WO1994009048A1 - Polyurethane network for biomedical use - Google Patents
Polyurethane network for biomedical use Download PDFInfo
- Publication number
- WO1994009048A1 WO1994009048A1 PCT/NL1993/000203 NL9300203W WO9409048A1 WO 1994009048 A1 WO1994009048 A1 WO 1994009048A1 NL 9300203 W NL9300203 W NL 9300203W WO 9409048 A1 WO9409048 A1 WO 9409048A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polyurethane
- diisocyanate
- use according
- functionality
- network
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/12—Polyurethanes from compounds containing nitrogen and active hydrogen, the nitrogen atom not being part of an isocyanate group
-
- 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
- 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
-
- 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3271—Hydroxyamines
- C08G18/3278—Hydroxyamines containing at least three hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
- G02B1/041—Lenses
- G02B1/043—Contact lenses
Definitions
- the invention relates to a densely crosslinked, glassy polyurethane network for biomedical uses.
- Crosslinked polyurethanes are known, particularly as rubberlike materials for use in the paint industry, car industry and in biomedical uses. Such polyurethanes possess good mechanical properties and can be processed in a reasonably simple manner.
- the present invention is based on the development of a new class of glassy crosslinked polyurethanes or polyurethane networks, prepared from low-molecular polyols in the absence of a solvent. Surprisingly, this yielded homogenous materials with good mechanical and optical properties, which can be used in the biomedical field. Accordingly, the invention relates to a crosslinked polyurethane network for biomedical uses which can be obtained by reacting one or more low-molecular polyols having a functionality of three or more and one or more polyisocyanates having a functionality of two or more in the absence of a solvent.
- Such networks have a large number of uses in the biomedical field. Examples of such uses are intraocular lenses, keratoprostheses, composites with hydroxyapatite as implants for hip joints or as tooth restoration material, and, filled or not filled, as bone cement for fixing implants and fractures.
- the preparation of the materials that are used according to the invention can be effected by reacting the starting components in the absence of a solvent. This yields homogenous materials with good mechanical and optical properties, while the absence of a solvent obviously imposes restrictions on the selection of the starting substances. These starting substances should be miscible with each other and should have a low reactivity relative to each other.
- the amounts of the starting components should be selected such that the number of hydroxyl groups and the number of isocyanate groups are substantially equal, i.e., there should be a stoichiometric proportion.
- the ratio of the amounts mentioned is between 0.95:1 and 1:1.05. More particularly, in biomedical uses it is preferred, for reasons of toxicity, not to use excess quantities of isocyanate groups.
- any non-converted isocyanate groups that are present react to form allophanate linkages or amines.
- the polyols are low-molecular.
- the molecular weight per hydroxyl group is meant.
- 3 or 4 functional polyols are started from, although higher functionalities can be used as well. Practically speaking, an upper limit lies at a functionality of 8.
- an upper limit lies at a functionality of 8.
- diols do not give rise to crosslinking, it is required either to keep the amount thereof low or to work substantially with isocyanates having a functionality of 3 or more.
- the number of hydroxyl groups originating from a diol will be less than approximately 10% of the total number of hydroxyl groups.
- Preferred polyols are selected from the group consisting of triethanolamine (TEA), triisopropanolamine, 1,1,1,- trimethylol-propane (TMP) , N,N,N' ,N' -tetrakis (2- hydroxypropyl) ethylenediamine (Quadrol) , octakis (2- hydroxypropyl) pentaerythrityltetraamine, tetrakis ⁇ - hydroxyethyl ⁇ methane, 1,1,1 trihydroxyethyl propane, 1,1,1 trihydroxyethylethane and other polyols. It is also possible to use a modified or unmodified pentaerythritol or inositol.
- the polyisocyanates that can be used according to the invention are the conventional diisocyanates and higher isocyanates, for instance selected from the group consisting of butanediisocyanate, hexa ethylene diisocyanate, dodecane diisocyanate, trans 1,4-cyclohexane diisocyanate, methylene dicyclohexane diisocyanate, lysine di- or triisocyanate, isophoron diisocyanate, p-phenylene diisocyanate, methylene diphenyl diisocyanate, triphenylmethanetriisocyanate, thiophosphoric acid tris (4-isocyanatiphenyl ester), polymeric methylene diphenyl diisocyanate, as well as trimerization products and adducts of these isocyanates, for instance on the basis of polyols. Examples of suitable polyols have been given hereinabove.
- the selection of the polyol and the polyisocyanate substantially depends on the intended use. For uses wherein the color preservation of the material is important, it may be preferred to use aliphatic isocyanates. It is known that aromatic isocyanates may give rise to discolorization. In view of the use in the biomedical field, it may be preferred that the isocyanates and polyols be based on or related to so- called body-intrinsic substances. In that case, in particular butanediisocyanate and lysine-diisocyanate may be preferred.
- the very high degree of crosslinking of the materials usually lessens the necessity of working with body- intrinsic substances, because decomposition hardly occurs, if at all, so that no decomposition products can enter the body.
- the polyurethane In the preparation of the polyurethanes it is preferred to start from pure and very dry starting substances, in an anhydrous environment.
- the polyurethane In the case where a stoichiometric or substantially stoichiometric proportion of the reactive components and a proper mixture thereof are used, the polyurethane is cured at a low temperature, after gelation optionally followed by curing above the glass transition temperature. In this manner, autoclavable materials are obtained. This may in particular be important in the case of materials to be implanted.
- a polyol obtained by alkoxylation of the corresponding amine it is preferred to use a polyol obtained by alkoxylation of the corresponding amine.
- This has the advantage that the nitrogen of the amine compound functions as a catalyst for the polyurethane reaction, so that no separate catalyst need be added. In view of the applicability for medical uses, this is of course an important advantage.
- a separate catalyst that is suitable for forming polyurethane such as tin octoate or triethylamine.
- composition and the properties of the eventual material to a substantial extent depend on the intended use. For many uses it is preferred to use a material whose glass transition temperature is at least 30°C. This glass transition temperature is measured on the dry, unswollen products.
- the liquid resin can be poured into a mould and cured or milled from a block of the polyurethane.
- the material can be sterilized by steam of for instance 120°C. Further, an important advantage is that during this sterilization by steam the network takes up water, so that the tolerance of the body of these materials is increased.
- the material is optically clear, while it is also advantageous if it is hydrophilic or rendered hydrophilic by a coating of a polymer or a protein such as polyacrylamide or heparin. A reasonable strength is desired, so that damage to the lens during implantation and use can be prevented.
- the lens can be made UV-absorbing by admixing a UV-absorber.
- a polyurethane is used with a maximum water uptake and a glass transition temperature of approximately 35°C.
- Suitable components for the manufacture are, for instance, Quadrol, copolymers of thriethanolamine with triisopropanolamine or Quadrol with hexamethylene diisocyanate.
- lysinediisocyanate or butanediisocyanate which is slightly preferred because of the relationship to substances in the body.
- a filler is hydroxyapatite, which can be incorporated into the network in particularly large amounts.
- the amount of hydroxyapatite is 25-95% by weight of the total composite consisting of network and hydroxyapatite.
- Hydroxyapatite has the important advantage that it is compatible with the body, while it also has a high modulus and a hardness and coefficient of expansion comparable with the human bone.
- hydroxyapatite in the polymeric network has the advantage that hydroxyapatite possesses reactive groups that react with isocyanates, so that a particularly good adhesion to the network is obtained.
- a good resistance to shock-loading and fatigue should be present, since the hip is to absorb a substantial force during walking, while, in view of the service life, the fatigue demands are quite heavy.
- the composites must satisfy yet other requirements when they are to be used for restoring teeth and molars. It is for instance important that the material is comparable with dental enamel in hardness and wear resistance, while possessing a great strength, impact strength and fatigue strength, also in the environment in the mouth. Obviously, the color should be comparable with that of teeth, while the thermal expansion should also correspond to the thermal expansion of the teeth or molars. Of course, a proper adhesion of the restoration material is also required.
- the material according to the invention proves to have these properties to a high degree.
- An important advantage of the materials according to the present invention is that the mixture of polyol, polyisocyanate and filler can be cured in the mouth, for instance by heating or by using a local microwave radiation source.
- the restoration material is obtained by mixing the two reaction components together, both filled with a suitable filler, such as hydroxyapatite. If so desired, the polyisocyanate may have been prepolymerized, so that the volatility and toxicity are decreased.
- the material according to the invention can also be used in the case of bone fractures or for fixing implants. At present, this involves the use of a bone cement based on diacrylates or metals, or polylactic acid bone plates.
- a bone cement can be developed which is not poisonous and which, by admixing hydroxyapatite, promotes the growth of bone.
- the hydroxyapatite to be used can be modified by a polyisocyanate so as to improve the adhesion to the hydroxyapatite and the wetting thereof with the resin. This modification can for instance be effected by mixing the hydroxyapatite with a polyisocyanate, such as HDI, and heating the mixture for some time.
- the resin quickly became viscous and started gelating 45 minutes after mixing.
- a clear and hard piece of polymer was formed. From this, the desired shape for an intraocular lens and keratoprosthesis were obtained by a cutting operation, in this case milling.
- the network had reacted completely to form a glassy and clear material.
- the glass temperature was approximately 85°C, no isocyanate groups could be detected by IR.
- the netted polyurethane was hard and slightly brittle.
- the material had an elasticity modulus of 3 GPa, a tensile strength of 90 MPa at an elongation at break of 15%. A rise in temperature rendered the material less rigid and brittle.
- Lenses and keratoprostheses were implanted in the eyes of chinchilla rabbits. The lenses were well tolerated and the cornea did not become clouded. Even one year after the operation, the cornea was still clear.
- Example I The process of Example I was repeated, while Coumarin 102 Laser dye was added to the resin for obtaining UV absorption.
- the Coumarin absorbed UV light under 400 nm and gave the lens a blue-yellow fluorescent coloration.
- the other properties were not influenced.
- Example I The process of Example I was repeated, but after degassing a different method for shaping the intraocular lens (IOL) was used.
- IOL intraocular lens
- the other method for realizing an IOL is pouring the resin into a polished steel mold of the desired shape.
- complex shapes can be obtained with a very high surface quality.
- the mold was dried in an oven and provided with a surface coating. Pouring out and curing in the mold took place in a glovebox with nitrogen atmosphere.
- a Silicon solution in isopropanol Serva chem was used as surface coating. After wetting, the silicon layer was dried in air at 110°C for 2 hours.
- an article for instance a cylindrical implant, can be made.
- the article was obtained by curing a resin in a mould. The mixture was cured at room temperature for 1 day and subsequently at 105°C in vacuum for 20 hours. After curing of the polyurethane, the article was removed from the mould. Properties:
- the polyurethane network had a glass temperature of 73°C, but after forced water uptake at 100°C the Tg decreased to 33°C.
- the network takes up 5% by weight of water.
- Implantation of the articles in the abdomen of rats yielded highly encouraging results as far as tolerance and durability are concerned. Owing to the smooth surface, the articles were encapsulated only slightly (favorable) , the mechanical properties were maintained and the weight remained the same, i.e., hardly any degradation occurred, if at all.
- Example II the flask was disposed in an oil bath of 60°C. In this bath, 6.082 g of TMP were melted. Under vigorous agitation, 12.7 g of HDI were added. The liquids do not mix. Mixing took place only at 81°C. After stirring for 7 minutes, the mixture was cooled down quickly to room temperature. The TMP crystallized to form a white slurry. After heating to 81°C and stirring for 3 minutes, the resin remained clear during cooling down. Flask and resin were degassed at 80°C and 0.05 mbar for 5 minutes. After flushing three times with N2/vacuum, the resin was bubble-free and clear.
- the resin was poured into a 15 ml syringe.
- a teflon (TW20) hose with needle was attached to this.
- the hose length is 5 meters.
- TW20 teflon
- the viscous resin was forced into the hose.
- the polyurethane network had a refractive index of 1.48. Orienting tests demonstrated the optical conductivity of the fiber.
- the light conductor of polyurethane/teflon of a fiber length of 1 meter transmitted the light of a red LED with hardly any weakening.
- the polyurethane of TMP/HDI has a very low degree of swelling ( ⁇ 1%) in water and is resistant to solvents.
- the glass temperature was 85°C.
- Example II In the same manner as described in Example I, a number of polyurethane networks were prepared using a number of different starting products in different ratios. The glass transition temperatures of these products were determined and included in the tables.
Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU53778/94A AU5377894A (en) | 1992-10-13 | 1993-10-13 | Polyurethane network for biomedical use |
EP93924216A EP0665855A1 (en) | 1992-10-13 | 1993-10-13 | Polyurethane network for biomedical use |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
NL9201773 | 1992-10-13 | ||
NL9201773 | 1992-10-13 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1994009048A1 true WO1994009048A1 (en) | 1994-04-28 |
Family
ID=19861373
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/NL1993/000203 WO1994009048A1 (en) | 1992-10-13 | 1993-10-13 | Polyurethane network for biomedical use |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP0665855A1 (en) |
AU (1) | AU5377894A (en) |
WO (1) | WO1994009048A1 (en) |
Cited By (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0693294A2 (en) * | 1994-07-22 | 1996-01-24 | United States Surgical Corporation | Bioabsorbable branched polymers containing units derived from dioxanone and medical/surgical devices manufactured therefrom |
WO1999022780A1 (en) * | 1997-11-03 | 1999-05-14 | Artimplant Ab | Shaped bodies for use as implants in human medicine and method for the production of such shaped bodies |
US6339130B1 (en) | 1994-07-22 | 2002-01-15 | United States Surgical Corporation | Bioabsorbable branched polymers containing units derived from dioxanone and medical/surgical devices manufactured therefrom |
DE10242075A1 (en) * | 2002-09-11 | 2004-03-25 | Curasan Ag | New bone-adhesive polyurethane polymers obtained using polyester polyol component(s), having high tensile strength and useful e.g. for fixing bone or tooth fragments or filling cavities |
US7010205B2 (en) | 2003-09-29 | 2006-03-07 | Corning Incorporated | Coated optical fiber and optical fiber coating system including a hydrophilic primary coating |
WO2006098757A3 (en) * | 2004-08-16 | 2006-11-16 | Univ California | Shape memory polymers |
EP1789088A2 (en) * | 2004-03-24 | 2007-05-30 | Doctor's Research Group, Inc. | Methods of performing medical procedures that promote bone growth, methods of making compositions that promote bone growth, and apparatus for use in such methods |
US20120269218A1 (en) * | 2011-04-22 | 2012-10-25 | Lawrence Livermore National Security, Llc | Stabilization of green bodies via sacrificial gelling agent during electrophoretic deposition |
RU2519746C2 (en) * | 2008-11-20 | 2014-06-20 | Алькон Рисерч, Лтд. | Device for introduction of intraocular lens, containing cartridge with internal covering |
US9097835B2 (en) | 2008-12-29 | 2015-08-04 | Basf Se | Light guides made of thermoplastic polyurethanes |
US20150246998A1 (en) * | 2014-02-21 | 2015-09-03 | Bayer Materialscience Ag | TRANSPARENT POLYURETHANES WITH HIGH GLASS TRANSITION TEMPERATURE Tg |
US9327052B2 (en) | 2003-02-04 | 2016-05-03 | Warsaw Orthopedic, Inc. | Polyurethanes for osteoimplants |
US9453289B2 (en) | 2010-04-13 | 2016-09-27 | Lawrence Livermore National Security, Llc | Methods of three-dimensional electrophoretic deposition for ceramic and cermet applications and systems thereof |
WO2017066807A1 (en) * | 2015-10-15 | 2017-04-20 | Vanderbilt University | Nanocrystalline hydroxyapatite/polyurethane hybrid polymers and synthesis thereof |
US9745402B2 (en) | 2004-08-16 | 2017-08-29 | Lawrence Livermore National Security, Llc | Shape memory polymers |
US9852824B2 (en) | 2010-08-24 | 2017-12-26 | Lawrence Livermore National Security, Llc | Methods for controlling pore morphology in aerogels using electric fields and products thereof |
US11820852B2 (en) | 2004-08-16 | 2023-11-21 | Lawrence Livermore National Security, Llc | Shape memory polymers |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2968672A (en) * | 1957-03-19 | 1961-01-17 | Reichhold Chemicals Inc | Polyisocyanates containing tertiary amine structure |
US3102875A (en) * | 1953-08-07 | 1963-09-03 | Monsanto Chemicals | Polyurethane reaction product and method for making same |
EP0022215A1 (en) * | 1979-07-07 | 1981-01-14 | Bayer Ag | Process for the manufacture of moulded polyurethane-based articles |
US4285073A (en) * | 1980-02-11 | 1981-08-25 | Thermo Electron Corporation | Keratoprosthetic polyurethane |
FR2540878A1 (en) * | 1983-02-11 | 1984-08-17 | Hexcel France | Manufacture of moulded articles made of polyurethane from high-reactivity polyols and polyisocyanates |
-
1993
- 1993-10-13 WO PCT/NL1993/000203 patent/WO1994009048A1/en not_active Application Discontinuation
- 1993-10-13 AU AU53778/94A patent/AU5377894A/en not_active Abandoned
- 1993-10-13 EP EP93924216A patent/EP0665855A1/en not_active Withdrawn
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3102875A (en) * | 1953-08-07 | 1963-09-03 | Monsanto Chemicals | Polyurethane reaction product and method for making same |
US2968672A (en) * | 1957-03-19 | 1961-01-17 | Reichhold Chemicals Inc | Polyisocyanates containing tertiary amine structure |
EP0022215A1 (en) * | 1979-07-07 | 1981-01-14 | Bayer Ag | Process for the manufacture of moulded polyurethane-based articles |
US4285073A (en) * | 1980-02-11 | 1981-08-25 | Thermo Electron Corporation | Keratoprosthetic polyurethane |
FR2540878A1 (en) * | 1983-02-11 | 1984-08-17 | Hexcel France | Manufacture of moulded articles made of polyurethane from high-reactivity polyols and polyisocyanates |
Cited By (31)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0693294A2 (en) * | 1994-07-22 | 1996-01-24 | United States Surgical Corporation | Bioabsorbable branched polymers containing units derived from dioxanone and medical/surgical devices manufactured therefrom |
EP0693294A3 (en) * | 1994-07-22 | 1999-06-16 | United States Surgical Corporation | Bioabsorbable branched polymers containing units derived from dioxanone and medical/surgical devices manufactured therefrom |
US6339130B1 (en) | 1994-07-22 | 2002-01-15 | United States Surgical Corporation | Bioabsorbable branched polymers containing units derived from dioxanone and medical/surgical devices manufactured therefrom |
EP2301597A1 (en) * | 1994-07-22 | 2011-03-30 | United States Surgical Corporation | Bioabsorbable branched polymers containing units derived from dioxanone and medical/surgical devices manufactured therefrom |
EP2036582A1 (en) * | 1994-07-22 | 2009-03-18 | United States Surgical Corporation | Biobsorbable branched polymers containing units derived from dioxanone and medical/surgical devices manufactured therefrom |
WO1999022780A1 (en) * | 1997-11-03 | 1999-05-14 | Artimplant Ab | Shaped bodies for use as implants in human medicine and method for the production of such shaped bodies |
AU740604B2 (en) * | 1997-11-03 | 2001-11-08 | Artimplant Ab | Shaped bodies for use as implants in human medicine and method for the production of such shaped bodies |
US6436136B1 (en) | 1997-11-03 | 2002-08-20 | Artimplant Ab | Shaped bodies for use as implants in human medicine and method for the production of such shaped bodies |
DE10242075A1 (en) * | 2002-09-11 | 2004-03-25 | Curasan Ag | New bone-adhesive polyurethane polymers obtained using polyester polyol component(s), having high tensile strength and useful e.g. for fixing bone or tooth fragments or filling cavities |
DE10242075B4 (en) * | 2002-09-11 | 2007-02-01 | Curasan Ag | Bone-adhesive polyurethane polymer, process for its preparation and its uses |
US10322209B2 (en) | 2003-02-04 | 2019-06-18 | Warsaw Orthopedic, Inc. | Polyurethanes for osteoimplants |
US9327052B2 (en) | 2003-02-04 | 2016-05-03 | Warsaw Orthopedic, Inc. | Polyurethanes for osteoimplants |
US7010205B2 (en) | 2003-09-29 | 2006-03-07 | Corning Incorporated | Coated optical fiber and optical fiber coating system including a hydrophilic primary coating |
EP1789088A2 (en) * | 2004-03-24 | 2007-05-30 | Doctor's Research Group, Inc. | Methods of performing medical procedures that promote bone growth, methods of making compositions that promote bone growth, and apparatus for use in such methods |
EP1789088A4 (en) * | 2004-03-24 | 2009-12-30 | Doctor S Res Group Inc | Methods of performing medical procedures that promote bone growth, methods of making compositions that promote bone growth, and apparatus for use in such methods |
US11820852B2 (en) | 2004-08-16 | 2023-11-21 | Lawrence Livermore National Security, Llc | Shape memory polymers |
US11453740B2 (en) | 2004-08-16 | 2022-09-27 | Lawrence Livermore National Security, Llc | Shape memory polymers |
US10526437B2 (en) | 2004-08-16 | 2020-01-07 | Lawrence Livermore National Security, Llc | Shape memory polymers |
US9745402B2 (en) | 2004-08-16 | 2017-08-29 | Lawrence Livermore National Security, Llc | Shape memory polymers |
WO2006098757A3 (en) * | 2004-08-16 | 2006-11-16 | Univ California | Shape memory polymers |
RU2519746C2 (en) * | 2008-11-20 | 2014-06-20 | Алькон Рисерч, Лтд. | Device for introduction of intraocular lens, containing cartridge with internal covering |
US8821572B2 (en) | 2008-11-20 | 2014-09-02 | Alcon Research, Ltd. | Intraocular lens delivery device having a cartridge with an internal coating |
US9097835B2 (en) | 2008-12-29 | 2015-08-04 | Basf Se | Light guides made of thermoplastic polyurethanes |
US9453289B2 (en) | 2010-04-13 | 2016-09-27 | Lawrence Livermore National Security, Llc | Methods of three-dimensional electrophoretic deposition for ceramic and cermet applications and systems thereof |
US10407792B2 (en) | 2010-04-13 | 2019-09-10 | Lawrence Livermore National Security, Llc | Methods of three-dimensional electrophoretic deposition for ceramic and cermet applications and systems thereof |
US10533261B2 (en) | 2010-04-13 | 2020-01-14 | Lawrence Livermore National Security, Llc | Methods of three-dimensional electrophoretic deposition for ceramic and cermet applications and systems thereof |
US9852824B2 (en) | 2010-08-24 | 2017-12-26 | Lawrence Livermore National Security, Llc | Methods for controlling pore morphology in aerogels using electric fields and products thereof |
US9290855B2 (en) * | 2011-04-22 | 2016-03-22 | Lawrence Livermore National Security, Llc | Stabilization of green bodies via sacrificial gelling agent during electrophoretic deposition |
US20120269218A1 (en) * | 2011-04-22 | 2012-10-25 | Lawrence Livermore National Security, Llc | Stabilization of green bodies via sacrificial gelling agent during electrophoretic deposition |
US20150246998A1 (en) * | 2014-02-21 | 2015-09-03 | Bayer Materialscience Ag | TRANSPARENT POLYURETHANES WITH HIGH GLASS TRANSITION TEMPERATURE Tg |
WO2017066807A1 (en) * | 2015-10-15 | 2017-04-20 | Vanderbilt University | Nanocrystalline hydroxyapatite/polyurethane hybrid polymers and synthesis thereof |
Also Published As
Publication number | Publication date |
---|---|
EP0665855A1 (en) | 1995-08-09 |
AU5377894A (en) | 1994-05-09 |
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