WO1997042200A1 - Composes organosilanes rendus stables a l'eau et procedes d'utilisation associes - Google Patents

Composes organosilanes rendus stables a l'eau et procedes d'utilisation associes Download PDF

Info

Publication number
WO1997042200A1
WO1997042200A1 PCT/US1997/008913 US9708913W WO9742200A1 WO 1997042200 A1 WO1997042200 A1 WO 1997042200A1 US 9708913 W US9708913 W US 9708913W WO 9742200 A1 WO9742200 A1 WO 9742200A1
Authority
WO
WIPO (PCT)
Prior art keywords
alkyl
independently
carbon atoms
compound
integer
Prior art date
Application number
PCT/US1997/008913
Other languages
English (en)
Inventor
Jacques Elfersy
Timoth C. Moses
Lanny S. Liebeskind
Gary D. Allred
Original Assignee
Bioshield Technologies, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bioshield Technologies, Inc. filed Critical Bioshield Technologies, Inc.
Priority to NZ329397A priority Critical patent/NZ329397A/xx
Priority to BR9702243-8A priority patent/BR9702243A/pt
Priority to IL12255597A priority patent/IL122555A/en
Priority to AU30113/97A priority patent/AU3011397A/en
Publication of WO1997042200A1 publication Critical patent/WO1997042200A1/fr

Links

Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/64—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
    • 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
    • A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L3/00—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
    • A23L3/34—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals
    • A23L3/3454—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of liquids or solids
    • A23L3/3463—Organic compounds; Microorganisms; Enzymes
    • A23L3/3481—Organic compounds containing oxygen
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L3/00—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
    • A23L3/34—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals
    • A23L3/3454—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of liquids or solids
    • A23L3/3463—Organic compounds; Microorganisms; Enzymes
    • A23L3/3544—Organic compounds containing hetero rings
    • 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
    • A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
    • A61L29/08—Materials for coatings
    • A61L29/085—Macromolecular materials
    • 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
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/08—Materials for coatings
    • A61L31/10—Macromolecular materials
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
    • C03C17/30—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C07F9/091—Esters of phosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
    • D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
    • D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
    • D06M15/03—Polysaccharides or derivatives thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
    • D06P1/5264—Macromolecular compounds obtained otherwise than by reactions involving only unsaturated carbon-to-carbon bonds
    • D06P1/5292—Macromolecular compounds obtained otherwise than by reactions involving only unsaturated carbon-to-carbon bonds containing Si-atoms
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/62—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds with sulfate, sulfonate, sulfenic or sulfinic groups
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2204/00—Glasses, glazes or enamels with special properties
    • C03C2204/02—Antibacterial glass, glaze or enamel

Definitions

  • the invention relates to organosilane compounds, products and methods for their use.
  • this invention provides water-stable organosilane compounds, products, and compositions for treating various substrates, articles treated with the compounds, products and compositions, and methods of treatment using the compounds, products and compositions.
  • R is a nonhydrolizable organic group, such as, but not limited to, alkyl, aromatic, organofunctio ⁇ al, or a combination thereof
  • X is al oxy, such as methoxy or ethoxy, are prone to self-condensation rendering such organosilanes unstable in water over commercially relevant periods of time.
  • X can be a halogen, such as Ci, Br, or I, and is similarly liberated as HCl, HBr, or HI.
  • the X moiety reacts with various hydroxyl containing molecules in aqueous media to liberate methanol, ethanol, HCl, HBr, HI, H 2 O, acetic acid, or an unsubst ⁇ tuted or substituted carboxylic acid and to form the hydroxylated, but condensation-prone compound.
  • organosilanes R B SL ⁇ where n is an integer from 0 to 2, hydrolysis of the first two X groups with water produces a species bearing -Si(OH) 2 - units which can self- condense through the hydroxyl moieries to linear and/or cyclic oligomers possessing the partial structure HO-Si-(O-Si) mn ⁇ -O-Si-O-Si-O-Si-OH, where mm is an mteger such that an oligomer is formed.
  • RSiX 3 hydrolysis of the third X group generates a silanetriol (RSi(OH) j ) which produces insoluble organosilicon polymers through linear and/or cyclic self-condensation of the Si(OH) units.
  • This water induced self-condensation generally precludes storage of most organosilanes R ⁇ SiX ⁇ , where n ranges from 0 to 2, inclusive, in water.
  • n ranges from 0 to 2, inclusive
  • 3- (trimethoxysilyl)propyl-dimethyloctadecyl ammonium chloride is a water activated antimicrobial integrated system which is capable of binding to a wide variety of natural and synthetic substrates, including fibers and fabrics, to produce a durable surface or fabric coating.
  • 3-(TrimethoxysiIyl)propyl-dimethyloctadecyl ammonium chloride is
  • the C It hydrocarbon chain quaternary ammonium portion of the molecule in Scheme 1 possesses long-acting antimicrobial properties and provides initial association with the surface of the substrate through ionic bonds and/or electrostatic interaction. Moreover, in the presence of water and as generally described above, the propyl trimethoxysilane portion of the molecule rapidly converts into a propyl trihydroxysilyl moiety and polymerizes through Si-O bonds to hydroxylated surfaces of the substrate and through intermolecular O-Si bonds.
  • the traditional method of use of 3- (trimethoxysiiyl)propyl-dimethyloctadecyl ammonium chloride is to add a dilute solution of 3-(trimethoxysiIyI)propyl-dimethyloctadecyl ammonium chloride in metha ⁇ ol to water.
  • This addition rapidly converts the -Si(OCH 3 ) 3 portion of the molecule into a reactive -Si(OH) 3 group thereby activating the molecule.
  • the activated 3- (trifaydroxys_lyl)propyl-dimethyloctadecyl ammonium chloride system -must then be used within a short period of time, such as a few hours to at most about 12 hours, to treat a surface or fabric to produce a permanent surface coating.
  • Scheme 2 shows a two-stage process which is believed to represent the coating reaction.
  • organosilanes in water such as the activated mixture of 3-(trihydroxysilyl)propyl-dimethyloctadecyl ammonium chloride and water, are generally unstable and prone to self-condensation.
  • the mixture of 3- (trihydroxysilyl)propyl-dimethyloctadecyl ammonium chloride and water begins to lose effectiveness in as little as four to eight hours.
  • Gel formation in this and similar silane formulations in water begins to occur in even shorter times.
  • the limitations of such organosilanes in aqueous media are further described in United States Patent No. 5, 11,585, the contents of which are hereby incorporated by this reference.
  • such products are notorious for agitation difficulty during the addition of the silane to water.
  • quaternary ammonium silicon compounds as antimicrobial agents in accordance with the prior art is well known and taught in a wide variety of United States patents, e.g., 3,560,385; 3,794,736; 3,814,739, the contents of which are hereby incorporated by this reference. It is also taught that these compounds possess certain antimicrobial properties which make them valuable and very useful for a variety of surfaces, substrates, instruments and applications (see, e.g., United States Patent Nos.
  • the present invention fulfills these needs by providing water-stable organosilane compounds, products (i.e., the compounds or compositions formed from performing a specified reaction) and compositions, methods for their use, and articles prepared usmg the compounds, products, and compositions.
  • the compounds, products, and compositions of the present invention are non-toxic, non-flammable, simple, economical and are operable over a wide variety of pH ranges.
  • the present invention provides the product formed from reacting an organosilane of the formula I ⁇ SiX ⁇ where n is an integer of from 0 to 3, preferably 0 to 2; each is, independently, a nonhydrolizable organic group; and each X is, independently, a hydrolyzable group, with a polyol containing at least three hydroxy groups, wherein any two of the at least three hydroxy groups are separated by at least three intervening atoms.
  • the present invention provides a compound having the formula (R ⁇ SiQO ⁇ J ⁇ ,), wherein n is an integer of from 0 to 3, preferably 0 to 2; y is an integer of from 1 to 4; each R is, independently, a nonhydrolizable organic group; each X is, independently, a hydrolyzable group; and each R, is, independently, a polyol containing at least three hydroxy groups, wherein any two of the at least three hydroxy groups are separated by at least three intervening atoms and wherein the polyol is bonded to the Si by removal of the hydrogen from one of the at least three hydroxy groups such that the oxygen of the one of the at least three hydroxy groups is bonded to Si.
  • the present invention provides a compound having the formula Vm, IX, X or XI:
  • R JO , Rj,, and R 32 are, independently, benzyl, polyether, lower alkyl alcohol, lower alkoxy of from 1 to 4 carbon atoms, alkyl of from i to about 22 carbon atoms, preferably 1 to about 10 carbon atoms, and ⁇ where the ring is unsaturated is, CH, N, N ⁇ , N + (alkyl), N ⁇ ary.), ⁇ (benzyl), N-CH 2 -N, NH- CHj-N, N + (alkyl)-CH 2 -N, N ary -CHj-N, or wherein the ring is unsubstituted or
  • the present invention provides a compound having the formula XHI:
  • the present invention provides a water stable composition, comprising the product or compound of the invention and water.
  • the present invention provides a composition for treating a substrate, comprising a carrier and an effective amount of the product or compound of the invention.
  • the present invention provides a compound having the formula (R) n Si(X) 4 _-_ j ,(R 4 i) y wherein n is an integer of from 0 to 3, preferably 0 to 2; y is an integer of from 1 to 4; each R is, mdependently, a nonhydrolizable organic group; each X is, independently, a hydrolyzable group; and each R, is, independently, a poly(tetrahydrofi ⁇ ran), a poly(vinyl) alcohol, hydroxyethyl cellulose, starch, or a cellulosic derivative, COntaining at least three hydroxy groups, wherein any two of the at least three hydroxy groups are separated by at least three intervening atoms and wherein the , ! bonded to the Si by removal of the hydrogen from one of the at least three hydroxy groups such that the oxygen of the one of the at least three hydroxy groups is bonded to Si.
  • the present invention provides a product formed from reacting an organosilane of the formula H, HI, IV, or V: (R 1 ) 3 SiR 1 N + (R 3 )(R,)(R J )Y- (H)
  • R 3S is H, halogen, R M and R 37 are, independently, halogen, H, alkyl of from 1 to about 8 carbon atoms, isobuty phenyl, or n-octyl;
  • R 2 is benzyl, vinyl or alkyl of from 1 to about 3 carbon atoms;
  • R 3 and « are, independently, lower alkyl alcohol of from 1 to 4 carbon atoms, lower alkoxy of from 1 to 4 carbon atoms, or alkyl of from 1 to about 22 carbon atoms, preferably 1 to about 10 carbon atoms, preferably 1 to about 10 carbon atoms; or R 3 and , can, together, form a morpholine or cyclic
  • R 7 where the ring is saturated, is CH 2 , O, S, NH,
  • R I0 is, independently benzyl, polyether, lower alkyl alcohol of from 1 to 4 carbon atoms, lower alkoxy of from 1 to 4 carbon atoms, or alkyl of from 1 to about 22 carbon atoms, preferably 1 to about 10 carbon atoms, and R 7 , where the ring is unsaturated is, CH, N, N ⁇ , N alkyl), N aryl), or N benzyl)- CH 2 -N; wherein the ring is unsubstituted or substituted with alkyl of from 1 to 22 carbon atoms, ester, aldehyde, carboxylate, amide, thionamide, nitro, amine, or halide; Rj is lower alkyl alcohol, CH 2 C ⁇ Hj, polyether, alkyl, alkoxy, perfluoroalkyl, pefluoroalkylsulfonate, or perfluoroalkylcarboxylate wherein the alkyl, alkoxy, perfluoro, per
  • the present invention provides a product as described above, wherein the polyol is of the formula XIV: HOCH ⁇ CtC ⁇ OPO ⁇ ) ⁇ ,)! ⁇ (XTV) or is aryl substituted with from 2 to 6 moieties of -(OCEy C ⁇ OH ⁇ ; wherein aa is an integer of from 0 to 4; each R ⁇ is, independently, O 2 or OH; and each ⁇ t is, independently, H, a mono- or di-valent cation, or OR ⁇ where R ⁇ is alkyl of from 1 to 22 carbon atoms, lower alkyl alcohol of from 1 to 4 carbon atoms, or alkoxy of from 1 to 4 carbon atoms.
  • the present invention provides a method of treating a substrate, comprising contacting the substrate with a sufficient amount of the product, compound or composition of the invention for a period of time sufficient for treatment of the substrate.
  • the present invention provides a treated substrate having adhered thereto the product, compound or composition of the invention.
  • the present invention provides a method of dyeing and treating a substrate, comprising contacting the substrate with an aqueous composition comprising an aqueous soluble dye suitable for dyeing a substrate and the product formed from reacting an organosilane of the formula -SiX ⁇ where n is an integer of from 0 to 3, preferably 0 to 2; each R is, independently, a nonhydrolizable organic group; and each X is, independently, a hydrolyzable group, with a polyol containing at least three hydroxy groups, wherein any two of the at least three hydroxy groups are separated by at least three intervening atoms, for a period of time sufficient to dye and treat the substrate.
  • the present invention provides a method of antimicrobially treating a food article, comprising contacting the food article with an effective amount of the product formed from reacting an antimicrobial organosilane of the formula R ⁇ SiX ⁇ where n is an integer of from 0 to 3, preferably 0 to 2; each R is, independently, a nonhydrolizable organic group; and each X is, independently, a hydrolyzable group, with a polyol containing at least three hydroxy groups, wherein any two of the at least three hydroxy groups are separated by at least three intervening atoms, for a period of time sufficient to antimicrobially treat the food article.
  • an antimicrobial organosilane of the formula R ⁇ SiX ⁇ where n is an integer of from 0 to 3, preferably 0 to 2; each R is, independently, a nonhydrolizable organic group; and each X is, independently, a hydrolyzable group, with a polyol containing at least three hydroxy groups, wherein any two of the at
  • the present invention provides a method of antimicrobially coating a fluid container used for containing a human or animal consumable product, comprising contacting the container with an effective amount of the product formed from reacting an antimicrobial organosilane of the formula R ⁇ SiX ⁇ where n is an integer of from 0 to 3, preferably 0 to 2; each R is, independently, a nonhydrolizable organic group; and each X is, independently, a hydrolyzable group, with a polyol containing at least three hydroxy groups, wherein any two of the at least three hydroxy groups are separated by at least three intervening atoms, for a period of time sufficient to antimicrobially coat the container.
  • an antimicrobial organosilane of the formula R ⁇ SiX ⁇ where n is an integer of from 0 to 3, preferably 0 to 2; each R is, independently, a nonhydrolizable organic group; and each X is, independently, a hydrolyzable group, with a polyol containing at least three
  • the present invention provides a method of antimicrobially coating a latex medical article for use in a human or animal medical procedure, comprising contacting the article with an effective amount of the product formed from reacting an antimicrobial organosilane of the formula I ⁇ SiX ⁇ where n is an integer of from 0 to 3, preferably 0 to 2; each R is, independently, a nonhydrolizable organic group; and each X is, independently, a hydrolyzable group, with a polyol containing at least three hydroxy groups, wherein any two of the at least three hydroxy groups are separated by at least three intervening atoms, for a period of time sufficient to antimicrobially coat the article.
  • an antimicrobial organosilane of the formula I ⁇ SiX ⁇ where n is an integer of from 0 to 3, preferably 0 to 2; each R is, independently, a nonhydrolizable organic group; and each X is, independently, a hydrolyzable group, with a polyol containing at least three
  • a further embodiment of the present invention provides a method of antimicrobially treating a substrate selected the group consisting of a concrete pipe, a tooth brush, a comb, a hair brush, a denture, an orthodontic retainer, a spa or pool filter, an air filter, an HVAC air system, a cabin air system, a marble article, a statue, an exposed work of art, an HDP plastic cover, a silicone or TEFLON® coated fiberglass article, a Dryvitt finish, a stucco finish, blended cotton, a bio-film, a bio-adhesive, a single ply roofing, a roofing shingle, and a fiberglass reinforcement product, comprising contacting the substrate with an effective amount of the product formed from reacting an antimicrobial organosilane of the formula B- j SiX ⁇ where n is an integer of from 0 to 3, preferably 0 to 2; each R is, independently, a nonhydrolizable organic group; and each X is, independently, a hydrolyzable group,
  • the present invention also provides a method of antimicrobially enhancing a product of rubbing alcohol, a flower preservative, or a waterproofing solution, comprising admixing with the product an effective amount of the product formed from reacting an antimicrobial organosilane of the formula R n SiX ⁇ where n is an integer of from 0 to 3, preferably 0 to 2; each R is, independently, a nonhydrolizable organic group; and each X is, independently, a hydrolyzable group, with a polyol containing at least three hydroxy groups, wherein any two of the at least three hydroxy groups are separated by at least three intervening atoms, for a period of time sufficient to antimicrobially enhance the product.
  • alkyl refers to a branched or unbranched saturated hydrocarbon group of 1 to 24 carbon atoms, such as methyl ("Me”), ethyl ("Et”), n-propyl, isopropyl, /.-butyl, isobutyl, /-butyl, octyl, decyl, tetradecyl, hexadecyl, eicosyl, tetracosyl and the like.
  • Preferred alkyl groups herein contain from 1 to 12 carbon atoms.
  • the term "lower alkyl” intends an alkyl group of from one to six carbon atoms, preferably from one to four carbon atoms.
  • cycloalkyl intends a cyclic alkyl group of from three to eight, preferably five or six carbon atoms.
  • “Lower alkyl alcohol” refers to lower alkyl having attached thereto one or more hydroxy moieties, such as, but not limited to, -CH 2 CH 2 OH, CH 2 CH(OH)CH 3 , CH 2 OH CHjCHjCHaOH, CH 2 CH 2 CH(OH)CH 3 , CH 2 CH 2 CH(OH)CH 2 OH, or CH 2 CH(OH)CH(OH)CH 3 .
  • alkoxy intends an alkyl group bound through a single, terminal ether linkage; that is, an "alkoxy” group may be defined as -OR where R is alkyl as defined above.
  • a "lower alkoxy” group intends an alkoxy group containing from one to six, more preferably from one to four, carbon atoms.
  • Polyether refers to a compound or moiety possessing multiple ether linkages, such as, but not limited to, polyethylene glycols or polypropylene glycols.
  • Polyalkylethers refers to alkyls interconnected by or otherwise possessing multiple ether linkages.
  • optional or “optionally” means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where said event or circumstance occurs and instances where it does not.
  • optionally substituted lower alkyl means that the lower alkyl group may or may not be substituted and that the description includes both unsubstituted lower alkyl and lower alkyl where there is substitution.
  • an effective amount of a compound, product, or composition as provided herein is meant a sufficient amount of the compound, product or composition to provide the desired result.
  • the exact amount required will vary from substrate to substrate, depending on the particular compound, product or composition used, its mode of administration, and the like. Thus, it is not always possible to specify an exact "effective amount.” However, an appropriate effective amount may be determined by one of ordinary skill in the art using only routine experimentation.
  • aryl refers to a compound or moiety whose molecules have a ring or multiple ring structure characteristic of benzene, naphthalene, phenanthrene, anthracene, etc., i.e., either the six-carbon ring of benzene or the condensed six-carbon rings of the other aromatic derivatives, including, but not limited to phenyl, benzyl, naphthyl, benzylidine, xylil, styrene, styryl, phenethyl, phenylene, benzenetriyi, etc.
  • aromatic refers to the group of unsaturated cyclic hydrocarbons, typified by benzene, having a 6-carbon ring containing three double bonds or multiple attached benzene rings. Moreover, certain five membered cyclic compounds, such as furan (heterocyclic), are analogous to aromatic compounds. Aromatics include the cyclic compounds based upon a benzene functionality, as specified for "aryl” above. Moreover, the term “cyclic” is used to refer to all aliphatic or aromatic hydrocarbons having one or more closed rings, whether unsaturated or saturated. Preferably, cyclic compounds possess rings of from 5 to 7 carbon atoms, preferably 6 carbon atoms.
  • Such rings fall into three classes: alicyclic, aromatic ("arene”), and heterocychc.
  • unsaturated refers to such compound or moiety possessing at least one double or triple bond or otherwise constituting an aromatic compound or moiety.
  • unsaturated refers to compounds or moieties possessing no double or triple bonds, i.e., where all available valence bonds of an atom, especially carbon, are attached to other atoms.
  • heteroaryl refers to an aryl where one or more of the carbon atoms of a ring have been substituted with a heteroatom, including, but not limited to, O, N, or S.
  • heterocyclic compound or moiety where one or more of the carbon atoms of the ring has been substituted with a heteroatom, including, but not limited to, O, N, or S.
  • lower refers to a moiety having from 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms.
  • suitable is used to refer a moiety which is compatible with the compounds, products, or compositions as provided herein for the stated purpose. Suitability for the stated purpose may be determined by one of ordinary skill in the art using only routine experimentation.
  • substituted is used to refer, generally, to a carbon or suitable heteroatom having a hydrogen or other atom removed and replaced with a further moiety.
  • halogen, hydroxy, and nitrogen based substitutions of hydrocarbon hydrogens are contemplated as within the scope of the present invention for the claimed structures.
  • substituted refer to substitutions which do not change the basic and novel utility of the underlying compounds, products or compositions of the present invention.
  • Unsubstituted refers to a structure wherein the reference atom does not have any further moieties attached thereto or substituted therefor.
  • branched is used to refer, generally, to a moiety having.a carbon chain backbone, e.g., alkyl or alkoxy, wherein the backbone may contain one or more subordinate carbon chain branches.
  • branched is used to refer, generally, to a moiety having.a carbon chain backbone, e.g., alkyl or alkoxy, wherein the backbone may contain one or more subordinate carbon chain branches.
  • isobutyl, t-butyl, isopropyl, CH.CH a C(CH,)(H)CH I CH 3 , CH_C(CH_CH 3 )(H)CH 2 CH 3 , CH 2 CH 2 C(CH 3 )_CH 3 , and CH j CH j CfCH j would all be considered branched moieties.
  • branched variations of the moieties herein described refer to variations which do not change the basic and novel utility of the underlying compounds, products or compositions of the present invention.
  • Unbranched refers to a structure wherein the carbon chain does not have any branches thereon, i.e., where the carbon chain extends in a direct line.
  • acyl refers to organic acid derived moieties of the formula RCOX where R is an organic molecule and X, instead of being hydroxy, is replaced with another substituent, preferably, a suitable anion, such as a halogen , including, but not limited to, F, Cl, Br or I.
  • perfluoro or “perfluoro- analog” refers to a hydrocarbon where the hydrogen atoms attached to carbons have been replaced with F atoms. Preferably, but not necessarily, in perfluoro- analogs, most if not all of the H atoms are replaced with F atoms.
  • a "fluoro-" analog is contemplated to indicate a hydrocarbon where at least one hydrogen atom attached to a carbon is replaced with an F atom.
  • substrate refers to any article, product, or other surface that can be treated with the inventive compounds, preferably as enumerated hereinbelow under the heading Uses, as described in the Examples hereto, and as specified in the relevant claims appended hereto.
  • Suitable substrates are generally characterized in preferably having a negatively charged surface of oxygen atoms, or any surface capable of electrostatically, ionically or covaie ⁇ tly adhering or binding to the compounds, products, or compositions pf the present invention.
  • the adhering or binding occurs at the silicon atom of the organosilane portion of the compounds, products, or compositions of the present invention, but such binding is not a requirement. Therefore, as used herein, the term “adhere” is meant to refer to ionic, covalent, electrostatic, or other chemical attachment of a compound, product or composition to a substrate.
  • the term "antimicrobially enhancing” refers to the use of the compounds, products, or compositions of the present invention, preferably those wherein the organosilane has antimicrobial activity, along with other ingredients, surfactants, fillers, wetting agents, pigments, dyes, antimigrants, etc., to create a composition or solution capable of fulfilling its original purpose, based upon the other ingredients, and also of providing antimicrobial protection during ihe particular application.
  • the term “enhance” refers to the addition of antimicrobial activity to such compositions or solutions where no such activity previously existed, or to the increase of antimicrobial activity wherein the starting compositions or solutions inherently possessed antimicrobial activity.
  • hydrolyzable refers to whether the moiety is capable of or prone to hydrolysis (i.e., splitting of the molecule or moiety into two or more new molecules or moieties) in aqueous or other suitable media.
  • nonhydrolizable refers to moieties that are not prone to or capable of hydrolysis in aqueous or other suitable media.
  • catio ⁇ ic is used to refer to any compound, ion or moiety possessing a positive charge.
  • anionic is used to refer to any compound, ion or moiety possessing a negative charge.
  • divalent and “divalent” are used to refer to moieties having valances of one and two, respectively.
  • the ter ⁇ i “salt” is meant to apply in its generally defined sense as "compound formed by replacing all or part of the hydrogen ions of an acid with one or more cations of a base. " Sec. e.g., American Heritage Dictionary, Definition of "Salt” (1981).
  • suitable salts for the present invention may be formed by replacing a hydrogen ion of a moiety with a cation, such as K*, Na + , Ca 2+ , Mg 2 *, etc.
  • a cation such as K*, Na + , Ca 2+ , Mg 2 *, etc.
  • other suitable methods of generating salts are specified throughout this specification and are within the scope of the present definition. It is believed that, for the purposes of the present invention, the specific identity of the cation used for forming the salt is of lesser importance than the chemical structure of the anion of which the salt is formed.
  • food article refers to perishable or nonperishable foods such as meats, fruits and vegetables, and also refers to other foods such as grains and dairy products.
  • the food articles referred to herein are those which are perishable or prone to spoilage upon exposure to microbes or other pathogens.
  • a “consumable product” is meant to refer to food articles, fluids for drinking, medicines for ingestion or any other product introduced internally via any means into a human or animal.
  • antimicrobial is used in its general sense to refer to the property of the described compound, product, composition or article to prevent or reduce the growth, spread, formation or other livelihood of organisms such as bacteria, viruses, protozoa, molds, or other organisms likely to cause spoilage or infection.
  • medical article is used to refer to any suitable substrate which is or may come into contact with medical patients (human or animal) , medical caregivers, bodily fluids, or any other source of contamination or infection generally associated with hospitals, clinics, physician's offices, etc.
  • stabilizer is used to refer to the class of polyols as specified herein wherein any two of the at least three hydroxy groups are separated by at least three atoms. Such compounds have been found to stabilize the organosilanes of the invention by preventing self-condensation or other inactivation of the resulting compounds and products.
  • halogen are used to refer to Fluorine "F”, Chlorine “Cl”, Bromine “Br”, Iodine “I”, and Astatine “At”.
  • halogen or halide refers to F, Cl, or Br.
  • halide is meant to include these halogens.
  • the present invention provides the product formed from reacting an organosilane of the formula -.SiX ⁇ where n is an integer of from 0 to 3, preferably 0 to 2; each R is, independently, a nonhydrolizable organic group; and each X is, independently, a hydrolyzable group, with a polyol containing at least three hydroxy groups, wherein any two (i.e., any selected combination of two hydroxy groups from all of the possible pairs of two such groups) of the at least three hydroxy groups are separated by at least three intervening atoms.
  • V " is halide, sulfate, tosyiate, carboxylate, polycarboxylate, alkyl, arylsulfonate, phosphate, phosphonate, borate, or boronate.
  • W is alkyl of from 1 to 22 carbon atoms, more preferably, of from 1 to 10 carbon atoms, even more preferably from 1 to 3 carbon atoms.
  • W is polyether, more preferably a polypropyieneglycol or a polyethyleneglycol.
  • W is aryl, preferably, phenyl or benzyl.
  • W is heretoraryl, wherein the one or more heteroatoms are, independently, N, O, or S.
  • the invention provides the product described above, wherein the organosilane is of the formula ⁇ , IH, IV, or V: (II) 22
  • benzyl is as described above; wherein the ring is unsubstituted or substituted with alkyl of from 1 to 22 carbon atoms, more preferably of from 1 to 10 carbon atoms, most preferably of from 1 to 3 carbon atoms, ester, aldehyde, carboxylate (preferably acetoxy, acetyl, acyl or perfluorocarboxylate), amide, thionamide, nitro, amine, or halide, most preferably Cl, Br, or I;
  • R_$ is lower alkyl alcohol, preferably of from 1 to 6 carbon atoms, more preferably of from 1 to 4 carbon atoms, CH 2 C 6 H j , polyether, such as a polyethyleneglycol or a polypropylene glycol, alkyl of from 1 to 22 carbon atoms, more preferably of from 1 to 10 carbon atoms, most preferably of from 1 to 6 carbon atoms, alkoxy, of from 1 to 22 carbon atoms, more
  • each of Y and V is, independently, halide, sulfate, tosylate, carboxylate, polycarboxylate, alkyl, arylsulfonate, phosphate, phosphonate, borate, or boronate.
  • the present invention provides the product as described above wherein the polyol is a compound having the formula VH:
  • R 12 (R 13 )C[(CH 2 ) r R 14 ] 2 (VII) wherein s is an integer of from 1 to 2;
  • R l2 is (CH- ⁇ where g is an integer of from 0 to 10, preferably of from 1 to 6, and more preferably of from 1 to 3, lower alkyl of from 1 to about 4 carbon atoms, lower alkoxy of from 1 to about 4 carbon atoms, N(R, 5 )(R ⁇ 6 ), N(H)(CH-) 3 OSO 3 H N(H)(CH2) 3 OS0 3 H N(H)(CH,)jOSO,H, N CH ⁇ CH ⁇ SO/, *r(CK 3 ) 3 T, W(R perennial)(R lt ) R 9 )T, where R 15 , R 16 , R 17 , and R restroom are, independently, H, O, or lower alkyl of from 1 to about 4 carbon atoms, polyalkyl ester, benzyl, or R I3 and R
  • each R l4 is, independently, OH or where j is an integer of from 0 to 5, preferably of from 0 to 2, more preferably 0, and wherein one of the R, moieties is bonded to the Si by removal of the hydrogen from a hydroxy such that the oxygen of the hydroxy is bonded to Si; or a perfluoro- analog, i.e. wherein one or more of the hydrocarbon H atoms are replaced with F atoms; or a mixture thereof.
  • g is an integer of from 0 to 3;
  • R J2 is (CH 2 ) g R I4 , lower alkyl of from 1 to about 4 carbon atoms, lower alkoxy of from 1 to about 4 carbon atoms, N(R, 5 )(R 16 ), N(H)(CH 2 ) 3 OSO 3 H N*(CH 3 ) 2 (CH a )_SO J ⁇ N + (CH 3 ) 3 T ⁇ or N * (R.
  • R 13 is H, OH, (CH ⁇ R.,,, (CH 2 )OPO 3 H 2 , or (CHJPOjHj, lower alkyl of from 1 to 4 carbon atoms, lower alkoxy of from 1 to about 4 carbon atoms, and each R I4 is, independently, OH or [-CH 2 C(CH 2 OH) 2 CH 2 O] j -H where j is an integer of from 0 to 5 and wherein one of the R, 4 moieties is bonded to the Si by removal of the hydrogen from a hydroxy such that the oxygen of the hydroxy is bonded to Si.
  • R- 2 is (CH ⁇ j R ⁇ , lower alkyl of from 1 to about 4 carbon atoms, or lower alkoxy of from 1 to about 4 carbon atoms.
  • R I2 is NOR-u) ⁇ , ⁇ , N(H)(CH 2 ) 3 OS0 3 H, N + (CH 3 ) 2 (CH 2 ) 3 SO 3 -,
  • g is an integer of from 0 to 3;
  • R 12 is (CH 2 ) ⁇ R M , lower alkyl of from 1 to about 4 carbon atoms, lower alkoxy of from 1 to about 4 carbon atoms, N(R, 5 )(R l ⁇ ), N(H)(CH 2 ) 3 OSO 3 H, NfH CH ⁇ OSO j H, or N + (R l7 )(R lt )(R . ,)T-; and each R u is OH.
  • g is an integer of from 0 to 3;
  • R !2 is (CHj).R u , lower alkyl of from 1 to about 4 carbon atoms, lower alkoxy of from 1 to about 4 carbon atoms, N(R, 5 )(R l6 ), NfHXCH ⁇ OSO j H, NfHXCH ⁇ OSO j H, N(H)(CH 2 ) 3 OSO 3 H N + (CH 3 ) 2 (CH 2 ) 3 SO,-, >r(CH,) 3 r, orl (Rmony)(R u ) R l9 )T; and each R u is, independently, [-CH 2 C(CH 2 OH) 2 CH 2 O] r H where j is an integer of from 0 to 5 and wherein one of the R, 4 moieties is bonded to the Si by removal of the hydrogen from a hydroxy such that the oxygen of the hydroxy is bonded to Si.
  • the present invention provides a compound having the formula (R) n Si(X) ⁇ . y (Rêt) y wherein n is an integer of from 0 to 3; y is an integer of from 1 to 4; each R is, independently, a nonhydrolizable organic group, preferably a quaternary ammonium moiety; each X is, independently, a hydrolyzable group, preferably methoxy or ethoxy; and each , t is, independently, a polyol containing at least three hydroxy groups, wherein any two of the at least three hydroxy groups are separated by at least three intervening atoms and wherein the polyol is bonded to the Si by removal of the hydrogen from one of the at least three hydroxy groups such that the oxygen of the one of the at least three hydroxy groups is bonded to Si.
  • the present invention provides a compound having the formula VBI, IX, X or XI:
  • each of Q and U is, independently, halide, sulfate, tosylate, carboxylate, polycarboxylate, alkyl, arylsulfonate, phosphate, phosphonate, borate, or boronate.
  • the compound is of the formula VHI. In a further embodiment, the compound is of the formula C. In another further embodiment, the compound is of the formula X. In yet another further embodiment, the compound is of the formula XI.
  • the present invention provides the compound as described above, wherein R 2 -. is H or OH
  • R JJ and R ⁇ are, independently, halogen, H, CH 2 OH N(CH 2 CH 2 OH) 2 CH 3 + Q-, NHj, NOj, N(H)(CH 2 ) 3 OSO 3 H N + (CH 3 ) 2 (CH 2 ) 3 SO 3 -, N(CH 3 ) 3 + Q-,
  • R ⁇ .and R 2 are, independently, N(H)R 34 (CF 2 ) C CF 3 .
  • R a and R 24 are, independently, (W) p ZO.
  • Ro and R 24 are, independently, (W) ⁇ LS(0) r
  • R a and R 24 are, independently, (V ⁇ -Z ⁇ N.
  • R a and R j4 are, independently,
  • R JJ and R 24 are, independently, (W).Z 6 PO 3 .
  • R ⁇ and ⁇ are, independently, lower alkyl alcohol, lower alkoxy of from 1 to 4 carbon atoms, or alkyl of from 1 to about 22 carbon atoms, preferably 1 to about 10 carbon atoms, preferably of from 1 to 4 carbon atoms.
  • R M and ⁇ together, form a morpholine or cyclic or heterocychc, unsaturated or saturated, five to seven-membered ring of the formula XH and R ⁇ where the ring is saturated, is CH 2 , O, S, NH NH- + , NCH 2 CH 2 NH 2 , NCH 2 CH 2 NH 3 + , NCH 2 CH 2 N(R.)(R*), N(alkyl), N(aryl), N(benzyl) where R 30 , R 3 ⁇ , and R 32 are, independently, benzyl, polyether, lower alkyl alcohol, lower alkoxy of from 1 to 4 carbon atoms, alkyl of from 1 to about 22 carbon atoms, preferably 1 to about 10 carbon atoms, and R ⁇ where the ring is unsaturated is, CH N, N * H, N ⁇ alkyl), N * (aryl), N * (be ⁇ zy ⁇ ), N-CH 2 -N, N ⁇ - CH 2 -N
  • R 26 and R 27 together, form a morpholine or cyclic or heterocychc, saturated, five to seven-membered ring of the formula XII and R w is CH 2 , O, S, NH NH 2 + , NCH 2 CH 2 NH 2 , NCH 2 CH 2 NH 3 + , NCH 2 CH 2 N(R,)(R,), NCH 2 CH 2 N + (R M )(R 31 )(R 32 )- N(alkyl), N(aryl), N(benzyl) where R 30 , R 31 , and R 32 are, independently, benzyl, polyether, lower alkyl alcohol, lower alkoxy of from 1 to 4 carbon atoms, alkyl of from 1 to about 22 carbon atoms, preferably 1 to about 10 carbon atoms.
  • R 26 and Ry- can, together, form a morpholine or cyclic or heterocychc, unsaturated, five to seven-membered ring of the formula XH and R ⁇ is, CH N, N ⁇ , N + (alkyl), N (aryl), ⁇ (benzyl), N-CH 2 -N, NT ⁇ -CH 2 -N, N alkyl)-CH 2 -N, N * (a ⁇ yl)-CH N, or N * (benzyI)-CHj-N.
  • the ring is unsubstituted or substituted with alkyl of from 1 to 22 carbon atoms, ester, aldehyde, carboxylate, amide, thionamide, nitro, amine, or halide.
  • R 2 is lower alkyl alcohol, CH 2 C 6 H 5 , alkyl, alkoxy.
  • R 2 is polyether.
  • R 2 is perfluoroalkyl, pefluoroalkylsulfonate, or perfluoroalkylcarboxylate.
  • the present invention provides a compound having the formula XHI:
  • R._ (R. 3 )( ⁇ M )SiR, 5 >T(R 4 ,) 2 (R, 7 )X- (XDT)
  • X is halogen such as CL Br, or I, preferably Cl
  • R ⁇ is lower alkyl of from 1 to 3 carbon atoms, preferably 3 carbon atoms
  • R ⁇ is lower alkyl of from 1 to 3 carbon atoms, preferably 1 carbon atoms
  • R ⁇ is alkyl of from 1 to 22 carbon atoms, preferably of from 10 to 20 carbon atoms, more preferably of from 14 to 18 carbon atoms and most preferably of 18 carbon atoms
  • R, 2 , R- ⁇ and R ⁇ are, independently, OH, CH 2 OH, or (- wherein each Z is, independently, -CH 2 OH -CH 3 , - H -NO - , provided that at least one of R ⁇ R, 3 , and ⁇ is not OH or CH 2 OH
  • the present invention provides the compound of formula X ⁇ i wherein R, 7 is C fatigueH 37 .
  • R ⁇ 2 , R, 3 , and u are, independently, OH CH 2 OH or -OCH 2 -C(CH 2 OH) 3 .
  • R ⁇ 2 , R restroom, and R ⁇ are, independently, OH CH 2 OH or -OCH 2 C(CH 2 OH) 2 (CH 3 ).
  • R 42 , R 3 , and R w are, independently, OH CH 2 OH or - OCH 2 C(CH 2 OH) 2 (NH 2 ) .
  • R ⁇ , R ⁇ , and R are, independently, OH CH 2 OH or -OCH 2 C(CH 2 OH) 2 (N ⁇ 2 ).
  • R «, andmen are, independently, OH CH 2 OH or -
  • R 42 , R ⁇ , and R ⁇ are, independently, OH CH 2 OH or OCH 2 C(CH 2 OH) 2 [(CH 2 )PO 3 H 2 ].
  • R 3 , and ⁇ are, independently, OH CH 2 OH or - OCH 2 C(CH 2 OH) 2 [N * (CH j ) 3 ]Cl " .
  • B ⁇ R ⁇ 3 , and R represent are, independently, OH CHjOH or -OCH 2 C(CH 2 OH) 2 [N(H)(CH 2 ) 3 OS0 3 H].
  • R ⁇ 2 , R ⁇ 3 , and R ⁇ are, independently, OH CH 2 OH or -
  • the present invention provides, a water stable composition, comprising the product as described above and water.
  • the invention also provides a water stable composition, comprising one or more of the compounds as described above and water.
  • the organosilane is 3- (trihydroxysiiyl)propyldimethyloctadecyl ammonium chloride and the polyol is pentaerythritol.
  • the organosilane is 3- (trihydroxysilyl)propyldirnethyloctadecyl ammonium chloride and the polyol is tris(hydroxymethyI)ethane.
  • the organosilane is 3- (trihydroxysilyl)propyldimethyloctadecyl ammonium chloride and the polyol is 5 dipentaerythritol, tripentaerythritol, tetrapentaerythritol, tris(hydroxymethyl)propane, tris(hydroxymethyl)nitromethane, tris(hydroxymethyl)aminomethane, or tris(hydroxymethyl)methanetrimethyl ammonium iodide.
  • the present invention also provides a composition for treatbg a 0 substrate, comprising a carrier and an effective amount of the product as described above.
  • the present invention provides a composition for treating a substrate, comprising a carrier and an effective amount of the compound as described above.
  • the carrier is other than water.
  • the organosilane is
  • the organositol is pentaerythritol, dipentaerythritol, 0 -tripentaerythritol, tetrapentaerythritol, tris(hydroxymethyl)ethane, * ⁇ tris(hydroxymethyl)propane, tris(hydroxymethyI)nitromethane, tris(hydroxymethyl)aminomethane, or tris(hydroxymethyl)methanetrimethyl ammonium iodide.
  • the organositol is pentaerythritol, dipentaerythritol, 0 -tripentaerythritol, tetrapentaerythritol, tris(hydroxymethyl)ethane, * ⁇ tris(hydroxymethyl)propane, tris(hydroxymethyI)nitromethane, tris(hydroxymethyl)aminomethane, or tris(hydroxymethyl)methanetrimethyl ammonium iodide.
  • the organosilane is NH 2 (CH 2 ) 2 NH(CH 2 ) 3 Si(OCH 3 ) 3> NH 2 (CH 2 ) 3 Si(OCH 3 ) 3 , NH 2 (CH 2 ) 3 Si(OCH 2 CH 3 ) classroom Cl(CH 2 ) 3 Si(OCH 3 ) 3 , Cl(CH 2 ) 3 Si(OCH 2 CH 3 ) 3 , C CH ⁇ j SiCl j , 25 C 3 HjO 2 (CH 2 ) 3 Si(OCH 3 ) 3 , C 4 H 5 O 2 (CH 2 ) 3 Si(OCH 3 ) j ,
  • the present invention provides a compound having the formula (R S X ⁇ . y ⁇ R J y wherein n is an integer of from 0 to 3, preferably 0 to 2; y is an integer of from 1 to 4; each R is, independently, a nonhydrolizable organic group; each X is, independently, a hydrolyzable group; and each R, is, independently, a poly(tetrahydrofuran), a poly(vinyl) alcohol, hydroxyethyl cellulose, starch, or a cellulosic derivative, containing at least three hydroxy groups, wherein any two of the at least three hydroxy groups are separated by at least three intervening atoms and wherein the R ⁇ bonded to the Si by removal of the hydrogen from one of the at least three hydroxy groups such that the oxygen of the one of the at least three hydroxy groups is bonded to Si.
  • the present invention also provides a product from reacting an organosilane of the formula II, III, IV, or V:
  • the present invention also provides a product produced as described above, but where the polyol is a phosphorylated pentaerythritol or a pentaerythritol substituted aryl.
  • the polyol is of the formula XTV: (HOCH 2 ) friendshipC[CH 2 OP(R ⁇ 0 )(R 61 )] 4 ⁇ (XIV) or is aryl, preferably phenyl, substituted with from 2 to 6 moieties of - (OCH 2 )C(CH 2 OH) 3 , wherein the substitutions are ortho, meta, or para with respect to one another, wherein aa is an integer of from 0 to 4, preferably 1 to 2, more preferably 1; each R ⁇ , is, independently, O 2 or OH an each R «, is, independently, H a mono- or di-valent cation, such as, but not limited to, K + , Na + , Ca *2 , or Mg +2 , or OR ⁇ where ⁇ is alkyl of from 1 to 22 carbon atoms, preferably of from 1 to 10 carbon atoms, more preferably lower alkyl of from 1 to 6 carbon atoms, or is lower alkyl alcohol
  • the present invention also provides a method of treating a substrate, comprising contacting the substrate with a sufficient amount of the product as described above for a period of time sufficient for treatment of the substrate.
  • the present invention provides a method of treating a substrate, comprising contacting the substrate with a sufficient amount of the compound as described above for a period of time sufficient for treatment of the substrate.
  • the present invention provides a treated substrate having adhered thereto the product as described above.
  • the present invention provides a treated substrate having adhered thereto the compound as described above.
  • the present invention provides a method of dyeing and treating a substrate, comprising contacting the substrate with an aqueous (i.e., substantially water soluble) composition comprising an aqueous soluble dye suitable for dyeing a substrate and the product formed from reacting an organosilane of the formula R-SiX ⁇ where n is an integer of from 0 to 3, preferably 0 to 2; each R is, mdependently, a nonhydrolizable organic group; and each X is, independently, a hydrolizable group, with a polyol containing at least three hydroxy groups, wherein any two of the at least three hydroxy groups are separated by at least three intervening atoms, for a period of time sufficient to dye and treat the substrate.
  • an organosilane of the formula R-SiX ⁇ where n is an integer of from 0 to 3, preferably 0 to 2; each R is, mdependently, a nonhydrolizable organic group; and each X is, independently, a hydrolizable group
  • the present invention provides a method of antimicrobially treating a food article, comprising contacting the food article with an effective amount of the product formed from reacting an antimicrobial organosilane of the formula R-SiX ⁇ where n is an integer of from 0 to 3, preferably 0 to 2; each R is, independently, a nonhydrolizable organic group; and each X is, independently, a hydrolizable group, with a polyol containing at least three hydroxy groups, wherein any two of the at least three hydroxy groups are separated by at least three intervening atoms, for a period of time sufficient to antimicrobially treat the food article.
  • an antimicrobial organosilane of the formula R-SiX ⁇ where n is an integer of from 0 to 3, preferably 0 to 2; each R is, independently, a nonhydrolizable organic group; and each X is, independently, a hydrolizable group, with a polyol containing at least three hydroxy groups, wherein any two of the at least three
  • the present invention provides a method of antimicrobially coating a fluid container used for containing a human or animal consumable product, comprising contacting the container with an effective amount of the product formed from reacting an antimicrobial organosilane of the formula R ⁇ SiX ⁇ where n is an integer of from 0 to 3, preferably 0 to 2; each R is, independently, a nonhydrolizable organic group; and each X is, independently, a hydrolizable group, with a polyol containing at least three hydroxy groups, wherein any two of the at least three hydroxy groups are separated by at least three intervening atoms, for a period of time sufficient to antimicrobially coat the container.
  • an antimicrobial organosilane of the formula R ⁇ SiX ⁇ where n is an integer of from 0 to 3, preferably 0 to 2; each R is, independently, a nonhydrolizable organic group; and each X is, independently, a hydrolizable group, with a polyol containing at least three hydroxy groups
  • the present invention provides a method of antimicrobially coating a latex medical article for use in a human or animal medical procedure, comprising contacting the article with an effective amount of the product formed from reacting an antimicrobial organosilane of the formula R-.SiX ⁇ where n is an integer of from 0 to 3, preferably 0 to 2; each R is, independently, a nonhydrolizable organic group; and each X is, independently, a hydrolizable group, with a polyol containing at least three hydroxy groups, wherein any two of the at least three hydroxy groups are separated by at least three intervening atoms, for a period of time sufficient to antimicrobially coat the article.
  • the article is a surgical glove.
  • the present invention provides a method of antimicrobially treating a substrate selected from the group consisting of a concrete pipe, a tooth brush, a comb, a hair brush, a denture, an orthodontic retainer, a spa or pool filter, an air filter, an HVAC air system, a cabin air system, a marble article, a statue, an exposed work of art, an HDP plastic cover, a silicone or TEFLON® coated fiberglass article, a Dryvitt finish, a stucco finish, blended cotton, a bio-film, a bio-adhesive, a single ply roofing, a roofing shingle, and a fiberglass reinforcement product, comprising contacting the substrate with an effective amount of the product formed from reacting an antimicrobial organosilane of the formula R-SiX ⁇ where n is an integer of from 0 to 3, preferably 0 to 2; each R is, independently, a nonhydrolizable organic group; and each X is, independently, a hydrolizable group, with
  • the present invention provides a method of antimicrobially enhancing a product of nibbing alcohol, a flower preservative, or a waterproofing solution, comprising admixing with the product an effective amount of the product formed from reacting an antimicrobial organosilane of the formula R- ⁇ iX ⁇ where n is an integer of from 0 to 3, preferably 0 to 2; each R is, independently, a nonhydrolizable organic group; and each X is, independently, a hydrolyzable group, with a polyol containing at least three hydroxy groups, wherein any two of the at least three hydroxy groups are separated by at least three intervening atoms, for a period of time sufficient to antimicrobially enhance the product.
  • the present invention provides water-stabilized and solubilized organosilane compounds, products and compositions, methods for their use, and articles prepared using the compounds, products and compositions.
  • the present invention is useful in stabilizing a broad variety of organosilanes of the general formula R n Si ⁇ where n is an integer of from 0 to 3, preferably 0 to 2; R is a nonhydrolizable organic group, such as but not limited to, alkyl, aromatic, organofunctional, or a combination thereof; and X is halogen, such as but not limited to, Cl, Br, or I, or X is hydroxy, alkoxy such as methoxy or ethoxy, acetoxy, or unsubstituted or substituted acyl.
  • the present invention employs from about 0.001 % to about 15 % by weight of an organosilane containing hydrolyzable groups and from about 0.25 to about 5.0 molar equivalents, preferably from 1 to about 2 molar equivalents of a polyol stabilizer of the invention.
  • the compounds, products and compositions of the present invention are prepared by admixing or dissolving any of the described polyol stabilizers in less than the final desired volume of water, adding the any of the desired organosilanes to the water solution, and then diluting further with water to the desired concentration.
  • This preparation is preferably for water soluble stabilizers, such as pentaerythritol, tris(hydroxymethyl) ethane, tris(hydr ⁇ 7me ⁇ yl)nitromethane, etc.
  • stabilizers such as pentaerythritol, tris(hydroxymethyl) ethane, tris(hydr ⁇ 7me ⁇ yl)nitromethane, etc.
  • additional stability is achieved by directly forming a trioxab ⁇ eyclooctyl species and the organosilane may be reacted with the stabilizer in a non-aqueous solvent.
  • the remaining solvent e.g., methanol
  • Both of these methods provide stable, clear solutions of the organosilane which are capable of coating surfaces with the organosilane upon treatment of the surface with the solution.
  • the solutions are stable within a pH range of from about 2.0 to about 10.5, preferably from about 2.0 to about 7.0, for extended periods, up to several months or longer. Higher pH stability ( > 7.0) is also within the scope of the present invention, as further separately described below.
  • the solutions of the present invention are, in certain preferred embodiments, useful for the application of various organosilane coupling agents to surfaces in industrial and household uses without the use of toxic and/or flammable organic solvents.
  • the present invention is useful for stabilizing organosilanes of the general formula R-SiX ⁇ where n is an integer of from 0 to 3, preferably 0 to 2; R is a nonhydrolizable organic group (alkyl, aromatic, organofunctional, or a combination thereof); and X is hydroxy, alkoxy, preferably methoxy or ethoxy, halogen, preferably Cl, Br, or I, acetoxy, acyl or substituted acyl, or a hydrolyzable polymer or other moiety prone to hydrolysis and/or environmentally harmful.
  • organosilanes used in the practice of the present invention need not be, and often are not, water soluble.
  • the organosilanes selected for use in the present invention are solubilized in water by the stabilizer.
  • organosilanes are suitable for the present stabilization procedures to produce water-stabilized compounds, products and compositions.
  • United States Patents 5,411,585; 5,064,613; 5,145,592, and the publication entitled "A Guide to DC Silane Coupling Agent” (Dow Corning, 1990) disclose many suitable organosilanes. The contents of these references are hereby incorporated in their entirety herein by this reference for the teachings of suitable organosilanes.
  • These organosilanes are suitable for the formation of the water-stabilized organosilane compounds, products and compositions of the present invention.
  • silanes for use in the compounds, products and compositions and methods of the present invention include silanes of the following formulae:
  • each R is, independently, halogen [Cl, Br, I, F] or R ⁇ O, where R ⁇ is H, alkyl of from 1 to about 6 carbon atoms, unsubstituted or substituted, preferably from 1 to about 2 carbon atoms and more preferably 1 carbon atom, or acetyl- or other acyl, including substituted acyl, or R ⁇ O can be derived from any hydroxylated polymer, hydroxylated liquid, or hydroxylated solid regardless of water solubility, or R $ O can be derived from any polyether such as, but not limited to, polyethyleneglycols or polypropyleneglycols, such as poly(propyleneglycol)triol (glycerol propoxylate); j is unsubstituted or substituted benzyl- or an unsubstituted or substituted alkyl of from 1 to about 3 carbons atoms, preferably alkyl of from 1 to 3 carbon atoms; R 3 and R 4 are
  • k is an integer from 0 to 2 and R 7 , where the ring is saturated, is CH 2 , O, S, NH, NH 2 *. NCH 2 CH 2 NH 2 , NCH 2 CH 2 NH 3 *. NCHjCHaNt ⁇ H ,), NCH 2 CH 2 N + ( 8 )(R 9 )(R ⁇ o), N(alkyl), N(aryl), N(benzyl), and R 7 , where the ring is unsaturated is, N. N + H, N*(aikyl), N + (aryl), N*(benzyl).
  • R 8 , R, and R, 0 are, independently, benzyl, polyether, lower alkyl alcohol of from 1 to 4 carbon atoms, lower alkoxy of from 1 to 4 carbon atoms, or alkyl of from 1 to about 22 carbon atoms, preferably 1 to about 10 carbon atoms;
  • Rj is CH 2 C 6 H S , CH 2 CH 2 OH, CH 2 CH(OH)CH 3 , a polyether such as polyethyleneglycol: -(CH 2 CH 2 O) t H, polypropyleneglycol: -(CH 2 CH(CH 3 )O) t H, or alkylated polyoxyethylene: - (CH 2 CH 2 O),B where B is alkyl of from 1 to 22 carbon atoms, unsub
  • Preferred organosilanes include, but are not limited to:
  • 3-aminopropyltriethoxysilane NH 2 (CH 2 ) 3 Si(OCH 2 CH 3 ) 3 , '-! 3-chloropropyltrimethoxysilane: CKCH ⁇ SifOCH ⁇ , - ⁇ 3-chloropropyltriethoxysilane: Cl(CH 2 ) 3 Si(OCH 2 CHj) 3 , 3-chloropropyltrichlorosilane: Cl(CH 2 ) 3 SiCl 3 , -"> 3-glycidoxypropyltrimethoxysilane: C 3 H 5 O 2 (CH 2 ) 3 Si(OCH 3 ) 3 , ⁇ 3 -glycidoxypropyltriethoxy silane: C 3 H 5 ⁇ 2 (CH 2 ) 3 Si(OCH 2 CH 3 ) 3 , - 3-methacryloxypropyltrimethoxysilane: C 4 H 5 O 2 (CH 2 ) 3 Si(OCH 3 ) 3 ,
  • preferred stabilizers of the present invention preferably contain at least three hydroxy groups, where any two of the three hydroxy groups are preferably separated by at least three intervening atoms, i.e., (HO-A-B-C-OH).
  • Such stabilizers can stabilize aqueous solutions of the above-described organosilanes R-SiX ⁇ and are generally useful for stabilization of all such solutions where n is an integer from 0 to 2 and where water solubility or minimization or prevention of water-induced, silanol self-condensation (and associated polymerization) is desired.
  • preferred stabilizers are polyols containing three or more OH groups and having at least three carbon atoms separating any two OH groups.
  • suitable stabilizers of the present invention are of the formula:
  • o is an integer of from 2 to 3; q is an integer greater than 0, preferably 1 or 2; p is an integer from 0 to 1; W is alkyl, polyether, aryl or heteroaryl; Rrud and R 33 are, independently, halogen [Cl, Br, I, F], H, CH 2 OH, N(CH 2 CH 2 OH) 2 CH 3 *V ⁇ hydrocarbon, a heteroatom, or any other suitable functionaiized substituent such that the final formulation is soluble in water.
  • R t , or R 33 moieties include, but arc not limited to, NH 2 , NO 2 , ZO (where Z is H, alkyl, organofunctional alkyl, aryl, organofunctional aryl, or heteroaryl) , ZS(O) r (where Z is H, Na, or any other mono- or di-valent cation including ammonium, alkyl, organofunctional alkyl, aryl, organofunctional aryl, or heteroaryl and r is an integer from 0 to 2), Z,Z 2 N(where Z, and Z * .
  • Z 3 Z 4 Z 5 N + X " (where Z 3 , Z 4 , and Z s are, independently, alkyl, organofunctional alkyl, aryl, organofunctional aryl, or heteroaryl), Z 6 PO 3 (where Z 6 is H, Na, or any other mono- or di-valent cation including ammonium, alkyl, organofunctional alkyl, aryl, organofunctional aryl, or heteroaryl), and N(H)R 34 (CF 2 ) e CF 3 where R u is CO or SO 2 and e is an integer of from 1 to 22; and V is halogen [F, Cl, Br, or I], sulfate, tosylate or carboxylate, such as acetate, polycarboxylate salts ⁇ functionaiized carboxylate, such as trifluoroacetate and perfluoroalkylcarbox
  • stabilizers useful for practicing the present invention are of the general formula:
  • R I2 and R 13 are, independently, H, OH, alkyl of from 1 to about 4 carbon atoms, unsubstituted or substituted with OH, carboxylate, or phosphate esters, such as, but not limited to, CH 2 CO 2 * , CH 2 OPO 3 " , CH 2 CH 2 OH, CH 2 CH 2 OPO 3 " .
  • R, 2 and R I3 may also be N, unsubstituted (amino, i.e., NH 2 ) or substituted with O (nitro, e., NO 2 ) or substituted to produce an amide, sulfonamide, phosphonamide, oxime, thionamide, quaternary ammonium, imine, imide (such as succinimide) , guanidine, amine oxide (such as NfOJ sj si, where ⁇ and R ⁇ are, independently, lower alkyl alcohol of from 1 to 4 carbon atoms, lower alkoxy of from 1 to 4 carbon atoms, or alkyl of from 1 to about 4 carbon atoms.
  • preferable stabilizers may be of the following formulae: (HOCH 2 ) 3 CN(R 14 )(R 15 ) or
  • R M and R 15 are, independently, H, -O- (i.e., nitro functionality) or alkyl of from 1 to about 4 carbon atoms, unsubstituted or substituted with OH, or piperazine, piperazine derivatives, morpholine, polyalkylether, or benzyl;
  • R 16 is H, phenyl or alkyl of from 1 to 22 carbons, unsubstituted or substituted with OH, phenyl- or can be polyalkylether, such as polyethylene glycol;
  • U is halogen [F, Cl, Br, or I], sulfate, tosylate or carboxylate, such as acetate, polycarboxylate salts, functionaiized carboxylate, such as trifluoroacetate and perfluoroalkylcarboxylates, or other alkyl and arylsulfonate salts including trifluoromethylsulfonate and perfluoroalkylsulfonate
  • stabilizers suitable for the present invention preferably require O atoms (usually from hydroxy groups) to be separated by at least three carbons because of favored formation of 6-membered rings consisting of -O-Si-0- from the organosilane and the three atoms (usually carbon) from the stabilizer.
  • organosilanes of the formula R-SiX ⁇ where n is 0 or 1, up to two of the six-membered rings can be generated at any particular silicon atom.
  • organosilanes of the formula R-SiX, ⁇ , where n is 2 only one 6-membered ring can form. For example, see Scheme 3.
  • organosilanes of the formula RSiX 3 can generate up to two 6-membered rings for each available silicon atom. But the existence of one or two of the described rings on a particular silicon atom is not critical to the operability of the products, compounds, products and compositions and methods of the present invention, and is instead offered for explication of the believed mechanism by which the present invention operates. With this in mind, not wishing to be bound by theory, it is possible that one or more of the following structures or equilibrations leads to the surprising stabilized organosilanes of the present invention:
  • the stabilizers produce organosilanes, RSiX 3 , possessing two of the indicated 6-membered rings:
  • the stabilizers produce an equilibrating mixture of organosilanes, RSiX 3 , existing predominantly as the species possessing one of the indicated 6-membered rings, but in equilibrium with a species possessing two of the indicated 6-membered rings:
  • the stabilizers produce an equilibrating mixture of 0 organosilanes, RSiX 3 , existing predominantly as the species possessing none of the 6- rnembered rings, but in equilibrium with the species possessing one of the indicated 6-membered rings and the species possessing two of the indicated 6-membered rings:
  • the stabilizers are not covalently attached to the organosilane ,
  • the stabilizers form linear and/or cyclic oligomers (linear shown below) consisting of regular repeating units of RSi(OH) 3 condensed with (HOCH j )CZ units, wherein stabilization is achieved by preventing formation of O-Si- O-Si-O-Si-0 polymers and, concurrently, retaining water solubility. Even in this scenario, the formation of a small equilibrium of the 6-membered ring compounds may be important to the stabilization mechanism:
  • the stabilizers form linear and/or cyclic oligomers (linear shown below) consisting of both regular repeating units of RSi(OH) 3 condensed with (HOCHj)CZ units and sections containing some short 0-Si-O-Si-O-Si-O polymeric units, wherein stabilization is achieved by preventing formation of extensive O-Si-O- Si-O-Si-O polymers (linear and/or cyclic) and, concurrently, retaining water 0 solubility. Even in this scenario, the formation of a small equilibrium of the 6- membered ring compounds may be important to the stabilization mechanism:
  • Scheme 3 shows the reaction scheme for preparing 3-(trimethoxysUyl)propyl-c-imethy.octadccyl ammonium chloride, and subsequent hydrolysis and conversion to the fully-complexcd pentaerythritol-
  • the viscosity of the water-stabilized quaternary ammonium silane may be varied as follows.
  • a solvent such as methanol
  • the resultant pentaerythritol-stabilized aqueous solution undergoes slight gelling leading to a viscous solution after aging.
  • the binding properties of the organosilane are retained in the YJSCOUS product.
  • the solutions are non-viscous after several months, even at the same pH.
  • stabilizers include, but are not limited to: polyols such as pentaerythritol -and its higher homologues, i.e., dipentaerythritol, tripentaerythritol, tetrapentaerythritol, etc., tris(hydroxymethyl)ethane, tris(hydroxymethyl)ptopane, tris (hydroxy methyl) nitromethane , tris(hydroxymethyl) aminomethane , tris(hydroxymethyl)methanetrimethylammonium iodide, and tris(hydroxymethyl)nitromethane.
  • polyols such as pentaerythritol -and its higher homologues, i.e., dipentaerythritol, tripentaerythritol, tetrapentaerythritol, etc.
  • tris(hydroxymethyl)ethane tris(hydroxymethyl)ptopane
  • poly(tetrahydrofuran), poly(vinyI) alcohol, hydroxyethyl cellulose, starch and cellulosic derivatives also possess water solubilizing and/or stabilizing utility.
  • the stabilizer is tris(hydroxymethyl)methanetrimethylammonium iodide
  • several stabilized organosilanes can be prepared as stable, water-soluble powders by reacting the starting organosilane with the stabilizer in an inert organic solvent and distilling off the methanol that is formed to produce the corresponding trioxasilabicyclooctyl compound (see Formula 1 below) as a stable, water-soluble powder.
  • Such products are useful for convenience of storage and transportation and for blendmg with water immiscible media such as plasticizers and plastics, clays, mortar, fillers, dyes and pigments.
  • water immiscible media such as plasticizers and plastics, clays, mortar, fillers, dyes and pigments.
  • such compositions could readily be delivered in an encapsulated or microencapsulated form, wherein the organosilane is regenerated by abrasion or erosion of the capsule thereby providing a continuous, intermittent, or otherwise predetermined supply of the organosilane.
  • the tris (hydroxy methyl) ethane- stabilized compound is soluble in methanol and probably other solvents. Therefore, that stabilizer could be used to prepare a concentrated, stabilized antimicrobial organosilane which is then diluted for use on-site. Moreover, this stabilizer could also, alternatively, be used to prepare a solid, stabilized antimicrobial organosilane for use by on-site addition of water. Such a concentrated or solid preparations would provide for significant savings cost in shipping and storage of the product. Moreover, the shelf-life of a methanol solution of the tris (hydroxymethyl) ethane stabilized compound is expected to be indefinite.
  • the present invention uses the organosilane-derived antimicrobial 3-(trimethoxysilyl)propyl-dimethyloctadecyl ammonium chloride, but exchanges up to three of the methoxy groups on the silane with a water-soluble stabilizer moiety. Moreover, any remaining methoxy groups on the silane are lost to hydrolysis.
  • Suitable water-soluble stabilizers moieties include polyols, such as but not limited to, tetraols, such as pentaerythritol or its higher homologues (dimers, trimers, etc.) , or chemically related variants of pentaerythritol.
  • the stabilizing compounds and methods of the present invention are useful for stabilizing organosilanes of the above-described general formula R-SiX ⁇ in water under either low or high pH conditions.
  • High pH stabilization occurs through the use of an excess (greater than one molar equivalent) of the stabilizer, or through the use of the stabilizers of the present invention in conjunction with other stabilizers already known to provide some enhancement of stability in water at various pH ranges. See, e.g. , U.S. Patent No. 5,411,585 (which is herein incorporated by this reference), which discloses certain stabilizers.
  • high pH stability could be achieved through any one of three methods. First, the use of excess (preferably 2.0 to 5.0, or more, molar equivalents) of stabilizer.
  • Preferable functional groups R, 7 include, but are not limited to, COOH, COONa, -P(O)(OH) 2 , -P(O)(ONa) 2 , -P(O)(OH)(OR ]8 ), -P(O)(ONa)(OR 18 ), -SO 3 H, -SO 3 Na, -B(OH) 2 , - B(OH)(ONa), or -B(ONa) 2 where R 18 is alkyl or perfluoroalkyl, branched or unbranched, of from 1 to 22 carbon atoms, aryl or heteroaryl, such as phenyl or benzyl, polyether, such as a polyethylene glycol or polypropylene glycol.
  • any hydrogen of a selected hydroxy groups could be replaced with any other suitable mono-valent or di-valent cation, such as, but certainly not limited to, Na", K ⁇ NH/ , Mg 2* , Ca 2+ , or N(R 70 V where R 70 is alkyl or perfluoroalkyl, branched or unbranched, of from 1 to 22 carbon atoms, aryl or heteroaryl, such as phenyl or benzyl, polyether, such as a polyethylene glycol or polypropylene glycol.
  • any other suitable mono-valent or di-valent cation such as, but certainly not limited to, Na", K ⁇ NH/ , Mg 2* , Ca 2+ , or N(R 70 V where R 70 is alkyl or perfluoroalkyl, branched or unbranched, of from 1 to 22 carbon atoms, aryl or heteroaryl, such as phenyl or benzyl, polyether, such as a polyethylene glycol or polypropy
  • the compounds, products and compositions of the present invention are useful for a multitude of purposes. Such purposes include any known use for the preferred starting material organosilanes of the above-described general formula.
  • the presently described, water-stabilized, organosilane compounds, products and compositions are suitable to applications such as: 1) treatment of surfaces, including fillers and pigments, 2) additives to coatings such as dyes, or 3) as additives to organic monomers (such as acrylics) prior to formation of the respective polymer.
  • organosilane quaternary ammonium compounds such as 3-(trimethoxysilyl)propyl-dimethyloctadecyl ammonium chloride as surface bonding antimicrobial agents
  • organofunctional silanes are contemplated, such as the use of the compounds, products and compositions of the invention in coating applications which include the treatment of surfaces or particles (pigments or fillers), in primers, in paints, inks, dyes and adhesives, and as reactive intermediates for silicone resin synthesis.
  • the present invention can be used to prepare, inter alia, agricultural products, cleaning compositions, antimicrobial sponges, antimicrobial bleaching agents, antimicrobial fillers for paints, plastics, or concrete, and to treat concrete structures such as livestock shelters, where microbial infestation is a problem.
  • surfaces and substrates treatable with the compounds, products and compositions of the invention solution include, but are not limited to, textiles, carpet, carpet backing, upholstery, clothing, sponges, plastics, metals, surgical dressings, masonry, silica, sand, alumina, aluminum chlorohydrate, titanium dioxide, calcium carbonate, wood, glass beads, containers, tiles, floors, curtains, marine products, tents, backpacks, roofing, siding, fencing, trim, insulation, wall-board, trash receptacles, outdoor gear, water purification systems, and soil.
  • articles treatable with the compounds, products and compositions of the invention include, but are not limited to, air filters and materials used for the manufacture thereof, aquarium filters, buffer pads, fiberfill for upholstery, fiberglass ductboard, underwear and outerwear apparel, polyurethane and polyethylene foam, sand bags, tarpaulins, sails, ropes, shoes, socks, towels, disposal wipes, hosiery and intimate apparel; cosmetics, lotions, creams, ointments, disinfectant sanitizers, wood preservatives, plastics, adhesives, paints, pulp, paper, cooling water, and laundry additives and non-food or food contacting surfaces in general.
  • treatment generally involves contacting the article to be treated with a water-stabilized organosilane solution of the present invention, comprising the organosilane-stabilizer derived compound in an aqueous solution, for a period of time sufficient for permanent bonding of the active organosilane ingredient (or portion thereof) to the article.
  • a water-stabilized organosilane solution of the present invention comprising the organosilane-stabilizer derived compound in an aqueous solution
  • treatment begins almost immediately upon contact, but preferably requires from about 15 seconds to about 48 hours, more preferably from about 1 minute to about 24 hours, even more preferably from about five minutes to 1 hour, and even more preferably for about 30 minutes.
  • the solutions of the present invention can be added to pigments and fillers and stirred therewith for several (2-3) minutes.
  • the solutions can be added to an emulsion or other existing formulation prior to use.
  • the solutions can be used in addition to, with or as a spray coolant for extruded fibers.
  • the compositions can be used in padding processes as are known in textile mills.
  • the surface or fabric may, optionally, be heated to further complete bonding of the compound, product, or composition to the surface or substrate.
  • the water-stable organosilane compounds, products and compositions of the present invention are, therefore, advantageous in treating a variety of substrates without the use of toxic organic solvents, and provide for the safe, long-term storage of activated organosilanol compound which can be used without further preparation.
  • the stabilization scheme described herein does not interfere with the binding of the organosilane (or at least the core, operative portion thereof) to the substrate.
  • the present invention provides a generally applicable scheme for solvating some water insoluble organosilanes.
  • organosilanes I ⁇ SiX ⁇ are prepared, dissolved, stored, applied, and in any way used in water.
  • organosilanes R-SiX ⁇ in other solvents or mixed in other media (solids, polymer mixes, fillers, pigments, powders, dyes or emulsions) where exposure to water occurs but could be detrimental due to undesired or untimely self-condensation of the silanol.
  • stabilizing compounds and methods could be used in addition to or in conjunction with various art-known stabilization methods for organosilanes, such as the use of ionic or non-ionic surfactants and detergents.
  • the compounds, products and compositions of the present invention lead to improved wetting and/or coating because the partially hydrolyzed stabilizer/organosilane complex is dense in hydroxyl groups, thus providing for increased hydrogen-bonding to surface OH groups.
  • present compounds, products and compositions can be used in the incorporation of an organosilane antimicrobial agent in most textile goods (woven and non-woven) and yarns (synthetic and natural).
  • the process provides articles that are durable and the process itself is effective and does not require additional manufacturing steps or increase manufacturing cost.
  • incorporation process 1 does not add any additional step in the manufacturing process and does not require any equipment modification; and 2) is believed not to lose its antimicrobial characteristics and its effectiveness during further production of the textile goods.
  • the water-stable compounds, products and compositions of the present invention during the dye process not only would the organosilane antimicrobial agent remain unaffected by the dying agent, but the end-product textile goods would also exhibit excellent dyeing properties.
  • the water-stabilized organosilane compounds, products and compositions of the present invention are useful for a number of applications where the previous instability, insolubility prevented or, at least, hindered or restricted use of some organosilane agents.
  • the previous instability, insolubility prevented or, at least, hindered or restricted use of some organosilane agents are useful for a number of applications where the previous instability, insolubility prevented or, at least, hindered or restricted use of some organosilane agents.
  • Treating food crops (e.g., perishables such as vegetables, fruits, or grains) after removal (picked/harvested) with the compounds, products and compositions of the present invention imparts antimicrobial protection to the outer surface of the food crop. It is believed that such protection occurs without diffusing, migrating or leaching the antimicrobial agent from the bonded antimicrobial coating of the food item, and provides prolonged, safe and non-toxic antimicrobial protection.
  • the method involves treating fruits and vegetables in the rinse cycle, during or after the normal cleaning/ water spraying or during or after blanching. Thorough cleaning of fruits and vegetables at the processing plant is preferred for initially removing microorganisms.
  • machines are used initially to remove soil, chemicals used in growing, spoilage bacteria, and other foreign materials. These machines also use high velocity water sprays to clean the products. After the cleaning, raw foods or other crop materials are prepared for further processing such blanching (i.e., the food is immersed in water at 190 to 210 degrees F. or exposed to steam).
  • Microorganisms are controlled by the production plant up until the fruit or vegetable is removed. But once it is removed, organisms such as yeast, mold, and bacteria, begin to multiply, causing the food to loose flavor and change in color and texture. To keep the food from spoiling, a number of methods have been employed, such as refrigerators, to slow down the microorganisms and delay deterioration. Unfortunately, such known methods will preserve raw foods for few weeks at the most.
  • the compounds, products and compositions of the present invention can preserve these items for extended periods. For instance, the compositions, products, or compounds may be added to an existing water line feeding the sprayers for the foods, where such sprayers are used. Otherwise, a simple dipping process may be used, where the dipping requires only a few seconds to impart antimicrobial protection. Low concentrations of 0.1 to 1 % aqueous solution (0.1 to 1% by volume) of the compositions provide satisfactory results. In addition, it is believed that the presently described method can also control pathogens on poultry carcasses and in other susceptible meat and fish.
  • the present compounds, products and compositions can be used to treat these articles to prevent microbial growth and contamination by coating an effective amount of the products and compounds of the invention thereon.
  • the articles employed can be coated by allowing for 1 to 2 minutes submersion (e.g., by dipping) , and thereafter, the treated surface is allowed to dry at room temperature. The article is then rinsed of any excess antimicrobial agent.
  • Thorough cleaning and sterilization is a preferred step in removing the microorganisms on the surface of the article prior to "coating" the said articles.
  • concentrations of 10% or more by volume of the compounds, products and compositions of the invention are used for long lasting protection.
  • Treating surgical gloves with the compounds, products and compositions of the present invention before or during a surgical procedure can kill microorganisms on contact without. It is believed that the treated gloves do not diffuse or leach the antimicrobial agent from the glove surface and provide prolonged antimicrobial activity with safe and non-toxic antimicrobial protection.
  • Surgical gloves are treated, preferably, by submersing in the solution of Example I, diluted to 1% W/V for at least 30 seconds. This method will permit doctors to use and, if necessary, re-use the same gloves (even without removing them) without undue fear of contamination.
  • HDP high density polyester fabric plastic covers for dump sites, water reservoirs and generally for soil protection
  • a method of treating blended cotton before or after picking machines make the cotton into rolls or laps
  • the present invention provides the following water-stable, pentaerythritol-modified silylated quaternary ammonium salt of formula A:
  • n is an integer from 1 to 3. While the present Example is described with reference to formula A, it is expressly understood that variations in the specified structure are possible. Therefore, the products produced by admixing the silanes of the present invention with the stabilizers of the present invention are also within the scope of the present invention, as claimed. It is believed that the preferred molecule of formula A is a water soluble linear and/or cross-linked oligomer generated by the formation of an equilibrating mixture of intramolecular O-Si-O bonds within the same molecule of formula A and by the formation of intermolecular O-Si-O bonds between different molecules of formula A, as shown in formula B:
  • X is, independently, H or intra- or intermolecular linkages to other molecules of formula A.
  • the pentaerythritol is most likely partially liberated and the product is hydrolyzed to 3- (trihydroxysilyl)propyldimethyioctadecyl ammonium chloride.
  • liberation is not necessary for the operability of the present invention. Its occurrence or non-occurrence does not detract from the general efficacy of the compounds, products and compositions of the present invention. Instead, the notion that pentaerythritol (or any other of the present stabilizers) is liberated is offered as one possible explanation of the surprising utility and efficacy of the claimed invention.
  • the stabilizer must be liberated when the organosilane bonds to a substrate. Because bonding to the substrate can occur through a combination of ionic, hydrogen or covalent bonds, it is likely that the modified organosilanes of the present invention retain the stabilizer moiety, at least to some degree, even after bonding to the substrate.
  • a 5% W V (weight/volume) aqueous solution of 3-(trimethoxysilyl)propyldimethyloctadecyl ammonium chloride was prepared as follows.
  • a 22 L reaction flask was charged with 6250 g. (21.0 Mol.) of dimethyloctadecylamine, 5844 g. (29.4 Mol.) of 3-chloropropyltrimethoxysilane, and 76 g. (0.84 Mol.) of trioxane.
  • the mixture was heated to 140 °C for 12 hours while stirring and is then cooled to 80 °C. 2 L of methanol was then added and the mixture is cooled to approximately 40 °C.
  • the pentaerythritol stabilized 3-(trimethoxysilyl)propyldimethyloctadecyl ammonium chloride is soluble in water up to concentrations of approximately 15% W/V.
  • concentrations of approximately 15% W/V concentrations of approximately 15% W/V.
  • solubility of other organosilanes may vary and depends upon the specific stabilizer used.
  • trioxasilylbicyclooctyl species there may be scenarios where it will be desirable or necessary to pre-form the trioxasilylbicyclooctyl species under anhydrous conditions. This may be necessary where the stabilizer is insoluble in water, or sufficient alcoholysis does not occur in aqueous conditions.
  • the presently contemplated preferred mode for preparing trioxasilylbicyclooctyl species using 3- chloropropyltrimethoxysilane as the organosilane, and tris(hydroxymethyl)methane as the stabilizer was as follows:
  • a 500 ml round-bottomed flask was charged with toluene (100 ml), sec-butyl alcohol (5 ml), 3-chloropropyltrimethoxysila ⁇ e (50 g, 252 mmol), and tris(hydroxymethyl)ethane (36.27g, 302 mmol).
  • the flask was outfitted with a distillation head and receiver and heated to 110 °C for 14 hours after which the theoretical amount of methanol had collected in the receiving flask.
  • the resulting clear mixture was cooled to room temperature and solvents removed under reduced pressure.
  • the pentaerythritol or other polyol can be added to the reaction flask at the beginning, and the methanol produced by the alcoholysis collected by distillation.
  • Samples of pentaerythritol-stabilized 3-(trimethoxysilyI)propyldimethyloctadecyl ammonium chloride were stable for at least 6 months when stored at room temperature.
  • the pH of the solution was from about 4.0 to about 6.7.
  • the samples were stable for up to one month.
  • Below pH about 2.0 samples were stable for up to one week.
  • at pH 7.0 to about 10.2 the samples were also stable for at least one month.
  • Above pH 11.0 however, the samples were unstable and become hazy within minutes. In such cases, the compounds, products and compositions would benefit from the high pH stabilization procedures as described herein. Similar results were found for samples of tris(hydroxymethyl)ethane-stabilized 3-(trimethoxysilyl)propyldimethyloctadecyl ammonium chloride, which showed stability for at least 6 months when stored at room temperature.
  • Table 1 summarizes stability data based upon appearance of the preparation after the specified period of time:
  • Table 1 Stability of unstabilized and stabilized 3- (trimethoxysilyl)propyldimethyloctadecyl ammonium chloride
  • Chloropropyl trimethoxysilane, CI(CH 2 ) 3 Si(OMe) 3 is insoluble in water.
  • addition of C ⁇ CH ⁇ S ⁇ OMe) to water containing pentaerythritol produced a clear solution after standing overnight. Therefore, water insoluble silanes such as Cl(CH 2 ) 3 Si(OMe) 3 can be used in any application where a water solution of a functionaiized organosilane finds utility.
  • the process was carried out as follows. In a dye bath were mixed the following ingredients: antimicrobial agent, pigment color (dyes), binder, antimigrant, wetter, ammonia. Into this bath, a polyester camper material was immersed. After treatment, the antimicrobial effectiveness of the polyester camper was tested and found to exhibit antimicrobial properties.
  • the antimicrobial testing involved the Southern Phenix Textile Fabric 401 A Gray, Style 6048 subjected to the Dow Corning "Shake Flask Test".
  • Southern Phenix a full scale run at the factory was performed by Southern Phenix to determine whether the composition of Example I could be incorporated in the dye process. The following steps were followed. A preparatory treatment including scouring of the fabric to remove oils, dirt, lint and any residue of sizing compounds followed by drying to remove excess moisture was undertaken. The fabric was then immersed in a dye bath having the following ingredients, added at room temperature in the order listed to a 500 gal. kettle:
  • the sample was then treated with this composition by the known padding process at 50 yards/minute.
  • the dye fabric in this example was then dried (as is generally contemplated when dyeing articles) and tested. The results demonstrated that the antimicrobial agent could be incorporated into the fabric during the dye process without affecting either the antimicrobial properties or the dyeing process.
  • the spunbonded polyester sample filter material was submersed in a solution of the composition of Example I. The sample was allowed to soak for 1-2 minutes, and the treated surface was allowed to dry at air temperature (68-72 °F). The results showed that the treated filter material was prevented from building up any significant amount of microorganisms. These results required no pH adjustment unlike some other filter treatments.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Textile Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Microbiology (AREA)
  • Epidemiology (AREA)
  • Food Science & Technology (AREA)
  • Veterinary Medicine (AREA)
  • Public Health (AREA)
  • Animal Behavior & Ethology (AREA)
  • Polymers & Plastics (AREA)
  • Nutrition Science (AREA)
  • Biochemistry (AREA)
  • Materials Engineering (AREA)
  • Pest Control & Pesticides (AREA)
  • Zoology (AREA)
  • Molecular Biology (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Agronomy & Crop Science (AREA)
  • Wood Science & Technology (AREA)
  • Dentistry (AREA)
  • Plant Pathology (AREA)
  • Environmental Sciences (AREA)
  • Heart & Thoracic Surgery (AREA)
  • Surgery (AREA)
  • Vascular Medicine (AREA)
  • Inorganic Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne le produit de réaction d'un organosilane qui renferme éventuellement un groupe organique non hydrolysable, mais renferme un ou plusieurs groupes hydrolysables, avec un polyol contenant au moins trois groupes hydroxy, dont deux sont séparés par au moins trois atomes intermédiaires. Elle concerne également des composés organosilanes rendus stables à l'eau; une composition stable fabriquée à partir du produit ou du composé et d'eau; un procédé permettant de traiter un substrat en le mettant en contact avec le produit, le composé ou la composition pendant une durée suffisante pour traiter le substrat; un substrat traité recouvert du produit, du composé ou de la composition; un procédé permettant de teindre et de traiter un substrat; un procédé permettant de soumettre un article alimentaire à un traitement antimicrobien; un procédé permettant d'appliquer un revêtement antimicrobien sur un récipient pour fluides; et enfin un procédé permettant d'appliquer un revêtement antimicrobien sur un article médical en latex.
PCT/US1997/008913 1996-05-07 1997-05-07 Composes organosilanes rendus stables a l'eau et procedes d'utilisation associes WO1997042200A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
NZ329397A NZ329397A (en) 1997-05-07 1997-05-07 organosilane compounds and antimicrobial compounds containing a organosilane and polyol reaction product
BR9702243-8A BR9702243A (pt) 1996-05-07 1997-05-07 Compostos de organossilanos estabilizados em água e métodos para uso dos mesmos.
IL12255597A IL122555A (en) 1996-05-07 1997-05-07 Water-resistant argosilene compounds and methods of use
AU30113/97A AU3011397A (en) 1996-05-07 1997-05-07 Water-stabilized organosilane compounds and methods for using the same

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US1698596P 1996-05-07 1996-05-07
US65587396A 1996-05-07 1996-05-07
US60/016,985 1996-05-07
US08/655,873 1996-05-07

Publications (1)

Publication Number Publication Date
WO1997042200A1 true WO1997042200A1 (fr) 1997-11-13

Family

ID=26689309

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1997/008913 WO1997042200A1 (fr) 1996-05-07 1997-05-07 Composes organosilanes rendus stables a l'eau et procedes d'utilisation associes

Country Status (4)

Country Link
AU (1) AU3011397A (fr)
BR (1) BR9702243A (fr)
IL (1) IL122555A (fr)
WO (1) WO1997042200A1 (fr)

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0877027A2 (fr) * 1997-05-07 1998-11-11 Bioshield Technologies, Inc. Organosilanes stables à l'eau et leurs procédés d'utilisation
WO1999003865A1 (fr) * 1997-07-18 1999-01-28 Bioshield Technologies, Inc. Composes d'organosilane stables a l'eau et procedes d'utilisation de ces composes
WO1999032157A2 (fr) * 1997-12-23 1999-07-01 Biosafe, Inc. Procede de creation d'un agent biostatique au moyen de polymeres reticules enchevetres
FR2843759A1 (fr) * 2002-08-20 2004-02-27 Louis Rousseau Procede pour le traitement en surface des fibres hydrophiles d'un substrat, naturel ou synthetique
EP1628639A2 (fr) * 2003-05-22 2006-03-01 Coating Systems Laboratories, Inc. Revetements organo ammonium quaternaires antimicrobiens
WO2009045771A3 (fr) * 2007-10-01 2009-05-22 3M Innovative Properties Co Compositions éther silane fluorées cationiques et procédés associés
US7851653B2 (en) 2005-03-22 2010-12-14 Biosafe, Inc. Method of creating a solvent-free polymeric silicon-containing quaternary ammonium antimicrobial agent having superior sustained antimicrobial properties
WO2011127336A1 (fr) * 2010-04-09 2011-10-13 Dow Corning Corporation Silane
US8357751B2 (en) 2007-12-03 2013-01-22 3M Innovative Properties Company Cationic polymeric fluorinated ether silane compositions and methods of use
US8378018B2 (en) 2007-12-03 2013-02-19 3M Innovative Properties Company Cationic polymeric fluorinated ether silane compositions and methods of use
US8501641B2 (en) 2007-10-01 2013-08-06 3M Innovative Properties Company Compositions comprising cationic fluorinated ether silanes, and related methods
KR101460352B1 (ko) 2014-02-28 2014-11-10 동우 화인켐 주식회사 점착제 조성물
ES2553158A1 (es) * 2014-06-04 2015-12-04 Universitat Politècnica De Catalunya Líquido iónico para la extracción de compuestos de boro y composición y procedimientos correspondientes
WO2016029010A1 (fr) * 2014-08-20 2016-02-25 Parasol Medical LLC Cathéters soumis à un traitement antimicrobien
US9333484B2 (en) 2012-12-26 2016-05-10 Exxonmobil Research And Engineering Company Reversible CO2 fixation via self-assembled siloxanes
CN105646563A (zh) * 2016-01-27 2016-06-08 于美宁 一种有机硅季铵盐抗菌剂及其制备方法
US9364572B2 (en) 2003-05-22 2016-06-14 Coating Systems Laboratories, Inc. Static fluid disinfecting systems and related methods
US9764264B2 (en) 2003-05-22 2017-09-19 Coating Systems Laboratories, Inc. Ballast water treatment systems
CN112480163A (zh) * 2021-01-13 2021-03-12 北京万博汇佳科贸有限公司 一种有机硅季铵盐、其制备方法及其应用
EP3808891A1 (fr) * 2015-02-27 2021-04-21 Livinguard AG Textiles ayant des propriétés anti-microbiennes
CN115181271A (zh) * 2022-08-17 2022-10-14 浙江工业职业技术学院 含氟乙烯基聚硅氧烷和印花原糊及其制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4408996A (en) * 1981-10-09 1983-10-11 Burlington Industries, Inc. Process for dyeing absorbent microbiocidal fabric and product so produced
US4414268A (en) * 1981-10-09 1983-11-08 Burlington Industries, Inc. Absorbent microbiocidal fabric and process for making same
US4772593A (en) * 1985-07-01 1988-09-20 The Dow Chemical Company Alkoxysilane compounds in the treatment of swine dysentery
US5411585A (en) * 1991-02-15 1995-05-02 S. C. Johnson & Son, Inc. Production of stable hydrolyzable organosilane solutions
EP0675128A1 (fr) * 1994-03-31 1995-10-04 Hüls America Inc. Procédé de préparation de compositions

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4408996A (en) * 1981-10-09 1983-10-11 Burlington Industries, Inc. Process for dyeing absorbent microbiocidal fabric and product so produced
US4414268A (en) * 1981-10-09 1983-11-08 Burlington Industries, Inc. Absorbent microbiocidal fabric and process for making same
US4772593A (en) * 1985-07-01 1988-09-20 The Dow Chemical Company Alkoxysilane compounds in the treatment of swine dysentery
US5411585A (en) * 1991-02-15 1995-05-02 S. C. Johnson & Son, Inc. Production of stable hydrolyzable organosilane solutions
EP0675128A1 (fr) * 1994-03-31 1995-10-04 Hüls America Inc. Procédé de préparation de compositions

Cited By (38)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0877027A2 (fr) * 1997-05-07 1998-11-11 Bioshield Technologies, Inc. Organosilanes stables à l'eau et leurs procédés d'utilisation
EP0877027A3 (fr) * 1997-05-07 1999-09-01 Bioshield Technologies, Inc. Organosilanes stables à l'eau et leurs procédés d'utilisation
US6120587A (en) * 1997-05-07 2000-09-19 Bioshield Technologies, Inc. Water-stabilized organosilane compounds and methods for using the same
US6469120B1 (en) 1997-05-07 2002-10-22 Bioshield Technologies, Inc. Water-stabilized organosilane compounds and methods for using the same
WO1999003865A1 (fr) * 1997-07-18 1999-01-28 Bioshield Technologies, Inc. Composes d'organosilane stables a l'eau et procedes d'utilisation de ces composes
WO1999032157A2 (fr) * 1997-12-23 1999-07-01 Biosafe, Inc. Procede de creation d'un agent biostatique au moyen de polymeres reticules enchevetres
WO1999032157A3 (fr) * 1997-12-23 1999-09-10 Biosafe Inc Procede de creation d'un agent biostatique au moyen de polymeres reticules enchevetres
US6572926B1 (en) 1997-12-23 2003-06-03 Biosafe, Inc. Biostatic product using interpenetrating network polymers
FR2843759A1 (fr) * 2002-08-20 2004-02-27 Louis Rousseau Procede pour le traitement en surface des fibres hydrophiles d'un substrat, naturel ou synthetique
EP1628639A2 (fr) * 2003-05-22 2006-03-01 Coating Systems Laboratories, Inc. Revetements organo ammonium quaternaires antimicrobiens
EP1628639A4 (fr) * 2003-05-22 2007-05-02 Coating Systems Lab Inc Revetements organo ammonium quaternaires antimicrobiens
US9764264B2 (en) 2003-05-22 2017-09-19 Coating Systems Laboratories, Inc. Ballast water treatment systems
AU2004243046B2 (en) * 2003-05-22 2009-11-05 Coating Systems Laboratories, Inc. Antimicrobial quaternary ammonium organosilane coatings
AP2148A (en) * 2003-05-22 2010-09-01 Coating Systems Lab Inc Antimicrobial quarternary ammonium organosilane coatings.
US9364572B2 (en) 2003-05-22 2016-06-14 Coating Systems Laboratories, Inc. Static fluid disinfecting systems and related methods
US7851653B2 (en) 2005-03-22 2010-12-14 Biosafe, Inc. Method of creating a solvent-free polymeric silicon-containing quaternary ammonium antimicrobial agent having superior sustained antimicrobial properties
US7858141B2 (en) 2005-03-22 2010-12-28 Biosafe Inc. Method of creating a sustained silicon-containing quaternary ammonium antimicrobial agent within a polymeric material
US8080170B2 (en) * 2007-10-01 2011-12-20 3M Innovative Properties Company Cationic fluorinated ether silane compositions and related methods
US8501641B2 (en) 2007-10-01 2013-08-06 3M Innovative Properties Company Compositions comprising cationic fluorinated ether silanes, and related methods
WO2009045771A3 (fr) * 2007-10-01 2009-05-22 3M Innovative Properties Co Compositions éther silane fluorées cationiques et procédés associés
CN105037412A (zh) * 2007-10-01 2015-11-11 3M创新有限公司 阳离子氟化醚硅烷组合物以及相关方法
JP2010540644A (ja) * 2007-10-01 2010-12-24 スリーエム イノベイティブ プロパティズ カンパニー カチオン性のフッ素化エーテル型シラン組成物及び関連する方法
US8357751B2 (en) 2007-12-03 2013-01-22 3M Innovative Properties Company Cationic polymeric fluorinated ether silane compositions and methods of use
US8378018B2 (en) 2007-12-03 2013-02-19 3M Innovative Properties Company Cationic polymeric fluorinated ether silane compositions and methods of use
US8614275B2 (en) 2007-12-03 2013-12-24 3M Innovative Properties Company Cationic polymeric fluorinated ether silane compositions and methods of use
US8669319B2 (en) 2007-12-03 2014-03-11 3M Innovative Properties Company Cationic polymeric fluorinated ether silane compositions and methods of use
WO2011127336A1 (fr) * 2010-04-09 2011-10-13 Dow Corning Corporation Silane
US9333484B2 (en) 2012-12-26 2016-05-10 Exxonmobil Research And Engineering Company Reversible CO2 fixation via self-assembled siloxanes
US10329459B2 (en) 2014-02-28 2019-06-25 Dongwoo Fine-Chem Co., Ltd. Adhesive composition
WO2015130023A1 (fr) * 2014-02-28 2015-09-03 동우화인켐 주식회사 Composition adhésive
KR101460352B1 (ko) 2014-02-28 2014-11-10 동우 화인켐 주식회사 점착제 조성물
ES2553158A1 (es) * 2014-06-04 2015-12-04 Universitat Politècnica De Catalunya Líquido iónico para la extracción de compuestos de boro y composición y procedimientos correspondientes
WO2016029010A1 (fr) * 2014-08-20 2016-02-25 Parasol Medical LLC Cathéters soumis à un traitement antimicrobien
EP3808891A1 (fr) * 2015-02-27 2021-04-21 Livinguard AG Textiles ayant des propriétés anti-microbiennes
CN105646563A (zh) * 2016-01-27 2016-06-08 于美宁 一种有机硅季铵盐抗菌剂及其制备方法
CN112480163A (zh) * 2021-01-13 2021-03-12 北京万博汇佳科贸有限公司 一种有机硅季铵盐、其制备方法及其应用
CN115181271A (zh) * 2022-08-17 2022-10-14 浙江工业职业技术学院 含氟乙烯基聚硅氧烷和印花原糊及其制备方法
CN115181271B (zh) * 2022-08-17 2024-02-09 浙江工业职业技术学院 含氟乙烯基聚硅氧烷和印花原糊及其制备方法

Also Published As

Publication number Publication date
AU3011397A (en) 1997-11-26
IL122555A0 (en) 1998-06-15
BR9702243A (pt) 1999-12-28
IL122555A (en) 2002-12-01

Similar Documents

Publication Publication Date Title
US5959014A (en) Water-stabilized organosilane compounds and methods for using the same
US6632805B1 (en) Methods for using water-stabilized organosilanes
US6113815A (en) Ether-stabilized organosilane compositions and methods for using the same
US6762172B1 (en) Water-stabilized organosilane compounds and methods for using the same
US7732395B2 (en) Water-stabilized antimicrobial organosilane products, compositions, and methods for using the same
US6120587A (en) Water-stabilized organosilane compounds and methods for using the same
US20090074971A1 (en) Water-Stabilized Antimicrobial Organosilane Compositions, and Methods for Using the Same
WO1997042200A1 (fr) Composes organosilanes rendus stables a l'eau et procedes d'utilisation associes
US7851459B2 (en) Methods for diluting water-stabilized antimicrobial organosilane compositions
EP0996625A1 (fr) Composes d'organosilane stables a l'eau et leur utilisation
AU771983B2 (en) Water-stabilized organosilane compounds and methods for use
JPH11322767A (ja) 水安定化オルガノシランおよび使用方法
CA2412715A1 (fr) Methodes d'utilisation d'organosilanes stabilises a l'eau
MXPA00000625A (en) Water-stabilized organosilane compounds and their use
MXPA00000627A (en) Water-stabilized organosilane compounds and methods for using the same

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AL AU BA BB BG BR CA CN CU CZ EE GE HU IL IS JP KP KR LC LK LR LT LV MG MK MN MX NO NZ PL RO SG SI SK TR TT UA UG UZ VN AM AZ BY KG KZ MD RU TJ TM

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH KE LS MW SD SZ UG AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN ML MR NE SN TD TG

WWE Wipo information: entry into national phase

Ref document number: 329397

Country of ref document: NZ

WWE Wipo information: entry into national phase

Ref document number: PA/a/1998/000185

Country of ref document: MX

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

Ref country code: JP

Ref document number: 97540279

Format of ref document f/p: F

NENP Non-entry into the national phase

Ref country code: CA

122 Ep: pct application non-entry in european phase