WO1999003866A1 - Composes d'organosilane stables a l'eau et leur utilisation - Google Patents

Composes d'organosilane stables a l'eau et leur utilisation Download PDF

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Publication number
WO1999003866A1
WO1999003866A1 PCT/US1998/014985 US9814985W WO9903866A1 WO 1999003866 A1 WO1999003866 A1 WO 1999003866A1 US 9814985 W US9814985 W US 9814985W WO 9903866 A1 WO9903866 A1 WO 9903866A1
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WIPO (PCT)
Prior art keywords
cooch
alkyl
nhc
organosilane
independently
Prior art date
Application number
PCT/US1998/014985
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English (en)
Inventor
Jacques E. Elfersy
Joachim Berkner
Timothy C. Moses
Original Assignee
Bioshield Technologies, Inc.
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Publication date
Application filed by Bioshield Technologies, Inc. filed Critical Bioshield Technologies, Inc.
Priority to EP98935832A priority Critical patent/EP0996625A1/fr
Priority to CA002296395A priority patent/CA2296395A1/fr
Priority to BR9812101-4A priority patent/BR9812101A/pt
Priority to AU85004/98A priority patent/AU8500498A/en
Priority to JP2000503089A priority patent/JP2001510197A/ja
Publication of WO1999003866A1 publication Critical patent/WO1999003866A1/fr

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    • 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
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/28—Materials for coating prostheses
    • A61L27/34—Macromolecular materials
    • 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

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.
  • the X moiety reacts with various hydroxyl containing molecules in aqueous media to liberate methanol, ethanol, HC1, HBr, HI, H 2 0, acetic acid, or an unsubstituted or substituted carboxylic acid and to form the hydroxylated, but condensation- prone compound.
  • organosilanes R-SiX,,.-, 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 moieties to linear and/or cyclic oligomers possessing the partial structure HO-Si- (0-Si) mm -0-Si-0-Si-0-Si-OH, where mm is an integer such that an oligomer is formed.
  • RSiX 3 hydrolysis of the third X group generates a silanetriol (RSi(OH) 3 ) 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 4 . n , where n ranges from 0 to 2, inclusive, in water.
  • n ranges from 0 to 2, inclusive
  • Dow Corning 5700 One commerciallyrelevant example of an organosilane suffering from such undesirable self-condensation is the antimicrobial Dow Corning 5700 (Dow Corning Corporation, Midland, MI).
  • the literature describes the active ingredient of Dow Corning 5700 as 3- (trimethoxysilyl)propyl-dimethyloctadecyl ammonium chloride.
  • the correct active ingredient is more likely 3-(trihydroxysilyl)propyl- dimethyloctadecyl ammonium chloride.
  • Dow Corning 5700 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-(Trimethoxysilyl)propyl-dimethyloctadecyl ammonium chloride is prepared by quaternization of dimethyloctadecylamine with 3-chloropropyl trimethoxysilane.
  • the C,g hydrocarbon chain quaternary ammonium portion of the molecule possesses long-acting antimicrobial properties and provides initial association with the surface of the substrate through ionic bonds and/or electrostatic interaction.
  • the treated surface becomes permanently coated with a covalently bound octadecylammonium ion, providing a durable, long-actingantimicrobialcoatingthat is able to destroy microbes that come into contact with the surface.
  • organosilanes in water such as the activated mixture of 3-(trimethoxysilyl)propyl-dimethyloctadecyl ammonium chloride and water, are generally unstable and prone to self-condensation.
  • the mixture of 3-(trimethoxysilyl)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 shortertimes.
  • the limitationsof such organosilanes in aqueous media are further described in United States Patent No. 5,411,585, 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.
  • organosilane compositions which are essentially non-toxic or of low toxicity, non-flammable, uniformly dispersable and simple and economical to use and stable in water when further diluted with water.
  • 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 using the compounds, products, and compositions.
  • the present invention provides the product formed from mixing an organosilane of the formula R-SiX,.. where n is an integerof from 0 to 3, preferably 0 to 2; each R is, independently, a nonhydrolyzable organic group; and each X is, independently, a hydrolyzable group (hereinafter, "organosilane of interest"); with an organic carbonate, preferably propylene carbonate.
  • this invention provides a water-stable composition, comprising the product or composition 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 method of treating a substrate, comprising mixing 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 composition for treating a substrate by incorporation in the substrate.
  • the present invention provides a composition for treating a substrate by incorporation into a polymer backbone.
  • the present invention provides a composition as a concentrated solution, easily diluted with water, providing a water stable composition.
  • the present invention provides a composition as a concentrated solution which is the product of the synthesis of the compounds it comprises.
  • the present invention provides a treated substrate having adhered thereto or dispersed therein the product, compound, or composition of the invention.
  • the present invention provides a method of dyeing and treating a substrate, comprising contactingthe substrate with an aqueous composition comprising an aqueous soluble dye suitable for dyeing a substrate and the product formed from mixing an organosilane of interest with an organic carbonate.
  • a further embodiment of the present invention provides a method of antimicrobially treating a substrate selected from the group consisting of a concrete pipe, a tooth brush, a food article, fluid container, latex medical article, gloves, shoes, 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, a PE, PP or polyester 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 mixing an antimicrobial organosilane of interest with an organic carbonate.
  • 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 mixing an antimicrobial organosilane of interest with an organic carbonate.
  • a further embodiment of this invention is a method for making an organosilane of interest from starting materials in an aqueous solution in the presence of an organic carbonate.
  • alkyl refers to a branched or unbranched saturated hydrocarbon group of 1 to 24 carbon atoms, such as methyl ("Me”), ethyl ("Et”), «-propyl, isopropyl, «-butyl, isobutyl, t-butyl, octyl, decyl, tetradecyl, hexadecyl, eicosyl, tetracosyl, and the like.
  • Alkyl alcohol refers to an 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, CH 2 CH 2 CH 2 OH, 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.
  • Glycol refers to glycol compounds, which includes, but is not limited to, ethylene glycol, propylene glycol, butylene glycol, isobutylene glycol or hexylene glycol.
  • Polyglycol refers to a compound or moiety which takes the polymeric form of glycol, such as, but not limited to, polyethylene glycol or poly propylene glycol. Polyglycol would also include, for example, block and copolymers of ethylene glycol and propylene glycol. Polyglycols useful in the subject invention may have an average molecular weight of up to about 10,000 g/mol.
  • Polyalkylethers refers to alkyls or alkyl alcohols interconnected by or otherwise possessing multiple ether linkages. Polyalkylethers useful in the subject invention may have an average molecular weight of up to about 10,000 g/mol .
  • Alkyl glycol refers to an alkyl connected to a glycol through an ether linkage.
  • An example of an alkyl glycol includes, but is not limited to, butyl glycol.
  • Alkyl polyglycol refers to alkyl connected to a polyglycol through and ether linkage. Alkyl polyglycol compounds useful in the subject invention may have an average molecular weight of up to 10,000 g/mol.
  • 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 alkyls and lower alkyls 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 practical to specify an exact "effective amount,” especially because a range of amounts or concentrations will usually be effective. However, an appropriate effective amount may be determined by one of ordinary skill in the art using only routine experimentation as a matter of optimization.
  • the term “cyclic” is used to refer to all aliphatic or aromatic hydrocarbons having one or more closed rings, whether unsaturated or saturated.
  • cyclic compounds possess rings of from 5 to 7 atoms, preferably 6 carbon atoms. Such rings fall into three classes: alicyclic, aromatic (“arene”), and heterocyclic. Moreover, when used with respect to cyclic compounds or moieties, the term “unsaturated” refers to such compound or moiety possessing at least one double or triple bond or otherwise constituting an aromatic compound or moiety.
  • saturated refers to compounds or moieties possessing no double or triple bonds within the ring, i.e., where all available valence bonds of an atom, especially carbon, are attached to other atoms.
  • heterocyclic refers to a cyclic 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.
  • aryl and “aromatic” are used interchangeably herein and refer to a compound or moiety whose molecules have a ring or multiple (poly) ring structure characteristic of benzene, naphthalene, phenanthrene, anthracene, etc.
  • aryls or aromatics also include, but are not limited to, phenyl, benzyl, naphthyl, benzylidine, xylil, styrene, styryl, phenethyl, phenylene, benzenetriyl, etc.
  • heteroaryl and “heteroaromatic” are used interchangeably and refer 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.
  • cyclic alcohol refers to a cyclic molecule substituted with one or more hydroxy moieties. Examples include, but are not limited to, Phenol and cyclohexanol.
  • 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 refers 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.
  • isobutyl, t-butyl, isopropyl, CH 2 CH 2 C(CH 3 )(H)CH 2 CH 3 , CH 2 C(CH 2 CH 3 )(H)CH 2 CH 3 , OLCliC CH, )CH, , and CH CH C(C ) 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 RCO where R is an organic molecule. The free valance on C is used to bond to other groups or atoms.
  • acyloxy refers to organic acid derived moieties of the formula
  • RCOX where R is an organic molecule and X, instead of being hydroxy, represents oxygen attached to another group or atom.
  • 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 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 by either having a negatively charged surface of oxygen atoms, or any surface capable of electrostatically, ionically, or covalently adhering or binding to the compounds, products, or compositions of the present invention.
  • the adhering or binding occurs at the silicon atoms of the organosilane portion of the compounds, products, or compositions of the present invention, but such binding is not a requirement.
  • Substrate also refers to materials that are treated by incorporation of the compounds and/or compositions of the present invention. Incorporation in this case includes the process of blending and mixing, and incorporation by becoming part of the material, i.e., polymer backbone and cement. 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 "antimicrobiallyenhancing” 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 the 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 where the starting compositions or solutions already possessed antimicrobial activity.
  • hydro lyzable 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.
  • nonhydrolyzable refers to moieties that are not prone to or capable of hydrolysis in aqueous or other suitable media.
  • cationic 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.
  • salts are 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.” See, e.g., American Heritage Dictionary, Definition of "Salt” (1981). Therefore, 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. In addition, other suitable methods of generating salts are specified throughout this specification and are within the scope of the present definition. 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 carbonates. 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 and simplifying transportation, dilution with water, and stabilization in water.
  • the present invention provides the product formed from mixing an 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 nonhydrolyzableorganic group; and each X is, independently, a hydrolyzable group; with an organic carbonate.
  • each R is, independently, alkyl; of from 1 to 24 carbon atoms, ethylene glycol, propylene glycol, butyl glycol, pentyl glycol, hexyl glycol, alkyl glycol with 2 to 24 carbon atoms, aromatic, heteroaromatic, saturated and unsaturated aliphatic cyclic molecule, each with ring sizes of from 3 to 8 carbon atoms and in addition in hetero-cycles N, O, S in place of carbon atoms in any number and combination, alkyl alcohol, polyethylene glycol, polypropylene glycol, block and co-polymers of ethylene and propylene glycol and block and copolymers of ethylene glycol, propylene glycol, butyl glycol, pentyl glycol, hexyl glycol, alkyl glycol with 2 to 24 carbon atoms, alkyl triol with 3 to 24 carbon atoms, alkyl tetrol with 4 to 24 carbon atoms, and alkyl pentol with 5
  • the molecular weight of the carbonate is up to approximately 10,000 grams/mol average molecular weight.
  • the invention provides the product described above, wherein the organosilane is of the formula II, III, IV or V
  • each R is independently, halogen or RgO, where R ⁇ is H, alkyl of from 1 to about 24 carbon atoms, acetyl, acetoxy, acyl, acyloxy, propylene glycol, ethylene glycol, polyethylene glycol, polypropylene glycol, block and copolymers of ethylene and propylene glycol, the alkyl monoether of from 1 to 24 carbons of the following: propylene glycol, ethylene glycol, polyethylene glycol, polypropylene glycol, block and copolymers of ethylene and propylene glycol; or the monoester of a carbonic acid of from 1 to 24 carbons and at least one of the following: propylene glycol, ethylene glycol, polyethylene glycol, polypropylene glycol, block and copolymers of ethylene and propylene glycol; sorbitan esters and their ethers; phenolic compounds substituted with an alkyl of from about 1 to 24 carbons, such as octy
  • R 35 is R 6 , H, halogen (such as CI, Br, F, or I), NH 2 (CH 2 ) 2 NHR 2 , NH 2 R 2 , C 3 H 5 0 2 R 2 , C 4 H 5 0 2 R 2 , NaO(CH 3 0)P(0)R 2 , or C1CH 2 C 6 H 4 R 2 ;
  • halogen such as CI, Br, F, or I
  • R 36 and R 37 are, independently, R 35 , halogen, H, alkyl, preferably of from 1 to 4 carbon atoms, more preferably of from 1 to 2 carbon atoms, isobutyl, phenyl, or n-octyl;
  • R 2 is R , benzyl, vinyl or alkyl;
  • R 3 and R 4 are, independently, R 35 , alkyl alcohol, alkoxy, alkyl of from 1 to 24 carbon atoms, preferably 1 to about 10 carbon atoms, more preferably alkyl of from 1 to 4 carbon atoms, or more preferably of from 1 to 2 carbon atoms;
  • R 3 and R 4 can, together, form a morpholine or cyclic or heterocyclic, unsaturated or saturated, five to seven-membered ring of the formula VI:
  • k in an integer from 0 to 2, preferably 0 to 1 , most preferably 1 , R 7 , where the ring is saturated is CH 3 , O, S, NH, NH 2 + , NCH 2 CH 2 NH 2 ,
  • R 8 , R, and R 10 is independently, benzyl, R 37 , polyglycol, preferably of from 1 to 4 carbon atoms, alkyl alcohol, preferably of from 1 to 4 carbon atoms, alkoxy, preferably of from 1 to 4 carbon atoms, or alkyl, from 1 to 24 carbon atoms, preferably 1 to about 10 carbon atoms, and the "alkyl” specified above is of from 1 to 3 carbon atoms, the "aryl” is more preferably phenyl or benzyl, and R 7 , where the ring is unsaturated is CH, N, N ⁇ , N + (alkyl), N"(aryl), N + (benzyl), N-CH 2 -N,
  • the ring provided by formula VI represents R 3 or R 4 , independently.
  • the nitrogen in formula II or III that is part of the ring structure of formula VI is replaced by CH or CH 2 or saturated with hydrogen or alkyl substitution of from 1 to about 24 carbons by removal of a positive charge.
  • This ring is attached to the nitrogen in structure II or III, by removing any one hydrogen from the structure and placing a bond from the nitrogen of II or III to the atom missing the hydrogen.
  • R 5 is alkyl alcohol, preferably of from 1 to 6 carbon atoms, more preferably of from 1 to 4 carbon atoms, R 35 , CH 2 C 6 H 5 , polyglycol, such as a polyethylene glycol or a polypropylene glycol, alkyl of from 1 to 24 carbon atoms, preferably of from 1 to 10 carbon atoms, most preferably of from 1 to 6 carbon atoms, alkoxy, of from 1 to 24 carbon atoms, more preferably of from 1 to 10 carbon atoms, most preferably of from 1 to 6 carbon atoms, perfluoroalkyl, of from 1 to 24 carbon atoms, more preferably of from 1 to 10 carbon atoms, most preferably of from 1 to 6 carbon atoms, perfluoroalkylsulfonate, of from 1 to 24 carbon atoms, more preferably of from 1 to 10 carbon atoms, most preferably of from 1 to 6 carbon atoms, perfluoroalkylcarboxylate, or is
  • the present invention provides a composition for treating a substrate, comprising a carrier and an effective amount of an organosilane of interest and a carbonate as described herein.
  • the carrier may be water, or in further embodiments, the carrier is other than water.
  • the present invention also provides a product resulting from mixing an organosilane of the formula II, III, IV, or V:
  • the present invention also provides a method of treating a substrate, comprising contacting the substrate with a sufficient amount of the composition 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 produced by contacting the organosilane and the carbonate as described above.
  • the present invention provides a treated substrate having adhered thereto a compound produced by contacting the organosilane and the carbonate 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 mixing an organosilane of interest with an organic carbonate.
  • an aqueous (i.e., substantially water soluble) composition comprising an aqueous soluble dye suitable for dyeing a substrate and the product formed from mixing an organosilane of interest with an organic carbonate.
  • the present invention provides a method of antimicrobially treating a substrate selected from the group consisting of a concrete pipe, food article, fluid container, glove, shower curtain, shower door, latex medical article, 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, a PP, PE or polyester 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 mixing an antimicrobial organosilane of interest with an organic carbonate.
  • a substrate selected from the group consisting of a concrete pipe, food article, fluid container, glove, shower curtain, shower door, latex
  • a further embodiment of the present invention 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 mixing an antimicrobial organosilane of interest with an organic carbonate.
  • the present invention provides water-stabilized and solubilized organosilane compounds, products, and compositions, methods of 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 nonhydrolyzable 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, CI, Br, or I, or X is hydroxy, alkoxy such as methoxy or ethoxy, acetoxy, or unsubstituted or substituted acyl or acyloxy.
  • X is prone to react with various hydroxyl containing molecules.
  • the present invention employs a carbonate as solvent.
  • the silane and carbonate mixture are stable.
  • the carbonate silane mixtures often are less flammable than methanol mixtures and are easier to dissolve in water than many silanes in methanol.
  • the stabilizers are not sufficiently water-soluble, additional stability is achieved by mixing the organosilane with the stabilizer in a non-aqueous solvent.
  • the remaining solvent e.g., methanol
  • an organosilane-stabilizing effect in water may still be achieved by admixing the organosilane with, for example, a carbonate in water, followed by filtration.
  • the solutions are stable for extended periods, from several days to several months. It will also be recognized that while aqueous silane stock solutions of up to 45% silane may be stabilized by carbonates disclosed herein, working silane concentrations tend to be in the 0.001- 10% silane range where the stabilization effects of the herein disclosed stabilizers are less challenged by the higher silane concentrations required in stock solutions. Acid pHs appear to be preferred, but not required, for stability of the solutions of the subject invention.
  • 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.
  • One of ordinary skill in the art would recognize that the above preparation steps are merely guidelines and such a person would, without undue experimentation, be able to prepare the composition by varying the parameters for contacting or mixing the organosilane and the polyol and order of introduction of reagents and starting materials without deviating from the basic and novel characteristics of the present invention.
  • the present invention is useful for stabilizing organosilanes of the general formula R-SiX ⁇ n where n is an integer of from 0 to 3, preferably 0 to 2; R is a nonhydrolyzable organic group (alkyl, aromatic, organofunctional or a combination thereof); and X is hydroxy, alkoxy, preferably methoxy or ethoxy, halogen, preferably CI, Br, or I, acetoxy, acyl or substituted acyl, acyloxy, or a hydrolyzable polymer or other moiety prone to hydrolysis and/or environmental harmfulness.
  • the organosilanes used in the practice of the present invention need not be, and often are not, water soluble. By varying the stabilizer and preparation method, the organosilanes selected for use in the present invention are solubilized in water by the stabilizer.
  • 4,390,712 is hereby incorporated by reference for its teaching of siloxane synthesis in an aqueous medium.
  • aqueous siloxane synthesis methods of the 4,390,712 patent are modified to advantage by performing the siloxane synthesis in the presence of the carbonate stabilizer as defined herein, thereby forming a stabilized siloxane-water composition while still taking advantage of the accelerated kinetics of siloxane formation in aqueous media noted in the 4,390,712 patent.
  • a further embodiment of this invention is a method for making an organosilane of the formula R_SiX 4 .
  • the archetypal example of carbonate of the instant invention is propylene carbonate with an organic carbonate.
  • Preferred silanes for use in the compounds, products and compositions and methods of the present invention include silanes of the following formula:
  • each R is, independently, halogen [CI, Br, I, F] or ⁇ 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 and acyloxy; 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 polyglycol such as, but not limited to, polyethyleneglycols or polypropyleneglycols, such as poly(propyleneglycol)triol(glycerol propoxylate); R 2 is unsubstituted or substituted benzyl- or an unsubstituted or substituted alkyl of from 1 to about 3 carbon atoms, preferably alkyl of from 1 to 3 carbon atoms; R
  • 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 + , NCH 2 CH 2 N(R 8 )(R,), NCH 2 CH 2 N + (R 8 )(R 9 )(R 10 ), N(alkyl), N(aryl), N(benzyl), and R 7 , where the ring is unsaturated is, N, N ⁇ , N + (alkyl), N + (aryl), N + (benzyl), N-CH 2 -N, N ⁇ -CH 2 -N, N + (alkyl)-CH 2 -N, N + (aryl)-CH 2 -N, or N + (benzyl)-CH 2 -N where R 8 , R,, and R 10 are, independently, benzyl, polyglycol, lower alkyl alcohol of from 1 to 4 carbon atoms,
  • organosilanes include, but are not limited to: 3-(trimethoxysilyl)propyldimethyloctadecyl ammonium chloride,
  • 3-methacryloxypropyltrimethoxysilane C 4 H 5 0 2 (CH 2 ) 3 Si(OCH 3 ) 3
  • 3-methacryloxypropyltriethoxysilane C 4 H 5 0 2 (CH 2 ) 3 Si(0CH 2 CH 3 ) 3
  • methyldichlorosilane CH 3 SiHCl 2
  • silane-modified melamine Dow Corning Q 1 -6106, sodium (trihydroxysilyl)propylmethylphosphonate: NaO(CH 3 0)P(0)(CH 2 ) 3 Si(OH) 3 , trichlorosilane, SiHCl 3 , n-2-vinylbenzylamino-ethyl-3-aminopropyltrimethoxysilane
  • HCL Dow Corning Z-6032
  • organosilane as a UV protectant
  • para-amino benzoic acid, cinnamic acid, benzoic acid and benzophenone are active ingredients.
  • These compounds and their alkyl derivatives attached to a siloxane are part of this invention.
  • Carbonate stabilizers according to the invention are described by formula la and lb:
  • R is, independently, alkyl; of from 1 to 24 carbon atoms, ethylene glycol, propylene glycol, butyl glycol, pentyl glycol, hexyl glycol, alkyl glycol with 2 to 24 carbon atoms, aromatic, heteroaromatic, or saturated and unsaturated aliphatic cyclic molecule, each with ring sizes of from 3 to 8 carbon atoms and in addition in hetero-cycles N, O, S in place of carbon atoms in any number and combination, alkyl polyol, polyethylene glycol, polypropylene glycol, block and co-polymers of ethylene and propylene glycol and block and copolymers of ethylene glycol, propylene glycol, butyl glycol, pentyl glycol, hexyl glycol, alkyl glycol with 2 to 24 carbon atoms, alkyl triol with 3 to 24 carbon atoms, alkyl tetrol with 4 to 24 carbon atoms, and alkyl pentol
  • 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, 3) as additives to organic monomers (such as acrylics) prior to formation of the respective polymer, 4) addition to the polymer prior to processing into final products, or 5) incorporation into polymer or substrate backbone, such as polyester or concrete.
  • organosilane quaternary ammonium compounds such as 3-(trimethoxysilyl)propyl-dimethyloctadecyammonium chloride as surface bonding antimicrobial agents
  • organofunctionalsilanes 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 or mixing 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.
  • organosilane-carbonate mixtures accordingto the invention can be used directly without dilution with water, or, alternatively, dilutions with solvents other than water can be used according to the invention
  • treatment begins immediately upon contact, but preferably requires from about 15 seconds to about 48 hours.
  • the composition of the invention may be placed in a high intensity solid mixer and formed into a powder which is then dried. The dried powder may then be used in a sprayer, if desired.
  • the solutions may be wiped onto the substrate and applied using sponges or cloths, etc.
  • 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.
  • 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 R tl SiX 4 . n are prepared, dissolved, stored, applied, and in any way used in water.
  • organosilanes R prisSiX 4 . n 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.
  • 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.
  • one embodiment of the subject invention is directed toward a method of treating a substrate to render the substrate resistant to stains.
  • 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 characteristicsand its effectiveness during further production of the textile goods.
  • the water-stable compounds, products and compositionsof 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-stabilizedorganosilane compounds, products and compositionsof 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.
  • Treating food crops (e.g., perishables such as vegetables, fruits, or grains) after removal (pickled/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 less by weight of the compounds, products and compositions of the invention in water 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 . 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 submerging 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.
  • Treating polymers and other materials such as concrete by incorporation into the bulk material protects from deterioration, odor build-up and potentially harmful contamination of the surface. Incorporation of a sun protection into polymers and/or application of sun protection to the surface extends the life of the product and reduces damage to products and skin.
  • HDP high density polyester fabric plastic covers for dump sites, water reservoirs and generally for soil protection 8.
  • Liquid Additive as flower water preservative for potted plants and cut flowers
  • Siliconeand Teflon coated Fiberglass with antimicrobial protection including acrylic backing wall covering
  • a method of treating blended cotton before or after picking machines make the cotton into rolls or laps
  • silane in the following examples is Dow Coming 5772 or a silane of similar composition as Dow Coming 5772. Both are collectively referred to as silane concentrate.
  • a solution or mixture is considered stable if an aqueous solution can be produced and remain without precipitation of the silane for a longer time than would be expected for the non- stabilized silane. If the silane itself is insoluble in water then the formation of an aqueous solution is a benefit within the scope of the invention.
  • Example 2 The following table lists examples of mixtures and their stability. The entries are in weight percent of total mixture. A solution 50 weight percent silane concentrate and 50 weight percent propylene carbonate was prepared and then diluted with water according to the table.
  • reaction product of the previous example was dissolved in water, to prepare stable silane water mixtures.
  • Sample 2 of the previous example was after 35 days diluted further with 4 parts water and applied to white textile fabric. After drying, the fabric was hand washed in running water 20 times. The sample was again allowed to dry and then tested according to Dow Coming Corporate Test Method 0923. In this test method the fabric sample is placed together with an inoculated nutrient solution into an erlenmeyer flask. For this experiment the procedure was slightly modified, the mixture was shaken for 24 hours instead of 1 hour and the organism used was aspergillus niger instead of klebsiella pneumoniae. Percent reduction is determined by counting the organisms at zero time and at the end of the experiment. The percent reduction found in this example was 99.98%.

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Abstract

L'invention concerne une composition produite par mélange d'un organosilane avec un carbonate organique; des composés d'organosilane stables à l'eau; une composition stable à l'eau, produite à partir de la composition de carbonate organique et d'organosilane, ainsi que d'eau; un procédé de traitement d'un substrat par mélange ou mise en contact du substrat avec le produit, le composé ou la composition de cette invention, durant une période suffisante pour le traitement du substrat; un substrat traité auquel adhère le produit, le composé ou la composition de cette invention; un procédé de teinture et de traitement d'un substrat; un procédé de traitement antimicrobien d'un article alimentaire; un procédé d'enduction antimicrobienne d'un récipient de liquide; et un procédé d'enduction antimicrobien d'un article médical en latex.
PCT/US1998/014985 1997-07-17 1998-07-17 Composes d'organosilane stables a l'eau et leur utilisation WO1999003866A1 (fr)

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EP98935832A EP0996625A1 (fr) 1997-07-17 1998-07-17 Composes d'organosilane stables a l'eau et leur utilisation
CA002296395A CA2296395A1 (fr) 1997-07-17 1998-07-17 Composes d'organosilane stables a l'eau et leur utilisation
BR9812101-4A BR9812101A (pt) 1997-07-17 1998-07-17 Compostos de organossilano e uso dos mesmos
AU85004/98A AU8500498A (en) 1997-07-17 1998-07-17 Water-stabilized organosilane compounds and their use
JP2000503089A JP2001510197A (ja) 1997-07-17 1998-07-17 水安定化オルガノシラン化合物およびその使用

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WO2000078770A1 (fr) * 1999-06-19 2000-12-28 Clariant Gmbh Formulations de siloxanes quaternaires antimicrobiennes, leur production et leur utilisation
WO2003063917A1 (fr) * 2002-01-31 2003-08-07 The Titan Corporation Procedes de traitement de surfaces
EP1972330A3 (fr) * 2008-06-13 2009-02-18 Clariant International Ltd. Compositions cosmétiques ou pharmaceutiques comportant des polysiloxanes modifiés avec un groupe de carbamate leastone
WO2009045771A3 (fr) * 2007-10-01 2009-05-22 3M Innovative Properties Co Compositions éther silane fluorées cationiques et procédés associés
EP2535376A1 (fr) * 2011-06-14 2012-12-19 Merz+Benteli AG Composition à plusieurs composants comme colle pour matériaux difficiles à coller
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
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

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US8257780B2 (en) * 2003-10-31 2012-09-04 Resource Development L.L.C. Therapeutic composition containing an organosilane quaternary compound and hydrogen peroxide for treating skin disorders and methods of using
JP4578089B2 (ja) * 2003-11-26 2010-11-10 北興化学工業株式会社 液状農薬製剤
US7589054B2 (en) * 2007-01-02 2009-09-15 Resource Development L.L.C. Clathrates of an organosilane quaternary ammonium compound and urea and methods of use

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US5174813A (en) * 1991-11-07 1992-12-29 Dow Corning Corporation Polish containing derivatized amine functional organosilicon compounds
US5389364A (en) * 1993-08-06 1995-02-14 Dow Corning Corporation Conditioning hair with aminosilane reaction products with lactones or carbonates
WO1998026028A1 (fr) * 1996-12-09 1998-06-18 Orr William C Compositions de carburant caracterisees par une stabilite amelioree dudit carburant

Cited By (19)

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US6376696B1 (en) 1999-06-19 2002-04-23 Clariant Gmbh Antimicrobial siloxane quat formulations and their preparation and use
WO2000078770A1 (fr) * 1999-06-19 2000-12-28 Clariant Gmbh Formulations de siloxanes quaternaires antimicrobiennes, leur production et leur utilisation
WO2003063917A1 (fr) * 2002-01-31 2003-08-07 The Titan Corporation Procedes de traitement de surfaces
US8501641B2 (en) 2007-10-01 2013-08-06 3M Innovative Properties Company Compositions comprising cationic fluorinated ether silanes, and related methods
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
WO2009045771A3 (fr) * 2007-10-01 2009-05-22 3M Innovative Properties Co Compositions éther silane fluorées cationiques et procédés associés
US8080170B2 (en) * 2007-10-01 2011-12-20 3M Innovative Properties Company Cationic fluorinated ether silane compositions and related methods
US8614275B2 (en) 2007-12-03 2013-12-24 3M Innovative Properties Company Cationic polymeric fluorinated ether silane compositions and methods of use
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
US8669319B2 (en) 2007-12-03 2014-03-11 3M Innovative Properties Company Cationic polymeric fluorinated ether silane compositions and methods of use
CN102065835B (zh) * 2008-06-13 2012-11-28 科莱恩金融(Bvi)有限公司 含有用至少一种氨基甲酸酯改性的聚硅氧烷的化妆品或药物组合物
WO2009149879A1 (fr) * 2008-06-13 2009-12-17 Clariant International Ltd Compositions cosmétiques ou pharmaceutiques comprenant des polysiloxanes modifiés avec au moins un groupe carbamate
EP1972330A3 (fr) * 2008-06-13 2009-02-18 Clariant International Ltd. Compositions cosmétiques ou pharmaceutiques comportant des polysiloxanes modifiés avec un groupe de carbamate leastone
EP2535376A1 (fr) * 2011-06-14 2012-12-19 Merz+Benteli AG Composition à plusieurs composants comme colle pour matériaux difficiles à coller
KR101460352B1 (ko) 2014-02-28 2014-11-10 동우 화인켐 주식회사 점착제 조성물
WO2015130023A1 (fr) * 2014-02-28 2015-09-03 동우화인켐 주식회사 Composition adhésive
US10329459B2 (en) 2014-02-28 2019-06-25 Dongwoo Fine-Chem Co., Ltd. Adhesive composition
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

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