[go: up one dir, main page]

WO2000067812A1 - Biostabilite de structures polymeres - Google Patents

Biostabilite de structures polymeres Download PDF

Info

Publication number
WO2000067812A1
WO2000067812A1 PCT/IE1999/000038 IE9900038W WO0067812A1 WO 2000067812 A1 WO2000067812 A1 WO 2000067812A1 IE 9900038 W IE9900038 W IE 9900038W WO 0067812 A1 WO0067812 A1 WO 0067812A1
Authority
WO
WIPO (PCT)
Prior art keywords
biostable
polyether polyurethane
diisocyanate
polyurethane article
article
Prior art date
Application number
PCT/IE1999/000038
Other languages
English (en)
Inventor
Eamon Brady
Fergal Farrell
Ann Marie Cannon
Original Assignee
Salviac Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Salviac Limited filed Critical Salviac Limited
Priority to AU38446/99A priority Critical patent/AU3844699A/en
Priority to PCT/IE1999/000038 priority patent/WO2000067812A1/fr
Priority to IE20000347A priority patent/IE20000347A1/en
Priority to PCT/IE2000/000059 priority patent/WO2000067815A1/fr
Priority to EP00927682A priority patent/EP1176995A1/fr
Priority to DE60003178T priority patent/DE60003178T2/de
Priority to EP00925547A priority patent/EP1176993B1/fr
Priority to EP00927681A priority patent/EP1176994A1/fr
Priority to AU46066/00A priority patent/AU4606600A/en
Priority to IE20000344A priority patent/IE20000344A1/en
Priority to AT00925547T priority patent/ATE242017T1/de
Priority to AU44266/00A priority patent/AU4426600A/en
Priority to AU46067/00A priority patent/AU4606700A/en
Priority to IE20000346A priority patent/IE20000346A1/en
Priority to PCT/IE2000/000058 priority patent/WO2000067814A1/fr
Priority to PCT/IE2000/000056 priority patent/WO2000067813A1/fr
Publication of WO2000067812A1 publication Critical patent/WO2000067812A1/fr
Priority to US09/985,821 priority patent/US20020072584A1/en
Priority to US09/985,819 priority patent/US20020072550A1/en
Priority to US09/985,822 priority patent/US20020142413A1/en
Priority to US11/152,780 priority patent/US20070003594A1/en
Priority to US12/271,336 priority patent/US8168431B2/en

Links

Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/04—Macromolecular materials
    • A61L31/06—Macromolecular materials obtained otherwise than 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
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/14—Macromolecular materials
    • A61L27/18—Macromolecular materials obtained otherwise than 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
    • A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
    • A61L29/04—Macromolecular materials
    • A61L29/06—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2101/00—Manufacture of cellular products

Definitions

  • This invention relates to biostable biocompatible polymeric structures suitable for long term implantation within a living human body and as a suitable substratum for cell growth technologies.
  • Flexible polyurethane foams have been manufactured for more than thirty years from polyisocyanates and polymeric polyols. They have been used in the production of elastomers, flexible and rigid foams, coatings, adhesives and many other products in the industrial sector.
  • the most commonly used polyisocyanate has been TDI (Toluene Diisocyanate) but in recent years this has been replaced with MDI (Diphenylmethane Diisocyanates).
  • TDI Toluene Diisocyanate
  • MDI Diphenylmethane Diisocyanates
  • foamed materials based on polyurethane and other polymer systems derived from organic polysiloxanes in industrial applications is also well established.
  • the formulation and processing conditions used during manufacture affects the properties of the foam product. They can vary in texture from soft flexible foams used in cushioning applications to hard rigid materials used as insulating or structural materials.
  • the density and strength of the material can also be affected by the formulation.
  • a method for manufacturing a biostable biocompatible polymeric material comprising the step of forming a three dimensional cross linked structure of the polymeric material and treating the structure to remove impurities.
  • the structure is treated by solvent extraction.
  • the solubility parameter of the solvent extraction system is selected for compatibility with the solubility parameter of the polymeric material or its phases.
  • the solubility parameter of the solvent extraction system is within ⁇ 8
  • the method includes the step of removing residual solvent from the structure, after solvent extraction.
  • residual solvent is removed by treatment with water.
  • the biostable biocompatible material may for example be a polyether polyurethane or a polycarbonate urethane or polycarbonate urethane urea or a polydimethylsiloxane urethane urea.
  • the material is in the form of a medical implant.
  • the implant may be a septal defect occluder, a vessel occluder, a vessel defect occluder, a mammary prosthesis, a muscle bulking agent, a gynecological implant or an embolic filter.
  • the material may be in the form of a substratum for tissue and/ or cell growth.
  • the material forms a cell matrix for cell growth technologies, tissue repair and in drug delivery applications.
  • the article may be formed from an organic diisocyanate, a polyether polyol, a chain extender and a blowing agent.
  • the blowing agent is preferably water.
  • the density of the article is preferably less than 1200kg/m 3 , ideally less than 200kg/m 3 .
  • the ratios of the reaction components are selected to promote the formation of a three dimensional porous molecular structure of polyether urethane biomaterial.
  • the article may be processed by a metering and mixing process, wherein the chemical components are aggressively mixed and dispensed into a vessel and chain extension and blowing reactions occur substantially simultaneously.
  • the article is processed by a reactive moulding process, wherein the chemical components are mixed and dispensed into a vessel wherein chain extension occurs.
  • the article may be processed in two stages, a first stage involving a reaction process in which the number of isocyanate linkages in the reaction vessel is approximately equal to the number of active hydrogens in the vessel.
  • the article may also be processed by a reactive blowing process, in which the chemical components are aggressively mixed and dispensed substantially continuously and expand and chain extend substantially simultaneously to form a continuous block of foam which is subsequently cut or machined into a desired geometry.
  • the density of the article is preferably controlled by controlling the pressure in the reaction vessel.
  • the biostable polyether polyurethane article has a pore size of from 10 microns to 900 microns.
  • the biostable polyether polyurethane article according to claim 25 having a pore size of between 35 microns to 200 microns.
  • the invention provides a biostable polyether polyurethane wherein the urea linkages are derived from a water isocyanate reaction present in the hard segment phase.
  • the percentage of urea linkages in the hard segment phase is greater than 0.5%.
  • the invention provides a biostable polyether polyurethane wherein biuret linkages exist in the hard segment phase.
  • the invention provides a biostable polyether polyurethane wherein aliphatic linkages exist in the hard segment phase.
  • the biostable polyurethane devices of this invention are derived from organic diisocyanates and polyether polyols, polyether copolymer polyols or combinations thereof and are chain extended with either diamine, diol, water or mixtures of the above chain extenders.
  • the reaction step converts the chemical precursors into a 3 dimensional molecular cross-linked structure, simultaneously forming a low density porous material.
  • a 3 dimensional network of this kind is insoluble and intractable. Manufacturing the article by this method produces a material with minimal internal stress, enhancing biostability.
  • the polyether biomaterial is a three dimensional structure at a molecular level allows it to be processed aggressively to remove residual chemicals from the process.
  • Low molecular weight chemicals have the potential to leach from the article and result in toxic reactions in living cells.
  • the downstream processing of the article expands the biomaterials volume at a molecular level. This expansion aids in the removal of leachables such as catalyts, oligomers and free monomers.
  • the solvent extraction process also reduces any internal stresses within the material.
  • the solvent expands the material when it penetrates between the molecular chains.
  • the 3-dimensional cross links provides the materials with molecular memory and prevents the molecular structure being soluble in the solvent. However, the molecular chains in this state can orient themselves into a preferred relaxed conformation, thereby relieving the material of any internal stresses.
  • This process enhances the material biocompatible for use as an implantable medical device or as a 3 dimensional matrix for use as a cell scaffold in tissue engineering applications. Altering the chemical precursors and the processing conditions of the material may alter the pore size and the density of the material, as required, to meet the requirements of the application.
  • the biostable polyurethanes of this invention are useful for the manufacture of catheters, vascular grafts, septal occluders, vessel occluders, embolisation devices, mammary prosthesis, pacemaker leads and other such implant, blood contacting devices and as cell scaffolds to support cell growth.
  • biostable polyurethanes of this invention are based on organic diisocyanates, polyether copolymer polyols, polyether homopolymers and diol, diamine or water chain extenders and combinations thereof.
  • the product of this invention has applications in the medical device and tissue engineering sectors, however the material can also be used as a cell scaffold to support cell growth.
  • This material is suitable for these applications since it was designed such that an aggressive solvent extraction process can be applied to remove potential leachables from the material. Typically it is these leachables that are responsible for cytotoxic responses to polyurethane materials.
  • the solvent extraction system detailed in this invention allows the use of solvents with a solubility parameter similar to that of the polymer, allowing the polymer to swell and the leachables to be removed by the solvent from the material.
  • organic diisocyanates are of the general formula: R-(NCO) n
  • R is an aliphatic, aromatic, cycloaliphatic, or an aliphatic-aromatic hydrocarbon entity containing between 4 and 24 carbon atoms and "n" varies between 1.85 and 3. More preferably, R contains between 4 and 13 carbon atoms. Where n is 2, a polymer with a linear molecular structure may be produced. A three dimensional molecular network may be produced where n varies from 1.85 to 3. Ideally n should be between 1.9 and 2.2.
  • Suitable isocyanates include: p-phenylene diisocyanate, tetramethylene diisocyanate, cyclohexane 1, 2-diisocyanate, m-tetramethylxylene diisocyanate, hexamethylene diisocyanate, 2,4 diphenylmethane diisocyanate, 4,4 diphenylmethane diisocyanate, 2,4 toluene diisocyanate, 2, 6 toluene diisocyanate, cyclohexane 1,4 diisocyanate, isophorone diisocyanate, 4,4 - dicyclohexylmethane diisocyanate, 4,4 -dicyclohexylmethane diisocyanate, and mixtures of the above.
  • isocyanates can be used to manufacture suitable materials; 2,4 diphenylmethane diisocyanate, 4,4 diphenylmethane diisocyanate, 2,4 toluene diisocyanate, 2, 6 toluene diisocyanate, cyclohexane 1,4 diisocyanate, isophorone diisocyanate, 4,4 -dicyclohexylmethane diisocyanate, and mixtures of the above.
  • diisocyanates can be used to manufacture suitable polyurethanes: 2,4 diphenylmethane diisocyanate, 4,4 diphenylmethane diisocyanate, 4,4 -dicyclohexylmethane diisocyanate.
  • Polyether polyols that may be used include products obtained by the polymerisation of cyclic oxide, for example, ethylene oxide, propylene oxide, butylene oxide, or tetrahydrofuran in the presence of polyfunctional initiators.
  • Suitable initiator compounds contain plurality of active hydrogen atoms including water and polyols, e.g., ethylene glycol, propylene glycol, diethylene glycol, resorcinol, bisphenol A, cyclohexane dimethanol, gylcerol, trimethylolpropane,
  • Useful polyether polyols include polytetramethylene glycols obtained by the polymerisation of tetrahydrofuran.
  • the polytetramethylene glycols used in this invention having varying molecular weights of between 600 and 3000. Polyols of differing molecular weights can be used together in a single formulation.
  • the polyether polyurethanes of this invention are based on diol, diamine, alkanolamine, water chain extenders or mixtures of these.
  • Diol chain extenders react with isocyanate to generate urethane linkages.
  • Diamine and water generate urea linkages and alkanol amines can generate both urethane and urea linkages.
  • the use of water as a chain extender in low density, three dimensional biomedical polyurethanes is unusual as with most conventional biomedical polyurethanes water is viewed as an impurity.
  • the water chain extension reactions generate urea linkages in the hard segment and carbon dioxide is given off as a by-product.
  • the carbon dioxide generated from the water isocyanate reaction series can be used to influence the density of the material by generating a cellular structure.
  • Polyurethanes with a high concentration of urea linkages in the hard phase tend to be strong elastomers with good flex lives.
  • the carbon dioxide generated as a by-product of the isocyanate-water-isocyanate reaction series can be employed to generate a cell structure in the material.
  • a surfactant With the use of a surfactant, the size and porosity of this cell structure can be controlled.
  • the manufacturing control over the pore size of the material has important implications in the application of the article. In cell growth technology the pore sizes can be modified to accommodate cells and modify the cell to surface ratio.
  • the level of water used in the reaction determines the amount of carbon dioxide generated and the hard segment content of the polymer.
  • the amount of carbon dioxide generated plays an important role in the density of the polyurethane.
  • the density can be controlled independently of the hard segment content by controlling the pressure of the reaction/forming chamber.
  • biostable polyurethanes of this invention can be manufactured with densities ranging from 15kg/m 3 to 1200kg/m 3 virtually independent of the hard segment content.
  • Low density articles used in medical applications are desirable since the wrapping profile of the article is reduced and the delivery device profile is minimised, giving rise to a wider range of applications.
  • biostable polyurethanes of this invention involves the reaction of -OH groups from the polyol with -NCO groups from the diisocyanate to form urethane linkages. These chemical groups are reacted in approximately equivalent ratios for the generation of linear polymers and with slight excess for a crosslinked (three-dimensional) molecular structure.
  • Secondary chain extenders may be employed to alter the hard segment content or to alter specific properties. Manufacturing foams of the lowest densities per this invention is carried out by a combination of a water blown reaction, in a depressurised reactive/forming vessel and the incorporation of a physical blowing agent into the formulation. Secondary chain extenders can be either diamine, diol or alkanol amine based and should have a functionality of two or greater. Diol chain extenders are preferred.
  • chain extenders include, ethylene glycol, 1,4 butanediol, diethylene glycol, triethylene glycol, 1,2 propane diol, 1,3 propane diol, 1,5 pentane diol, ethylene diamine, 1,4 diaminobutane, 1,6 diaminohexane, 1,7 diaminoheptane, 1,8 diaminooctane, and 1,5 diaminopentane.
  • catalysts may be preferred or not.
  • polyols as isocyanate reactive compounds, it is preferred to use catalysts for urethane formation.
  • Catalysts for polyurethane formation that may be used are compounds, which promote the reaction between isocyanate and hydroxyl groups.
  • Such catalysts are widely available in the marketplace and include organic and inorganic salts of bismuth, lead, tin, iron, antimony, cadmium, cobalt, aluminum, mercury, zinc, cerium, molybdenum, vanadium, copper, manganese and zirconium, as well as phosphines and tertiary amines.
  • Tertiary amines are an important class of catalyst in which the nitrogen atom is not directly attached to an aromatic ring.
  • tertiary amines are: triethylamine, N,N,N',N'-tetramemylenediamine, N-N,N',N'-tetramethyl-l,3- butanediamine, bis-2-dimethylaminoethyl ether, N,N-dimethylcyclohexylamine, N,N-dimethylbenzylamine, N-methylmorpholine, N-ethylmorpholine, 1,4- diazabicyclo-[2.2.2] octane and the like.
  • Biostable articles of this invention can be chemically prepared via the following methods: The one shot process in which the diisocyanate, the polyol and the chain extender are mixed and reacted in one step.
  • the prepolymer method wherein an isocyanate-terminated prepolymer is first prepared and then the system is chain extended.
  • the quasiprepolymer system wherein some of the polyol is reacted with the isocyanate to generate an isocyanate terminated prepolymer in an excess of isocyanate.
  • the remaining polyol and chain extenders are subsequently added to facilitate chain extension.
  • Biostable articles of this invention may be processed by any of the following techniques: • Reactive blow moulding process, wherein the chemical ingredients for this invention are fed though two or three lines to a mixing head where it is aggressively mixed and dispensed into a mould and chain extension and blowing reactions occur simultaneously.
  • This process is suitable for the manufacture of a three dimensional molecular structure and is suited to the manufacture of low density porous and non-porous articles.
  • the shot size used in this invention is 0.5g to lOg producing a three dimensional low density porous foam.
  • Reactive blowing process wherein the chemical ingredients are aggressively mixed and dispensed in a continuous fashion and expand and chain extend simultaneously to form a continuous block of foam which is subsequently cut or machined into useful shapes. This process is suitable for the manufacture of a three dimensional molecular structure and is suited to the manufacture of low density porous and non-porous articles.
  • the biostable polyurethane of this invention is solvent extracted to enhance the biocompatibility of the polyurethane article. This process can be applied to all polyurethane materials.
  • the material of this invention has a structure that is three dimensional and crosslinked at a molecular level. This allows for use of more aggressive solvents with similar solubility parameters without destroying the integrity of the material. The process allows any internal stresses to be relieved, enhancing bio stability.
  • Biocompatibility of a material in contact with bodily fluids is a primary function of two variables :
  • Leachables with the implant the severity of the inflammation of the surrounding tissue is strongly dependant on the type and quantity of products which can migrate from the implant to the surrounding tissue. Leachables can be removed from the foam via solvent extraction.
  • the solubility and hydrogen bonding parameters of the solvent will affect the suitability of the solvent.
  • the solubility of polyurethane foams is typically in the region of 17 -28 MPa I/2 .
  • the solvent system used for the extract system should have a solubility parameter close to in the same range as the foam.
  • Solvent that may be used are : methylethyl ketone, tetrahydrofuran, dimethylformamide, 1,2 - dichloroethane, n-heptane, diethylether, acetonitrile, propan-2-ol, methanol and combinations of the above.
  • the leachables from the polymer are drawn into the solvent if the leachables are soluble in the solvent system.
  • solubility parameter of the solvent system is close to that of the volume of the polymer will extend and allow extraction of low molecular weight species. It is important to maintain the integrity of the foam during this process.
  • the residual solvent is removed from the structure using a water extraction step.
  • the molecular memory allows it to return to its original configuration.
  • the article may be used as a cell scaffold to provide a substratum to promote the growth of adherent cell lines.
  • Cells may be seeded onto the material, attach to the cell scaffold and replicate in a physiologically suitable environment.
  • the nature of the article provides a large surface: area ratio, to enable cells infiltrate the material.
  • the nature of the 3 dimensional material also allows the diffusion of nutrients and oxygen into the media and the diffusion of waste metabolites and carbon dioxide gas to leach from the three dimensional structure of the article.
  • the cells can also secrete proteins as determined by the genetic make up of the cell. As a result of the open cell structure of the material, cell - cell interactions can take place forming the basis of tissue formation.
  • This article has a number of applications in the field of cell growth/tissue engineering not limited to
  • the treatment of polymeric structures to remove impurities may be applied to any suitable polymeric material.
  • the invention may be applied to the polycarbonate urethane material described in or co-pending PCT application No IE 98/00091, filed November 9, 1998, the entire contents of which are incorporated herein by reference.

Landscapes

  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Epidemiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Heart & Thoracic Surgery (AREA)
  • Surgery (AREA)
  • Vascular Medicine (AREA)
  • Dermatology (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Transplantation (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Materials For Medical Uses (AREA)

Abstract

La présente invention concerne un procédé de fabrication d'un matériau polymère biostable biocompatible consistant à former une structure réticulée tridimensionnelle à partir du matériau polymère, et à traiter cette structure avec extraction par solvant pour en éliminer les impuretés. Le matériau polymère biocompatible se présente sous la forme d'un implant médical ou d'un substrat de tissu et/ou de croissance cellulaire.
PCT/IE1999/000038 1999-05-07 1999-05-07 Biostabilite de structures polymeres WO2000067812A1 (fr)

Priority Applications (21)

Application Number Priority Date Filing Date Title
AU38446/99A AU3844699A (en) 1999-05-07 1999-05-07 Biostability of polymeric structures
PCT/IE1999/000038 WO2000067812A1 (fr) 1999-05-07 1999-05-07 Biostabilite de structures polymeres
IE20000344A IE20000344A1 (en) 1999-05-07 2000-05-08 Biostable Implants
AU44266/00A AU4426600A (en) 1999-05-07 2000-05-08 Biostable polyurethane products
EP00927682A EP1176995A1 (fr) 1999-05-07 2000-05-08 Charpente pour genie tissulaire
DE60003178T DE60003178T2 (de) 1999-05-07 2000-05-08 Biostabile polyurethanprodukte
EP00925547A EP1176993B1 (fr) 1999-05-07 2000-05-08 Articles en polyurethanne stables du point de vue biologique
EP00927681A EP1176994A1 (fr) 1999-05-07 2000-05-08 Biostabilite de structures polymeriques
AU46066/00A AU4606600A (en) 1999-05-07 2000-05-08 Biostability of polymeric structures
IE20000347A IE20000347A1 (en) 1999-05-07 2000-05-08 Tissue Engineering
AT00925547T ATE242017T1 (de) 1999-05-07 2000-05-08 Biostabile polyurethanprodukte
PCT/IE2000/000059 WO2000067815A1 (fr) 1999-05-07 2000-05-08 Charpente pour genie tissulaire
AU46067/00A AU4606700A (en) 1999-05-07 2000-05-08 A tissue engineering scaffold
IE20000346A IE20000346A1 (en) 1999-05-07 2000-05-08 A polymeric structure
PCT/IE2000/000058 WO2000067814A1 (fr) 1999-05-07 2000-05-08 Biostabilite de structures polymeriques
PCT/IE2000/000056 WO2000067813A1 (fr) 1999-05-07 2000-05-08 Articles en polyurethanne stables du point de vue biologique
US09/985,821 US20020072584A1 (en) 1999-05-07 2001-11-06 Biostability of polymeric structures
US09/985,819 US20020072550A1 (en) 1999-05-07 2001-11-06 Biostable polyurethane products
US09/985,822 US20020142413A1 (en) 1999-05-07 2001-11-06 Tissue engineering scaffold
US11/152,780 US20070003594A1 (en) 1999-05-07 2005-06-15 Tissue engineering scaffold
US12/271,336 US8168431B2 (en) 1999-05-07 2008-11-14 Tissue engineering scaffold comprising polyurethane material having voids interconnected by pores

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/IE1999/000038 WO2000067812A1 (fr) 1999-05-07 1999-05-07 Biostabilite de structures polymeres

Publications (1)

Publication Number Publication Date
WO2000067812A1 true WO2000067812A1 (fr) 2000-11-16

Family

ID=11042520

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IE1999/000038 WO2000067812A1 (fr) 1999-05-07 1999-05-07 Biostabilite de structures polymeres

Country Status (2)

Country Link
AU (1) AU3844699A (fr)
WO (1) WO2000067812A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005030281A3 (fr) * 2003-09-26 2005-07-07 Hexabio 4 Al Du Doyen Brus Soc Materiau polyurethane pour des protheses moulees implantables
WO2005089778A1 (fr) * 2004-03-24 2005-09-29 Commonwealth Scientific And Industrial Research Organisation Polyurethanne et urees de polyurethanne biodegradables
ES2289918A1 (es) * 2005-07-11 2008-02-01 Natalya Andriiv Galatenko Material de tunica endoprostetica.
AU2005223917B2 (en) * 2004-03-24 2010-01-21 Polynovo Biomaterials Pty Limited Biodegradable polyurethane and polyurethane ureas
CN108610466A (zh) * 2018-05-17 2018-10-02 山东大学 一种以聚硅氧烷完全替代聚醚的聚脲弹性体及其制备方法
CN113621304A (zh) * 2021-08-06 2021-11-09 浙江禾欣科技有限公司 一种自消光水性聚氨酯树脂及其制备方法

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0189178A2 (fr) * 1985-01-25 1986-07-30 Hydromer, Inc. Mousse d'interpolymère de polyuréthane-poly(N-vinyllactame) hydrophile et flexible à cellules ouvertes et produits dentaires et biomédicaux fabriqués à partir de celle-ci
EP0335664A2 (fr) * 1988-03-28 1989-10-04 Becton, Dickinson and Company Polyétheréthanes fluorés et les dispositifs médicaux à partir de ceux-ci
US5229431A (en) * 1990-06-15 1993-07-20 Corvita Corporation Crack-resistant polycarbonate urethane polymer prostheses and the like
US5376117A (en) * 1991-10-25 1994-12-27 Corvita Corporation Breast prostheses
US5436291A (en) * 1992-07-09 1995-07-25 University Of Michigan, The Board Of . . . Calcification-resistant synthetic biomaterials
US5545708A (en) * 1993-07-14 1996-08-13 Becton, Dickinson And Company Thermoplastic polyurethane method of making same and forming a medical article therefrom
EP0822208A1 (fr) * 1996-07-31 1998-02-04 Basf Aktiengesellschaft Procédé de préparation des polyuréthanes ayant un durcissement amélioré
US5728762A (en) * 1994-11-16 1998-03-17 Tyndale Plains-Hunter, Ltd. Polyether polyurethane polymers, gels, solutions and uses thereof
WO1998011854A1 (fr) * 1996-09-20 1998-03-26 Tyndale Plains-Hunter, Ltd. Polyurethannes de polyether hydrophiles contenant de l'acide carboxylique

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0189178A2 (fr) * 1985-01-25 1986-07-30 Hydromer, Inc. Mousse d'interpolymère de polyuréthane-poly(N-vinyllactame) hydrophile et flexible à cellules ouvertes et produits dentaires et biomédicaux fabriqués à partir de celle-ci
EP0335664A2 (fr) * 1988-03-28 1989-10-04 Becton, Dickinson and Company Polyétheréthanes fluorés et les dispositifs médicaux à partir de ceux-ci
US5229431A (en) * 1990-06-15 1993-07-20 Corvita Corporation Crack-resistant polycarbonate urethane polymer prostheses and the like
US5376117A (en) * 1991-10-25 1994-12-27 Corvita Corporation Breast prostheses
US5436291A (en) * 1992-07-09 1995-07-25 University Of Michigan, The Board Of . . . Calcification-resistant synthetic biomaterials
US5545708A (en) * 1993-07-14 1996-08-13 Becton, Dickinson And Company Thermoplastic polyurethane method of making same and forming a medical article therefrom
US5728762A (en) * 1994-11-16 1998-03-17 Tyndale Plains-Hunter, Ltd. Polyether polyurethane polymers, gels, solutions and uses thereof
EP0822208A1 (fr) * 1996-07-31 1998-02-04 Basf Aktiengesellschaft Procédé de préparation des polyuréthanes ayant un durcissement amélioré
WO1998011854A1 (fr) * 1996-09-20 1998-03-26 Tyndale Plains-Hunter, Ltd. Polyurethannes de polyether hydrophiles contenant de l'acide carboxylique

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005030281A3 (fr) * 2003-09-26 2005-07-07 Hexabio 4 Al Du Doyen Brus Soc Materiau polyurethane pour des protheses moulees implantables
WO2005089778A1 (fr) * 2004-03-24 2005-09-29 Commonwealth Scientific And Industrial Research Organisation Polyurethanne et urees de polyurethanne biodegradables
JP2007530101A (ja) * 2004-03-24 2007-11-01 コモンウエルス サイエンティフィック アンド インダストリアル リサーチ オーガナイゼーション 生分解性ポリウレタン及びポリウレタン尿素
AU2005223917B2 (en) * 2004-03-24 2010-01-21 Polynovo Biomaterials Pty Limited Biodegradable polyurethane and polyurethane ureas
CN1950098B (zh) * 2004-03-24 2013-02-27 宝利诺沃生物材料有限公司 生物可降解聚氨酯和聚氨酯脲
US9034378B2 (en) * 2004-03-24 2015-05-19 Polynovo Biomaterials Pty Ltd Biodegradable polyurethane and polyurethane ureas
US9540478B2 (en) 2004-03-24 2017-01-10 Polynovo Biomaterials Pty. Limited Biodegradable polyurethane and polyurethane ureas
ES2289918A1 (es) * 2005-07-11 2008-02-01 Natalya Andriiv Galatenko Material de tunica endoprostetica.
ES2289918B2 (es) * 2005-07-11 2009-04-01 Nataliya Andrii Galatenko Material de tunica endoprotesica.
CN108610466A (zh) * 2018-05-17 2018-10-02 山东大学 一种以聚硅氧烷完全替代聚醚的聚脲弹性体及其制备方法
CN108610466B (zh) * 2018-05-17 2021-04-06 山东大学 一种以聚硅氧烷完全替代聚醚的聚脲弹性体及其制备方法
CN113621304A (zh) * 2021-08-06 2021-11-09 浙江禾欣科技有限公司 一种自消光水性聚氨酯树脂及其制备方法

Also Published As

Publication number Publication date
AU3844699A (en) 2000-11-21

Similar Documents

Publication Publication Date Title
US6177522B1 (en) Biostable polycarbonate urethane products
US8168431B2 (en) Tissue engineering scaffold comprising polyurethane material having voids interconnected by pores
US5254662A (en) Biostable polyurethane products
US5374704A (en) Pure, in particular catalyst-free polyurethanes
CA1338678C (fr) Polyurethanes hydrophiliques possedant une resistance amelioree
US20110028661A1 (en) Hybrid polyurethane block copolymers with thermoplastic processability and thermoset properties
WO2000067811A1 (fr) Produit de polyether-polyurethane biostable
EP0335664A2 (fr) Polyétheréthanes fluorés et les dispositifs médicaux à partir de ceux-ci
JPH04226119A (ja) 生体内で安定なポリウレタンおよびその製造方法
EP2001923A1 (fr) Polyurethanes biologiquement stables
CN114456346B (zh) 具有生物稳定性和力学稳定性的聚氨酯及制备方法与应用
WO2000067812A1 (fr) Biostabilite de structures polymeres
AU664158B2 (en) Biostable polyurethane products
Caldera-Villalobos et al. Hydrophilic polyurethanes: a brief review from the synthesis to biomedical applications
IE980918A1 (en) Biostable polycarbonate urethane products
IE20000347A1 (en) Tissue Engineering
IE20000346A1 (en) A polymeric structure

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AL AM AT AU AZ BA BB BG BR BY CA CH CN CU CZ DE DE DK DK EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT UA UG US UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW SD SL SZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
WA Withdrawal of international application
REG Reference to national code

Ref country code: DE

Ref legal event code: 8642