilcrobial polymer blends which contain the abovementioned polymers of monomers of the formula I and at least one further polymer.
  • the antimicrobial polymers are produced by polymerizing monomers of the formula I with at least one further aliphatic unsaturated monomer.
  • the acrylic acid or methacrylic acid compounds already mentioned can be used as further aliphatic unsaturated monomers.
  • the other polymer in the polymer blend generally has no antimicrobial effect.
  • the production of the antimicrobial polymer blends can in principle by all methods known in the art, such as. B. "HG-Elias, Macromolecules, Vol. 2, 5th Edition, pp. 620 ff.”, Are described in detail.
  • the polymers when melt-mixing two pre-formed polymers, the polymers present as granules or powder on roller mills, in kneaders or with extruders. In the case of thermoplastics, this is heated above the glass or melting temperature.
  • mixing solutions independently prepared solutions of the two polymers in the same solvent are used.
  • polyurethanes polyamides, polyesters and ethers, polyether block amides, polystyrene, polyvinyl chloride, polycarbonates, polyorganosiloxanes, polyolefins, polysulfones, polyisoprene, polychloroprene, polytetrafluoroethylene (PTFE), polyterephthalates and / or their copolymers.
  • the antimilcrobial polymer in the polymer blend should have a proportion of 0.2 to 70, preferably 0.2 to 30, particularly preferably 1 to 20% by weight.
  • the antimicrobial polymers according to the invention or the corresponding blends can be applied to a surface as a coating by known methods, such as dipping, spraying or brushing the coating formulation.
  • Ethanol, methanol, water-alcohol mixtures, methyl ethyl ketone, diethyl ether, dioxane, hexane, heptane, benzene, toluene, chloroform, dichloromethane, tetrahydrofuran and acetonitrile have proven themselves as solvent constituents of the coating formulation, but other solvents can also be used if they are sufficient
  • solutions with solids contents of 3 to 80% by weight, for example approximately 10% by weight, have proven themselves in practice and generally result in coherent coatings covering the substrate surface with layer thicknesses which can be more than 0.1 ⁇ m.
  • the antimicrobial polymers according to the invention or the polymer blends as a coating can also be used as a melt, for. B. by coextrusion by dipping, spraying or Painting can be applied to the substrates.
  • antimicrobial polymers or polymer blends according to the invention can also be used as additives and components for the formulation of polymer blends, paints, varnishes and biocides.
  • polymers or polymer blends according to the invention are used as an additive or component in paints, lacquers or biocides, lower concentrations, for. B. in the lower percentage or alcohol range may be sufficient for an antimilcrobial effect.
  • the polymers can be obtained by graft-polymerizing a substrate with monomers of the formula I and optionally at least one aliphatic unsaturated monomer.
  • the grafting of the substrate enables the antimicrobial polymer to be covalently bound to the substrate. All polymeric materials, such as the plastics already mentioned, can be used as substrates.
  • the surfaces of the substrates can be activated by a number of methods before the graft polymerization. All standard methods for activating polymer surfaces can be used here; For example, the activation of the substrate before the graft polymerization can be carried out by UV radiation, plasma treatment, corona treatment, flame treatment, ozonization, electrical discharge or ⁇ radiation.
  • 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 e.g. B a UV excimer device
  • mercury vapor lamps are also suitable for substrate activation, provided that 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.
  • photosensitizer can also be used to activate the substrate before the graft polymerization with UV radiation.
  • the photosensitizer such as. B. Benzophenone applied to the substrate surface and 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 achieved according to the invention by plasma treatment using an RF or microwave plasma (Hexagon, Fa. Technics Plasma, 85551 Kirchheim, Germany) in air, nitrogen or argon atmosphere.
  • the exposure times are generally 2 seconds to 30 minutes, preferably 5 seconds to 10 minutes.
  • the energy input for laboratory devices is between 100 and 500 W, preferably between 200 and 300 W.
  • Corona devices (SOFTAL, Hamburg, Germany) can also be used for activation.
  • the exposure times in this case are usually 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 flame barrier front, can be built in a simple manner or, for example, can be obtained from ARCOTEC, 71297 Mönsheim, 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 due to intimate contact with a cooled metal surface on the side facing away from the flame side Substrate surface is easily reached.
  • the activation by flame treatment is accordingly limited to relatively thin, flat substrates.
  • the exposure times generally range from 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 graft polymerization 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.
  • Z. B the radiation of a UV excimer of the wavelengths 250 to 500 nm, preferably from 290 to 320 nm.
  • Mercury vapor lamps are also suitable here, provided that they emit considerable amounts of radiation in the ranges mentioned.
  • the exposure times are generally 10 seconds to 30 minutes, preferably 2 to 15 minutes.
  • initiators in the manufacture of the polymers according to the invention u. a.
  • Azonitriles, alkyl peroxides, hydroperoxides, acyl peroxides, peroxoketones, peresters, peroxocarbonates, peroxodisulfate, persulfate and all customary photoinitiators such as e.g. B. use acetophenones, ⁇ -hydroxy ketones, dimethyl ketals and and benzophenone.
  • the polymerization initiation can also be carried out thermally or, as already stated, by electromagnetic radiation, such as. B. UV light or ⁇ radiation.
  • antimicrobial polymers or polymer blends according to the invention for the production of antimicrobially active products.
  • Such products are preferably based on polyamides, polyurethanes, polyether block amides, polyester amides or imides, PVC, polyolefins, silicones, polysiloxanes, polymethacrylate or polyterephthalates, metals, glasses and ceramics, which have surfaces coated with polymers or blends according to the invention.
  • Antimilcrobially active products of this type are, for example, machine parts for food processing, components of air conditioning systems, coated pipes, semi-finished products, roofing, bathroom and toilet articles, kitchen 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 polymers or blends according to the invention can be used wherever there is a lack of bacteria, algae and fungi, i.e. microbicidal surfaces or surfaces with non-stick properties.
  • Examples of use for the polymers or polymer blends according to the invention, for. B. as a coating of a substrate can be found in the following areas:
  • Marine ship hulls, port facilities, buoys, drilling platforms, ballast water tanks House: roofs, cellars, walls, facades, greenhouses, sun protection, garden fences, wood protection, tarpaulins, textile fabrics - Sanitary: Public toilets, bathrooms, shower curtains, toiletries, swimming pool, sauna, joints , Sealing compounds
  • Machine parts air conditioners, ion exchangers, process water, solar systems, heat exchangers, bioreactors, membranes
  • Medical technology contact lenses, diapers, membranes, implants, catheters, tubes, cover foils, surgical cutlery
  • Articles of daily use car seats, clothing (stockings, sportswear), hospital furnishings, door handles, telephone receivers, public transport, animal cages, cash registers, carpeting, wallpapers, telephone receivers, handrails for meetings, door and door handles
  • the polymers or polymer blends can also be used in the form of lacquers, protective coatings or coatings. Here it makes sense to use existing paint systems such as B. to use acrylic paints.
  • the polymers or polymer blends can also be used as a paint additive in the maritime sector, in particular when avoiding barnacle larvae on ship hulls, generally as an additive in an antifouling paint, here in particular in saline seawater.
  • antimicrobial polymers or polymer blends according to the invention can be used as additives in the formulation of cosmetic products, e.g. for pastes and ointments.
  • the proportion of polymers or polymer blends according to the invention can be reduced here, depending on the effectiveness of the polymer and the formulation, down to the lower percent or per mille range.
  • the polymers or polymer blends according to the invention are furthermore used as a biofouling inhibitor, in particular in cooling circuits.
  • a biofouling inhibitor in particular in cooling circuits.
  • microbicidal substances such as formalin is not possible with open cooling systems, as are common in power plants or chemical plants.
  • microbicidal substances are often highly corrosive or foam-forming, which prevents use in such systems.
  • the dispersed form of the polymers or their blends can be in the manufacturing process itself z. B. by emulsion polymerization, precipitation or suspension polymerization or subsequently by grinding z. B. can be obtained in a jet mill.
  • the particles obtained in this way are preferably used in a size distribution of 0.001 to 3 mm (as ball diameter), so that on the one hand a large surface is available for killing the bacteria or algae, and on the other hand where necessary, the separation from the cooling water, for. B. is easily possible by filtration.
  • the method can e.g. B. be exercised in such a way that part (5-10%) of the polymers / blends used are continuously removed from the system and replaced by a corresponding amount of fresh material.
  • antimicrobial copolymer / blend can be added, if necessary, while checking the bacterial count of the water.
  • 0.1 - 100 g of antimicrobial polymer or its blends per m 3 of cooling water are sufficient.
  • the product is then dried in vacuo at 50 ° C. for 24 hours.
  • 2 g of the product are dissolved in 10 g of tetrahydrofuran and applied to a 0.5 cm thick and 2 by 2 cm aluminum plate using a 100 micrometer doctor blade.
  • the plate is then dried at 50 ° C for 24 hours.
  • Example la The coated side of the aluminum plate from Example 1 is placed on the bottom of a beaker containing 20 ml of a test germ suspension of Staphylococcus aureus contains and shaken. After a contact time of 3 hours, 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 decreased from 10 7 to 10 3 germs per ml.
  • Example 1 The coated aluminum side of Example 1 is placed on the bottom of a beaker containing 20 ml of a test microbial suspension of Pseudomonas aeruginosa and shaken. After a contact time of 6 hours, 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 decreased from 10 7 to 10 4 germs per ml.
  • the product is then dried for 24 hours at 50 ° C. in a vacuum. 2 g of the product are dissolved in 10 g of tetrahydrofuran and applied to a 0.5 cm thick and 2 by 2 cm aluminum plate using a 100 micrometer doctor blade. After a contact time of 6 hours, 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 decreased from 10 7 to 10 3 germs per ml.
  • Example 2 The coated aluminum side of Example 2 is placed on the bottom of a beaker containing 20 ml of a test germ suspension of Staphylococcus aureus and shaken. After a contact time of 3 hours, 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 decreased from 10 7 to 10 4 germs per ml.
  • Example 2b
  • Example 2 The coated aluminum side of Example 2 is placed on the bottom of a beaker containing 20 ml of a test microbial suspension of Pseudomonas aeruginosa and shaken. After a contact time of 6 hours, 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 decreased from 10 7 to 10 4 germs per ml.
  • the product is then dried in vacuo at 50 ° C. for 24 hours.
  • 2 g of the product are dissolved in 10 g of tetrahydrofuran and applied to a 0.5 cm thick and 2 by 2 cm aluminum plate using a 100 micrometer doctor blade.
  • the plate is then dried at 50 ° C for 24 hours.
  • Example 3 The coated aluminum side of Example 3 is placed on the bottom of a beaker containing 20 ml of a test germ suspension of Staphylococcus aureus and shaken. After a contact time of 4 hours, 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 decreased from 10 7 to 10 3 germs per ml.
  • the aluminum plate from Example 3 is placed with its coated side up on the bottom of a beaker containing 20 ml of a test microbial suspension of Pseudomonas aeruginosa and shaken. After a contact time of 8 hours, 1 ml of Test microbial suspension removed, and the number of bacteria in the test batch determined. After this time the number of germs has decreased from 10 7 to 10 4 germs per ml.
  • Example 4 The coated aluminum side of Example 4 is placed on the bottom of a beaker containing 20 ml of a test germ suspension of Staphylococcus aureus and shaken. After a contact time of 4 hours, 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 decreased from 10 7 to 10 4 germs per ml.
  • Example 4 The coated aluminum side of Example 4 is placed on the bottom of a beaker containing 20 ml of a test microbial suspension of Pseudomonas aeruginosa and shaken. After a contact time of 8 hours, 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 decreased from 10 7 to 10 4 germs per ml.
  • the product is then dried in vacuo at 50 ° C. for 24 hours.
  • 6 g of the product are dissolved in 32 g of diisononyl phthalate.
  • 64 g of polyvinyl chloride granules are added to this mixture, the mixture being stirred intimately until it becomes pasty.
  • 20 g of the paste obtained are spread onto a metal plate using a doctor blade in such a way that a layer thickness of 0.7 mm is established.
  • the plate with the paste on it is then heated to 200 ° C. for 2 minutes, during which the paste gels and a soft PVC film is formed.
  • Example 5a A 3 by 3 cm piece of the soft PVC film from Example 5 is placed on the bottom of a beaker containing 20 ml of a test germ suspension of Staphylococcus aureus and shaken. After a contact time of 3 hours, 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 decreased from 10 7 to 10 4 germs per ml.
  • a 3 by 3 cm piece of the soft PVC film from Example 5 is placed on the bottom of a beaker containing 20 ml of a test germ suspension of Pseudomonas aeruginosa and shaken. After a contact time of 6 hours, 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 decreased from 10 7 to 10 4 germs per ml.
  • the product is then dried in vacuo at 50 ° C. for 24 hours.
  • 2 g of the product are mixed in 32 g of Isononyl phthalate dissolved.
  • 64 g of polyvinyl chloride granules are added to this mixture, the mixture being stirred intimately until it becomes pasty.
  • 20 g of the paste obtained are spread onto a metal plate using a doctor blade in such a way that a layer thickness of 0.7 mm is established.
  • the plate with the paste on it is then heated to 200 ° C. for 2 minutes, during which the paste gels and a soft PVC film is formed.
  • a 3 by 3 cm piece of the soft PVC film from Example 6 is placed on the bottom of a beaker containing 20 ml of a test germ suspension of Staphylococcus aureus and shaken. After a contact time of 3 hours, 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 .
  • Example 6b A 3 by 3 cm piece of the soft PVC film from Example 6 is placed on the bottom of a beaker containing 20 ml of a test germ suspension of Pseudomonas aeruginosa and shaken. After a contact time of 6 hours, 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 5 .
  • the product is then dried in vacuo at 50 ° C. for 24 hours.
  • 2 g of the product are dissolved in 32 g of diisononyl phthalate.
  • 64 g of polyvinyl chloride granules are added to this mixture, the mixture being stirred intimately until it becomes pasty.
  • 20 g of the paste obtained are spread onto a metal plate with a squeegee in such a way that they set a layer thickness of 0.7 mm.
  • the plate with the paste on it is then heated to 200 ° C. for 2 minutes, the paste gelling and a soft PVC film being produced.
  • a 3 by 3 cm piece of the soft PVC film from Example 7 is placed on the bottom of a beaker containing 20 ml of a test germ suspension of Staphylococcus aureus and shaken. After a contact time of 3 hours, 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 .
  • a 3 by 3 cm piece of the soft PVC film from Example 7 is placed on the bottom of a beaker containing 20 ml of a test germ suspension of Pseudomonas aeruginosa and shaken. After a contact time of 6 hours, 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 5 .
  • Example 8 12 g of acrylic acid tert-butylamide (from Aldrich) and 90 ml of ethanol are placed in a three-necked flask and heated to 65 ° C. under a stream of argon. Then 0.23 g of azobisisobutyronitrile dissolved in 6 ml of ethyl methyl ketone are slowly added dropwise with stirring. The mixture is heated to 70 ° C. and stirred at this temperature for 72 hours. After this time, the reaction mixture is stirred into 0.5 1 of water, the polymeric product precipitating. After filtering off the product, the filter residue is rinsed with 20 ml of n-hexane in order to remove any remaining monomers. The product is then dried for 24 hours at 50 ° C in a vacuum. 5 g of the product are stirred into 95 g of an acrylic varnish called Rowacryl G-31293 from ROWA.
  • a 5 x 5 cm aluminum plate is treated with the one treated in this way Brush acrylic paint from Example 8 and then dry in a drying cabinet at 35 ° C for 24 hours.
  • This aluminum plate is placed with its coated side up on the bottom of a beaker containing 20 ml of a test germ suspension of Staphylococcus aureus and shaken. After a contact time of 3 hours, 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 .
  • a 5 x 5 cm aluminum plate is coated with the acrylic lacquer treated in this way from Example 8 and then dried in a drying cabinet at 35 ° C. for 24 hours.
  • This aluminum plate is placed with its coated side up on the bottom of a beaker containing 20 ml of a test microbial suspension of Pseudomonas aeruginosa and shaken. After a contact time of 6 hours, 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 .
  • a 5 x 5 cm aluminum plate is coated with the acrylic lacquer treated in this way from Example 9 and then dried in a drying cabinet at 35 ° C. for 24 hours.
  • This aluminum plate is with its coated side facing up placed on the bottom of a beaker containing 20 ml of a test germ suspension of Staphylococcus aureus and shaken. After a contact time of 3 hours, 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 .
  • a 5 x 5 cm aluminum plate is coated with the acrylic lacquer treated in this way from Example 9 and then dried in a drying cabinet at 35 ° C. for 24 hours.
  • This aluminum plate is placed with its coated side up on the bottom of a beaker containing 20 ml of a test microbial suspension of Pseudomonas aeruginosa and shaken. After a contact time of 6 hours, 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 5 .
  • the product is then dried for 24 hours at 50 ° C in a vacuum. 5 g of the product are stirred into 95 g of Plextol D 510 from PolymerLatex, an aqueous dispersion of a methacrylic acid ester / acrylic acid ester copolymer.
  • Example 10 Spread the dispersion from Example 10 and then dry it in a drying cabinet at 35 ° C. for 24 hours.
  • This aluminum plate is placed with its coated side up on the bottom of a beaker containing 20 ml of a test microbial suspension Contains and shaken Staphylococcus aureus. After a contact time of 3 hours, 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 .
  • a 5 x 5 cm aluminum plate is coated with the dispersion from Example 10 treated in this way and then dried in a drying cabinet at 35 ° C. for a period of 24 hours.
  • This aluminum plate is placed with its coated side up on the bottom of a beaker containing 20 ml of a test microbial suspension of Pseudomonas aeruginosa and shaken. After a contact time of 6 hours, 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 5 .
  • Example 11 12 g of isopropyl methacrylamide (Aldrich) and 90 ml of ethanol are placed in a three-necked flask and heated to 65 ° C. under a stream of argon. Then 0.23 g of azobisisobutyronitrile dissolved in 6 ml of ethyl methyl ketone are slowly added dropwise with stirring. The mixture is heated to 70 ° C. and stirred at this temperature for 72 hours. After this time, the reaction mixture is stirred into 0.5 1 n-hexane, the polymeric product precipitating. After filtering off the product, the filter residue is rinsed with 20 ml of n-hexane in order to remove any remaining monomers.
  • the product is then dried for 24 hours at 50 ° C in a vacuum. 2 g of the product are stirred into 98 g of Plextol D 510 from PolymerLatex, an aqueous dispersion of a methacrylic acid ester / acrylic acid ester copolymer.
  • a 5 by 5 cm aluminum plate is coated with the dispersion from Example 11 treated in this way and then dried in a drying cabinet at 35 ° C. for 24 hours.
  • This aluminum plate is placed with its coated side up on the bottom of a beaker containing 20 ml of a test germ suspension of Staphylococcus aureus and shaken. After a contact time of 3 hours, 1 ml taken from the test microbial suspension, and the number of microbes determined in the test batch. After this time, the number of germs has dropped from 10 7 to 10 5 .
  • Example 11b Using a brush, a 5 by 5 cm aluminum plate is coated with the dispersion from Example 11 treated in this way and then dried in a drying cabinet at 35 ° C. for a period of 24 hours. This aluminum plate is placed with its coated side up on the bottom of a beaker containing 20 ml of a test microbial suspension of Pseudomonas aeruginosa and shaken. After a contact time of 6 hours, 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 5 .

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  • Agronomy & Crop Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Environmental Sciences (AREA)
  • Materials Engineering (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
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Abstract

L'invention concerne des polymères antimicrobiens ou leurs mélanges de polymères obtenus par polymérisation d'un monomère de la formule (I), où R1 = -H ou -CH¿3? ; R2 = H, un reste de carbure d'hydrogène aliphatique ramifié ou non ramifié avec 1 à 10 atomes de carbone et R?3¿ = H, un reste de carbure d'hydrogène aliphatique ramifié ou non ramifié avec 1 à 10 atomes de carbone et éventuellement leur mélange ultérieur avec au moins un autre polymère. Les polymères ou mélanges de polymères antimicrobiens peuvent être utilisés comme revêtement microbicide de substrats ainsi que dans des vernis ou des peintures protectrices.
PCT/EP2001/004640 2000-05-17 2001-04-25 Polymeres et melanges d'alkylacrylamides polymeriques antimicrobiens WO2001087998A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2001256322A AU2001256322A1 (en) 2000-05-17 2001-04-25 Antimicrobial polymers and polymer blends made of polymer alkyl acrylamides

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2000124270 DE10024270A1 (de) 2000-05-17 2000-05-17 Antimikrobielle Polymere und Polymerblends aus polymeren Alkylacrylamiden
DE10024270.7 2000-05-17

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WO2001087998A2 true WO2001087998A2 (fr) 2001-11-22
WO2001087998A3 WO2001087998A3 (fr) 2004-03-25

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AU (1) AU2001256322A1 (fr)
DE (1) DE10024270A1 (fr)
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WO2002069709A1 (fr) * 2001-03-08 2002-09-12 Creavis Gesellschaft Für Technologie Und Innovation Mbh Systemes de fluides microbicides contenant des polymeres antimicrobiens
WO2002080674A1 (fr) * 2001-04-06 2002-10-17 Creavis Gesellschaft Für Technologie Und Innovation Mbh Systemes de conservation antimicrobiens pour produits alimentaires
DE10235948A1 (de) * 2002-08-06 2004-03-04 Envicon Klärtechnik Verwaltungsgesellschaft mbH Durchströmter Hohlkörper
CN104358104A (zh) * 2014-11-07 2015-02-18 江南大学 一种利用电子辐射技术制备抗菌纺织品的方法
US10138307B2 (en) 2013-01-31 2018-11-27 Fachhochschule Münster Antimicrobial polymer

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DE10110885A1 (de) * 2001-03-07 2002-09-12 Creavis Tech & Innovation Gmbh Mokrobizide Trennsysteme
DE10137978A1 (de) * 2001-08-02 2003-02-13 Creavis Tech & Innovation Gmbh Antimikrobielle Reinigungsmittel
DE10319652A1 (de) * 2003-05-02 2004-11-25 Ophardt Hygiene Technik Gmbh & Co Kg Vorrichtungen mit verbesserter Hygiene
WO2006032603A1 (fr) * 2004-09-24 2006-03-30 Abb Research Ltd Dispositif de prehension
DE102006023415A1 (de) 2006-05-17 2007-11-22 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verwendung von aminmodifizierten Siloxanen als Schutzmittel in Beschichtungen und Werkstücken
DE102008048385A1 (de) * 2008-09-22 2010-03-25 Behr Gmbh & Co. Kg Klimaanlage und Verfahren zur Herstellung einer Klimaanlage
DE102009040089A1 (de) * 2009-09-04 2011-07-21 Beiersdorf AG, 20253 Zubereitungen mit wasserunlöslichen polymeren Aminen zur Verminderung von Körpergeruch
DE102009047589B4 (de) 2009-12-07 2014-01-16 Kuraray Europe Gmbh Verfahren zur Beschichtung von Substraten mit antimikrobiellen Beschichtungsmassen auf Basis von Polyvinylacetalen
WO2014097309A1 (fr) 2012-12-17 2014-06-26 Asian Paints Ltd. Revêtement autonettoyant répondant à des stimuli
CN110194889B (zh) * 2018-02-27 2022-11-15 嘉丰工业科技（惠州）有限公司 一种制备抗微生物附着的改性热塑性塑料及产品的方法及用于制备改性热塑性塑料的组合物

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002069709A1 (fr) * 2001-03-08 2002-09-12 Creavis Gesellschaft Für Technologie Und Innovation Mbh Systemes de fluides microbicides contenant des polymeres antimicrobiens
WO2002080674A1 (fr) * 2001-04-06 2002-10-17 Creavis Gesellschaft Für Technologie Und Innovation Mbh Systemes de conservation antimicrobiens pour produits alimentaires
DE10235948A1 (de) * 2002-08-06 2004-03-04 Envicon Klärtechnik Verwaltungsgesellschaft mbH Durchströmter Hohlkörper
US10138307B2 (en) 2013-01-31 2018-11-27 Fachhochschule Münster Antimicrobial polymer
CN104358104A (zh) * 2014-11-07 2015-02-18 江南大学 一种利用电子辐射技术制备抗菌纺织品的方法

Also Published As

Publication number Publication date
WO2001087998A3 (fr) 2004-03-25
DE10024270A1 (de) 2001-11-22
AU2001256322A1 (en) 2001-11-26

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