WO2011065809A2 - Matériaux composites de matrice polymère avec des agents de renforcement de différentes morphologies et procédés de synthèse de ces matériaux - Google Patents

Matériaux composites de matrice polymère avec des agents de renforcement de différentes morphologies et procédés de synthèse de ces matériaux Download PDF

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Publication number
WO2011065809A2
WO2011065809A2 PCT/MX2010/000140 MX2010000140W WO2011065809A2 WO 2011065809 A2 WO2011065809 A2 WO 2011065809A2 MX 2010000140 W MX2010000140 W MX 2010000140W WO 2011065809 A2 WO2011065809 A2 WO 2011065809A2
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composite materials
barium sulfate
polymer matrix
synthesis process
matrix composite
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PCT/MX2010/000140
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English (en)
Spanish (es)
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WO2011065809A3 (fr
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Issis Claudette Romero Ibarra
Antonio Sanchez Solis
Octavio Mareto Brito
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Universidad Nacional Autonoma De Mexico
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Publication of WO2011065809A2 publication Critical patent/WO2011065809A2/fr
Publication of WO2011065809A3 publication Critical patent/WO2011065809A3/fr

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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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • 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
    • C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2371/02—Polyalkylene oxides
    • 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
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes

Definitions

  • the objective of the present invention is to obtain composite materials, formed by a polymer matrix, reinforced with barium sulfate, which can be of nano or micrometric size, and of different morphologies, obtained by several simple synthesis procedures, being cheaper than conventional methods
  • the properties of the materials are increased by adding reinforcing elements or particles, which allows for a greater number of applications.
  • Reinforcers may be present in the form of fibers or agglomerates, either spherical or donut-shaped.
  • the characteristics and properties of the materials depend largely on the synthesis procedures used, causing them to have applications that fall within the fields of biomedicine, pharmacy, paints, pigments and textile industry.
  • polymeric materials for use in the biomedical industry, for applications such as coatings, artificial hearts, catheters, pacemakers and replacement of structural tissue. For this reason, the study of materials that meet the characteristics needed for these applications is increasingly important.
  • polymers most used in these applications are polyurethane, as mentioned in Hsu S., Chou C. 2004, Enhanced biostabiliy of polyurethane containing gold nanoparticles.
  • the mechanical and rheological properties depend on the shape, size, distance between the particles and their orientation in the dispersed phase.
  • a reinforcer in addition to maintaining or improving the mechanical properties, it is possible to produce a radiopaque polymer by incorporating an additive or an opaque pigment to X-rays, as is the case of BaS0 4 .
  • An advantage of the radiopaque polymer is its transparency, even with the additive incorporated.
  • These materials have other properties such as biocompatibility, both of the polymer and of the additive, in addition to being a biologically inert material.
  • materials with superior properties can be produced compared to the polymer matrix: Saha MC, Kabir Md.
  • thermoplatic polyurethane / nanoclay composites Materials Science and Engineering C, article in press. Carbon nanotubes, silicon carbide, and carbon black have also been used, as detailed in Gunes S., Cao F., Jana S. C, 2008, Evaluation of nanoparticulate fillers for development of shape memory polyurethane nanocomposites.
  • barium sulfate is used as a reinforcer for polyurethane such as WO 00/14165, WO 02/30994, WO 00/57932, WO 2005/054133, JP 2006-1 10224, JP 2000-217903, JP 10- 033680, JP2000-203890, 2002-269141 or US 2009020042, or as a reinforcer for polyoxymethylene EP1828308 and US20040630704P.
  • Barium sulfate is added in different proportions, such as 20%, in the case of JP2006-1 10224 and JP10-033680, or even amounts as small as 0.1% in JP02-269141.
  • the size of the reinforcing particles ranges from micrometer sizes, such as metal salts of 5 ⁇ in 15 to 90% by weight, US 4935019, and in intervals of 20 to 500 ⁇ depending on the size and type of marker, US6340367 B1. On the other hand in nanometric sizes from 10 to 300 nm, publication number JP2000-203890. Other examples vary the size of the metal salt from 0.1 to 5 ⁇ using 0.2 to 40% by weight, US
  • BaS0 4 is chemically inert, insoluble and does not substantially modify the transparency and biocompatibility of the polymer matrix: US 668983 B1.
  • Some methods of obtaining these materials are the use of aqueous mixtures of the salts with the polymer, coating them with metals as detailed in EP1828308 and JP02269141.
  • additives such as halogenated compounds, preferably using bromine: US4722344, US5177170 and US5346981.
  • Bismuth salts have also been used, as shown in US 3618614, which although they are radiopaque compounds have the disadvantage that by incorporating this type of additive the polymer is not transparent.
  • the use of water in the manufacturing methods causes the formation of bubbles, which is detrimental due to the difficulty of its processing and the decrease in mechanical properties, such is the case of breakage deformation, stress strain, Young's module and impact resistance: Lu G.
  • the present invention relates to new materials formed by a polymer matrix, reinforced with barium sulfate with morphologies that can be in the form of fibers or agglomerates of particles in the form of donuts or spheres, as well as simple synthesis procedures for their obtaining. Depending on the synthesis procedures used, reinforcers with different morphologies can be obtained.
  • the composite materials obtained, barium polymer sulfate are opaque to X-rays with low percentages of the additive, even 1%, transparent, biocompatible, bioinert, maintain their mechanical properties with respect to the precursor polymer, are easily processable, do not have formation of bubbles and are of lower cost. These materials and their synthesis procedures would replace the current ones, eliminating some of their disadvantages.
  • Another advantage of the present invention is that adding less barium sulfate significantly reduces the costs of the material obtained.
  • adding nano or micro particles increases the contact surface of barium sulfate, so it is necessary to add a smaller amount of this substance, also reducing costs. All the necessary properties for its applications remain unchanged, such as radiopacity, transparency, inert to the fluids present in the human organism and biocompatibility, among others.
  • the mechanical properties are not affected by the introduction or decrease of the percentage of the reinforcing element in the form of spherical particles.
  • the materials thus obtained could be used as pigments, in the paint industry, as fibers in the textile industry, coatings and in biomedicine for biomedical devices such as prostheses, heart valves and catheters. To achieve as effective compounds as possible, several simple synthesis procedures were used. DETAILED DESCRIPTION OF THE INVENTION
  • the present invention relates to a composite material obtained by combining a polymer matrix and a reinforcing element, characterized in that the polymer matrix can be polyurethane or polyoxymethylene, and barium sulfate as a reinforcer.
  • the polymer matrix can be polyurethane or polyoxymethylene, and barium sulfate as a reinforcer.
  • These materials are characterized in that they can be used as pigments, coatings, in the textile industry, as well as in biomedicine. In particular in biomedicine, its use would be for biomedical devices such as prostheses, heart valves, catheters and coatings. In the textile industry it would be used for the manufacture of threads for use in the manufacture of fabrics and meshes.
  • reinforcers which depend on the procedures for obtaining them, and can be fibers or agglomerates, either spherical or donut-shaped.
  • the addition of the reinforcers increases their mechanical properties, in addition to their radiopacity. Different particle morphologies affect the mechanical, optical and theological properties.
  • the composite materials of the present invention formed by a matrix that can be made of polyurethane or polyoxymethylene, reinforced with barium sulfate, have structural and morphological characteristics that are characterized in that they have at least one, or a combination, of the following properties:
  • Composite materials formed by particle agglomerates have spherical aggregates with sizes ranging from 0.5 to 5 ⁇ , formed by individual particles from 0.02 to 0.1 pm, and reinforcer volumes ranging from 0.5 to 10%.
  • Composite materials formed by agglomerates of individual particles of 0.02 to 0.1 ⁇ have aggregates in the form of donuts with outside diameters ranging from 0.5 to 5 pm and diameters interiors between 0.01 to 1 ⁇ , with reinforcer volumes ranging from 0.5 to 10.0%.
  • Composite materials formed by fibers have fibers with a diameter of 0.1 to 0.5 pm, with volumetric fractions of the reinforcer ranging from 0.5 to 10.0%.
  • the compound compounds of the present invention are obtained by the method that is comprised of the following steps:
  • Solutions of BaCI 2 and a stabilizing agent are mixed, which can be the salt of ethylenediaminetetraacetic acid, sodium polyacrylate or a mixture of 2-amino-2-methylpropanol with an associative polymer, maintaining the pH between 3 and 10.
  • the amounts of Reagents used correspond to molar ratios BaCI 2 / Stabilizing agent between 0.005 and 1.5.
  • the precipitates obtained are washed with distilled water and dried at a temperature between 50 and 200 ° C for a time between 10 and 35 h.f.
  • the polymer in the form of granules which can be polyurethane or polyoxymethylene, is dried in a dehumidifier at temperatures between 60 and 160 ° C for times between 8 and 15 h.
  • the mixture thus obtained is processed by means of a twin screw extrusion equipment maintaining the spindle speed between 2 and 35 RMP, maintaining the temperature between 130 and 220 ° C.
  • the extruded material is injected by molding in a temperature range between 150 and 270 ° C.
  • the concentrations of the solutions in part 1a are as follows: BaCI 2 from 0.05 to 1.0 M and stabilizing agent between 0.05 and 0.8 M, preferably solutions with the following concentrations: BaCI 2 0.1 M, 0.1 M stabilizing agent for the salt of ethylenediaminetetraacetic acid. and sodium polyacrylate, and 0.5 M for the 2-amino-2-methylpropanol / associative polymer mixture, which are mixed keeping the pH at 4.0 when the stabilizing agent is the salt of ethylenediaminetetraacetic acid, at 8.0 when the stabilizing agent is sodium polyacrylate and in 9.0 when the stabilizing agent is 2-amino-2-methylpropanol / associative polymer.
  • the associative polymer referred to in item 1a is the commercial polymer Primal TT-935 of Rhom and Haas at 0.02 M, in a volumetric ratio between the Primal and the 0.5 M amino-2-methylpropanol of 42: 8.
  • the concentration of the sodium sulfate solution in item 1 b. is preferably 0.1 M.
  • the resulting mixture in item 1a is allowed to stand for 1 h when the stabilizing agent is the salt of ethylenediaminetetraacetic acid, 6 days when the stabilizing agent is sodium polyacrylate and 5 days when the stabilizing agent is 2-amino -2-methylpropanol / associative polymer.
  • the collected precipitates are washed with distilled water and dried at a temperature of about 10 ° C for an approximate time of 24 h.
  • the antifoam referred to in item 1g is commercial A204 or A289 of Aldrich.
  • the granules of the polymers referred to in subparagraph 1f., are preferably dried in a dehumidifier at 10 ° C for 12 h.
  • the mass ratios of the components of subsection 1f. are preferably the following: 1% BaS0 4 particles, 98.5% polymer granules and 0.5% antifoam.
  • the extrusion process referred to in paragraph 1 h. Is preferably carried out at a spindle speed of 5 RMP when the polymer is polyurethane, with a temperature profile of 175 ° C for the feeding zone, 180 ° C for the supply zone, 180 ° C for the compression zone and 188 ° C for the dosing zone.
  • the spindle speed is 25 RMP and the extrusion process temperatures are 180-180-185-185 ° C respectively.
  • the temperatures used in the injection molding process referred to in subparagraph 1 i., are: for polyurethane 180 ° C for the feeding zone and 210, 210 and 220 ° C for the dosing zone, while which for the polyoxymethylene are 220, 210, 210 and 200 ° C.
  • the composite materials obtained by these methods of synthesis are characterized in that they have a homogeneous distribution of barium sulfate as a reinforcer in the form of: spherical agglomerates from 0.5 to 10.0% by volume of spherical particles, with agglomerate size from 0.5 to 5 pm, with size of 5 individual particles from 0.02 to 0.1 pm, when the stabilizing agent is the salt of ethylenediaminetetraacetic acid; 0.5 to 10.0% fibers with a diameter of 0.1 to 0.5 pm when the stabilizing agent is sodium polyacrylate; and donuts 0.5 to 10.0% by volume, with outside diameters ranging from 0.05 to 5 pm and internal diameters between 0.01 to 1 pm, when the stabilizing agent is 2-amino-2 methylpropanol / associative polymer.
  • the present invention also relates to the use of composite materials formed by the polymer matrix of polyoxymethylene or polyurethane and the Barium sulfate booster, in biomedicine for biomedical devices such as prostheses, coatings, heart valves and catheters.
  • the compounds of the present invention can also be used as pigments or in the textile industry, in the manufacture of threads for the manufacture of fabrics and meshes.
  • Example 1 Synthesis of polyurethane matrix composite material with reinforcements in the form of spherical agglomerates.
  • a mixture of 6g of BaS0 4 particles, 600g of the granules of the already dried polymer and 3g of a commercial antifoam agent Aldrich A204 or A289 is prepared.
  • the mixture is fed to a double spindle extrusion equipment with spindle speed of 5 RMP, with a temperature profile of 175 ° C for the feeding zone, 180 for the supply zone, 180 for the compression zone and 188 ° C for the dosing area.
  • the extruded material is injected by molding in a temperature range of 180 for the feeding zone, 210, 210 and 220 ° C for the dosing zone.
  • Figure 1 the morphology of the spherical agglomerations of barium sulfate particles, between 0.5 and 5 ⁇ , formed by particles between 0.02 to 0.1 pm can be observed by scanning electron microscopy.
  • Figure 2 the composite material whose microstructure is shown in Figure 2 is obtained.
  • Figure 3 shows the results of the radiopacity test, where the material is observed by means of an x-ray and with different thicknesses. The greater radiopacity of the reinforced polyurethane, on the right, compared to the virgin polyurethane, on the left, is shown comparatively.
  • 600 g of polyoxymethylene granules are dried in a dehumidifier at 10 ° C for 12 h.
  • Solutions of 400 mL of 0.1M barium chloride and 400mL 0.1M sodium polyacrylate are mixed, keeping the pH at 8 under vigorous stirring and room temperature.
  • a solution of 400 mL of 0.1 M sodium sulfate is then added.
  • the solution is allowed to stand for 6 days for the formation and growth of the fibers.
  • the collected precipitate is washed with distilled water and dried at 10 ° C for 24 h.
  • a mixture of 6 g of BaS0 4 particles, 600 g of the polymer granules and 3 g of a commercial antifoam agent Aldrich A204 or A289 is prepared.
  • the mixture is fed to a twin-screw extrusion equipment with spindle speed of 25 RMP, with a temperature profile of 180 ° C for the feeding zone, 180 ° C for the supply zone, 185 ° C for the zone compression and 185 ° C for the dosing area.
  • the extruded material is then injected by molding in a temperature range of 220 ° C for the feeding zone and 210-210-200 ° C for the dosing zone.
  • Figure 4 the morphology of the fibers obtained, whose diameter is between 0.1 to 0.5 pm, can be observed by scanning electron microscopy.
  • Figure 5 shows the results of the radiopacity test, where the material is observed by means of an X-ray and with different thicknesses .
  • the greater radiopacity of the reinforced polyoxymethylene is shown comparatively, on the right, compared to the virgin, on the left.
  • Example 3 Synthesis of polyoxymethylene matrix composite material with agglomerated donut-like reinforcements.
  • 600 g of polyoxymethylene granules are dried in a dehumidifier at 10 ° C for 12 h.
  • 200 mL of 0.5 M amino-2-methylpropanol and 1 L of a commercial primal TT-935 Rhom and Haas 0.02 M associative polymer are mixed. This solution is vigorously stirred and allowed to stand for 48 h so that its pH is stabilized in 9.0.
  • 50 mL solutions of 50 mL 0.1 M barium chloride and 50 mL of 0.1 M sodium sulfate are mixed with the precipitates.
  • the precipitates obtained are decanted, washed with distilled water and dried at a temperature between 1-10 ° C for a 24 hours time. Subsequently, a mixture of 6g of BaS0 4 particles, 600g of the polymer granules and 3g of a commercial antifoam agent Aldrich A204 or A289 is prepared. The mixture is fed to a twin-screw extrusion equipment with spindle speed of 25 RMP, with a temperature profile of 180 ° C for the feeding zone, 180 ° C for the supply zone, 185 ° C for the zone compression and 185 ° C for the dosing area.
  • the extruded material is then injected by molding at temperatures of 220 ° C for the feeding zone and 210-210-200 ° C for the dosing zone.
  • Figure 7 it can be observed by scanning electron microscopy the morphology of the particle agglomerates in the form of donuts with outside diameters ranging from 0.05 to 5 prn and internal diameters between 0.01 to 1 pm, with volumes of the reinforcer ranging 0.5 to 10.0%.
  • the composite material whose microstructure is observed in Figure 8 is obtained.
  • Figure 9 shows the results of the radiopacity test, where the material is observed by means of an x-ray and with different thicknesses . The greater radiopacity of the reinforced polyoxymethylene is shown comparatively, on the right, compared to the virgin, on the left.
  • Figure 1 shows a micrograph obtained by scanning electron microscopy where the agglomeration of barium sulfate particles can be seen.
  • Figure 2 shows a scanning electron microscopy image of the composite material, polyurethane reinforced with spherical barium sulfate agglomerates.
  • Figure 4 shows a micrograph obtained by scanning electron microscopy, where barium sulfate fibers are seen.
  • Figure 7 shows a micrograph obtained by scanning electron microscopy, where the agglomeration of barium sulfate particles forming donuts can be seen.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Materials For Medical Uses (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Medicines Containing Antibodies Or Antigens For Use As Internal Diagnostic Agents (AREA)

Abstract

Le sulfate de baryum, utilisé comme agent de renforcement, peut présenter des morphologies telles que des fibres, des agglomérés sphériques ou une forme de coussin en anneau, en fonction du processus de synthèse utilisé. Le rapport élevé surface/volume de ces agents de renforcement fait que l'utilisation de petites quantités dans des matrices polymères est suffisante pour obtenir un matériau radio-opaque et pour que les propriétés mécaniques soit similaires ou légèrement supérieures au polymère sans renforcement. Les matériaux composites ainsi obtenus peuvent notamment être utilisés comme biomatériaux pour la fabrication de cathéters, de coeurs artificiels, tout comme dans l'industrie textile et dans le domaine des pigments.
PCT/MX2010/000140 2009-11-27 2010-11-26 Matériaux composites de matrice polymère avec des agents de renforcement de différentes morphologies et procédés de synthèse de ces matériaux WO2011065809A2 (fr)

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MXMX/A/2009/012860 2009-11-27
MX2009012860A MX339572B (es) 2009-11-27 2009-11-27 Materiales compuestos de matriz polimerica con reforzantes de diferentes morfologias y sus procedimientos de sintesis.

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Cited By (11)

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Publication number Priority date Publication date Assignee Title
WO2014163795A1 (fr) * 2013-03-13 2014-10-09 W. L. Gore & Associates, Inc. Composites polymeres durables a haute resistance pour implant et articles produits a partir de ceux-ci
US8945212B2 (en) 2011-04-01 2015-02-03 W. L. Gore & Associates, Inc. Durable multi-layer high strength polymer composite suitable for implant and articles produced therefrom
US8961599B2 (en) 2011-04-01 2015-02-24 W. L. Gore & Associates, Inc. Durable high strength polymer composite suitable for implant and articles produced therefrom
US9554900B2 (en) 2011-04-01 2017-01-31 W. L. Gore & Associates, Inc. Durable high strength polymer composites suitable for implant and articles produced therefrom
US9744033B2 (en) 2011-04-01 2017-08-29 W.L. Gore & Associates, Inc. Elastomeric leaflet for prosthetic heart valves
US9801712B2 (en) 2011-04-01 2017-10-31 W. L. Gore & Associates, Inc. Coherent single layer high strength synthetic polymer composites for prosthetic valves
US10342658B2 (en) 2011-04-01 2019-07-09 W. L. Gore & Associates, Inc. Methods of making durable multi-layer high strength polymer composite suitable for implant and articles produced therefrom
US11129622B2 (en) 2015-05-14 2021-09-28 W. L. Gore & Associates, Inc. Devices and methods for occlusion of an atrial appendage
US11173023B2 (en) 2017-10-16 2021-11-16 W. L. Gore & Associates, Inc. Medical devices and anchors therefor
US11457925B2 (en) 2011-09-16 2022-10-04 W. L. Gore & Associates, Inc. Occlusive devices
US11911258B2 (en) 2013-06-26 2024-02-27 W. L. Gore & Associates, Inc. Space filling devices

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Cited By (20)

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US10993803B2 (en) 2011-04-01 2021-05-04 W. L. Gore & Associates, Inc. Elastomeric leaflet for prosthetic heart valves
US10548724B2 (en) 2011-04-01 2020-02-04 W. L. Gore & Associates, Inc. Coherent single layer high strength synthetic polymer composites for prosthetic valves
US8961599B2 (en) 2011-04-01 2015-02-24 W. L. Gore & Associates, Inc. Durable high strength polymer composite suitable for implant and articles produced therefrom
US9801712B2 (en) 2011-04-01 2017-10-31 W. L. Gore & Associates, Inc. Coherent single layer high strength synthetic polymer composites for prosthetic valves
US9554900B2 (en) 2011-04-01 2017-01-31 W. L. Gore & Associates, Inc. Durable high strength polymer composites suitable for implant and articles produced therefrom
US9744033B2 (en) 2011-04-01 2017-08-29 W.L. Gore & Associates, Inc. Elastomeric leaflet for prosthetic heart valves
US9770327B2 (en) 2011-04-01 2017-09-26 W. L. Gore & Associates, Inc. Methods of making a prosthetic valve with a durable high strength polymer composite leaflet
US10022219B2 (en) 2011-04-01 2018-07-17 W. L. Gore & Associates, Inc. Durable multi-layer high strength polymer composite suitable for implant and articles produced therefrom
US10653518B2 (en) 2011-04-01 2020-05-19 W. L. Gore & Associates, Inc. Methods of making a durable multi-layer high strength polymer composite suitable for prosthetic valves
US8945212B2 (en) 2011-04-01 2015-02-03 W. L. Gore & Associates, Inc. Durable multi-layer high strength polymer composite suitable for implant and articles produced therefrom
US9795475B2 (en) 2011-04-01 2017-10-24 W.L. Gore & Associates, Inc. Durable high strength polymer composite suitable for implant and articles produced therefrom
US10342658B2 (en) 2011-04-01 2019-07-09 W. L. Gore & Associates, Inc. Methods of making durable multi-layer high strength polymer composite suitable for implant and articles produced therefrom
US10470878B2 (en) 2011-04-01 2019-11-12 W. L. Gore & Associates, Inc. Durable high strength polymer composites suitable for implant and articles produced therefrom
US11457925B2 (en) 2011-09-16 2022-10-04 W. L. Gore & Associates, Inc. Occlusive devices
WO2014163795A1 (fr) * 2013-03-13 2014-10-09 W. L. Gore & Associates, Inc. Composites polymeres durables a haute resistance pour implant et articles produits a partir de ceux-ci
EP3459498A1 (fr) * 2013-03-13 2019-03-27 W. L. Gore & Associates Inc Valve cardiaque prothétique comprenant des composites de polymères durables de haute résistance adaptés pour un implant
CN105007955A (zh) * 2013-03-13 2015-10-28 W.L.戈尔及同仁股份有限公司 适用于植入物的耐用高强度聚合物复合材料及其制品
US11911258B2 (en) 2013-06-26 2024-02-27 W. L. Gore & Associates, Inc. Space filling devices
US11129622B2 (en) 2015-05-14 2021-09-28 W. L. Gore & Associates, Inc. Devices and methods for occlusion of an atrial appendage
US11173023B2 (en) 2017-10-16 2021-11-16 W. L. Gore & Associates, Inc. Medical devices and anchors therefor

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