WO1990012605A1 - Biodegradable composites for internal medical use - Google Patents
Biodegradable composites for internal medical use Download PDFInfo
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- WO1990012605A1 WO1990012605A1 PCT/US1990/002281 US9002281W WO9012605A1 WO 1990012605 A1 WO1990012605 A1 WO 1990012605A1 US 9002281 W US9002281 W US 9002281W WO 9012605 A1 WO9012605 A1 WO 9012605A1
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- WIPO (PCT)
- Prior art keywords
- reinforced
- poly
- bioerodible
- composite
- calcium
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- 0 C**(*)C(O*C)(Oc1c2)Oc1c1OC(*3**3)(OC(C)*)Oc2c1 Chemical compound C**(*)C(O*C)(Oc1c2)Oc1c1OC(*3**3)(OC(C)*)Oc2c1 0.000 description 1
Classifications
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- 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
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/58—Materials at least partially resorbable by the body
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- 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
- A61L27/40—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
- A61L27/44—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
- A61L27/46—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix with phosphorus-containing inorganic fillers
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- 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
- A61L27/40—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
- A61L27/44—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
- A61L27/48—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix with macromolecular fillers
Definitions
- This invention relates to biodegradable composites for internal use. That is, it relates to composites made up of biodegradable substrate and a bio ⁇ degradable reinforcement which can be used internally in the body of a human or animal for bone fixation or the like. In this use, the composites gradually completely degrade to soluble products.
- this invention relates to the use of poly(ortho esters) as the erodible substrate and to the use of calcium-sodium metaphosphate fibers as the reinforcement in such composites.
- Metal plates, pins, rods, and screws are used for rigid internal fixation of bones and tendons which have been damaged by trauma or reconfigured surgically to correct defects occurring congenitally, developmentally or as the result of disease. These devices are most commonly fabricated from stainless steel and align bone fragments by bringing their edges into close proximity. Due to device structural stiffness they control relative motion to allow bone union. For healing, the stabilization must persist for several weeks or months without device break- -2-
- fixation implants Some attempts at reducing the rigidity of fixation implants have included the use of permanent implants made from titanium alloys, polymers and carbon- reinforced polymers such as nylon, polyether sulphone and polymethylmethacrylate. These implants lessen stress shielding but still may need to be removed after the bone heals. Beginning in 1971, investigators reported the possibility of employing implants fabricated from ateri- als which gradually break down or dissolve when placed in the body.
- An implant formed of a biodegradable material which meets basic design criteria, including biocompatibility (sterilizability and low toxicity) , compatibility for intraoperative reshaping (where needed) and sufficient initial strength and stiffness, has two major advantages over conventional implants: (a) It al ⁇ lows gradual load transfer to the healing bone as it degrades and (b) It eliminates the need for surgical removal.
- Typical fibers used as reinforcements in these composites are carbon fibers and other n ⁇ ndegradable materials, biodegradable inorganic polymers and biodegradable organic polymers.
- Some of the reinforcements used in these prior studies have been nonerodible - for example, carbon fibers, glass filaments and the like. While these materials can give dramatic increases in initial strength to composites over their polymer matrix alone they have the medically unacceptable problem of leaving behind finely divided nondegradable debris when the substrate disappears and also sometimes giving rise to rapid losses of strength during environmental exposure.
- Typical biodegradable polymers include self-reinforcement where the reinforcement is made of polymers of the same material as the polymer matrix but with the reinforcing polymer having a high degree of orientation of polymer chains for increased strength.
- one organic material for example poly(glycolic acid) fibers, can be used in another organic material such as poly(lactic acid).
- Pure PLLA is very durable, or nondegradable, depending on the user's point of view. It retains nearly all of its physical integrity after 150 days of implanta ⁇ tion. The same s-tudy reported that a 50-50 PLLA-PDLLA copolymer degraded to 31% of its initial strength in 30 days of implantation. Many workers in the field have looked at the physical and erosion properties of erodible or degradabie polymers, each seeking a composite system which will have physical support properties which lead to optimal healing and degradation properties which lead to prompt clearance of the implant from the system without any premature degradation which would compromise the desired physical.properties.
- the substrate polymer is an ortho ester formed by the re ⁇ action of a acetal having a functionality of two or more with a polyol, which term includes alcohols and phenols.
- the re ⁇ inforcement material in the composites is calcium-sodium metaphosphate (“CSM”) fibers.
- this invention concerns implan able composites made from these two materials.
- this invention concerns implantable composites fabricated from these ortho ester substrate polymers and an erodible reinforcement, gener ⁇ ally.
- this invention concerns implantable composites fabricated from the CSM fiber materials and erodible substrates of the art.
- this invention concerns implantable reinforcement devices fabricated from these materials.
- this invention relates to a method of treating the CSM fibers, and the product thereof to make them more compatible with the poly(ortho ester) substrates.
- Figure 1 is a graph illustrating the degradation of certain composites of this invention in simulated internal media as determined by measuring flexural strength
- Figure 2 is a graph illustrating the degradation of certain composites of this invention in simulated internal media as determined by measuring flexural modulus
- Figure 3a is a graph illustrating the degrada ⁇ tion of certain composites of this invention as well as materials not in accord with this invention in simulated internal media as determined by measuring compressive strength
- Figure 3b is a graph illustrating the degrada ⁇ tion of certain composites of this invention as well as materials not in accord with this invention in simulated internal media as determined by measuring compressive modulus;
- Figure 4a is a graph illustrating the degrada- tion of certain composites of this invention as well as materials not in accord with this invention in simulated internal media as determined by measuring tensile strength;
- Figure 4b is a graph illustrating the degrada- tion of certain composites of this invention as well as materials not in accord with this invention in simulated internal media as determined by measuring tensile modulus;
- Figures 5a and 5b are bar graphs illustrating the improvement in properties of POE materials achieved with reinforcement.
- Figures 6a and 6b are bar graphs illustrating the improvement in properties of poly(lactic acid) materials achieved with reinforcement.
- substrate materials for use in the composites of this invention are the poly(ortho ester) materials formed from ketene acetals and polyols. These materials are described in United States patent number 4,304,767. This patent is incorporated herein by reference. These ortho ester polymers have repeating mer units represented by the general formulas:
- n is an integer substantially greater than 10; wherein R.,, R-, R ⁇ and R, are the same or different essentially hydrocarbon groups, R. and R ⁇ being separate groups or parts of a cyclic group and R 3 and R 4 being separate groups or parts of a cyclic group; R ⁇ is an essentially hydrocarbon group which is the residue of a polyol R ⁇ (OH) wherein n is an integer equal to two or more, such polyol being a single molecular species or a mixture of molecular species; R g is a valence bond or an essentially hydrocarbon group; R- and R « are hydrogen or essentially hydrocarbon groups which may be separate groups or may form parts of a cyclic group; and wherein such linear chains may be crosslinked to similar chains
- h is an integer substantially greater than 10; wherein R. and R ⁇ are hydrogen or the same or different essentially hydrocarbon groups and may be separate groups or may form parts of a cyclic group; f jis a quadrivalent organic grouping; R., and R. are hydrogen or the same or different essentially hydrocarbon groups and may be separate groups or may form parts of a cyclic group; R_ is an essentially hydrocarbon group which is the residue of a
- polyol R ⁇ (0H) wherein a is an integer equal to two or more, such polyol being a single molecular species or a mixture of molecular species; and wherein such linear chain may be crosslinked with other similar chains.
- These ortho ester polymers are preferably formed 15 by a (Condensation reaction between ketene acetals having a funetjlonality of two or more and hydroxyl compounds having a functionality Of two or more.
- a di-ketene acetal has a functionality of
- a tri-ketene acetal has a functionality of three, etc.
- functionality refers to the hydroxyl groups present in the polyol.
- ketene acetals are of two types. Th ⁇ first is as follows :
- terminal R groups are the same or different, and can be H or essentially hydrocarbon groups, primarily alkyl, aryl, cycloaliphatic or aralkyl groups, and may be saturated or unsaturated, and R is a quadravalent group ⁇ ing or atom.
- essentially hydrocarbon is meant that the groups R may contain hetero atoms provided they do not inhibit polymerization with a polyol to an unacceptable degree, do not inhibit degradation of the polymer to an unacceptable degree and do not give rise to toxic or dif ⁇ ficultly metabolizable degradation products.
- the formula- tion R-R indicates that the two R groups may be joined together to form a cyclic group or may be separate unconnected groups.
- the second type of ketene acetal is as follows:
- terminal R groups are the same or different essentially hydrocarbon groups
- the R' groups are hydrogen or essentially hydrocarbon groups
- R" is a bivalent organic grouping which is also essentially hydrocarbon.
- R is derived from the polyol and n is an integer greater than one and usually 100 to 300 or greater.
- the Type II monomers polymerize with diols to produce linear polymers as follows:
- crosslinked polymers will result. As noted below crosslinking may also be achieved by other crosslinking agents.
- Exemplary polyols suitable as reactants include diols, triols, and the like that can enter into the polymerization reaction without adversely affecting it or the polymeric product.
- the polyols are known to the art in reported synthesis and they are commercially available. Generally, they include aliphatic diols, triols and the like of the straight or branched chain type.
- Representative polyols are alkane polyols having a terminal hydroxyl group at the terminus of an alkylene chain of the formula
- R is an alkylene chain of 2 to 12 carbon atoms and y is 0 to 6.
- Typical diols named as the glycols, include 1,2-propylene glycol, 1,5-pentylene glycol, 3,6-diethyl- 1,9-nonylene glycol, trans-eyelohexanedimethanol and the like.
- Polyols containing more than 2 reactive hydroxyl radicals suitable for use herein include polyhydroxyl compounds such as 1,2,3,4,5,6-hexanehexol; 1,2,3- pr ⁇ panetriol; 1,5,12-dodecanetriol; 1,2,6-hexanetriol and the like.
- polystyrene resin suitable for synthesizing the poly(ortho esters) include polyglycols containing a repeating glycol monoether moiety -OCH 2 (CH 2 ) OH wherein p is 1 to 5.
- poly(ortho esters) are polyhydroxyl compounds having 2 or more reactive hydroxyl groups such as pentaerythritol and dipentaerythritol.
- phenolic polyols two or more phenolic hydroxyl groups
- mixed phenolic-alcoholic polyols may be employed.
- mixtures of two or more polyols may be employed. Examples of polyols and of mixed phenoloic- alcoholic polyols are as follows: -15-
- 4,4'-isipropylidenediphenol bisphenol A
- 4-hydroxybenzylalcohol 4-hydroxybenzylalcohol
- non-phenolic polyols having aromatic linking groups between the hydroxyl groups e.g. 1,4-dihydroxymethylbenzene.
- tri- (and higher) hydric phenols may be used such as pyrogallol; hydroxyhydroquinone; phloruglucinol; and propyl gallate.
- the composites may include substrate polymers other than the above-described ortho esters.
- substrate materials include poly(lactic acid) including “PLLA', “PDLLA” and combinations of "PLLA” and “PDLLA”; poly(glycolic acid) ("PGA") copolymers of L-lactide and epsilon-caprolactone; polycaprolactone ("PCL”); PCL/PDLLA copolymers; polypropylene fumarate; polyiminocarbonate; copolymers of polyhydroxybutrate/polyhydroxyvalerate; poly(alkylene oxalates); poly(ester-amide) and the polyanhydrides described by K.W. Leong et al., J. Biomed. Res. Vol 19 pp.941-955, (1985) incorporated by reference.
- substrate materials include poly(lactic acid) including "PLLA', "PDLLA” and combinations of "PLLA” and “PDLLA”; poly(glycolic acid) (“PGA”) copolymers
- the composites of this invention employ calcium-sodium-methaphosphate (“CSM”) fibers as reinforcements.
- CSM calcium-sodium-methaphosphate
- CSM is described in the United States Patent 4,346,828, which patent is herein in ⁇ corporated by reference. This patent teaches the prepara ⁇ tion and use of asbestiform calcium-sodium-methaphosphate (“CSM”) crystals as reinforcement-filler materials. This material has been promoted by and is available as a developmental scale chemical from Monsanto Company (St. Louis, Missouri) and has been proposed as use as a -16-
- the CSM materials were proposed as an alterna ⁇ tive to asbestos. As described by Bruce Monzyk in September-October 1986, Plastics Compounding, pp. 42-46, this material was developed as an insoluble fiber that would degrade naturally if ingested or inhaled.
- This material an inorganic covalently bonded polyphosphate having sodium and calcium cations adjacent to and ionically bonded to the polymer can generally be used as distributed by Monsanto.
- this material may lead to pre ⁇ mature breakdown of the orthoester because it tends to have an acidic surface. This can be easily prevented by blocking some of the acidic functions on the raw fiber such as by treating with a silylating agent as will be demonstrated in the preparation section.
- the composites of this invention contain at least two materials: a substrate polymer and a fibrous reinforcement.
- the amount of reinforcement should be an effective reinforcing amount or level.
- An "effective re ⁇ inforcing" amount is such as to not be so great as to destroy the continuous phase presented by the polymer matrix and thus degrade the mechanical properties of the composite but large enough to effectively reinforce the substrate.
- the weight ratio of substrate to reinforcement is from about 90:10 to about 10:90 with more preferred materials having a ratio of from about 80:20 to about 20:80.
- the composites may contain additional materials as well, as long as these additional materials are nontoxic and biocompatible and have physical and -17-
- these composites could contain pharmaceutically acceptable plasticizer ⁇ , mold release agents, radioimaging materials, or the ke. Other materials can be present as well, including excipients to promote or regulate erosion and degradation, and pharmaceutically active materials such as bone growth factors, drugs such as antibiotics or the like.
- the composites are typically formed by admixing the j xeinforcement, which is most commonly in a loose fiber form but hich could also be in the form of fabrics, felts, or the"like, if desired and if compatible with the properties of the reinforcement, with the substrate polymer ⁇ r a polymer precursor in a fluid state.
- This material can them be cast into shapes desired for medical reinforcement applications or it can be cast into billets from which the desired shapes can be machined.
- the substrate and fiber can be dry-mixed and formed into the desired shapes by injection molding, hot-pressing, transfer molding and the like.
- the actual forming techniques employed are known in the art and will depend upon whether the polymer is thermoplastic or thermorigid and also will depend upon whether it is the polymer itself which is being formed or rather a fluid precursor which is then solidified by curing or the like.
- the final form of the reinforcements produced according to the invention can include the various shapes described heretofore for medical reinforcement purposes. These shapes include, without limitation, rods, pins, screws, plates and the like. -18-
- CSM-reinforced POE composite is as follows:
- CSM calcium-sodium metaphosphate
- a basic coupling agent such as a' diamine silane (Dow Corning, Z-6020) may be bond-ed to- the CSM fiber surface. This may be carried out as follows: - in a 250 ml beaker add 99.7 ml of methanol (EM).
- a linear ortho ester polymer (POE) is prepared from 3,9-feis-(ethylidene 2,4,8,10-tetraoxa- ** spiro[5.5]-undecane) and a 60:40 mole ratio of rigid trans-cyclohexanedimethanol and flexible 1,6-hexane-diol using the general methods set forth in the examples of United States patent number 4,304,767.
- One of the several repeat preparations is carried out as follows: -20-
- the polymerization is initiated by the addition of 2 ml of a solution of p-toluenesulfonic acid (20 mg/ml) in tetrahydrofuran.
- the polymerization temperature rapidly rises to the boiling point of tetrahydrofuran, then gradually decreases.
- Stirring is continued for about 2 hr., 10 ml of triethylamine stabilizer added, and the re ⁇ action mixture then very slowly poured with vigorous stirring into about 15 gallons of methanol containing 100 ml of triethylamine.
- the precipitated polymer is collected by vacuum filtration and dried in a vacuum oven at 60°C for 24 hrs.
- the weight of the dried polymer was 346.03 (98.8% yield).
- the molecular weight determined by light scattering was 95,300.
- CSM fibers is achieved by simply dry-mixing the appropri- -21-
- Hot-Pressing of Composites - set and heat the platens of a Carver Press to
- thermocouple temperature probe into the die
- Acute toxicity screening was performed on ethylene oxide sterilized samples. Cytotoxicity was determined by agar overlay as ⁇ ay of direct ⁇ amples. USP Toxicity Class VI tests (systemic and intracutaneous injection of extracts, 37°C for 9 hours) and USP Implanta ⁇ tion XXI tests (intramuscular implantation, followed by gross and macroscopic examination) were conducted. Flexural modulus and flexural strength were measured in accordance with ASTM Standard D 790-81 (3 pt. bend). Specimens were immersed in Tris-buffered saline, pH 5.0 and 7.4 (aerated), at 37 C and tested after 1, 3, and 6 weeks expo ⁇ ure. Another set of specimens was ir- radiated with 2.5 Mrad of gamma radiation and exposed to aerated Tris-buffered saline, pH 7.4, at 37°C. All mechanical testing was performed in triplicate.
- POE poly(ortho ester)
- CLLA epsilon-caprolactone/L-lactide
- NCAP degradable glassy 10 ⁇ odium-calcium-aluminum-polyphosphate
- CSM crystal ⁇ line calcium-sodium-metapho ⁇ phate
- NCAP fiber and CSM fiber were submitted for acute toxicity screening by standard Tissue Culture •**•* • ⁇ Agar Overlay Assay (cytotoxicity), USP Class VI (systemic and intracutaneous toxicity) and USP XXI (intramuscular implantation) protocols.
- NCAP and CSM fibers were rated nontoxic in the cytotoxicity, systemic and intracutaneous toxicity and intramuscular implantation. Responses were comparable to 5 negative controls. -24-
- necrotic foci were observed in 12 of 22 NCAP-containing specimens, while only 2 of 14 CSM-containing specimens and 2 of 11 CLLA 90:10 copolymer specimens showed necrosi ⁇ . However, the necrosis was localized and as ⁇ ociated with the fibrous capsule. None of the implanted sites exhibited the uniform zone associated with gros ⁇ leeching of toxic substance ⁇ from the implant material.
- Bone histologic examination revealed a mild proliferation of fibrous connective tissue on the periosteal ⁇ urface for all specimens. This tissue varied in thickness and contained lymphocytes and macrophages. The bone showed no evidence of necrosis or toxicity.
- Figures 3a and 3b show compressive ⁇ trength and stiffness after in vitro exposure.
- CLLA 10:90 and POE polymers with NCAP fibers started out much stiffer and stronger than the rest, but degraded quickly.
- Figures 4a and 4b show tensile strength and stiffnes ⁇ after in vitro exposure.
- CLLA 10:90/NCAP and POE/CSM started out with relatively high stiffness and strength, but only POE/CSM retained significant strength at 6 and 12 weeks.
- CLLA 10:90/NCAP had the highest modulus initially, but at 6 weeks, POE/CSM was several times stiffer than all other materials.
- Other results of mechanical tests on pure ortho ester and lactic acid sustrates and reinforced composites based on these substrates are presented in Figures 5a, 5b, 6a and 6b. These results show that the CSM fibers -25-
Abstract
Description
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Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US07/345,034 US5108755A (en) | 1989-04-27 | 1989-04-27 | Biodegradable composites for internal medical use |
US345,034 | 1989-04-27 |
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WO1990012605A1 true WO1990012605A1 (en) | 1990-11-01 |
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PCT/US1990/002281 WO1990012605A1 (en) | 1989-04-27 | 1990-04-25 | Biodegradable composites for internal medical use |
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US (1) | US5108755A (en) |
EP (1) | EP0422208A1 (en) |
JP (1) | JPH03505541A (en) |
CA (1) | CA2031529A1 (en) |
WO (1) | WO1990012605A1 (en) |
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EP0552433A1 (en) * | 1991-11-27 | 1993-07-28 | American Cyanamid Company | Polymeric surgical staple |
DE4244000A1 (en) * | 1992-12-23 | 1994-06-30 | Buck Chem Tech Werke | Biodegradable packaging material |
WO1997038741A1 (en) * | 1996-04-12 | 1997-10-23 | Biovision Gmbh Entwicklung, Herstellung Und Vertrieb Von Biomaterialien In Ilmenau | Process for producing a biodegradable bone replacement and implant material, as well as biodegradable bone replacement and implant material |
WO1999011296A2 (en) * | 1997-09-02 | 1999-03-11 | Bionx Implants Oy | Bioactive and biodegradable composites of polymers and ceramics or glasses |
WO1999011296A3 (en) * | 1997-09-02 | 1999-06-24 | Bionx Implants Oy | Bioactive and biodegradable composites of polymers and ceramics or glasses |
US7541049B1 (en) | 1997-09-02 | 2009-06-02 | Linvatec Biomaterials Oy | Bioactive and biodegradable composites of polymers and ceramics or glasses and method to manufacture such composites |
US6406711B1 (en) | 1998-07-03 | 2002-06-18 | Jin-Yong Lee | Bone regeneration material |
EP0968729A2 (en) * | 1998-07-03 | 2000-01-05 | Jin-Yong Lee | Bone regeneration material |
EP0968729A3 (en) * | 1998-07-03 | 2000-01-12 | Jin-Yong Lee | Bone regeneration material |
US6398814B1 (en) | 1998-09-14 | 2002-06-04 | Bionx Implants Oy | Bioabsorbable two-dimensional multi-layer composite device and a method of manufacturing same |
US6350284B1 (en) | 1998-09-14 | 2002-02-26 | Bionx Implants, Oy | Bioabsorbable, layered composite material for guided bone tissue regeneration |
US7875697B2 (en) | 2006-06-29 | 2011-01-25 | Medtronic, Inc. | Poly(orthoester) polymers, and methods of making and using same |
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US8475823B2 (en) | 2008-04-18 | 2013-07-02 | Medtronic, Inc. | Baclofen formulation in a polyorthoester carrier |
US8940315B2 (en) | 2008-04-18 | 2015-01-27 | Medtronic, Inc. | Benzodiazepine formulation in a polyorthoester carrier |
US8956642B2 (en) | 2008-04-18 | 2015-02-17 | Medtronic, Inc. | Bupivacaine formulation in a polyorthoester carrier |
WO2021094227A1 (en) | 2019-11-15 | 2021-05-20 | Evonik Operations Gmbh | Fiber reinforced compositions and methods of manufacture for medical device applications |
Also Published As
Publication number | Publication date |
---|---|
EP0422208A1 (en) | 1991-04-17 |
JPH03505541A (en) | 1991-12-05 |
US5108755A (en) | 1992-04-28 |
CA2031529A1 (en) | 1990-10-28 |
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