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WO1999003424A1 - Procede pour preparer des polymeres silicones - Google Patents

Procede pour preparer des polymeres silicones Download PDF

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Publication number
WO1999003424A1
WO1999003424A1 PCT/US1998/015267 US9815267W WO9903424A1 WO 1999003424 A1 WO1999003424 A1 WO 1999003424A1 US 9815267 W US9815267 W US 9815267W WO 9903424 A1 WO9903424 A1 WO 9903424A1
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WO
WIPO (PCT)
Prior art keywords
polymer precursor
silicone polymer
cross
coating
silicone
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Ceased
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PCT/US1998/015267
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English (en)
Inventor
Vittoria Fruci
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Individual
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Individual
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Publication date
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Priority to AU86607/98A priority Critical patent/AU8660798A/en
Publication of WO1999003424A1 publication Critical patent/WO1999003424A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/245—Differential crosslinking of one polymer with one crosslinking type, e.g. surface crosslinking
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42—Use of materials characterised by their function or physical properties
    • A61L15/58—Adhesives
    • 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
    • A61L24/00—Surgical adhesives or cements; Adhesives for colostomy devices
    • A61L24/04—Surgical adhesives or cements; Adhesives for colostomy devices containing macromolecular materials
    • A61L24/046—Surgical adhesives or cements; Adhesives for colostomy devices containing macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B63—SHIPS OR OTHER WATERBORNE VESSELS; RELATED EQUIPMENT
    • B63B—SHIPS OR OTHER WATERBORNE VESSELS; EQUIPMENT FOR SHIPPING 
    • B63B1/00—Hydrodynamic or hydrostatic features of hulls or of hydrofoils
    • B63B1/32—Other means for varying the inherent hydrodynamic characteristics of hulls
    • B63B1/34—Other means for varying the inherent hydrodynamic characteristics of hulls by reducing surface friction
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2383/04—Polysiloxanes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T70/00—Maritime or waterways transport
    • Y02T70/10—Measures concerning design or construction of watercraft hulls

Definitions

  • the present invention relates, generally, to methods for preparing silicone polymer compositions and, more particularly, to methods for preparing silicone polymer compositions having adhesive and drag-reducing surfaces.
  • U.S. Patent No. 2,937,976 to Granahan uses a drag reducing gel for a razor blade
  • U.S. Patent No. 4,385,134 to Foscante teaches use of a drag-reducing, antifouling coating for boat hulls.
  • the primary cause of drag on boat hulls is the growth of marine organisms on the hull.
  • antifouling coatings -contain a toxicant agent which controls the growth of marine organisms.
  • a need continues to exist for a method of reducing drag which is easy to carry out, which can be used for pre-existing objects, and which imparts to the object long-lasting resistance to oxidation, water seepage, bacterial degradation, and the like.
  • the present invention is directed, in part, to meeting this need.
  • Prosthetic devices are widely employed for functional or cosmetic purposes to correct congenital, developmental, or acquired defect. Since facial appearance and expression are both highly visible, defects of the head and neck areas come under closer scrutiny than defects of other body parts. Therefore, preparation of maxillofacial prosthetics requires the use of both art and science to reconstruct defects.
  • Intraoral prostheses are usually fabricated in association with a partial or complete denture. Retention of intraoral prostheses usually pose few problems except in a completely edentulous patient having markedly resorbed ridges, poor quality bony or soft tissue undercuts, and a bulky or weighty obturator. Extraoral prostheses pose more retentive as well as aesthetic problems.
  • a major disadvantage for a patient wearing an extraoral prosthetic device is the potential for dislodgement during normal activity and the accompanying patient embarrassment.
  • a number of different types of polymeric materials have been utilized as base materials for prostheses. Principal among these polymers have been the silicone rubbers and polyurethanes . These elastomeric polymers are used for most extraoral prostheses because of the life-like qualities that can be imparted to them. These qualities include flexibility and the ability to be colored. This coloring is accomplished by adding fibers or pigment to the prepolymer or by tattooing the completed prostheses to conform them closely to the skin tones of the areas contiguous to the reconstructive ⁇ site. The chemical inertness of these polymers, once cured, is a major factor in their popularity for maxillofacial prosthetic reconstruction.
  • the present invention relates to a method for producing a silicone polymeric composition having an adhesive surface.
  • a silicone polymer precursor is provided, and the silicone polymer precursor's surface is contacted with a cross-linking inhibitor.
  • the silicone polymer precursor's surface is agitated under conditions effective to cause the cross-linking inhibitor to mix with the silicone polymer precursor's surface.
  • the silicone polymer precursor is polymerized and cured under conditions which are effective to polymerize and crosslink the silicone polymer precursor without cross-linking the surface of the silicone polymer precursor contacted with the cross-linking inhibitor. In this manner, a silicone polymeric composition having an adhesive surface is produced.
  • the present invention also relates to a method for attaching a medical implant to a biological material .
  • the implant is coated with a silicone polymer precursor to form a coating on the implant, and the silicone polymer precursor coating' s surface is contacted with a cross-linking inhibitor and agitated under conditions effective to cause the cross-linking inhibitor to mix with the silicone polymer precursor coatings 's surface.
  • a coated implant having an adhesive surface is formed.
  • the adhesive surface of the coated implant is then contacted with the biological material under conditions effective to attach the medical implant to the biological material.
  • the present invention relates to a method for producing a silicone polymeric composition having a drag-reducing surface.
  • the surface of a silicone polymer precursor is contacted with a cross-linking inhibitor, and the silicone polymer precursor's surface is agitated under conditions effective to cause the cross-linking inhibitor to mix with the silicone polymer precursor's surface.
  • the silicone polymer precursor is polymerized and cured under conditions effective to polymerize and cross-link the silicone polymer precursor without cross-link the surface of the silicone polymer precursor. In this manner, a silicone polymeric composition having a drag-reducing surface is produced.
  • the present invention relates to a method for reducing boat hull drag.
  • the method includes coating the boat hull with a silicone polymer precursor and contacting the silicone polymer precursor coating's surface with a cross-linking inhibitor. By polymerizing and curing the silicone polymer precursor coating under conditions effective to polymerize and cross-link the silicone polymer precursor coating without cross-linking the surface of the silicone polymer precursor coating contacted with the cross- linking inhibitor, the boat hull's drag is reduced.
  • the present invention provides a convenient method for producing silicone or silicone-coated materials having uncured surf ces. These uncured surfaces make the materials attractive for a number of applications.
  • the method permits creation of an adhesive surface on the atmosphere-to-sample side of a silicone polymer rather than on the mold-to-polymer side and permits the creation of adhesive surfaces on silicone objects which are shaped by methods other than molding processes, such as spin casting.
  • the methods do no require that the cross -linking inhibitor be incorporated in the silicone precursor prior to polymerization.
  • the method offers greater control and flexibility in the application of the cross-linking inhibitor to the silicone material and permits the efficient production of silicone or silicone-coated objects having a greater variety of sizes and shapes.
  • the present invention relates to a method for producing a silicone polymeric composition having an adhesive surface.
  • a silicone polymer precursor is provided, and the silicone polymer precursor's surface is contacted with a cross-linking inhibitor.
  • the silicone polymer precursor's surface is agitated under conditions effective to cause the cross-linking inhibitor to mix with the silicone polymer precursor's surface.
  • the silicone polymer precursor is then polymerized and cured under conditions which are effective to polymerize and cross-link the silicone polymer precursor without cross- linking the surface of the silicone polymer precursor contacted with the cross-linking inhibitor. In this manner, a silicone polymeric composition having an adhesive surface is produced.
  • the silicone polymeric precursor can be, for example, silicone monomers or silicone prepolymers, the latter of which includes partially polymerized silicone monomer (i.e., polymeric silicone units having reactive groups attached hereto capable of further polymerization) and fully or substantially fully polymerized silicone which is uncured and/or unvulcanized.
  • the silicone polymer precursor can be precursors of polymeric silicone, or precursors of copolymers of silicone and other polymers, such as polyurethanes, polyacrylics , polyesters, polyolefins, polyacrylamides , and polyurethane .
  • Silicone polymer precursors which are partially or substantially fully polymerized prior to their contact with the cross-linking inhibitor can be prepared' by mixing silicone polymer precursor with a catalyst effective to polymerize some or substantially all of the silicone polymer precursor present.
  • Suitable catalysts are selected based upon the nature of the silicone polymer precursor used. For example, where the silicone polymer precursor is a commercially available silicone precursor, suitable catalysts are provided along with the commercial silicone precursor.
  • Suitable two-part commercially available silicone precursors include SILASTIC Medical Grade ETR Elastomers (e.g., Dow Corning Product Nos. Q7-4735, Q7-4750, and Q7-4765, and other products described in U.S. Patent No. 3,445,420 to Kookootsedes et al .
  • the amount of catalyst employed is not critical to the practice of the present invention, but it is preferred that the amount of catalyst be sufficient to polymerize substantially all (such as greater than 90%) of the silicone polymer precursor present.
  • the catalyst employed for polymerization of the silicone polymer precursor is one capable of catalyzing a condensation reaction between silicone atoms which are typically bonded to one or more hydroxy or halogen substituents .
  • the polymerization reaction can be carried out by heating the silicone polymer precursor to a temperature of from about 30°C to about 60°C for from about 5 hours to about 2 hours or at a temperature of from about 70°C to about 110°C for from about 30 minutes to about 15 minutes. Polymerization can also be carried out at room temperature or even lower, but this takes appreciably more time (about 1 day or more) .
  • silicones can also be used in the practice of the present invention. These include alkoxy- cured silicones, such as TRV5222, RTV5223, RTV5229, RTV5242, RTV5243, RTV5249, RTV160, RTV162, RTV167; acetoxy-cured silicones, such as RTV102, RTV103. RTV108, RTV109, IS802, IS803, IS808, RTV112, and RTV118 ; and high temperature or fuel resistant silicones, such as FRV1106, FRV1107, RTV1473, RTV133, RTV106, IS806, RTV116, RTV159, RTV142, and RTV157, all available from General Electric Co.
  • alkoxy- cured silicones such as TRV5222, RTV5223, RTV5229, RTV5242, RTV5243, RTV5249, RTV160, RTV162, RTV167
  • acetoxy-cured silicones such as RTV102, RTV103.
  • silicone polymer precursor When the silicone polymer precursor is polymerized prior to its being contacted with the cross- linking inhibitor, polymerization is typically carried out after the silicone polymer precursor has been fabricated into a desired shape.
  • a variety of different methods can be used to shape the silicone polymer precursor, including extrusion, spin-casting, calendaring, and molding techniques, such as injection molding. These and other techniques for shaping silicone products are described in, for example, Metevia et al . , "Fabricating Silicone Rubber,” in Hseih et al . , eds . , Controlled Release Systems: Fabrication Technology, Volume II, Boca Raton, Florida:CRC Press, pp. 111-136 (1988), which is hereby incorporated by reference.
  • the silicone polymer precursor can have the form of a thin layer, such as one having a thickness of from about 0.1 mm to about 30 mm.
  • the thin layer forms a coating on a substrate made of, for example, paper, wood, fiberglass, plastic, metal, glass, and mixtures thereof .
  • the substrate can be made of cured silicone, particularly where the substrate is a medical implant. Coating of the silicone polymer precursor onto the substrate can be achieved by a variety of different techniques, such as painting, dipping, sputtering, spraying, and the like.
  • the silicone polymer precursor is formed as a coating on a substrate, it is coated on the substrate prior to the introduction of the cross- linking inhibitor.
  • the coating can be formed prior to, during, or after the silicone polymer precursor is polymerized.
  • silicone monomer can be coated on the substrate and then partially or fully or substantially fully polymerized prior to introducing the cross-linking inhibitor.
  • the silicone monomer can be partially polymerized prior to coating the substrate.
  • it is advantageous to coat the substrate with the silicone polymer precursor during the early stages of the polymerization process because, during the later stages of the polymerization process, the silicone polymer precursor may become too viscous to form a uniformly thick coating on the substrate.
  • the partially polymerized silicone polymer precursor can be allowed to further polymerize prior to contacting it with the cross-linking inhibitor .
  • the polymerization process is carried out under conditions which are effective to polymerize the silicone polymer precursor to form an polymerized silicone material.
  • these conditions are preferably ineffective to cure the polymerized silicone polymer precursor.
  • cured silicone polymer is formed by a two step process: a relatively fast polymerization step in which the terminal groups of the silicone polymer precursor react together to form long linear chains of polymerized silicone; and a second, relatively slower step in which the long chains of polymerized silicone are cross-linked in a process known as curing.
  • Polymerized silicone polymer is characterized by its increased viscosity relative to the monomeric precursor but lacks the cross-links which make cured silicone resilient.
  • the surface of the silicone polymer precursor is contacted with a cross - linking inhibitor.
  • Suitable cross -linking inhibitors include carboxylic acids, particularly carboxylic acids having the formula R-COOH, where R represents a substituted or unsubstituted C1-C12 branched, cyclic, or linear alkyl or C6-C18 aryl group, such as acetic acid, propionic acid, and the like, metal salts of carboxylic acids, such as stannous octonate, chlorinated and butyl rubbers, sulfur containing solvents, plasticizer, tin containing compounds, oxidizing oils, linseed oils, putties, oils containing clays, and amine-containing plasticizers.
  • the particular cross-linking inhibitor used depends, in part, on the nature of the silicone polymer precursor employed.
  • silicone polymer precursors such as MDX 4- 4210, SILGARD 184 and 186, and SILASTIC 31-10, 31-12, and 31-20, are particularly compatible with inhibitors, such as chlorinated and butyl rubbers, sulfur containing solvents, plasticizer containing compounds, and tin containing compounds.
  • Silicone polymer precursors such as SILASTIC 382 and GE RTV-11, are compatible with inhibitors, such as the aforementioned oils as well as plasticizers, specifically amine containing plasticizers.
  • One particularly useful cross-linking inhibitor is a ketone.
  • the ketone is preferably provided in the form of a liquid, and, for example, can be acetone, methyl ethyl ketone, diethyl ketone, or combinations thereof. It is particularly preferred to use a cross- linking inhibitor which includes acetone and one or more of the following: water, an amine salt of a fatty acid amide of a hydrolyzed collagen, and an acid addition salt of a mono-fatty acid-amido substituted-trialkylamine cationic surfactant.
  • the cross-linking inhibitor includes from about 70 to about 90 wt% acetone, from about 5 to about 17 wt% water, from about 0.01 to about 0.15 wt% of an amine salt of a fatty acid amide of a hydrolyzed collagen, and from about 0.1 to about 0.8 wt% of an acid addition salt of a mono- fatty acid-amido substituted-trialkylamine cationic surfactant.
  • Suitable amine salts of a fatty acid amide of a hydrolyzed collagen include the aminomethylpropanol salt of the isostearic amide of hydrolyzed collagen, and suitable acid addition salts of a mono-fatty acid-amido substituted-trialkylamine cationic surfactant include cocamidopropyl dimethylaminopropionate .
  • Other suitable amine salts of a fatty acid amide of a hydrolyzed collagen and acid addition salts of a mono-fatty acid- amido substituted-trialkylamine cationic surfactant include those described in U.S. Patent No. 4,485,037 to Curtis ("Curtis”), which is hereby incorporated by reference.
  • the cross-linking inhibitor can be contacted with the silicone polymer precursor's surface directly or indirectly.
  • indirectly it is meant that the cross- linking inhibitor is first applied to an inert substrate which is then contacted with the silicone polymer precursor surface.
  • the cross-linking inhibitor such as a ketone or a composition which includes a ketone, can be applied to the surface of a mold, and the silicone polymer precursor can then be pressed into the mold so that the silicone polymer precursor's surface comes into contact with the cross- linking inhibitor on the mold's surface.
  • the cross-linking inhibitor is applied directly to the silicone polymer precursor's surface, such as by painting, spraying, sputtering, dipping, and the like, without first applying it to an inert substrate.
  • a ketone-containing cross- linking inhibiting composition can be painted, such as with a brush or a roller, on the silicone polymer precursor's surface.
  • agitation can be effected in a number of ways, such as by the use of brushes, rollers, spatulas, and the like.
  • brushing of the silicone polymer precursor's surface is continued for a period of time, preferably from about 1 minute to about 1 hour, to effect agitation.
  • the depth to which the cross-linking inhibitor mixes with the silicone polymer precursor's surface can be controlled.
  • agitation mixes the cross-linking inhibitor with the silicone polymer precursor's surface to a depth of from about 0.01 mm to about 25 mm, depending on the thickness of the silicone polymer precursor.
  • agitation is effective to mix the cross-linking inhibitor with the silicone polymer precursor' s surface to a depth of from about 10% to about 50% of the thickness of the silicone polymer precursor .
  • silicone polymer precursor was partially polymerized prior to contacting its surface with the cross-linking inhibitor
  • polymerization and curing is simply a continuation of the polymerization process coupled with curing.
  • silicone polymer precursor was unpolymerized
  • polymerization can be effected simply by the passage of time, or, alternatively, it can be accelerated by the presence of a catalyst, by the application of heat, or both using, for example, the methods and conditions described above for pre-polymerization.
  • curing can be carried out simply by the passage of time, or, alternatively, it can be accelerated by the application of, for example, heat.
  • curing can be effected by exposing the silicone polymer precursor to: a temperature of from about 35 °C to about 45 °C for from about 4 hours to about 6 hours; a temperature of from about 50 °C to about 60 °C for from about 1 hour to about 3 hours; a temperature of from about 65 °C to about 85 °C for from about 15 minutes to about 1 hour; a temperature of from about 90 °C to about 110 °C for from about 5 minutes to about 30 minutes.
  • curing can be carried out at room temperature in from about 12 hours to about 8 days, preferably from about 48 hours to about 8 days.
  • the bulk of the silicone polymer precursor becomes cross- linked, but the surface of the silicone polymer precursor which had been contacted with the cross-linking inhibitor remains uncured.
  • the non-cross-linked nature of the uncured surface imparts to that surface an adhesive quality which can be exploited in a variety of applications .
  • the adhesive silicone polymers can be used in any environment where self-adhesive cushioning materials are desired. For example, they can be used as furniture bumpers, as coatings for glass surfaces (e.g., windows and windshields) , and as soft antiskid mats, such as for diaper changing stations and bathtubs.
  • the adhesive silicone polymers of the present invention can also be used to reversibly adhere materials, such as artwork or advertisements, to vertical surfaces, such as walls, by applying sheets of the adhesive silicone polymer to the vertical surface with the adhesive side out.
  • the adhesive silicone polymers of the present invention can, alternatively, be used as a moisture and water resistant tape, such as for diapers or feminine hygiene products.
  • the adhesive silicone polymers can also be used to insulate glass and other surfaces, such as window panes and windshields, or to modify the surface energy of metals and other materials.
  • the method of the present invention can be advantageously used to attach a medical implant to a biological material.
  • the implant is first coated with a silicone polymer precursor.
  • the coated silicone polymer precursor coating has an exposed surface which is then contacted with a cross-linking inhibitor, such as those described above, particularly a ketone or a composition containing a ketone.
  • the silicone polymer precursor coating's surface can be, but need not be, agitated to mix the cross-linking inhibitor with the silicone polymer precursor coating' s surface to a desired depth. In this way the depth to which the silicone polymer precursor coating will remain uncured can be controlled.
  • the silicone polymer precursor coating is then polymerized and cured under conditions effective to polymerize and cross-link the silicone polymer precursor coating.
  • Conditions suitable for polymerizing and curing the silicone polymer precursor include those which were discussed above.
  • the surface of the silicone polymer precursor coating in contact with the cross-linking inhibitor remains uncured, which imparts to it an adhesive character.
  • the adhesive surface of the coated implant is then contacted with a biological material under conditions effective to attach the medical implant to the biological material .
  • the adhesive surface of the coated implant can simply be pressed against the biological material, for a period of time, typically from about 30 seconds to about 5 minutes, after which the adhesive surface of the coated implant remains attached to the biological material without further pressure.
  • other medically- acceptable adhesives such as dental adhesives, bone cement, tooth surface cement, tissue bonding cement; mechanical fasteners, such as screws, staples, or sutures; or combinations of these can be used in conjunction with the methods of the present invention.
  • drug-releasing patches are meant to include those which sustainedly release hormones, steroids (including contraceptive steroids), aspirin, anti-cancer agents, nicotine, and anti-inflamatories , as well as other agents described in Kydonieus, ed., Controlled Release Technologies: Methods, Grafs, and Applications, Volume II, Boca Ratoon, FloridarCRC Press (1980) ("Kydonieus”) and Wise, ed., Biopolymeric Controlled Release Systems, Volume II, Boca Ratoon, Florida:CRC Press (1984), which is hereby incorporated by reference.
  • monitoring devices such as those used to continuously monitor pulse, blood pressure, temperature, electrocardio activity, brain activity, and/or blood flow.
  • These implants can be made of cured silicone or of any material which is well suited for the function of the implant, such as plastics, fiberglass, metal, ceramics, and glass.
  • biological materials include, for example, skin, particularly human skin, bones, teeth, and the like.
  • the adhesive silicone polymers of the present invention can also be used to sustainedly deliver cleansing, antibacterial, or other materials in the same manner that conventional silicone polymers are used to release these materials in a controlled manner.
  • the adhesive silicone polymers of the present invention can contain an antibacterial, antifungal, antiviral, or antimildew agent which is sustainedly released therefrom. These materials are especially useful when adhered to surfaces where bacterial, fungal, viral, and/or mildew growth is particularly undesirable or likely. Such surfaces include sinks and cutting surfaces in the meat cutting and packing industries, public shower and bathroom surfaces, floors, and baby changing stations.
  • the adhesive silicone polymers of the present invention can also be used to make preformed bathtub caulk (adhesive side applied toward wall) , bathtub mats (adhesive side toward tub) , pool liners (adhesive side down) , and cushioning liners for sinks and floors (adhesive side down) .
  • the present invention in another aspect thereof, relates to a method for producing a silicone polymeric composition having a drag-reducing surface.
  • drag relates to the friction experienced by a body moving relative to, such as through, a fluid medium, particularly water or other aqueous medium.
  • the silicone polymeric composition having a drag reducing surface is prepared by contacting a silicone polymer precursor with a cross-linking inhibitor.
  • the silicone polymer precursor's surface is optionally agitated under conditions effective to cause the cross-linking inhibitor to mix with the silicone polymer precursor's surface.
  • the silicone polymer precursor is then polymerized and cured under conditions which are effective to polymerize and cross-link the silicone polymer precursor without cross -linking the surface of the silicone polymer precursor contacted with the cross-linking inhibitor. In this manner, a silicone polymeric composition having drag-reducing surface is produced .
  • Suitable silicone polymer precursors, cross- linking agents, and reaction conditions are the same as those specified above with regard to the method of producing a silicone polymeric composition having an adhesive surface of the present invention.
  • the methods of the present invention can be used to reduce the drag experienced by objects, particularly boat hulls, as they move through water or other aqueous media.
  • the method includes coating the boat hull with a silicone polymer precursor. Suitable silicone polymer precursors include those described above with respect to methods for producing silicone polymeric compositions having adhesive surfaces.
  • the boat hull can be coated by any conventional method, such as spraying, painting, sputtering, and the like.
  • the silicone polymer precursor coating' s surface is then contacted with a cross-linking inhibitor, such as those described above, particularly a ketone or a ketone- containing composition, such as, for example, those described in Curtis, which is hereby incorporated by reference.
  • the silicone polymer precursor coating is polymerized and cured under conditions effective to polymerize and cross-link the silicone polymer precursor coating.
  • Catalysts suitable for polymerizing and curing the silicone polymer precursor coating, as well as the conditions under which polymerization and curing can be effectively carried out include those specified above with regard to producing silicone polymeric compositions having adhesive surfaces.
  • the surface of the silicone polymer precursor coating which had been contacted with the cross -linking inhibitor remains non-cross-linked, thus producing a boat hull which exhibits reduced drag.
  • the silicone polymers of the present invention can also be used to reduce drag in other environments, such as the inside walls of pipes and ductwork.
  • Illustrative examples of pipes and ductwork include those used in power plant heat exchangers, condensers, and intake lines, minicipal and biological water supply lines, cooling circuits in oil refineries, sewage conduits, and catheters (e.g., those used for angiography or to deliver liquid to any internal organ or cavity) .
  • the silicone polymer precursor can be applied to the inside walls of pipes or ductwork and subsequently treated with a cross-linking inhibitor in a manner analogous to the process used to coat boat hulls, described above .
  • the silicone polymers can contain an agent which is sustainedly released to control, for example, fungal and bacterial growth.
  • agents for sustained release in these situations include, for example, antibacterial agents, antifungal agents, and combinations thereof. Further details regarding the incorporation of such agents in silicone materials can be found, for example, in Kydonieus, which are hereby incorporated by reference. The present invention is further illustrated by the following examples.
  • Silicone polymer precursor designated MDX4-4210 commercially available from Dow Corning Corp., Midland, Michigan, was prepared. Acetone-based and acetic acid-based cross-linking inhibitor agents were separately applied to selected atmosphere-to-precursor surfaces of the polymer. The surfaces where the inhibiting agents were applied were agitated to a depth of about 1-3 mm to thoroughly mix precursor and inhibitor until a change in consistency was noted. In some samples, agitation was performed at multiple times during the curing process including at the time of precursor preparation and up to approximately 2-3 hours into curing. In other samples, agitation was performed once either at the time of precursor preparation or at some time during the curing process up to approximately 2-3 hours into curing. The polymer was allowed to cure at room temperature for approximately 72 hours, or the polymer was heated at 100-150°F for approximately 2 hours. After complete curing, the surfaces of the polymer in contact with the cross- linking inhibitor agents were tacky and exhibited pressure sensitive adhesive properties.
  • Silicone polymer precursor mentioned in Example 1 was spread on to a previously cured sample of the same silicone precursor.
  • the same inhibitors as in Example 1 were separately added to the uncured atmosphere-to-precursor surfaces and agitated to thoroughly mix the uncured precursor and the inhibitor. This mixture was cured at room temperature for approximately 72 hours. Upon curing the polymer surfaces in contact with the cross-linking inhibitors were tacky and exhibited pressure sensitive adhesive properties.
  • Example 3
  • Example 2 GE RTV11 polymer, commercially available from General Electric Company, Poestenkill, New York, was prepared. The same inhibitors as in Example 1 were separately applied to selected atmosphere-to-precursor surfaces of the polymer. The area was agitated and the polymer was allowed to cure at room temperature for approximately 24 hours. Upon curing, the polymer surfaces in contact with the cross-linking inhibitors were tacky and exhibited pressure sensitive adhesive properties.
  • MAIR-IR Multiple Attenuated Internal Reflection Infrared

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Abstract

La présente invention concerne un procédé pour produire une composition polymère siliconée présentant une surface adhésive ou une surface réduisant la traînée. La surface d'un précurseur de polymère siliconé est mise en contact avec un inhibiteur de réticulation et est éventuellement soumise à agitation pour que l'inhibiteur de réticulation se mélange avec la surface du précurseur de polymère siliconé. Une composition polymère siliconée présentant une surface adhésive ou une surface réduisant la traînée est produite par polymérisation et durcissement du précurseur de polymère siliconé dans des conditions efficaces pour assurer la polymérisation et la réticulation de ce précurseur sans réticulation de sa surface mise en contact avec l'inhibiteur de réticulation. L'invention concerne également des procédés pour fixer un implant médical sur un matériau biologique et pour réduire la traînée de la coque d'un bateau. Le dispositif médical ou la coque de bateau sont revêtus d'un précurseur de polymère siliconé, lequel est ensuite mis en contact avec un inhibiteur de réticulation, la surface du revêtement constitué du précurseur de polymère siliconé est mise en contact avec un inhibiteur de réticulation, et ledit revêtement est polymérisé et durci dans des conditions efficaces pour assurer la polymérisation et la réticulation du précurseur sans réticulation de sa surface mise en contact avec l'inhibiteur de réticulation.
PCT/US1998/015267 1997-07-21 1998-07-21 Procede pour preparer des polymeres silicones Ceased WO1999003424A1 (fr)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002011680A1 (fr) * 2000-08-07 2002-02-14 S & C Polymer Silicon- und Composite-Spezialitäten GmbH Produits d'obturation au silicium et de fixation adhesifs
WO2004039908A1 (fr) * 2002-10-31 2004-05-13 Paul David Foreman Joint de vitrage
WO2005051442A1 (fr) * 2003-11-13 2005-06-09 Dow Corning Corporation Procede d'adhesion de gels de silicone a des plastiques
WO2007118477A1 (fr) * 2004-07-28 2007-10-25 Fortunato, Aldo Coque inférieure d'un bateau
ITBO20100454A1 (it) * 2010-07-15 2012-01-16 Maurizio Cirulli Composto a base siliconica, particolarmente per implantologia dentale
US20150328370A1 (en) * 2012-12-20 2015-11-19 Becton, Dickinson And Company Device and Method for Inhibiting Movement of a Medical Device in a Patient
RU2807821C1 (ru) * 2023-07-27 2023-11-21 Федеральное государственное автономное образовательное учреждение высшего образования "Российский университет дружбы народов имени Патриса Лумумбы" (РУДН) Способ изготовления силиконового адгезива для фиксации полимерных медицинских изделий на физиологических тканях челюстно-лицевой области

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4623593A (en) * 1983-07-12 1986-11-18 Keith Kent Self-adhesive polymer composition for use as prosthetic appliance

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4623593A (en) * 1983-07-12 1986-11-18 Keith Kent Self-adhesive polymer composition for use as prosthetic appliance

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002011680A1 (fr) * 2000-08-07 2002-02-14 S & C Polymer Silicon- und Composite-Spezialitäten GmbH Produits d'obturation au silicium et de fixation adhesifs
US7090498B2 (en) 2000-08-07 2006-08-15 S&C Polymer Silicon- Und Composite-Spezialitaten Gmbh Adhesive silicon filling and fixing materials
WO2004039908A1 (fr) * 2002-10-31 2004-05-13 Paul David Foreman Joint de vitrage
WO2005051442A1 (fr) * 2003-11-13 2005-06-09 Dow Corning Corporation Procede d'adhesion de gels de silicone a des plastiques
CN1878577B (zh) * 2003-11-13 2010-11-03 陶氏康宁公司 将硅氧烷凝胶粘附到塑料上的方法
US8101042B2 (en) 2003-11-13 2012-01-24 Dow Corning Corporation Method for adhering silicone gels to plastics
WO2007118477A1 (fr) * 2004-07-28 2007-10-25 Fortunato, Aldo Coque inférieure d'un bateau
ITBO20100454A1 (it) * 2010-07-15 2012-01-16 Maurizio Cirulli Composto a base siliconica, particolarmente per implantologia dentale
US20150328370A1 (en) * 2012-12-20 2015-11-19 Becton, Dickinson And Company Device and Method for Inhibiting Movement of a Medical Device in a Patient
US10799621B2 (en) * 2012-12-20 2020-10-13 Becton, Dickinson And Company Device and method for inhibiting movement of a medical device in a patient
RU2807821C1 (ru) * 2023-07-27 2023-11-21 Федеральное государственное автономное образовательное учреждение высшего образования "Российский университет дружбы народов имени Патриса Лумумбы" (РУДН) Способ изготовления силиконового адгезива для фиксации полимерных медицинских изделий на физиологических тканях челюстно-лицевой области

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