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WO1991012282A1 - Copolymeres avec action anti-microbienne inherente - Google Patents

Copolymeres avec action anti-microbienne inherente Download PDF

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Publication number
WO1991012282A1
WO1991012282A1 PCT/US1991/000926 US9100926W WO9112282A1 WO 1991012282 A1 WO1991012282 A1 WO 1991012282A1 US 9100926 W US9100926 W US 9100926W WO 9112282 A1 WO9112282 A1 WO 9112282A1
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Prior art keywords
copolymer
monomer
vinyl monomer
alkyl
independently
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Inventor
Alan D. Olstein
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HB Fuller Licensing and Financing Inc
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HB Fuller Licensing and Financing Inc
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C271/06—Esters of carbamic acids
    • C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
    • C07C271/10—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C271/12—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
    • 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
    • A01N25/08—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 containing solids as carriers or diluents
    • A01N25/10—Macromolecular compounds
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/12—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, neither directly attached to a ring nor the nitrogen atom being a member of a heterocyclic ring
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • 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
    • C08F246/00—Copolymers in which the nature of only the monomers in minority is defined

Definitions

  • This invention relates to copolymers with inherent antimicrobial activity that can be used in typical polymer applications.
  • the invention f rther relates to an inherently antimicrobial polymer latex and particularly to adhesive emulsions containing such copolymers. It further relates to inherently antimicrobial films and fibers comprising such copolymers.
  • Biocidal agents can be added to polymer compositions or articles to serve this function.
  • a biocidal agent cannot always be used.
  • the cost and the complexity of forming the film or fiber, adhesive composition, etc., with the antimicrobial can be prohibitive or detrimental to polymer properties.
  • Quaternary ammonium polymers are known to have biocidal properties.
  • U.S. Patent No. 4,532,128 illustrates certain quaternary ammonium polymers useful as preservatives for opthalmic solutions, hair care products, and topical pharmaceutical products.
  • U.S. Patent No. 4,429,096 relates to quarternary amine carbamate or urea compounds.
  • the compounds may be combined with acrylamide to yield oligomers used in water clarification, flocculation, and hair spray application.
  • the growth of a variety of organisms on surfaces and in bulk materials has been a problem for many years. Organisms taking the form of both unicellular and multi-cellular forms have caused infection in humans and other animals, spoilage of foods, caused chemical degradation of a variety of chemicals, and have foiled surfaces in marine environments. In many other areas, the growth of unicellular and multi-cellular organisms has been a cause of substantial economic loss and operational difficulty.
  • contamination with typically unicellular microorganisms can often degrade natural and synthetic polymers causing substantial reduction in the desirable physical and chemical properties of a number of feedstocks.
  • the infection of skin surfaces or wounds can cause significant illness, fever, and potential loss of limbs or lives of affected individuals.
  • compositions intended for the controlled release of a disinfectant from a film of stabilized hydrophilic polymer are disclosed in U.S. Pat. No. 3,966,902.
  • the polymer complexes are stabilized as a metal complex by the addition of an inorganic aluminum, zirconium or zinc salt, such as aluminum chloride, to the polymerization mixture.
  • the stabilization adjuvant is necessary because, upon contact with water, such films of simple hydrogels become highly swollen and rapidly elute their additives. Further, dry films, both simple and metal complexed hydrogels, do not adhere well to ceramic and other hard surfaces and can lose their adhesion completely when wetted.
  • Other antimicrobial agents have been combined with film-forming polymeric materials and have been used in the absence of a polymeric carrier.
  • U.S. Pat. No. 3,325,436 discloses bacterial resistant latexes that incorporate alpha, alpha'-azobis(chloroformamadine) .
  • U.S. Pat. No. 2,689,837 discloses polymeric vinyl halides having improved resistance to deterioration caused by fungal and bacterial attack, which incorporate copper 8-quinolinolate into the polymer.
  • U S. Pat. No. 3,577,516 discloses a spray-on bandage material using acrylate or methacrylate polymers that may contain germicides or fungicides. Phenols and thiophenols are well-known antimicrobial agents and have been incorporated into polymeric compounds.
  • 2,875,097 discloses the incorporation of phenolic compounds into polymers comprising heterocyclic nitrogen compounds. These polymers are typically used to render fabrics resistant to fungi and insect attack.
  • U.S. Pat. No. 2,873,263 discloses an antibacterial polymeric resin used for fabricating plastic articles. These resins are formed by polymerizing an unsaturated monomer such as an alkyl acrylate in the presence of certain aromatic phenols or phenolic analogs.
  • the invention provides a polymeric composition that yields biocidal polymers which may be incorporated into adhesives, latexes, fibers, fabrics, films, bulk polymer, etc.
  • the biocidal polymer inherently prevents growth of organisms through the presence of strongly biocidal groups in the copolymer or by adding the biocidal copolymer to another polymer biological degradation and may also be used as an anti-fouling coating and in water treatment applications.
  • the present invention provides an antimicrobial composition comprising a polymer made from a monomer having the active functional group according to the following general formula:
  • each R' is independently an H or Ci.s alkyl; each R is independently a C ⁇ * alkyl, C 1 . 2 alkyl substituted aryl, or a benzyl; and the molecular weight of the copolymer is at least about 20,000 weight average molecular weight. While the copolymer of the present invention may have a lower molecular weight, polymers having a weight of about 20,000 or greater provide preferable physical properties including viscosity, wetability when the polymer is used in solution, and osmotic responsiveness.
  • the polymeric material can be incorporated into an adhesive matrix, polymeric fibers, polymeric substrates, etc. Alternatively it may be used as an additive to adhesives, latexes, etc. When incorporated or added to polymers, the polymer displays biocidal properties.
  • Polymeric materials utilizing the biocide of the present invention can be a copolymer (a polymeric material having two or more monomer constituents), an oligopolymer (a relatively low molecular weight polymer), a terpolymer (a polymeric material having three or more monomers) , etc.
  • the invention also relates to a method of making polymeric substrates, polymeric compositions or any composition capable of receiving an additive as antimicrobial. Detailed Description of the Invention
  • the present invention discloses polymeric materials that have incorporated therein monomers having an antimicrobial activity.
  • the antimicrobial monomer may be polymerized into polymeric materials or antimicrobial polymers that may be added to other polymers.
  • the instant antimicrobial composition can be used in polymeric matrices such as adhesives, lubricants, latexes, etc.
  • the biocidal polymers of the present invention can be used in polymeric compositions that are often degraded by microrganisms or bacteria.
  • the instant antimicrobial composition may be applied in a number of ways.
  • Antimicrobial monomers can be copolymerized in an adhesive composition, latex composition, or materials such as fibers, films, adhesive substrates, etc., or may be incorporated in adhesives, latexes, etc., as an additive.
  • Possible polymeric materials in which the present invention may be incorporated into are vinyls, polyesters, polycarbonates, and the like.
  • the antimicrobial may be used at a concentration of about 0.001 to about 1 wt-%.
  • the onomeric materials used in preparing the biocidal polymers of the invention can be made by preparing a monomeric quaternary ammonium structure shown below.
  • the above monomer is copolymerized with at least one other vinyl monomer.
  • the quaternary monomer may comprise up to 99 mole percent of the copolymer, but has a preferred range of about 10-50 mole percent.
  • the percentage of the antimicrobial monomer and other monomers will vary depending on the required antimicrobial activity, required physical and chemical polymer properties, costs, etc.
  • the synthesis of the present invention begins with the synthesis of the quaternary monomer compound below.
  • quaternary amine monomer compounds of the invention are prepared by reacting a monoisocyanate " compound with a quaternary ammonium compound having a group with a reactive hydrogen compound.
  • the preferred monoisocyanate compound of the invention is the compound having a single polymerizable vinyl group and a single mono isocyanate group.
  • polymerization occurs through the vinyl group.
  • the formation of the quaternary compound occurs by reaction between the isocyanate group and the active hydrogen of the quaternary compound.
  • Preferred quaternary compounds comprise quaternary substituted alkanols and quaternary substituted alkyl amines.
  • the hydroxyl group of the alcohol is reacted with the isocyanate group producing a carbamate linkage.
  • the quaternary substituted amine compound is reacted with the isocyanate group producing a urea linkage.
  • the quaternary monomers of the invention can be prepared by reacting an isocyanate compound with a compound having an active hydrogen and amine functionality. That post reaction can be quaternized using conventional reactions. It is envisioned that amine functionality on the formed polymer material can be quaternized post polymerization. However, the preferred mode is to quaternize the amine prior to reaction with the isocyanate group or to quaternize the monomer after carbamate or urea formation.
  • the quaternary monomer compound can be polymerized with any number of comonomers to form either a latex or solution copolymer.
  • the vinyl unsaturated monomer can be an alpha- olefin monomer such as ethylene, propylene, butylene, isobutylene, hexene; styrene, alpha methylstyrene, vinyl chloride, vinyl acetate, acrylonitrile, ricinoleic acid, oleic acid, linoleic acid, butadiene, and the like.
  • Useful acrylic monomers include methacrylate, methylmethacrylate , hydroalkyl acrylate, hydroxy alkyl methacrylate, butyl acrylate, hexyl acrylate, cyclohexylacrylate, (2- hydroxyethyl) ethacrylate, (2- hydroxyethyl) ethacrylate, (2-hydroxyethyl) acrylate, (3-hydroxypropyl) ethacrylate,
  • SUBSTITUTESHEET (3-hydroxypropyl) acrylate, (3-hydroxypropyl) ethacrylate, (dimethylamino-ethyl) ethacrylate (pipiridinoethyl) methacrylate, (morpholinoethyl) methacrylate, and the like.
  • Useful unsaturated dicarboxylic acids include itaconic acid, aconitic acid, cinnamic acid, crotonic acid, mesaconic acid, maleic acid, fumaric acid, and the like; alpha, beta unsaturated dicarboxylic acid esters of the dicarboxylic acid esters described above including aromatic esters, cycloalkyl esters, alkyl esters, hydroxy alkyl esters, alkoxy alkyl esters, and the like.
  • Vinyl heterocyclic monomers which are useful in the present invention include 2-vinyl pyrrolidone, n-vinyl pyridine, and vinyl epsilon captrolactam among others.
  • cycloalkyl ester includes mono, bi and tricycloalkyl esters and the term “aromatic ester” includes heteroaromatic esters.
  • comonomers include vinyl monomers having glycidyl or other epoxy functional groups. Also useful are comonomers such as 7-methacryloxypropyl trimethoxysilane, allyl trimethoxysilane, 2-allyl phenol, N-allyl morpholine, allyl glycidyl ether, allyl cinnamate, and allyl undecylenate among others. Other comonomers useful in the present invention include perfluoroalkyl acrylates such as 2,2,2 trifluoroethyl acrylate, and 1H, 1H, 11H eicrafluoroundecyl acylate.
  • These monomers when polymerized with the quaternary monomer of the present invention are capable of preventing icrofouling and macrofouling.
  • This composition provides antifouling properties without the release of environmentally contaminating agents such as elemental tin or copper.
  • This composition has the potential for eliminating the need for ship dry-docking altogether.
  • the copolymer of the present invention should generally have an average molecular weight of about 20,000 to 10
  • SUBSTITUTESHEET million with a preferred range of molecular weights falling in excess of 2 million.
  • copolymers utilizing acrylamide of U.S. Patent No. 4,429,096 are not envisioned to be used with the present invention.
  • a copolymer of the quaternary amine compound of U.S. Patent No. 4,429,096 and acrylamide In order for a copolymer of the quaternary amine compound of U.S. Patent No. 4,429,096 and acrylamide to be water soluble, useful in water clarification, and useful in hair sprays as described in the specification, molecular weights of the polymers has to remain fairly low.
  • U.S. Patent No. 4,429,096 discloses polymers which, in their final form, are aqueous soluble acrylamide polymers incapable of becoming insoluble or emulsion polymers through radical reaction mechanisms.
  • the polymers of the present invention are formed from monomers which are chemically reactive through radical mechanisms to form, aqueous insoluble cross-linked antimicrobial materials.
  • the resulting emulsified or dispersed polymers are capable of forming a biologically active film on a chosen surface of deposition.
  • the polymers of the present invention provide a mix of polar and nonpolar character which maintains the polymeric film on the surface of deposition and has a hydroscopic nature which facilitates the biocidal action of the polymer.
  • the proportions of each monomer can vary widely.
  • the vinyl monomer may generally range from 1-99 mole percent and the monomer of the present invention may generally range from 1-99 mole percent, preferably from about 1 mole- % to 50 mole-% and most preferably from about 1-25 mole-% in latex polymer systems.
  • concentration of monomer of the present invention is substantially similar to that of latex polymers.
  • use of an organic solvent may tend to allow a greater concentration of active antimicrobial monomer.
  • SUBSTITUTESHEET proportions will vary according to the necessary antimicrobial action desired, the economics of employing a large amount of antimicrobials, and the requirements of the physical properties of the polymers such as strength, melting point, etc.
  • the polymerization can be generally carried out in a closed vessel under heated conditions to form either a latex or solution polymers.
  • Solution polymerization is generally carried out with the monomers in solution in an inert organic solvent such as tetrahydrofuran, methyl ethyl ketone, acetone, ethyl acetate, or other suitable solvents such as organic C 2 . alkanols.
  • Organic solvents can also be mixed with compatible amounts of water in emulsion or inverse emulsion systems. Preferred solvents are nontoxic and odorless.
  • Monomeric starting materials to form the biocidal polymers of the invention are typically dissolved or suspended in the solvent to a desired concentration.
  • the polymerization of the invention is typically performed at a concentration of about 12-60 wt-% of the monomers, preferably 2-25 wt-% of the monomers in the solvent material, although higher or lower concentrations may be employed depending on the given antimicrobial efficacy needed for any given application.
  • Polymerization reactions are typically initiated in a conventional manner, preferably by use of a suitable initiator.
  • Suitable initiators include 2,2'- azobis(2-methylpropanenitrile) (AIBN) , dibenzoyl peroxide, tertiary butyl peroctoate cumene hydroperoxide, diisopropyl percarbonate, ammonium persulfate, and the like, per se, or in combination with a reducing agent in the form of an oxidation reduction catalyst system.
  • AIBN 2,2'- azobis(2-methylpropanenitrile)
  • dibenzoyl peroxide dibenzoyl peroxide
  • tertiary butyl peroctoate cumene hydroperoxide diisopropyl percarbonate
  • ammonium persulfate and the like
  • SUBSTITUTESHEET temperature to avoid destructive exotherms, preferably to about 75-95°C.
  • the final produ t is purified to remove excess salts, amines and the like. Any known processes for isolating purifying polymers may be utilized. Some care should be taken to insure that no polymerization initiator remains in active form in the reaction mixture.
  • the molecular weight of the resulting polymer may vary. However, the molecular weight of the resulting copolymer is at least approximately 20,000. In the preferred embodiment, the molecular weight ranges from 20,000 to 10 million.
  • the monomer of the present invention may also be formulated into a latex polymer using an aqueous medium under substantially similar conditions to those used for solution polymerization.
  • latex generally refers to polymers which are dispersed within an aqueous carrier these polymers may have partially soluble or completely soluble comonomer constituents.
  • these polymers form a dispersion of colloidal particles suspended in an aqueous carrier which, once dried, form an antimicrobially active film.
  • the possible uses of the present invention are many.
  • the quaternary monomer in the present invention may be directly incorporated into polymeric 'film matrices, fibers, aqueous lattices, adhesives (both water-based and hot- melt), and may be used in anti-fouling coatings and water- treatment applications. Quaternary compounds may also be incorporated into the above systems as an additive.
  • the monomer of the present invention may be used to prepare copolymers or grafted copolymers.
  • Emulsion copolymers can be formed with the isocyanate-quaternary monomer of the present invention.
  • SUBSTITUTESHEET Comonomers including compounds such as styrene, and divinyl benzene among others can be used to make macroporous resins useful in the solid phase as disinfectants for water treatment.
  • the isocyanate-quaternary monomer of the present invention may also be copolymerized with urethane and acrylate type monomers to provide compositions useful as inhibiting corrosion in water base coatings and in powder coatings.
  • the isocyanate-quaternary monomer of the present invention may also be copolymerized with acrylonitrile to create fibers useful in the formation of antimicrobial non- woven materials for application in areas such as hospital and medical environments.
  • the isocyanate-quaternary monomer may also be used with comonomers such as quaternary monomers having epoxy functionalities to create resins useful as hard surface coatings in applications requiring environmental sanitization, sanitary paints, and as ionomeric adhesives.
  • the isocyanate-quaternary monomer of the present invention may also be copolymerized through grafting methods well known to those of skill in the art. For instance, the isocyanate-quaternary monomer may be grafted to form acrylic emulsion latexes in application for the formation of self-preserving paints, adhesives, and environmental coatings.
  • the isocyanate-quaternary monomer of the present invention may also be grafted onto cellulosic fibers again for the formation of non-woven compositions useful in medical and hospital environments among other areas.
  • the isocyanate-quaternary monomer may also be grafted onto latex rubbers to provide antimicrobial elastic substrates which for example, may be used to provide medical disposables such as surgical gloves.
  • the isocyanate-quaternary monomer may also be grafted onto nylon fibers to create membranes useful in the application of wound dressings as well as the creation of filter
  • SUBSTITUTESHEET materials which may be in turn used to provide highly pure pharmaceutical compositions.
  • EXAMPLE 1 Hydroxylated dialkyl-methyl quaternary ammonium chloride was synthesized by dissolving. 168.8 g, 0.55 moles of methyldidecyl amine (DAMA 1010-Ethyl Corp.) in 219g, 2.73 moles 2-chloroethanol, and heating to reflux in a three necked reactor vessel equipped with a reflux condenser, mechanical agitator and thermometer. The reaction was maintained at reflux for 5 hours until the starting tertiary amine was consumed (monitored by TLC) . Unreacted chloroethanol was distilled off leaving a viscous brown residue which was shown to be the desired hydroxylated quaternary ammonium compound by proton magnetic resonance spectroscopy. The residual chloroethanol could be removed by wiped film evaporation to ⁇ 0.001% by capillary gas chromatrography. This synthesis may also be completed using epichlorohydrin instead of 2- chloroethanol.
  • EXAMPLE 2 The mTMI-quaternary ammonium carbamate was synthesized by dissolving 99.0g, (0.253 mole) of the hydroxylated quaternary ammonium compound in 150 ml dry toluene. 50.81g, (0.253 mole) m-isopropenyl- ⁇ ' ⁇ dimethylbenzyl isocyanate (m-TMI) was added and brought to reflux. The reaction was catalyzed by addition of 3.0g (2% by weight) of potassium iodide-zinc acetate. After twenty-four hours a sample was withdrawn for IR and NMR analysis. Infra red analysis revealed a residual amount of isocyanate still present which was consumed by addition of a few drops of ethanolamine. Residual toluene was distilled off leaving
  • EXAMPLE 3 Synthesis of m-TMI quaternary ammonium urea monomer was initiated by dissolving 153.8g 3- dimethylaminopropylamine, 1.50 moles, in 250 ml dry toluene and adding 302.5g (1.50 moles) m-TMI by dropwise addition over a sixty minute period at room temperature. The reaction mixture was brought to 70°C and the isocyanate concentration was monitored by IR spectroscopy. After 3 hours, the NCO was no longer detectable spectroscopically and the solvent was evaporated off under reduced pressure. Obtained 118.8g of the m-TMI tertiary amine adduct (73% of Theoretical) as a white crystalline solid. The structure was confirmed by proton NMR.
  • the tertiary amine adduct was quaternized by alkylation with bromododecane. 97.6g 1-bromododecane was dissolved in 200 ml toluene and 118.8g of the tertiary amine adduct was added and brought to reflux. The reaction mixture was monitored by TLC and observed consumption of the starting amine after six hours of reflux. Proton NMR analysis confirmed modification of the 3° amine to produce the desired alkylation product. This monomer was incorporated into an acrylic emulsion latex system.
  • EXAMPLE 4 The monomers formulated in Examples 2 and 3 were then used to synthesize the copolymers of Example 4.
  • a hydroxyethylacrylate-quaternary ammonium carbamate copolymer was synthesized by dissolving 15g hydroxyethylacrylate and 15g of the quaternary ammonium carbamate in 60ml of isopropyl alcohol. 0.18g azobis- isobutyronitrile was added and reaction mixture was brought to 70°C for twenty-four hours and evaporated off the
  • SUBSTITUTESHEET isopropyl alcohol and unreacted hydroxyethylacrylate.
  • a water soluble polymer preparation was obtained which was evaluated for antimicrobial activity and molecular weight.
  • the organisms shown in Table 1 were grown in tryptic- soy yeast extract (TSYE) broth for 24 hours. During growth the temperaure was maintained at 37°C in a shaking water bath.
  • TTYE tryptic- soy yeast extract
  • the organisms were then spun down in sterile centrifuge tubes at 10,000 rpm for about five minutes and then decanted and resuspended in a phosphate buffer.
  • the cells were then concentrated into one sterile centrifuge tube and spun down again, and the liquid was decanted.
  • the cells were resuspended in five to ten mL of phosphate buffer, and spread on TSYE plates to determine the final concentration of cells. A final concentration of at least 1 x 10 6 in 10 mL was obtained for this experiment.
  • the amount of cells needed for the test was calculated in 10 mL of phosphate buffer.
  • Dilutions of the polymer were made in tubes of sterile phosphate buffer for a final volume of 10 mL.
  • the concentrations used to screen the polymer were 10, 100 and 200 ppm.
  • the tubes were then
  • SUBSTITUTESHEET inoculated with the organisms at a concentration of 1 x 10 6 CFU/ L along with a control tube containing 10 mL of phosphate buffer and the organisms.
  • a spread plate method was used to enumerate viable cells at zero time and 24 hours. The tubes were incubated in a 37°C shaking water bath during the 24 hour time period. The plates were incubated at 37°C for 48 hours. The plates were counted and converted to log values. Determination of logs of death in the polymer solution vs. the control were reported as minimum cidal concentration. Minimum cidal concentration is defined as the concentration of active ingredient necessary to provide greater than 5 log kill (CFU/ml) over a 24 hour period.
  • a latex emulsion containing the quaternary ammonium carbamate monomer was prepared by adding 31.1 wt-% of water and 0.1 wt-% of 0.05 molar sodium bicarbonate buffer to a jacketed and vented mixing vessel equipped with feed inlets. The charge was heated to 65°C under nitrogen purge. At 65°C, 0.15 wt-% each of ammonium persulfate and sodium metabisulfite as a catalyst was added and the monomer feed of, water (15.5 wt-%), surfactant
  • Yeast and molds including A. niqer (ATCC 9643), A. pullulans (ATCC 16622), P. funiculosum (ATCC 11797), C. albicans (ATCC 14053), and Saccharomyces cerevisiae (ATCC 9763) were used in the analysis.
  • Fifty gram samples of the latex suspension were then transferred to two ounce bottles, and inoculated with 0.5 ml of the mixed inocula, mixed with a sterile tongue depressor and the bottles covered.
  • the yeast and mold samples were determined separately so two samples of each adhesive was prepared, one for the yeast and one for the molds. The molds were incubated at room temperature and the yeast at 30°C.
  • the Prompt Inoculating System (BBL, Beeton Dickinson, Corp. ) was used to prepare a bacterial inocula containing 1.8 x 10 8 colony forming units per ml. 50 g of the polymer was transferred to autoclaved two ounce bottles. Each sample was inoculated with 0.5 ml of each of the bacterial suspensions being careful to mix the suspension before sampling. The sample was mixed thoroughly with a sterile tongue depressor, covered and then incubated at 37°C.
  • the sample with 2.5% (wt.) mTMI-Quat was susceptible to molds during the one month challenge test, but resistant to the bacterial and yeast inocula.
  • the sample with 5% (wt.) mTMI-Quat was resistant to the molds, yeast and bacteria during the challenge period of one month.
  • EXAMPLE 6 An acrylonitrile quaternary ammonium copolymer was prepared by the aqueous dispersion technique discussed by Freshour and Knorr in Fiber Chemistry pp. 171-371 starting with a monomer solution was 90% acrylonitrile, 5% methyl acrylate and 5% mTMI-quaternary ammonium carbamate monomer by
  • SUBSTITUTESHEET weight 100ml of water was blanketed with N 2 and brought to 58°C.
  • the monomers were added to reaction vessel and polymerization was initiated by addition of 0.8g of 77ppm ammonium persulfate, 2.0g, 11.5% hydrogen peroxide and 3.0g 7% thiourea.
  • the reaction mixture was agitated mechanically for 1 hour at 60°C during which time insoluble particles accumulated in suspension. Polymer chain propagation was quenched by addition of l.Og of 8% EDTA at 90 minutes.
  • Particulate polymer was washed with several volumes of water, filtered and air dried.
  • the polyacrylonitrile-quaternary ammonium carbamate copolymer was soluble in dimethyl formamide. Filaments of this material were prepared by extrusion of the polymer dope, 8% (w/w) , through an 18 gauge hypodermic needle into 5% aqueous dimethyl formamide bath at room temperature.
  • EXAMPLE 7 An mTMI-quaternary ammonium carbamate epoxy copolymer was prepared using 15g of isopropanol blanketed with N 2 and heated to 65°C, 0.20g azobis isobutyronitrile was dissolved. 5% of the termonomer mixture was charged into the reaction vessel: 12g (40%) mTMI-Quat, 16.5g (55%) Methyl methacrylate and 1.5g (5%) allylglycidyl ether. After 18 hours at 65°C the volatiles were distilled off. Residual unreacted monomer was removed by extraction with 3 volumes hexane. A yellow viscous polymer preparation was obtained which by IR, exhibited evidence of ester at 1740 cm, oxirane groups at 1250cm and aliphatic ether at 1100cm.
  • Synthesis of a water sensitive quat containing epoxy resin was initiated by charging a three necked round bottom flask with 12 g isopropanol and 0.18 g azobisisobutyro- nitrile and 2.0 g of the following monomer feed having 12.0 g mTMI-Quat (from Example 2), 16.5 g vinyl pyrrolidone, and 2.0 g allyl glycidyl ether.
  • the reaction vessel was brought to 65°C and blanketed with N 2 .
  • the monomer feed was commenced, and the temperature and agitation rate were held constant for 24 hours.
  • the volatiles were distilled under reduced pressure and the polymer was extracted with three volumes of hexane.
  • the polymer was found to have an equivalent weight of 2000, and was cured with the same amine epoxy curing agent as above.
  • Example 7 was tested using the organism E. coli, (ATCC 11229). The sample was run using the concentrations 10, 100 and 200 pp of the polymer. The logs of death at 0 time and 24 hours can be seen below.

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  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Environmental Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Zoology (AREA)
  • Plant Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Toxicology (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention se rapporte à des substances polymères utilisant des composés quaternaires comme agents biocides. Ces composés peuvent être copolymérisés avec des monomères vinyliques ou utilisés comme additif dans des systèmes de latex, d'émulsions ou d'adhésifs.
PCT/US1991/000926 1990-02-14 1991-02-12 Copolymeres avec action anti-microbienne inherente Ceased WO1991012282A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US47984090A 1990-02-14 1990-02-14
US479,840 1990-02-14

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WO1991012282A1 true WO1991012282A1 (fr) 1991-08-22

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Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995031730A1 (fr) * 1994-05-18 1995-11-23 Microquest Diagnostics, Inc. Procede de detection rapide d'un analyte
WO1998021253A1 (fr) * 1996-11-14 1998-05-22 Röhm Gmbh Polymeres a proprietes antimicrobiennes
EP0862859A1 (fr) * 1997-03-06 1998-09-09 Hüls Aktiengesellschaft Procédé de préparation matières plastiques antimicrobiennes
EP0862858A1 (fr) * 1997-03-06 1998-09-09 Hüls Aktiengesellschaft Procédé de préparation matières plastiques antimicrobiennes
DE19646965C2 (de) * 1996-11-14 1999-08-12 Roehm Gmbh Biophobe Polymere auf Acrylatbasis, Verfahren zu ihrer Herstellung und ihre Verwendung
WO2000069933A1 (fr) * 1999-05-12 2000-11-23 Creavis Gesellschaft Für Technologie Und Innovation Mbh Procede pour produire des surfaces polymeres a propriete microbicide intrinseque
WO2000069935A1 (fr) * 1999-05-12 2000-11-23 Creavis Gesellschaft Für Technologie Und Innovation Mbh Procede de preparation de surfaces polymeres a action microbicide
WO2000073262A1 (fr) * 1999-05-29 2000-12-07 Bayer Aktiengesellschaft Monomeres polymerisables olefiniquement insatures
EP0859547A4 (fr) * 1995-06-07 2000-12-20 Surmodics Inc Enrobages rendant les virus inactifs
US6482402B1 (en) * 1999-05-13 2002-11-19 Geltex Pharmaceuticals, Inc. Antimicrobial compositions and methods
DE10211562A1 (de) * 2002-03-15 2003-10-02 Fraunhofer Ges Forschung Antimikrobiell modifiziertes Substrat, Verfahren zu dessen Herstellung sowie dessen Verwendung
US6692732B2 (en) 1997-09-19 2004-02-17 Genzyme Corporation Ionic polymers as toxin-binding agents
US6767549B2 (en) 1996-06-24 2004-07-27 Genzyme Corporation Ionic polymers as anti-infective agents
WO2004106023A1 (fr) * 2002-04-21 2004-12-09 Quick-Med Technologies, Inc. Substances et procedes destines au traitement du bois d'oeuvre et d'autres produits du bois
WO2005007706A3 (fr) * 2003-07-03 2006-12-21 Dow Reichhold Specialty Latex Polymeres antimicrobiens et antistatiques et procedes d'utilisation sur divers substrats
EP1450966A4 (fr) * 2001-09-28 2009-09-09 Quick Med Technologies Inc Materiaux absorbants ayant des surfaces polymeres anti-microbiennes non lixiviables a liaison covalente, et procedes de fabrication correspondants
WO2015190118A1 (fr) * 2014-06-12 2015-12-17 広栄化学工業株式会社 Sel d'onium, copolymère d'acide acrylique contenant le sel d'onium et agent antistatique contenant ces derniers
US9220725B2 (en) 2006-08-24 2015-12-29 Mallard Creek Polymers, Inc. Cationic latex as a carrier for bioactive ingredients and methods for making and using the same
US20160102211A1 (en) * 2010-02-17 2016-04-14 Henry Company Llc Microbe mitigating architectural barriers, compositions for forming such barriers and related methods
US11134684B2 (en) 2005-08-24 2021-10-05 Purdue Research Foundation Method of using hydrophilized bactericidal polymers
US11421084B2 (en) 2017-05-27 2022-08-23 Poly Group LLC Dispersible antimicrobial complex and coatings therefrom
US11680116B2 (en) 2017-06-16 2023-06-20 Poly Group LLC Polymeric antimicrobial surfactant

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4429096A (en) * 1983-06-01 1984-01-31 American Cyanamid Company Quaternary amine carbamate or urea compounds based on isopropenyl-α,α-dimethylbenzyl isocyanate
US4532128A (en) * 1981-09-15 1985-07-30 Dynapol Quaternary ammonium group-containing polymers having antimicrobial activity
EP0169169A2 (fr) * 1984-07-18 1986-01-22 Sandoz Ag Composés aromatiques

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4532128A (en) * 1981-09-15 1985-07-30 Dynapol Quaternary ammonium group-containing polymers having antimicrobial activity
US4429096A (en) * 1983-06-01 1984-01-31 American Cyanamid Company Quaternary amine carbamate or urea compounds based on isopropenyl-α,α-dimethylbenzyl isocyanate
EP0169169A2 (fr) * 1984-07-18 1986-01-22 Sandoz Ag Composés aromatiques

Cited By (35)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6203856B1 (en) 1993-03-06 2001-03-20 Huels Aktiengesellschaft Process for the preparation of antimicrobial plastics
WO1995031730A1 (fr) * 1994-05-18 1995-11-23 Microquest Diagnostics, Inc. Procede de detection rapide d'un analyte
US5750357A (en) * 1994-05-18 1998-05-12 Microquest Diagnostics, Inc. Method of rapid analyte detection
EP0859547A4 (fr) * 1995-06-07 2000-12-20 Surmodics Inc Enrobages rendant les virus inactifs
US6767549B2 (en) 1996-06-24 2004-07-27 Genzyme Corporation Ionic polymers as anti-infective agents
WO1998021253A1 (fr) * 1996-11-14 1998-05-22 Röhm Gmbh Polymeres a proprietes antimicrobiennes
US6194530B1 (en) * 1996-11-14 2001-02-27 Roehm Gmbh Polymers with anti-microbial properties
DE19646965C2 (de) * 1996-11-14 1999-08-12 Roehm Gmbh Biophobe Polymere auf Acrylatbasis, Verfahren zu ihrer Herstellung und ihre Verwendung
US5967714A (en) * 1997-03-06 1999-10-19 Huels Aktiengesellschaft Process for the preparation of antimicrobial plastics
US6096800A (en) * 1997-03-06 2000-08-01 Huels Aktiengesellschaft Process for the preparation of antimicrobial plastics
EP0862858A1 (fr) * 1997-03-06 1998-09-09 Hüls Aktiengesellschaft Procédé de préparation matières plastiques antimicrobiennes
EP0862859A1 (fr) * 1997-03-06 1998-09-09 Hüls Aktiengesellschaft Procédé de préparation matières plastiques antimicrobiennes
US6692732B2 (en) 1997-09-19 2004-02-17 Genzyme Corporation Ionic polymers as toxin-binding agents
US7709694B2 (en) 1998-12-08 2010-05-04 Quick-Med Technologies, Inc. Materials with covalently-bonded, nonleachable, polymeric antimicrobial surfaces
WO2000069933A1 (fr) * 1999-05-12 2000-11-23 Creavis Gesellschaft Für Technologie Und Innovation Mbh Procede pour produire des surfaces polymeres a propriete microbicide intrinseque
WO2000069935A1 (fr) * 1999-05-12 2000-11-23 Creavis Gesellschaft Für Technologie Und Innovation Mbh Procede de preparation de surfaces polymeres a action microbicide
US6482402B1 (en) * 1999-05-13 2002-11-19 Geltex Pharmaceuticals, Inc. Antimicrobial compositions and methods
WO2000073262A1 (fr) * 1999-05-29 2000-12-07 Bayer Aktiengesellschaft Monomeres polymerisables olefiniquement insatures
EP1450966A4 (fr) * 2001-09-28 2009-09-09 Quick Med Technologies Inc Materiaux absorbants ayant des surfaces polymeres anti-microbiennes non lixiviables a liaison covalente, et procedes de fabrication correspondants
DE10211562B4 (de) * 2002-03-15 2006-09-28 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Antimikrobiell modifiziertes Substrat, Verfahren zu dessen Herstellung sowie dessen Verwendung
DE10211562A1 (de) * 2002-03-15 2003-10-02 Fraunhofer Ges Forschung Antimikrobiell modifiziertes Substrat, Verfahren zu dessen Herstellung sowie dessen Verwendung
WO2004106023A1 (fr) * 2002-04-21 2004-12-09 Quick-Med Technologies, Inc. Substances et procedes destines au traitement du bois d'oeuvre et d'autres produits du bois
WO2005007706A3 (fr) * 2003-07-03 2006-12-21 Dow Reichhold Specialty Latex Polymeres antimicrobiens et antistatiques et procedes d'utilisation sur divers substrats
US7491753B2 (en) 2003-07-03 2009-02-17 Mallard Creek Polymers, Inc. Antimicrobial and antistatic polymers and methods of using such polymers on various substrates
US11134684B2 (en) 2005-08-24 2021-10-05 Purdue Research Foundation Method of using hydrophilized bactericidal polymers
US11459415B2 (en) 2005-08-24 2022-10-04 Purdue Research Foundation Method of using hydrophilized bactericidal polymers
US9220725B2 (en) 2006-08-24 2015-12-29 Mallard Creek Polymers, Inc. Cationic latex as a carrier for bioactive ingredients and methods for making and using the same
US9758679B2 (en) * 2010-02-17 2017-09-12 Henry Company, Llc Microbe mitigating architectural barriers, compositions for forming such barriers and related methods
US20160102211A1 (en) * 2010-02-17 2016-04-14 Henry Company Llc Microbe mitigating architectural barriers, compositions for forming such barriers and related methods
JPWO2015190118A1 (ja) * 2014-06-12 2017-04-20 広栄化学工業株式会社 オニウム塩及び該オニウム塩を含有するアクリル酸共重合体並びにこれらを含有する帯電防止剤
WO2015190118A1 (fr) * 2014-06-12 2015-12-17 広栄化学工業株式会社 Sel d'onium, copolymère d'acide acrylique contenant le sel d'onium et agent antistatique contenant ces derniers
US11421084B2 (en) 2017-05-27 2022-08-23 Poly Group LLC Dispersible antimicrobial complex and coatings therefrom
US11760844B2 (en) 2017-05-27 2023-09-19 Poly Group LLC Dispersible antimicrobial complex and coatings therefrom
US11680116B2 (en) 2017-06-16 2023-06-20 Poly Group LLC Polymeric antimicrobial surfactant
US12286498B2 (en) 2017-06-16 2025-04-29 Poly Group LLC Polymeric antimicrobial surfactant

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