WO2003030940A1 - Procede de modification superficielle de surfaces de silicone - Google Patents

Procede de modification superficielle de surfaces de silicone Download PDF

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Publication number
WO2003030940A1
WO2003030940A1 PCT/US2002/032050 US0232050W WO03030940A1 WO 2003030940 A1 WO2003030940 A1 WO 2003030940A1 US 0232050 W US0232050 W US 0232050W WO 03030940 A1 WO03030940 A1 WO 03030940A1
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WIPO (PCT)
Prior art keywords
graft
solution
polymerization
siloxane
substrate
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PCT/US2002/032050
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English (en)
Inventor
Christopher W. Widenhouse
Eugene P. Goldberg
Original Assignee
University Of Florida
Jabar, Haseeb
Urbaniak, Daniel
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Publication date
Application filed by University Of Florida, Jabar, Haseeb, Urbaniak, Daniel filed Critical University Of Florida
Publication of WO2003030940A1 publication Critical patent/WO2003030940A1/fr
Priority to US10/820,139 priority Critical patent/US20050079365A1/en

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Classifications

    • 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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • C08J7/16—Chemical modification with polymerisable compounds
    • 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
    • A61L27/14—Macromolecular materials
    • A61L27/16—Macromolecular materials obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • A61L33/00—Antithrombogenic treatment of surgical articles, e.g. sutures, catheters, prostheses, or of articles for the manipulation or conditioning of blood; Materials for such treatment
    • A61L33/0076—Chemical modification of the substrate
    • A61L33/0088—Chemical modification of the substrate by grafting of a monomer onto the substrate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L39/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions of derivatives of such polymers
    • C08L39/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
    • C08L39/06—Homopolymers or copolymers of N-vinyl-pyrrolidones
    • 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

Definitions

  • the present invention relates to a method for modifying the surfaces of materials to impart desired characteristics thereto.
  • a specific material may meet most of the requirements of the proposed application, such as strength, weight, density, structure, machinability, electromagnetic properties, etc.; however, its surface characteristics may render it unsuitable for that particular use.
  • IOLs intraocular lenses
  • Most ocular implants are constructed of hydrophobic polymethyl methacrylate (PMMA) polymers because of their superior optical qualities, resistance to biodegradation, etc.
  • PMMA IOLs It is well documented in the prior art that a significant disadvantage inherent in PMMA IOLs resides in the potential for long-term abrasive interactions with sensitive tissues such as the iris, ciliary sulcus, etc., and that even brief contact between the corneal endothelium and hydrophobic polymer surfaces, i.e., PMMA, can result in extensive damage to the endothelium. See Katz et al, Trans. Am. Acad. Ophth., Vol. 83, p. 204-212 (1977).
  • Ocular implant surfaces have been coated with various hydrophilic polymer solutions or temporary soluble coatings such as methylcellulose, polyvinylpyrrolidone, etc., to reduce the degree of adhesion between the implant surfaces and endothelial tissue cells. While offering some temporary protection, these methods have not proven entirely satisfactory, since such coatings complicate surgery, do not adhere adequately to the implant surfaces, become dislodged or deteriorate after implantation, dissolve away rapidly during or soon after surgery, or may produce adverse post-operative complications. Moreover, it is difficult to control the thicknesses and uniformity of such coatings.
  • GDP Glow discharge plasma
  • GDP induced by an inductively coupled radio frequency current is a high-energy state of ionized gases formed by passing gas or vapor molecules through a high-energy field.
  • the resulting activated species possess sufficient energy to chemically alter the surface of a substrate placed in the GDP by generating activated surface species such as radicals or ion radicals. When exposed to air, these radicals or other activated sites can also combine with oxygen to form sites for further chemical reaction and polymerization with various vinyl monomers.
  • Furthennore, monomers present in the plasma may be activated and graft polymerized to activated sites on the substrate. Under GDP conditions, even relatively unreactive compounds such as benzene, toluene, perfiuoro propane, etc., which are not vinyl monomers may also be sufficiently activated to enable polymer-forming reactions.
  • hydrophobic polymers such as FEP (Teflon), PC (polycarbonate), PMMA (poly-methylmethacrylate), PDMSO (polydimethylsiloxane), PP (poly-propylene), etc.
  • FEP Teflon
  • PC polycarbonate
  • PMMA poly-methylmethacrylate
  • PDMSO polydimethylsiloxane
  • PP poly-propylene
  • Plasma treatment can cause chain scission, ablation, cross-linking, oxidation and other reactions to a depth of 50-100ANG or more depending on the substrate and experimental conditions [Wu et al, in Polymer Interphase and Adhesion, Chap. 9, p. 298, Marcel Dekker, New York (1982)].
  • Grafting is dependent on the prevalence of excited surface species such as radicals generated by gamma radiation, which in turn is dependent upon the energy required to form such activated species in a particular substrate. Therefore, substrates with high activation energies for radical formation relative to monomer solutions do not easily graft by gamma polymerization before extensive solution polymerization and gelation occurs, making sample removal and washing impractical.
  • hydrophilic surface modification of siloxane based polymers is especially difficult because of the extraordinary flexibility and mobility of the polysiloxane molecular change (for example polydimethylsiloxane).
  • polysiloxane molecular change for example polydimethylsiloxane.
  • To impart hydrophilic characteristics or increased wetting of the surfaces is a difficult problem often requiring methods such as radio frequency plasma techniques or a combination of several different steps. Even so, the prior art results have not been generally successful or practical.
  • siloxane based polymers by a method which includes the hydrolysis of the surface with acidic or basic compounds to tailor the binding capacity for ions, particularly metal ions, bivalent cations, organic macro anions, and organic macro cations, e.g. proteins, has also been taught in the literature.
  • This recent method involves first subjecting the substrate polymer to hydrolysis and then by exposing it to an ionic compound that will bond to the charges created by the hydrolysis.
  • This method is a two step process, and only involves charged particles or compounds, and does not involve the polymerization onto the silicone surface of a surface polymer.
  • An embodiment of the invention relates to a method for modifying the surface properties of a silicone or siloxane-based polymer or copolymer substrate comprising, (1) exposing the surface to a basic aqueous solution comprising a substance capable of graft- polymerization with the silicone or siloxane-based polymer or copolymer substrate, the aqueous solution having a pH above about 8.0, the exposure to the basic aqueous solution being for a time sufficient to enhance the graft-polymerization and (2) subjecting the surface and basic solution to conditions whereby the polymerizable substance is polymerized to form a graft-polymerized coating on the surface.
  • Another embodiment of the invention concerns the composition formed by the above- described method.
  • Still further embodiments of the invention are articles manufactured from the above- described compositions.
  • the present invention is predicated on the discovery that the graft-polymerization of a polymerizable substance to form a coating on the surface of a silicone or siloxane-based polymer and/or copolymer is greatly enhanced by the prior or simultaneous exposure of the surface to a basic aqueous solution having a pH above about 8.0.
  • siloxane-based polymers are subject to hydrolysis under basic conditions, i.e., pHs above about 8.0, and, the higher the pH, typically, the greater the degree of hydrolysis. It is theorized, therefore, that this hydrophilic propensity may, to some degree, be a contributing factor in the enhancement of the graft polymerization process.
  • the preferred agent for adjusting the pH of the aqueous solution is a metal hydroxide, more preferably alkali earth metal hydroxides, most preferably alkali metal hydroxides; the optimum agent comprising sodium or potassium hydroxide.
  • the polymerizable substance such as, e.g., N-vinylpyrrolidone (NVP)
  • NVP N-vinylpyrrolidone
  • surface graft polymerization of the NVP is greatly facilitated by the basic medium.
  • Surface polymerization of the NVP for example, thereby produces a more stable and lower contact angle, i.e., a more wettable surface, on silicones than is obtained by similarly conducted polymerizations at normal, near pHs of 6.0-8.0.
  • Solutions of NaOH in water were made at concentrations of 0.5, 1.0, 1.5, and 2.0% by weight (i.e., the 1.0% solution contained 1 gram of NaOH in 100 grams of water) and then used to make a 10% NVP solution by weight (i.e., 10 grams of NVP was added to 90 grams of a salt solution).
  • This solution was then subjected to vacuum degassing in order to remove as much dissolved oxygen and air from the solution as possible.
  • a vacuum was applied to the container containing the solution, and the solution was allowed to 'boil' and degas for approximately 5 minutes. Oxygen/air degassing may also be accomplished by bubbling argon through the solution for several minutes.
  • the solution was then added to glass vials which contained the silicone disk samples. The vials were closed with a plastic lid and placed into a cobalt-60 irradiator. The samples were exposed to gamma radiation at a dose rate of approximately 575 rads/min for a total exposed dose of approximately 0J3 Mrads.
  • the vials were removed from the irradiator, and the solution surrounding the samples was removed. The samples were then continuously washed in water with fresh water changes periodically until there were no traces of monomer or polymer remaining in the solution as measured with UV/Vis spectroscopy.
  • the samples were then analyzed and characterized with respect to wettability by surface contact angle, graft thickness, and surface chemistry as measured using XPS.
  • the modified samples were soaked in two separate solutions. Samples were soaked in either a saturated aqueous iodine solution for 12 hours or an aqueous 8% silver nitrate solution for 12 hours. The samples soaked in iodine were then rinsed in water for 12 hours and dried. The samples soaked in silver nitrate were immersed in a phosphate buffered formalin solution which caused the precipitation of silver chloride, silver oxide, and silver phosphate.
  • Both of these methods cause a coloration or staining of the grafted region because the iodine or silver nitrate solutions primarily penetrate the substrate surface to the extent that has been rendered hydrophilic by the surface modification.
  • These samples were then cross sectioned and examined by optical microscopy. All samples showed a surface graft. For example, using a 2% NaOH solution of monomer, the stained graft layer was approximately 7-10 ⁇ m.
  • a silicone sample that was not surface modified by the above-described method but was subjected to the staining procedure showed no evidence of surface modification as indicated by the lack of a brownish surface layer.
  • aqueous alcohol solutions were made using methanol or isopropanol in water at concentrations of 0.5, 25, 50, 75, and 95% by weight (i.e., the 25% isopropanol solution contained 25 grams of isopropanol and 75 grams of water). These solutions were then used to make a 10% NVP solution by weight (i.e., 10 grams of NVP was added to 90 grams of a salt solution).
  • 25% isopropanol in water consisted of 25 grams isopropanol and 75 grams of water; 25% methanol in water consisted of 25 grams methanol and 75 grams of water.
  • the alcohol solutions were then used to make 2% solutions of NaOH, KOH, NaCl, and KCI. To make these solutions, 2 grams of each salt was added to 100 grams of each of the above solutions.
  • Each of these alcoholic solutions was then used to make an approximately 10% solution with NNP by adding 10 grams of ⁇ NP monomer to 100 grams of each of the alcoholic salt solutions.
  • Example 1 Each of these solutions was then degassed as in Example 1 in order to remove as much dissolved oxygen and air from the solution as possible.
  • the solutions were then added to glass vials which contained the silicone disk samples.
  • the vials were closed with a plastic lid and placed into a cobalt-60 irradiator and exposed to gamma radiation as in Example 1.
  • the vials were removed from the irradiator, and the solution surrounding the samples was removed. The samples were then continuously washed in water with fresh water changes periodically until there were no traces of monomer or polymer remaining in the solution as measured with UV/Nis spectroscopy.
  • Example 1 The samples were washed and analyzed as in Example 1. All samples showed contact angles ⁇ 35° and surface graft by staining.
  • a solution of ⁇ aOH in water was made at a concentration of 0.5%. The solution was then used to make a 10% ⁇ NP solution by volume (i.e., 10 ml of ⁇ NP was added to 90 ml of base solution.
  • the 10% NNP/90% base solution was then added to glass vials containing one silicone disk each.
  • the vials were subjected to vacuum to remove as much dissolved oxygen and air from the solution and submerged disk as possible.
  • a vacuum was applied to the vials containing the solution and disks and allowed to "boil" and degas for approximately 2 minutes.
  • the vials were backfilled with argon gas, sealed with plastic lids and placed in a cobalt-60 irradiator.
  • the samples were exposed to gamma radiation at a dose rate of approximately 600 rads/minute for 80 minutes for a total exposed does of approximately 0.05 Mrads.
  • the vials were removed from the irradiator, and the solutions surrounding the samples were removed. The samples were then continuously washed in ultrapure water with fresh water changes periodically.
  • the samples were then analyzed and characterized with respect to surface contact angle using captive air bubble goniometry.
  • the average contact angle measured was 23° for the disks irradiated in grafting solutions using 0.5% ⁇ aOH silicone disks that were not treated had an average contact angle of 83%.
  • the samples were dried in a vacuum oven at room temperature for 12 hours and rehydrated and remeasured for contact angle.
  • the average contact angles measured were 27° for the rehydrated disks irradiated in grafting solutions using 0.5% ⁇ aOH.
  • the samples were dehydrated and rehydrated for several days and remeasured for contact angle again.
  • the average contact angles measured were 28° for the disks irradiated in grafting solutions using 0.5% ⁇ aOH.
  • graft polymerization may be induced by gamma or electron beam radiation initiation, ultraviolet (UN) radiation initiation, chemical initiation, electrochemical initiation, or any other conventional graft polymerization method.
  • Gamma and electron beam irradiation are the preferred modes of graft polymerization.
  • the total gamma or electron beam dose is in the range of from about 0.001 to about 0.5 Mrads
  • the gamma dose rate is in the range from about 10 to about 2500 rad/min
  • the electron beam dose rate is from about 10 to about 10 8 rads/min.
  • the invention is applicable to virtually any polysiloxane, or copolymer thereof with polyesters, polyolefins, polyurethanes, polyimides, polyamides, polysulfones, polysulfides, polyacrylates, polyacrylics, polystyrenes, polymethacrylates, ethylene-propylene copolymers, polybutadiene, styrenebutadiene copolymers, styrene-ethylene-butadiene copolymers, polycarbonates, fluorocarbon polymers, polyurethanes, polyvinylchloride, or mixtures thereof, as well as ceramics or metal composites wherein the above polymers and/or copolymers are utilized in the construction thereof.
  • Suitable polymerizable substances are monomers or oligomers such as: a) ⁇ -vinylpyrrolidone ⁇ NP, or b) 2-hydroxyethylmethacrylate (HEMA), or c) an alkali metal, e.g., the sodium or potassium salt of sulfopropyl acrylate ( ⁇ aSPA or KSPA), or d) a vinylsulfonic acid such as sulfoethylmethacrylate, sulfopropylmethacrylate, styrene sulfonic acid, 2-acrylamide-2-methyl-l -propane sulfonic acid, or vinylsulfonic acid, including mixtures and salts thereof, or e) an amino-functional monomer such as vinylpyridine, an aminostyrene, an aminoacrylate or an aminomethacrylate, including mixtures and salts thereof, or f) acrylamide, dimethylacrylamide, polyethylene glycol monomethacrylate, or
  • the monomer is preferably employed in a concentration in the range from about 0.01% to about 50%, by weight; most preferably in the range of 5-15%.
  • NaOH, KOH, Ca(OH) 2 , LiOH, and the like may be employed to fo ⁇ ri the basic hydrolyzing solution.
  • Organic bases that increase the pH of aqueous solutions may also be used and include, for example, amines and aminoalcohols such as triethylamine, ethanolamine and the like.
  • Salts which form ionic solutions in aqueous media such as NaCl, KCI, CaCl 2 , LiCI, Kl, Nal, etc, may also be used in conjunction with the base agents.
  • the method can further include pre-soaking the article surface in at least one of the monomers in a solution of from about 5% to about 95% by weight prior to conducting the polymerization for a period of time and at a temperature sufficient to facilitate diffusion of the monomer or monomers into the article surface.
  • the pre-soaking step may be conducted at a temperature in the range of from about 25° to about 90° C. and for a period of time of from about 0.25 to about 48 hours.
  • the method of the invention is extremely useful for imparting new surface properties to siloxane-based polymers. Siloxane based polymers are utilized for particular applications because they have specific electrical properties, specific properties of stretch, bend, and flexibility, and for the ease with which they can be manufactured into virtually any shape or final product desired.
  • the specific properties of the surface layer of siloxane polymers and copolymers are sometimes different than the desired properties. Rather than try to develop an entirely new material to replace the siloxane, it is often desired to just change the surface of the material by either adhering a polymer with the desired properties to the surface, or by chemically modifying the surface to have the desired properties.
  • Siloxane polymers are, by nature, hydrophobic, that is, they repel water. These devices typically will have better compatibility with human body tissues if they are hydrophilic or more water compatible.
  • the process of the present invention can be applied to very intricate shapes, designs, and complete medical devices, without damaging any of the properties that make siloxane based polymers the initial choice for the application.
  • An additional advantage of the process of the invention is that the surface, after it has been modified, can be loaded with drugs for a variety of purposes, e.g., the incorporation of a compound that will make the devices resistant to bacterial growth and infection.
  • examples of devices which are susceptible to modification according to the process of the invention include:
  • Glaucoma Shunts Surface interface devices for neural connections
  • the present invention provides, for the first time, a simplified process for the surface modification of siloxane based polymers and copolymers. Additionally, it offers the ability to surface modify other polymers and materials with a simple one step process. It offers manufacturers of siloxane-based devices the opportunity to impart surface modifications to improve the properties of specific devices in an easy and cost efficient manner.
  • the surface properties of these devices are enhanced, however, when made hydrophilic to facilitate the long-term success of these devices.
  • the present invention provides the art with the ability to impart hydrophilic and surface modified characteristics to the surface of these devices without altering the processing steps necessary to achieve the final form and function of the device.
  • an additional advantage of this system is the ability to incorporate drugs, biological molecules, pharmaceutical compounds, antibacterial agents and the like into the surface modification either during the process or after the process.
  • the present invention offers the ability to surface modify a final device and impart improved surface characteristics to the device as well as potentially render it resistant to infection by, e.g., incorporating therein an antibiotic.
  • other drugs may be loaded into the surface that allows the treatment of disease processes which necessitated the implantation of the device initially.
  • Virtually any therapeutically, prophylactically or diagnostically effective amount of a biologically active agent that is compatible with the silicone substrate and the polymer coating grafted thereto may be employed in the practice of the invention.
  • Suitable examples thereof include proteins, muteins and active fragments thereof, such as immunoglobulins, antibodies, cytokines (e.g., lymphokines, monokines, chemokines), interleukins, interferons (.beta.-IFN, .alpha. -IFN and . gamma. -IFN), erythropoietin, nucleases, tumor necrosis factor, colony stimulating factors, insulin, enzymes (e.g.
  • superoxide dismutase tissue plasminogen activator
  • tumor suppressors blood proteins, hormones and hormone analogs (e.g., growth hormone, adrenocorticotropic hormone and luteinizing hormone releasing hormone (LHRH)), vaccines (e.g., rumoral, bacterial and viral antigens), antigens, blood coagulation factors; growth factors; peptides such as protein inhibitors, protein antagonists, and protein agonists; nucleic acids, such as antisense molecules; oligonucleotides; and ribozymes.
  • hormones and hormone analogs e.g., growth hormone, adrenocorticotropic hormone and luteinizing hormone releasing hormone (LHRH)
  • vaccines e.g., rumoral, bacterial and viral antigens
  • antigens e.g., rumoral, bacterial and viral antigens
  • growth factors peptides such as protein inhibitors, protein antagonists, and protein agonists
  • Small molecular weight agents suitable for use in the invention include, antitumor agents such as bleomycin hydrochloride, carboplatin, methotrexate and adriamycin; antibiotics such as gentamicin, tetracycline hydrochloride and ampicillin; antipyretic, analgesic and anti-inflammatory agents; antitussives and expectorants such as ephedrine hydrochloride, methylephedrine hydrochloride, noscapine hydrochloride and codeine phosphate; sedatives such as chlorpromazine hydrochloride, procl lorperazine hydrochloride and atropine sulfate; muscle relaxants such as tubocurarine chloride; antiepileptics such as sodium phenytoin and ethosuximide; antiulcer agents such as metoclopramide; antidepressants such as clomipramine; antiallergic agents such as diphenhydramine; cardiotonics such as theophiUo

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Abstract

L'invention concerne un procédé de modification des propriétés de surface d'un substrat de polymère ou de copolymère à base de silicone ou de siloxane. Le procédé consiste à: 1) exposer la surface à une solution aqueuse basique comprenant une substance capable de polymérisation avec greffage avec le substrat de polymère ou de copolymère à base de silicone ou de siloxane, la solution aqueuse présentant un pH supérieur à environ 8,0 et l'exposition de la solution aqueuse basique s'effectuant pendant une durée suffisante pour améliorer la polymérisation avec greffage; et 2) exposer la surface et la solution basique à des conditions telles que la substance polymérisable soit polymérisée pour former sur la surface un revêtement polymérisé par greffage. L'invention concerne en outre des compositions de matières préparées au moyen du procédé de l'invention, ainsi que des articles fabriqués par ce procédé.
PCT/US2002/032050 2001-10-09 2002-10-09 Procede de modification superficielle de surfaces de silicone WO2003030940A1 (fr)

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US32729301P 2001-10-09 2001-10-09
US60/327,293 2001-10-09

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2550364C1 (ru) * 2013-11-20 2015-05-10 Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Российский химико-технологический университет им. Д.И. Менделеева (РХТУ им. Д.И. Менделеева) Способ модифицирования полидиметилсилоксана
WO2015160218A1 (fr) * 2014-04-17 2015-10-22 서울대학교산학협력단 Prothèse pour introduction in vivo, revêtue de polyphosphorylcholine réticulée
WO2018118963A1 (fr) * 2016-12-19 2018-06-28 Saint-Gobain Performance Plastics Corporation Composition à base de silicone et article fabriqué avec celle-ci
CN109137508A (zh) * 2018-07-18 2019-01-04 圣华盾防护科技股份有限公司 基于电子束辐照技术的棉织物抗菌及吸湿快干整理方法
CN114224822A (zh) * 2022-01-28 2022-03-25 复旦大学附属眼耳鼻喉科医院 一种眼部缓释给药植入物及其制造方法
EP4066867A4 (fr) * 2020-01-16 2023-05-31 Toray Industries, Inc. Procédé de production d'un dispositif médical

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US5674521A (en) * 1994-07-18 1997-10-07 University Of Cincinnati Enhanced loading of solutes into polymer gels and methods of use
US6387379B1 (en) * 1987-04-10 2002-05-14 University Of Florida Biofunctional surface modified ocular implants, surgical instruments, medical devices, prostheses, contact lenses and the like

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6387379B1 (en) * 1987-04-10 2002-05-14 University Of Florida Biofunctional surface modified ocular implants, surgical instruments, medical devices, prostheses, contact lenses and the like
US5674521A (en) * 1994-07-18 1997-10-07 University Of Cincinnati Enhanced loading of solutes into polymer gels and methods of use

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2550364C1 (ru) * 2013-11-20 2015-05-10 Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Российский химико-технологический университет им. Д.И. Менделеева (РХТУ им. Д.И. Менделеева) Способ модифицирования полидиметилсилоксана
WO2015160218A1 (fr) * 2014-04-17 2015-10-22 서울대학교산학협력단 Prothèse pour introduction in vivo, revêtue de polyphosphorylcholine réticulée
US11129706B2 (en) 2014-04-17 2021-09-28 Seoul National University R&Db Foundation Prosthesis for in vivo insertion, coated with cross-linked polyphosphorylcholine
US11925547B2 (en) 2014-04-17 2024-03-12 Seoul National University R&Db Foundation Prosthesis for in vivo insertion, coated with cross-linked polyphosphorylcholine
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