WO2002002158A1 - Materiaux polymeres biocompatibles - Google Patents

Materiaux polymeres biocompatibles Download PDF

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Publication number
WO2002002158A1
WO2002002158A1 PCT/GB2001/002792 GB0102792W WO0202158A1 WO 2002002158 A1 WO2002002158 A1 WO 2002002158A1 GB 0102792 W GB0102792 W GB 0102792W WO 0202158 A1 WO0202158 A1 WO 0202158A1
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WIPO (PCT)
Prior art keywords
unit
bio
copolymer
compatible
units
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PCT/GB2001/002792
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English (en)
Inventor
John Neil Devine
David John Kemmish
Brian Wilson
Ian Griffiths
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Victrex Manufacturing Limited
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Priority to AU66156/01A priority Critical patent/AU6615601A/en
Publication of WO2002002158A1 publication Critical patent/WO2002002158A1/fr

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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
    • A61L27/14—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

Definitions

  • This invention relates to bio-compatible polymeric materials and particularly, although not exclusively, provides a bio-compatible polymeric material, a method of producing and the use of such a material in medical treatment, for example in a prosthesis.
  • prosthetic devices such as ⁇ orthopaedic " , dental or maxillofacial " Implants.
  • ⁇ orthopaedic ⁇ orthopaedic
  • dental or maxillofacial Implants.
  • nearly half a million patients receive bone implants each year in the US with the majority being artificial hip and knee joints made from titanium or colbalt-chrome alloys.
  • these materials are too stiff leading to bone resorption, loosening of the implant and, consequently, have lifetimes of less than 10 years.
  • medical devices or prostheses such as pacemakers, vascular grafts, stents, heart valves, catheters and dental implants that contact body tissues or fluids of living persons or animals have been developed and used clinically.
  • a bio-compatible polymeric material for use in medical applications, wherein said material comprises a copolymer comprising a unit A in combination with a unit B and/or a unit C, wherein bio-compatible moieties are associated with said copolymer and A represents a semi-crystalline polyaryletherketone moiety, B represents a unit which is incompatible with unit A and C represents an amorphous polyaryletherketone or polyarylethersulphone unit.
  • B units are sufficiently chemically dissimilar to A units, such that blocks of B units selectively aggregate when the copolymer is cooled from the melt.
  • bio-compatible has generally been used to refer to a material which is compatible with use in medical applications, for example by not being toxic or otherwise harmful to living materials. It also encompasses materials which have a biological or physiological effect when associated with living materials.
  • Bio-compatible moieties suitably refer to moieties which are compatible with use in medical applications, for example by not being toxic or otherwise harmful to living material. Such bio-compatible moieties may be arranged to bond (for example to form ionic or covalent bonds) or otherwise interact with materials present in human or animal bodies in order to improve their integration and acceptance by such bodies .
  • said bio-compatible polymeric material has improved or enhanced bio-compatibility compared to said copolymer in the absence of associated bio-compatible moieties .
  • Bio-compatible moieties suitably include moieties arranged to reduce adverse biological reactions when the copolymeric material is introduced into (or otherwise associated with) a human or animal body.
  • adverse biological reactions associated with introduction into a human or animal body of said copolymer having said bio-compatible moieties may be less compared to use of the same copolymer but which does not include associated bio- compatible moieties.
  • said bio-compatible material preferably has greater bio-compatibility than a polymer comprising units of A alone.
  • bio-compatible moieties are associated with at least one of either unit B or unit C of said copolymer.
  • Said unit A preferably includes aromatic group containing moieties linked by -CO- and/or -Q- groups, where Q is an oxygen or sulphur atom.
  • Unit A preferably does not include -S0 2 - groups since such would tend to render the unit amorphous .
  • Unit A may include a first unit which is of general formula ox of general formula
  • said unit is semi-crystalline, wherein the phenyl moieties in units IV, IV*, V and V* are independently optionally substituted, wherein m,r,s,t,v,w and z independently represent zero or a positive integer, E and E' independently represent an oxygen or a sulphur atom or a direct link, G represents an oxygen or sulphur atom, a direct link or a -O-Ph-0- moiety where Ph represents a phenyl group and Ar is selected from one of the following moieties (i)*, (i)**, and (i) to (x) which is bonded via one or more of its phenyl moieties to adjacent moieties
  • a phenyl moiety may have 1,4- or 1,3-, especially 1,4-, linkages to moieties to which it is bonded.
  • a phenyl moiety described herein may be optionally substituted by one or more halogen, especially fluorine and chlorine, atoms or alkyl, cycloalkyl or phenyl groups.
  • Preferred alkyl groups are Ci-io especially C ⁇ - 4 , alkyl groups.
  • Preferred cycloalkyl groups include cyclohexyl and multicyclic groups , for example adamantyl .
  • said phenyl moieties are not optionally- substituted as described.
  • the respective phenylene moieties may independently have 1,4- or 1,3-linkages to the other moieties in the repeat units of formulae II and/or III.
  • said phenylene moieties have 1,4- linkages.
  • the polymeric chain of the copolymer does not include a -S- moiety.
  • G represents a direct link.
  • m is in the range 0-3, more preferably 0-2, especially 0-1.
  • r is in the range 0-3, more preferably 0-2, especially 0-1.
  • t is in the range 0-3, more preferably 0-2, especially 0-1.
  • s is 0 or 1.
  • v is 0 or 1.
  • w is 0 or 1.
  • z is 0 or 1
  • Ar is selected from the following moieties (xi)* (xi)**, and (xi) to (xxi) :
  • the middle phenyl may be 1,4- or 1,3- substituted.
  • (xv) is selected from a 1,2-, 1,3-, or a 1,5- moiety
  • (xvi) is selected from a 1,6-, 2,3-, 2,6- or a 2,7- moiety
  • (xvii) is selected from a 1,2-, 1,4-, 1,5- , 1,8- or a 2,6- moiety.
  • Said unit A may include a semi-crystalline unit which is of general formula IV or IV* as described above, provided said unit is crystallisable.
  • said unit A does not include any Ar group of formula (i)**, (ii) , (viii) , (ix) or (x) . More preferably, it may also not include an Ar group of formula (v) , (vi) or (vii) .
  • Preferred Ar groups consist of one or more phenyl groups in combination with one or more carbonyl and/or ether groups .
  • Said unit A preferably includes only unsubstituted phenyl moieties, ether moieties and ketone moieties. That is, unit A preferably does not include repeat units which include -S-, -S0 2 - or aromatic groups other than phenyl.
  • Preferred units A include :
  • E' represents a direct link
  • A represents 1
  • B represents 0, (i.e. polyetherketoneketone) .
  • E and E' represents oxygen atoms
  • G represents a direct link
  • r represents 1 (i.e. polyetheretherketoneketone) .
  • polymers described in (a) and (b) are preferred, with the polymer described in (a) being especially preferred.
  • crystallinity in a polymer is preferably measured by wide angle X-ray diffraction, for example as described by Blundell and Osborn (Polymer 24, 953, 1983) .
  • crystallinity may be assessed by Differential Scanning Calorimetry (DSC) .
  • Unit B may represent any unit which is incompatible with unit A and, to this end, B preferably includes fewer, suitably less than half or even a quarter of the number of ether moieties in unit A; suitably fewer, suitably less than half or even a quarter of the number of ketone moieties in unit A; and suitably fewer, suitably less than half or even a quarter of the number of phenyl moieties in unit A.
  • Unit B preferably does not include any ether moieties in its backbone. Preferably, it also does not include any ketone moieties in its backbone and, more preferably, does not include any phenyl moieties in its backbone.
  • An example of a unit B is a dimethylsiloxane, especially a polydimethylsiloxane, moiety.
  • B represents a unit which is bio-compatible, it may represent a unit which has a greater bio-compatibility than repeat unit A.
  • An example is the aforementioned polydimethylsiloxane .
  • Said unit C preferably includes aromatic group containing moieties linked by -S0 2 - and/or -CO- and/or -Q- groups, where Q is as described above provided, however, that said third unit suitably includes a means to render it amorphous (hereinafter said "amorphous means") and/or not crystallisable with polyarylether ketones or polyarylthioether ketones and/or not crystallisable with unit A described above.
  • amorphous means a means to render it amorphous
  • Said unit C may comprise a unit which is of formula - Q-Z-Q- wherein Z represents said aromatic group containing moiety, wherein said unit is not symmetrical about an imaginary line which passes through the two -Q- moieties provided, however, that said unit is not dihydroxybenzophenone substituted by groups Q at the 4- and 4'- positions (since such a benzophenone acts in the manner of a symmetrical moiety by virtue of the carbonyl group being substantially similar to an ether group thereby allowing the carbonyl group to be interchanged with an ether group in a polyaryletherketone crystal lattice) .
  • Said unit C, for example moiety Z may include a bulky group.
  • Said unit C, for example moiety Z may include one of the following moieties:
  • Said copolymer may be a random or block copolymer. It may include one or a plurality of units A (which may be identical but are more likely to be different, for example in terms of length and/or structure, whilst still being semi-crystalline as described) ; one or a plurality of units B (which may be identical but are more likely to be different, for example in terms of length and/or structure, whilst still being incompatible as described) and/or one or a plurality of units C (which may be identical but are more likely to be different, for example in terms of length and/or structure, whilst still being amorphous as described) .
  • units A which may be identical but are more likely to be different, for example in terms of length and/or structure, whilst still being semi-crystalline as described
  • units B which may be identical but are more likely to be different, for example in terms of length and/or structure, whilst still being incompatible as described
  • one or a plurality of units C which may be identical but are more likely to be
  • Said copolymer may have a structure selected from one of the following structures :
  • n represents an integer, for example in the range 1 to 100. It should be appreciated that where more than one unit
  • A, B and C is included in one of the above structures, one
  • A, B or C in a structure need not be identical in terms of length and/or structure as another A, B or C in the same structure.
  • an end unit of said copolymer i.e. a unit at the end of the polymer chain of the copolymer
  • a unit at an opposite end of the polymer chain may be an A or B unit, especially an A unit.
  • the number of A units ⁇ ' iri " said copolymer is equal to or greater than the number of B units. More preferably, the number of A units is greater than the number of B units.
  • the sum of the chain length (s) of A units in said copolymer is preferably greater than the sum of the chain lengt (s) of B units in the polymer.
  • a C unit is not present at the end of a polymer chain.
  • the number of A units in said copolymer is equal to or greater than the number of C units. More preferably, the number of A units is greater than the number of C units.
  • the sum of the chain length (s) of A units in said copolymer is preferably greater than the sum of the chain length (s) of C units in said polymer .
  • Said bio-compatible polymeric material may comprise a blend.
  • Said blend may include a polymer or copolymer of units IV, V, IV* and/or V* and, more preferably, includes a semi-crystalline polymer or copolymer which comprises units IV, V, IV* and/or V*.
  • Preferred polyaryletherketones are polymers consisting essentially of units (a), (b) , (c) , (d) or (e) described above (i.e. polyetheretherketone, polyetherketone, polyetherketoneketone, polyetherketoneetherketoneketone and polyetheretherketoneketone) together with said copolymer.
  • Said blend preferably includes a polyaryletherketone together with said copolymer and, of these, polyetheretherketone and polyetherketone are preferred and polyetheretherketone is especially preferred. 1 - 50wt% of said polyaryletherketone may be included in a said blend.
  • Said bio-compatible material may include one or more fillers for providing desired properties .
  • Said bio- compatible material preferably incorporates an X-ray contrast medium. Fillers and/or said X-ray contrast medium is/are preferably distributed substantially uniformly throughout said bio-compatible material.
  • an X-ray contrast medium suitably comprises less than 25wt%, preferably less than 20wt%, more preferably less than 15wt%, especially less than 10wt% of said bio-compatible material. Where it is provided, at least 2wt% may be included.
  • Preferred X-ray contrast mediums are particulate and preferably are inorganic . They preferably have low solubility in body fluids. They preferably also have a sufficient density compared to that of the polymeric material (s) in said bio-compatible material to create an image if the bio-compatible material is X-ray imaged. Barium sulphate and zirconium oxide are examples of X-ray contrast media. Said particulate material is suitably physically held in position by entrapment within the bio-compatible material.
  • a said bio-compatible moiety may be selected from an anticoagulant agent such as heparin and heparin sulfate, an antithrombotic agent, a clotting agent, a platelet agent, an anti-inflammatory agent, an antibody, an antigen, an immunoglobulin, a defence agent, an enzyme, a hormone, a growth factor, a neurotrans itter, a cytokine, a blood agent, a regulatory agent, a transport agent, a fibrous agent, a protein such as avidin, a glycoprotein, a globular protein, a structural protein, a membrane protein and a cell attachment protein, a peptide such as a glycopeptide, a structural peptide, a membrane peptide and a cell attachment peptide, a proteoglycan, a toxin, an antibiotic agent, an antibacterial agent, an antimicrobial agent such " as pe ⁇ cil i ⁇ ' , '" ticarcilliri, carbenicillin, ampicillin
  • poly (ethylene glycol) (PEG) poly (ethylene oxide) (PEO) , ethylene oxide- propylene oxide block co-polymers, poly(N-vinyl-2- pyrrolidone) (PNVP) , poly (2-hydroxyethyl methacrylate)
  • PEG poly (ethylene glycol)
  • PEO poly (ethylene oxide)
  • PEO poly (ethylene oxide)
  • PNVP poly(N-vinyl-2- pyrrolidone)
  • PNVP poly(N-vinyl-2- pyrrolidone)
  • HEMA HEMA co-polymers
  • poly (vinyl alcohol) (PVA) polyacrylamide, its derivatives, poly (methyl methacrylate) (PMMA) , suitably having a PEG chain on each of the side groups, polysiloxanes (e.g. polydimethylsiloxanes (PDMS) ) , ionic water-soluble polymers like poly (acrylic acid) (PAAc) ) and a polyurethane .
  • PVA poly (vinyl alcohol)
  • PMMA polyacrylamide
  • PMMA poly (methyl methacrylate)
  • PAAc ionic water-soluble polymers
  • PAAc ionic water-soluble polymers
  • said bio-compatible moieties may comprise bone morphogenic protein (BMP) as described in US4563489 and patents cited therein and the contents of the aforesaid are incorporated herein.
  • BMP bone morphogenic protein
  • Said BMP may be provided in combination, for example in admixture, with a physiologically acceptable biodegradable organic polymer and said biodegradable polymer may be associated with ends of said polymer of said bio-compatible polymeric material, for example by being covalently bonded to end groups.
  • the combination of said biodegradable polymer and BMP defines said bio-compatible moieties.
  • Said biodegradable polymer is preferably a biodegradable polylactic acid; or alternatively, other physiologically acceptable biodegradable organic polymers which are structurally equivalent to polylactic acid can be used as the delivery system for BMP.
  • examples include poly(hydroxy organic carboxylic acids) e.g. poly(hydroxy aliphatic carboxylic acids) , polyglycollic acid, polyglactin, polyglactic acid and poly adonic acids.
  • Linking moieties for example linking atoms or groups may extend between repeat units of the copolymer, especially in units B and/or C thereof, and said bio- compatible moieties.
  • Said linking moieties may be covalently bonded to respective repeat units of the copolymer.
  • Said linking moieties may be covalently bonded to said bio-compatible moieties or may otherwise be associated with said moieties.
  • a said linking moiety may be associated with a single bio-compatible moiety or, alternatively, a said linking moiety may be associated with more than one bio-compatible moiety.
  • said linking moiety may be mono-functional or multi-functional, for association with one or more bio- compatible moieties.
  • Multi-functional linking moieties may be able advantageously to be associated with more bio- compatible moieties and may, therefore, provide a means to increase the concentration of bio-compatible moieties associated with said copolymer.
  • bio-compatible moieties may be associated with said copolymer by any suitable means, for example covalent bond(s), hydrogen bond(s) , encapsulation in a matrix which is bonded to or otherwise interacts with said copolymer, or ionic interaction (s) , it is preferred that there are covalent bonds between the bio-compatible moieties and said copolymer or there are ionic interactions between said bio-compatible moieties and said copolymer.
  • a method of preparing a bio-compatible polymeric material including the step of preparing a copolymer comprising a unit A in combination with a unit B and/or with a unit C and optionally including the step of associating a bio-compatible moiety with the copolymer or, when said optional step is not undertaken, selecting at least one unit B or C which is itself bio-compatible, wherein A, B and C are as described according to said first aspect.
  • the copolymer made in the method is thermally stable at at least 350 °C, suitably thereby to allow thermal processing operations, for example injection moulding, extrusion and/or thermal spraying, without degradation.
  • said copolymer is preferably hydrolytically stable, suitably such that it may withstand long term aqueous contact that may result in use, for example when implanted in a human or animal body.
  • the copolymer may r ⁇ ot " be hyd oly ⁇ icalIy ""”" stable ⁇ until after bio-compatible moieties have been associated therewith.
  • units B and/or C in the bio-compatible polymeric material include associated bio-compatible moieties or are themselves bio-compatible, preferably to a greater extent than units A.
  • units A preferably, units A
  • the bio-compatible polymeric material have a lower bio-compatibility than other units in the material and preferably do not include associated, for example pendent, bio-compatible moieties.
  • unit A need not be functionalised. This may be advantageous since units B and/or C may be easier and/or cheaper to render bio- compatible compared to unit A which by virtue of its crystalline nature and/or relative inertness, may be more difficult to functionalise such that bio-compatible moieties may be associated therewith.
  • functionalistion of unit A would tend to disrupt the semi- crystalline nature of the unit.
  • the crystallinity of A is preserved and is, therefore, preferably present in said bio-compatible material prepared in the method.
  • a copolymer comprising units A and B wherein unit B includes pendent moieties with associated bio-compatible moieties.
  • the method may involve preparing a copolymer using a first monomer (which provides part of unit B) having a pendent functional group.
  • Said functional group is preferably pendent from an aryl, especially a phenyl, group and may be, for example, a -CN group.
  • the copolymer prepared suitably includes said pendent functional group which may then be treated to allow bio-compatible moieties to be associated with unit B.
  • a said -CN group may be hydrolysed to an acid group which may then be treated with a peptide, as described in Example Ic hereinafter.
  • the method of preparing said copolymer may comprise polycondensing said first monomer with a second monomer
  • B units are selected in the method to have functionalities that allow efficient and cost- effective attachment of bio-compatible moieties.
  • a specific example of said first embodiment is provided in Examples Ia-c.
  • a copolymer is prepared comprising units A and B wherein unit B is itself bio-compatible, suitably in the sense that it has a higher inherent bio-compatibility compared to unit A.
  • the method may involve preparing a copolymer using a first monomer (which provides part of unit A) and a second monomer
  • first and second monomers are preferably polycondensed. It is preferred that said first monomer is in fact a difunctional polymer, for example hydroxy- terminated polyetherether ketone, and said second monomer is a polymer arranged to be condensed with said polymer.
  • Said second monomer may be polydimethylsiloxane.
  • a block copolymer is formed.
  • a specific example of said second embodiment is provided in Examples II a and b.
  • a copolymer is prepared which includes units A and C wherein units C are preferably more easily functionalised compared to units A so that bio-compatible moieties can be associated with functionalised units C.
  • units C are preferably more easily functionalised compared to units A so that bio-compatible moieties can be associated with functionalised units C.
  • functional groups thereof may be more accessible and, therefore, more easily functionalised.
  • Units C can be functionalised, for example, by electrophilic substitution reactions of aromatic rings, such as by sulphonation, chlorosulphonation, nitration, acylation, halogenation, chloromethylation, phosphonylation, lithiation and (optionally-substituted) alkylation reactions.
  • a copolymer is prepared comprising units A, B and C.
  • Units B may optionally provide bio-compatibility as described according to the first and second embodiments; and unit C may optionally provide bio-compatibility as described according to the third embodiment provided that at least one of B and C provides bio-compatibility.
  • Bio-compatible moieties associated with B and C may be the same or different.
  • the polymer can contain A, B and C units that are either dispersed throughout the bulk of the material or in phase domains. For example, where a unit of A, B and/or C defines a relatively small block it may be dispersed; whereas where a block is relatively large domains will be defined. In some cases domains in the size range 0.5 to 400 ⁇ m may be formed. "
  • a blend is prepared comprising a first copolymer which comprises units A and B and a second copolymer which comprises units A and C.
  • Units B may optionally provide bio-compatibility as described according to the first or second embodiments; and units C may optionally provide bio-compatibility as described according to the third embodiment, provided that at least one of B and C provides bio-compatibility.
  • the components of the blend may be selected such that there is a tendency for one of the copolymers in the blend to separate from the other copolymer and migrate to a surface of a solid material made from the polymers. Migration may occur during a thermal treatment of the blend.
  • the components of the blend are selected such that a copolymer which migrates to the surface includes an associated bio-compatible moiety (especially wherein one of the units of the copolymer is bio-compatible) or is arranged to be functionalised for association with bio- compatible moieties.
  • a specific example of the fifth embodiment is provided in Examples Va-c.
  • the method of the second aspect preferably includes providing said copolymer as part of a solid material.
  • a polymeric material which includes said copolymer is formed into a solid.
  • the polymeric material may include said copolymer in combination with one or more other copolymers and/or polymers and/or with other materials, for example fillers, e.g.
  • the components of the polymeric material are preferably heated together, suitably at a temperature of at least 200 °C, preferably at least " 250 °C, more preferably " at least 300 °C, especially at least 350 °C, and formed into a desired shape.
  • moieties, especially units B and/or C are preferably available at the surface for providing bio-compatibility (e.g. where B and/or C are themselves bio-compatible) and/or for association with a bio-compatible moiety.
  • the polymeric material When in the desired shape, the polymeric material may define a homogenous mixture of the components thereof so that the concentration of respective components of the polymeric material at the surface is the same as in the bulk.
  • the copolymer and/or the polymeric material is such that the concentration of units B and/or C at the surface is greater than in the bulk -that is units B and/or C tend to migrate to the surface, suitably during thermal processing of the polymeric material .
  • said polymeric material may include a copolymer of structure A-B-A, suitably as the only organic copolymer and/or organic polymer present. After thermal processing it is found that the units B in the copolymer tend to phase separate from units A and surface bloom, suitably so that the concentration of B units at the surface is greater than would be expected if units B were uniformly or homogenously distributed throughout the solid.
  • said polymeric material comprises a copolymer of structure A-[A-B] n -B there is surface blooming of units B; if it comprises a copolymer of structure A-C-A there is surface blooming of units C; and if it comprises a copolymer of structure A-B- C-A there can be surface blooming of both units B and C.
  • the concentration of units B and/or C at the surface of the solid is greater than expected.
  • Units B and/or C at the surface are then available for association with bio-compatible moieties.
  • said polymeric material may include a copolymer of a type described according to said first aspect in combination with an additional polymer or an additional copolymer.
  • Said additional polymer or copolymer may include a polymer or copolymer of units IV, V, IV* and/or V* described above with reference to the first aspect and, more preferably, includes a semi-crystalline polymer or copolymer which comprises units IV, V, IV* and/or V* .
  • a preferred additional polymer or copolymer is a polyaryletherketone which may consist essentially of units (a) , (b) , (c) , (d) or (e) described above (i.e.
  • said polymeric material includes an additional polymer and/or copolymer
  • the copolymer and additional polymer and/or copolymer are selected so that there is a tendency for the copolymer (or parts thereof) to move away from the additional polymer and/or copolymer, suitably during thermal processing, and migrate towards the surface of the solid, suitably so that there is a greater concentration of units B and/or C of said copolymer at the surface compared to if the copolymer was homogenously dispersed throughout the solid.
  • units B and/or C are available for association with bio-compatible moieties.
  • said polymeric material includes a copolymer which includes units A and B together with a copolymer which includes units A and C.
  • a copolymer which includes units A and C Suitably one of the copolymers (especially that which includes units A and B) will be arranged to predominantly migrate to the surface.
  • said polymeric material includes a copolymer which includes units A and B together with a homopolymer which includes and, preferably, consists essentially of, units A. The copolymer suitably predominantly migrates to the surface.
  • the moieties, especially units B and/or C, available at the surface immediately after thermal processing of the polymeric material may: already include functional groups
  • FG which can be functionalised to enable association with bio-compatible moieties (the aforesaid first specific embodiment illustrates this) ; already include functional groups (FG) which are in themselves bio-compatible; comprise units B and/or C which is/are in themselves bio-compatible (the aforesaid second specific embodiment illustrates this) ; or may include moieties
  • the moieties, especially units B and/or C including functional groups FG, available at the surface may, optionally, be further functionalised, for example to provide linking moieties as described above, and then treated with a material (hereinafter "BCM material") for providing a bio-compatible moiety for association with the copolymer.
  • BCM material may react and/or become associated with functional groups of said copolymer, preferably with functional groups FG as described herein.
  • BCM material may be arranged to associate a polyurethane with said copolymer.
  • said copolymer may include hydroxy groups and said BCM material provides a diisocyanate and a diol; or said copolymer may include isocyanate groups and said BCM material provides a diisocyanate and a diol. In both cases, said BCM material may be provided by two different compounds .
  • a method of making a medical device or part thereof including the step of forming a layer of a bio-compatible polymeric material on the outside of a support material, wherein said bio-compatible polymeric material is as described according to said first aspect or is made as described according to said second aspect .
  • Said support material could comprise the same copolymer which is included in the layer of bio-compatible material, suitably before any subsequent treatment to associate it with bio-compatible moieties.
  • the method may include forming a polymeric material which includes said copolymer into a shape which represents or is a precursor of a medical device or part thereof. Formation into a shape may use any suitably method, for example moulding, machining of a blank, extrusion or the like. Then, the surface of said shape is suitably treated, for example to functionalise it and/or associate bio-compatible moieties with it.
  • said support material is made out of a material which is different to that of the material of the layer of bio-compatible material, suitably before any subsequent treatment to associate it with bio- compatible moieties .
  • Said support material may be made out of any suitable material, for example of a metal, or a plastics material.
  • said support - material comprises a polymer which preferably includes a moiety of formula I and/or a moiety of formula II and/or a moiety of formula III as described above.
  • the material which is to define the support material is formed into a desired shape by a suitable method, for example moulding, machining of a blank, extrusion or the like. Then, the layer of bio- compatible material is formed on the outside of the support material.
  • a polymeric material which includes said copolymer may be contacted with said support material and caused to bond thereto. Thereafter, optionally, said copolymer may be treated, for example to functionalise it and/or associate bio-compatible moieties with it.
  • Said support material suitably has a tensile strength (according to ISO R527) of at least 80, preferably at least 90, especially at least 95 MPa.
  • the tensile strength may be less than 360, suitably less than 250, preferably less than 140 MPa. It preferably has an elongate at break (according to ISO R527) of at least 40, preferably at least 50%. It preferably has a tensile modulus (according to ISO R527) of greater than 2.5, preferably greater than 3, especially greater than 3.5 GPa.
  • the tensile modulus may be less than 40, suitably less than 30, preferably less than 20, more preferably 5 less than 10 GPa.
  • flexural strength (according to ASTM D695) of at least 100, more preferably at least 110, especially at least 115 MPa.
  • the flexural strength may be less than 650, preferably less than 400, more preferably less than 260, especially less than 200
  • ⁇ IS0 ⁇ ⁇ R178 of at “ least 37 preferably at least 3.5, especially at least 4 GPa.
  • the flexural modulus may be less than 60, suitably less than 25, preferably less than
  • aforementioned properties can be adjusted by appropriate selection of polymers and/or any reinforcement means included in said support material to suit particular applications.
  • a continuous carbon fibre polyetheretherketone may typically have a tensile strength
  • a polyaryletherketone with 30% of high performance fibres may typically have a tensile strength of 224 MPa, a tensile modulus of 13 GPa,
  • the invention extends to a method of making a medical device or part thereof, the method comprising: forming a 30 material into a shape which represents or is a precursor of a device for use in medical applications wherein said material comprises a polymer; and treating material in said shape in order to define a layer on the outside of said shape, wherein said layer includes a bio-compatible polymeric material as described according to said first aspect .
  • the invention further extends to a device for use in medical applications, wherein said device comprises a bio- compatible polymeric material as described in any statement herein.
  • Said device suitably includes a support material and a """” Bio " compatible " po-lymer c- aterial-on-t " he”” ⁇ utside thereof .
  • Said device is preferably a prosthetic device, for example an implant such as an orthopaedic, dental or maxillofacial implant or a component thereof; or a device, for example a catheter, which is arranged to be temporarily associated with a human or animal body.
  • Said device is preferably a prosthetic device as described.
  • An orthopaedic device may be an implant for a body joint, for example a hip or knee joint or spine fusion device.
  • a said device may include a part or parts made out of said bio-compatible polymeric material and a part or parts made out of other materials.
  • said device includes at least 50wt%, preferably at least 65wt%, more preferably at least 80wt%, especially at least 95wt% of said bio-compatible polymeric material.
  • said device may consist essential of said bio- compatible polymeric material .
  • the invention extends to a method of making a medical device or part thereof, the method including the step of forming a layer (hereinafter an "X-ray contrast layer”) on the outside of a support material, wherein said layer includes an X-ray contrast medium.
  • a layer hereinafter an "X-ray contrast layer”
  • Said X-ray contrast layer may have any feature of a layer which includes a said bio-compatible polymeric material described herein.
  • Said support material may have any feature of a said support material described in any statement herein.
  • said support material includes a lower amount of X-ray contrast medium than said X-ray contrast layer.
  • said support material includes substantially no X-ray contrast medium.
  • Copolymers prepared as described in Examples I to V may be as follows :
  • Example I The copolymers B units contain chemical moieties that allow efficient and cost effective attachment of molecules that have enhanced biocompatability / bio-activity.
  • Example II The copolymer B units already contain moieties that have enhanced biocompatability / bio- activity.
  • Example III The copolymer contains amorphous polyaryletherketone, C units that are either dispersed throughout the bulk of the material or in phase domains . — he—amorphous—-units -allow -efficient -and cost effective attachment of molecules that enhance biological activity or biocompatability.
  • Example IV The copolymer contains A, B and C units that are either dispersed throughout the bulk of the material or in phase domains.
  • the B units can give the benefits described for Example I and II combined with the added functionality described in Example III or the ability to add a second biologically functional molecule (or attachment species) to amorphous units.
  • Example (V) A copolymer of A and B units blended with a copolymer of A and C units or A homopolymer.
  • the copolymer of A and B units will give the advantages described for Examples I and II and in some embodiments the copolymer will be sufficiently dissimilar to that constructed from A and C units (the other blend constituent) that it will phase separate and be prevalent on the surface.
  • the copolymer of A and C units will have the advantage described in Example III.
  • Example la Preparation of polyetheretherketone/PEN copolymer
  • the reaction mixture was allowed to cool, milled and washed with acetone and water.
  • the resulting polymer was dried in an air oven at 120°C.
  • the polymer had an IV of 1.15 and a Melt Viscosity (MV) of 0.37kNsm "2 measured at 400°C on a ram extruder at a shear rate of 1000 s "1 .
  • a film of the polymer from Example la 5cm x 2cm x 120 ⁇ m was prepared by compression moulding at 400°C for 5
  • Example lb The surface modified polyetheretherketone/PEN of Example lb was stirred at 10°C for 1 hr under an atmosphere of nitrogen in an aqueous solution of the water soluble carbodiimide, l-ethyl-3- (3-dimethylaminopropyl) - carbodiimide) (0.4g) dissolved in buffer at pH 4.5 (0.1M 2-
  • the sample was stirred at 20°C for 24 hr under an atmosphere of nitrogen in a solution of the peptide GRGDS (160mg) in phosphate-buffered saline solution (40ml) (Na 2 HP0 4 , 1.15g; KH 2 P0 4 , 0.2g; NaCl . 8g; KC1, 0.2g ; MgCl 2 , O.lg; CaCl 2 . 0. lg in 1 Litre of distilled water).
  • the functionalised polyetheretherketone/PEN was washed successively with phosphate buffer and distilled water.
  • the reaction mixture was allowed to cool, milled and washed with acetone and water.
  • the resulting polymer was dried in an air oven at 120°C.
  • the polymer had an IV of 0.41 and a Mn of 5000.
  • thermocouple A thoroughly dried 700ml flanged flask fitted with a ground glass Quickfit lid, stirrer/stirrer guide, nitrogen inlet and outlet and a thermocouple was charged with the polymer of Example Ila (30. Og, 0.006 mole) and 1- chloronaphthalene (450ml) , heated to 150°C and purged with nitrogen for 1 hour. The contents were heated under a nitrogen blanket to 240°C then a solution of bisdimethylamine-terminated polydimethylsiloxane (Mn 4800) (29.3g, 0.0061 mole) in 1-chloronaphthalene (50ml) was added over a period of 2 hours, while maintaining a nitrogen blanket. The temperature was held at 240°C for 90 mins after the addition was complete.
  • Mn 4800 bisdimethylamine-terminated polydimethylsiloxane
  • reaction mixture was allowed to cool to room temperature.
  • product was precipitated by pouring the reaction mixture into methanol (2.5 litres), recovered by filtration and dried under vacuum at 80°C for 16 hours.
  • a 1 litre round-bottomed flask fitted with a stirrer/stirrer guide, a solids addition funnel, nitrogen inlet and outlet and a thermocouple was charged with 1,2- dichloroethane (350ml), 3-fluorobenzoyl chloride (42.5g, 0.268 mole), diphenylether (68.08g, 0.4 mole) and isophthaloyl chloride (54.4g, 0.268 mole).
  • the additional funnel was charged with aluminium chloride (150.08g, 1.126 mole) and added gradually to the solution, under an atmosphere of nitrogen, so the temperature was maintained at 5°C. The mixture was allowed to warm up to room temperature, held for 1 hour, heated to 75°C and held for 5 hours.
  • the reaction mixture was homogeneous and viscous. It was allowed to cool to room temperature, then poured into cold, dilute hydrochloric acid (1 litre) . The suspension was distilled to remove 1, 2-dichloroethane. The crude product was recovered by filtration, washed with methanol, deionised water until the washings were neutral, then finally with methanol and dried at 50°C .under vacuum.
  • reaction solution was transferred via cannulae to a test tube containing PEKmK/polyetheretherketone film of
  • the solution was then allowed to warm to room temperature and stirred for a further 24 hours .
  • the films were then removed and washed with isopropanol (3 x 50ml) , methanol (3 x 50ml) and acetone (2 x 50ml) before being dried at room temperature for 24h.
  • the dried film was placed in a 250ml round bottomed flask fitted with a reflux condenser. To the flask was added 80ml of a 10% aqueous sodium hydroxide and 15ml of ethanol in order to facilitate complete hydrolysis of the nitrile to the carboxylic acid. The solution was heated to reflux for 12-24 hours in order to ensure complete hydrolysis. The solution was cooled and the film removed and placed in a solution of glacial acetic acid followed by washing with 2M HC1 and distilled water. The sample was dried at room temperature overnight .
  • Example Hid Reaction of surface modified PEKmK/polyetheretherketone containing carboxylic acid groups with the peptide GRGDS The surface modified PEKmK/polyetheretherketone of Example IIIc was stirred at 10°C for 1 hr under an atmosphere of nitrogen in an aqueous solution of the water soluble carbodiimide, l-ethyl-3- (3-dimethylaminopropyl) - carbodiimide) (0.4g) dissolved in buffer at pH 4.5 (0.1M 2- (N-morpholino) ethanesulphonic acid) (40ml) . The sample of PEKmK/polyetheretherketone was removed and washed with buffer solution.
  • Example IVc Preparation of polyethereth ⁇ rketone/PEKEI copolymers
  • a 700ml flanged flask fitted with a ground glass Quickfit lid, stirrer/stirrer guide, a nitrogen inlet and outlet and a thermocouple was charged with the product from Example IVb (26.97g, 0.03 mole), 4,4'- difluorobenzophenone (59.90g, 0.2745 mole), hydroquinone (33.03g, 0.30 mole) and diphenysulphone (180. Og) and purged with nitrogen for over 1 hour.
  • the contents were then heated under a nitrogen blanket to between 140 and 150°C to form an almost colourless solution. While maintaining a nitrogen blanket, dried sodium carbonate
  • the reaction mixture was allowed to cool, milled and washed with acetone and water.
  • the resulting polymer was dried in an air oven at 120°C.
  • the polymer had Inherent Viscosity (IV) of 1.21. IV is measured at 25°C on a solution of polymer in concentrated sulphuric acid of density 1.84gcm 3 , said solution containing 0. Ig of polymer per 100cm 3 of solution.
  • a Melt Viscosity (MV) of 0.43kNs ⁇ rf 2 measured at 400°C on a ram extruder at a shear rate of 1000 s "1 .
  • a dried film of the copolymer from Example IVd (5cm x 1 cm x 120 ⁇ m) was placed in a 250ml round bottomed flask fitted with a reflux condenser. To the flask was added 80ml of a 30% aqueous sodium hydroxide and 15ml of ethanol in order to facilitate the hydrolysis of the imide to the amic acid. The solution was heated to reflux for 24 hours. The solution was cooled and the film removed and placed in a solution of glacial acetic acid followed by washing with 2M HCl and distilled water. The sample was dried at room temperature overnight .
  • the surface modified polyetheretherketone/PEKEI from Example IVd was stirred at 10°C for 1 hr under an atmosphere of nitrogen in an aqueous solution of the water soluble carbodiimide, l-ethyl-3- (3-dimethylaminopropyl) - carbodiimide) (0.4g) dissolved in buffer at pH 4.5 (0.1M 2-
  • the sample was stirred at 20°C for 24 hr under an atmosphere of nitrogen in a solution of the peptide GRGDS (160mg) in phosphate-buffered saline solution (40ml) (Na 2 HP0 4 , 1.15g; KH 2 P0 4 , 0.2g; NaCl . 8g; KC1 , 0.2g; MgCl 2 , O.lg; CaCl 2 . 0. Ig in 1 Litre of distilled water).
  • the functionalised polyetheretherketone/PEKEI was washed successively with phosphate buffer and distilled water.
  • Example Va The blend of polyetheretherketone/PEN copolymer with polyaryletheretherketone
  • Example la 5 kg of the copolymer polyetheretherketone/PEN were prepared as described in Example la. These materials were in the form of a microporous polymeric flake. The flake was feed into the 32 mm cm single screw extruder to form a lace of densified polymer. The extruded lace was cooled in air post extruder and pellitised producing pellets of approximately 3 mm length and 2.5 mm diameter. These pellets were placed in clean aluminium trays at a depth of approximately 2.5 cm. The trays were placed in an air- circulating oven at 130 °C for 5 hours.
  • the resultant mixture was fed using a Brabender loss in weight feeder into a 25 mm KrausMaffei twin screw extruder.
  • the blended polymer was then extruded to form a lace that was cooled and pelletised as previously detailed.
  • the polymer blend was then injection moulded using a Neggri Bossi 100 tonnes clamping force moulder to form 150 mm x 150 mm x 6 mm plaques. These plaques were then treated in methods analogous to examples lb and Ic.
  • Example Vb The blend of PEKmK/polyetheretherketone Block Copolymer with polyetheretherketone/PEN copolymer
  • Example Vb is substantially similar to example Va except for the following; the PEKmK/polyetheretherketone block copolymer was prepared as described in example Illb and supplied as a micorporous flake. This flake was denisfied using a 32 mm single screw extruder as previously discussed. These pellets were dried and tumbled blended with an equal weight of' the densified polyetheretherketone/PEN copolymer. The premixture was then blended using a twin screw extruder and injection moulded as previously discussed. The plaques produced were treated in methods analogous to examples IB and IC.
  • Example Vc The blend of PEKmK/polyetheretherketone Block Copolymer with polyaryletheretherketone
  • Example Vc is substantially similar to example Vb except for the following; the PEKmK/polyetheretherketone block copolymer was prepared as described in example Illb and supplied as a micorporous flake. This flake was denisfied using a 32 mm single screw extruder as previously discussed. These pellets were dried and tumbled blended with an equal weight of the densified polyaryletheretherketone 381G supplied by Victrex pic. The premixture was then blended using a twin screw extruder and injection moulded as previously discussed.

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Abstract

L'invention concerne un matériau polymère biocompatible à utiliser dans des applications médicales, par exemple dans un implant orthopédique, qui comprend un copolymère comportant une unité A en combinaison avec une unité B et/ou une unité C. Dans ce matériau polymère, des fractions biocompatibles sont associées audit copolymère et A représente une fraction de polyaryléthercétone semi-cristalline (en particulier le polyétheréthercétone), B représente une unité qui est incompatible avec l'unité A (par ex. le diméthylpolysiloxane) et C représente une unité de polyaryléthercétone ou de polyaryléther sulfone amorphe. L'invention concerne également des procédés de préparation, des procédés d'utilisation et des dispositifs incorporant ce matériau polymère.
PCT/GB2001/002792 2000-06-24 2001-06-22 Materiaux polymeres biocompatibles WO2002002158A1 (fr)

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Cited By (68)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1813292A1 (fr) * 2006-01-25 2007-08-01 Inion Oy Implant chirurgical et procédé de fabrication
US7670282B2 (en) 2004-06-14 2010-03-02 Pneumrx, Inc. Lung access device
US7674293B2 (en) 2004-04-22 2010-03-09 Facet Solutions, Inc. Crossbar spinal prosthesis having a modular design and related implantation methods
WO2010030993A1 (fr) 2008-09-12 2010-03-18 Pneumrx, Inc. Modèles améliorés et/ou rallongés de dispositifs de réduction de volume pulmonaire à effraction minimale et leur mise en place
US7691145B2 (en) 1999-10-22 2010-04-06 Facet Solutions, Inc. Prostheses, systems and methods for replacement of natural facet joints with artificial facet joint surfaces
US7766891B2 (en) 2004-07-08 2010-08-03 Pneumrx, Inc. Lung device with sealing features
US7766938B2 (en) 2004-07-08 2010-08-03 Pneumrx, Inc. Pleural effusion treatment device, method and material
WO2010135352A1 (fr) 2009-05-18 2010-11-25 Pneumrx, Inc. Modification de section transversale durant le déploiement d'un dispositif allongé de réduction du volume pulmonaire
US7846162B2 (en) 2005-05-18 2010-12-07 Sonoma Orthopedic Products, Inc. Minimally invasive actuable bone fixation devices
EP2292188A2 (fr) 2002-11-27 2011-03-09 Conformis, Inc. Outils chirurgicaux pouvant etre selectionnes en fonction du patient
US7909825B2 (en) 2006-11-22 2011-03-22 Sonoma Orthepedic Products, Inc. Fracture fixation device, tools and methods
US7914556B2 (en) 2005-03-02 2011-03-29 Gmedelaware 2 Llc Arthroplasty revision system and method
EP2324799A2 (fr) 2004-11-24 2011-05-25 Conformis, Inc. Dispositifs d'arthroplastie de l'articulation du genou, sélectionnables selon le patient
EP2335654A1 (fr) 2003-11-25 2011-06-22 Conformis, Inc. Dispositifs d'arthroplastie d'articulation du genou selectionnables selon le patient
WO2011082149A1 (fr) 2009-12-31 2011-07-07 Sabic Innovative Plastics Ip B.V. Fil électrique comprenant une polycétone aromatique et une composition de copolymère séquencé polysiloxane/polyimide
US8013076B2 (en) 2008-03-17 2011-09-06 Sabic Innovative Plastics Ip B.V. Aromatic polyketone and polysiloxane/polyimide block copolymer composition
US8070811B2 (en) 1999-10-22 2011-12-06 Gmedelaware 2 Llc Facet arthroplasty devices and methods
USRE43282E1 (en) 1998-09-14 2012-03-27 The Board Of Trustees Of The Leland Stanford Junior University Assessing the condition of a joint and devising treatment
US8157837B2 (en) 2006-03-13 2012-04-17 Pneumrx, Inc. Minimally invasive lung volume reduction device and method
US8187303B2 (en) 2004-04-22 2012-05-29 Gmedelaware 2 Llc Anti-rotation fixation element for spinal prostheses
CN102492132A (zh) * 2011-12-09 2012-06-13 中橡集团炭黑工业研究设计院 含氰基聚芳醚酮类共聚物及其制备方法
US8221461B2 (en) 2004-10-25 2012-07-17 Gmedelaware 2 Llc Crossbar spinal prosthesis having a modular design and systems for treating spinal pathologies
US8231655B2 (en) 2003-07-08 2012-07-31 Gmedelaware 2 Llc Prostheses and methods for replacement of natural facet joints with artificial facet joint surfaces
US8287539B2 (en) 2005-05-18 2012-10-16 Sonoma Orthopedic Products, Inc. Fracture fixation device, tools and methods
EP2520255A1 (fr) 2005-11-21 2012-11-07 Vertegen, Inc. Dispositifs et procédés de traitement de facettes articulaires lombaires, d'articulations uncovertébrales, d'articulations costovertébrales et d'autres articulations
US8398681B2 (en) 2004-08-18 2013-03-19 Gmedelaware 2 Llc Adjacent level facet arthroplasty devices, spine stabilization systems, and methods
US8409254B2 (en) 2003-05-14 2013-04-02 Gmedelaware 2 Llc Prostheses, tools and methods for replacement of natural facet joints with artificial facet joint surfaces
US8496686B2 (en) 2005-03-22 2013-07-30 Gmedelaware 2 Llc Minimally invasive spine restoration systems, devices, methods and kits
WO2013131066A1 (fr) 2012-03-02 2013-09-06 Conformis, Inc. Implants du genou stabilisés postérieurs adaptés au patient, conceptions et procédés et outils associés
WO2013148943A2 (fr) 2012-03-30 2013-10-03 Sabic Innovative Plastics Ip B.V. Compresseurs incluant des composants polymères
EP2649951A2 (fr) 2006-02-06 2013-10-16 ConforMIS, Inc. Dispositifs d'arthroplastie articulaire et outils chirurgicaux selectionnables par le patient
US8675930B2 (en) 2004-04-22 2014-03-18 Gmedelaware 2 Llc Implantable orthopedic device component selection instrument and methods
US8702755B2 (en) 2006-08-11 2014-04-22 Gmedelaware 2 Llc Angled washer polyaxial connection for dynamic spine prosthesis
EP2754419A2 (fr) 2011-02-15 2014-07-16 Conformis, Inc. Implants orthopédiques améliorés et adaptés au patient, conceptions et outils associés
WO2014151557A2 (fr) 2013-03-15 2014-09-25 Pneumrx, Inc. Structures d'implant compressif à réduction de volume pulmonaire dans les voies aériennes à soulagement de couple
US8862202B2 (en) 1998-09-14 2014-10-14 The Board Of Trustees Of The Leland Stanford Junior University Assessing the condition of a joint and preventing damage
US8888800B2 (en) 2006-03-13 2014-11-18 Pneumrx, Inc. Lung volume reduction devices, methods, and systems
US8951260B2 (en) 2001-05-25 2015-02-10 Conformis, Inc. Surgical cutting guide
US8961516B2 (en) 2005-05-18 2015-02-24 Sonoma Orthopedic Products, Inc. Straight intramedullary fracture fixation devices and methods
US9017334B2 (en) 2009-02-24 2015-04-28 Microport Orthopedics Holdings Inc. Patient specific surgical guide locator and mount
US9023050B2 (en) 2001-05-25 2015-05-05 Conformis, Inc. Surgical tools for arthroplasty
US9055953B2 (en) 2001-05-25 2015-06-16 Conformis, Inc. Methods and compositions for articular repair
US9056016B2 (en) 2003-12-15 2015-06-16 Gmedelaware 2 Llc Polyaxial adjustment of facet joint prostheses
US9060820B2 (en) 2005-05-18 2015-06-23 Sonoma Orthopedic Products, Inc. Segmented intramedullary fracture fixation devices and methods
US9066728B2 (en) 2001-05-25 2015-06-30 Conformis, Inc. Surgical tools facilitating increased accuracy, speed and simplicity in performing joint arthroplasty
WO2015114427A1 (fr) 2014-01-31 2015-08-06 Sabic Global Technologies B.V. Composite fibre
US9125639B2 (en) 2004-11-23 2015-09-08 Pneumrx, Inc. Steerable device for accessing a target site and methods
US9155574B2 (en) 2006-05-17 2015-10-13 Sonoma Orthopedic Products, Inc. Bone fixation device, tools and methods
US9198766B2 (en) 2003-05-14 2015-12-01 Gmedelaware 2 Llc Prostheses, tools, and methods for replacement of natural facet joints with artificial facet joint surfaces
CN105175714A (zh) * 2015-09-23 2015-12-23 中橡集团炭黑工业研究设计院 一种制备氰基聚芳醚酮树脂的工艺方法
US9286686B2 (en) 1998-09-14 2016-03-15 The Board Of Trustees Of The Leland Stanford Junior University Assessing the condition of a joint and assessing cartilage loss
US9308053B2 (en) 2006-02-06 2016-04-12 Conformis, Inc. Patient-specific joint arthroplasty devices for ligament repair
US9326780B2 (en) 2006-02-06 2016-05-03 Conformis, Inc. Patient selectable joint arthroplasty devices and surgical tools incorporating anatomical relief
US9402633B2 (en) 2006-03-13 2016-08-02 Pneumrx, Inc. Torque alleviating intra-airway lung volume reduction compressive implant structures
US9486226B2 (en) 2012-04-18 2016-11-08 Conformis, Inc. Tibial guides, tools, and techniques for resecting the tibial plateau
US9579110B2 (en) 2001-05-25 2017-02-28 Conformis, Inc. Patient selectable joint arthroplasty devices and surgical tools
US9642632B2 (en) 2009-02-24 2017-05-09 Microport Orthopedics Holdings Inc. Orthopedic surgical guide
US9649117B2 (en) 2009-02-24 2017-05-16 Microport Orthopedics Holdings, Inc. Orthopedic surgical guide
US9675471B2 (en) 2012-06-11 2017-06-13 Conformis, Inc. Devices, techniques and methods for assessing joint spacing, balancing soft tissues and obtaining desired kinematics for joint implant components
EP3187153A2 (fr) 2005-09-30 2017-07-05 Conformis, Inc. Implant porteur
US9770278B2 (en) 2014-01-17 2017-09-26 Arthrex, Inc. Dual tip guide wire
US9801637B2 (en) 2006-03-13 2017-10-31 Pneumrx, Inc. Genetically-associated chronic obstructive pulmonary disease treatment
US9814499B2 (en) 2014-09-30 2017-11-14 Arthrex, Inc. Intramedullary fracture fixation devices and methods
US10390838B1 (en) 2014-08-20 2019-08-27 Pneumrx, Inc. Tuned strength chronic obstructive pulmonary disease treatment
US10537334B2 (en) 2013-10-25 2020-01-21 Pneumrx, Inc. Genetically-associated chronic obstructive pulmonary disease treatment
RU2716677C1 (ru) * 2018-12-03 2020-03-13 Федеральное государственное бюджетное образовательное учреждение высшего образования Санкт-Петербургская государственная академия ветеринарной медицины ФГБОУ ВО СПбГАВМ Способ изготовления анатомических копий костей методом отливки в силиконовой форме
WO2022230934A1 (fr) * 2021-04-27 2022-11-03 出光興産株式会社 Polyétheréthercétone, et procédé de fabrication de celui-ci
US12108959B2 (en) 2019-05-29 2024-10-08 Wright Medical Technology, Inc. Preparing a tibia for receiving tibial implant component of a replacement ankle

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4774296A (en) * 1985-05-02 1988-09-27 Amoco Corporation Block polymers containing a poly(aryl ether ketone) and methods for their production
US4968758A (en) * 1988-08-22 1990-11-06 Amoco Corporation Poly(aryl ether sulfone)-poly(aryl ether ketone) block copolymers block copolymers
WO1992007894A1 (fr) * 1990-10-26 1992-05-14 Raychem Limited Copolymeres ether-cetone-sulfone
EP0659389A1 (fr) * 1993-10-20 1995-06-28 Schneider (Europe) Ag Endoprothèse

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4774296A (en) * 1985-05-02 1988-09-27 Amoco Corporation Block polymers containing a poly(aryl ether ketone) and methods for their production
US4968758A (en) * 1988-08-22 1990-11-06 Amoco Corporation Poly(aryl ether sulfone)-poly(aryl ether ketone) block copolymers block copolymers
WO1992007894A1 (fr) * 1990-10-26 1992-05-14 Raychem Limited Copolymeres ether-cetone-sulfone
EP0659389A1 (fr) * 1993-10-20 1995-06-28 Schneider (Europe) Ag Endoprothèse

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CORFIELD G C ET AL: "SYNTHESIS AND PROPERTIES OF POLYETHERETHERKETONE- POLYDIMETHYLSILOXANE BLOCK COPOLYMERS", JOURNAL OF POLYMER SCIENCE, POLYMER CHEMISTRY EDITION, JOHN WILEY AND SONS. NEW YORK, US, vol. 28, no. 10, 1 September 1990 (1990-09-01), pages 2821 - 2836, XP000167855, ISSN: 0887-624X *
RISCH B G ET AL: "Structure-property behaviour of poly(ether ether ketone)-polydimethylsiloxane block copolymers and their ketamine precursors", POLYMER, ELSEVIER SCIENCE PUBLISHERS B.V, GB, vol. 37, no. 7, 1 March 1996 (1996-03-01), pages 1229 - 1242, XP004069364, ISSN: 0032-3861 *

Cited By (140)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8862202B2 (en) 1998-09-14 2014-10-14 The Board Of Trustees Of The Leland Stanford Junior University Assessing the condition of a joint and preventing damage
USRE43282E1 (en) 1998-09-14 2012-03-27 The Board Of Trustees Of The Leland Stanford Junior University Assessing the condition of a joint and devising treatment
US9286686B2 (en) 1998-09-14 2016-03-15 The Board Of Trustees Of The Leland Stanford Junior University Assessing the condition of a joint and assessing cartilage loss
US8066740B2 (en) 1999-10-22 2011-11-29 Gmedelaware 2 Llc Facet joint prostheses
US8092532B2 (en) 1999-10-22 2012-01-10 Gmedelaware 2 Llc Facet arthroplasty devices and methods
US7691145B2 (en) 1999-10-22 2010-04-06 Facet Solutions, Inc. Prostheses, systems and methods for replacement of natural facet joints with artificial facet joint surfaces
US8070811B2 (en) 1999-10-22 2011-12-06 Gmedelaware 2 Llc Facet arthroplasty devices and methods
US9186161B2 (en) 2001-05-25 2015-11-17 Conformis, Inc. Surgical tools for arthroplasty
US9055953B2 (en) 2001-05-25 2015-06-16 Conformis, Inc. Methods and compositions for articular repair
US9125672B2 (en) 2001-05-25 2015-09-08 Conformis, Inc. Joint arthroplasty devices and surgical tools
US9579110B2 (en) 2001-05-25 2017-02-28 Conformis, Inc. Patient selectable joint arthroplasty devices and surgical tools
US8951260B2 (en) 2001-05-25 2015-02-10 Conformis, Inc. Surgical cutting guide
US9125673B2 (en) 2001-05-25 2015-09-08 Conformis, Inc. Joint arthroplasty devices and surgical tools
US9107680B2 (en) 2001-05-25 2015-08-18 Conformis, Inc. Patient selectable joint arthroplasty devices and surgical tools
US9107679B2 (en) 2001-05-25 2015-08-18 Conformis, Inc. Patient selectable joint arthroplasty devices and surgical tools
US9084617B2 (en) 2001-05-25 2015-07-21 Conformis, Inc. Patient selectable joint arthroplasty devices and surgical tools
US9072531B2 (en) 2001-05-25 2015-07-07 Conformis, Inc. Patient selectable joint arthroplasty devices and surgical tools
US8951259B2 (en) 2001-05-25 2015-02-10 Conformis, Inc. Patient selectable joint arthroplasty devices and surgical tools
US9066728B2 (en) 2001-05-25 2015-06-30 Conformis, Inc. Surgical tools facilitating increased accuracy, speed and simplicity in performing joint arthroplasty
US8998915B2 (en) 2001-05-25 2015-04-07 Conformis, Inc. Joint arthroplasty devices and surgical tools
US9023050B2 (en) 2001-05-25 2015-05-05 Conformis, Inc. Surgical tools for arthroplasty
US9358018B2 (en) 2001-05-25 2016-06-07 Conformis, Inc. Joint arthroplasty devices and surgical tools
US9216025B2 (en) 2001-05-25 2015-12-22 Conformis, Inc. Joint arthroplasty devices and surgical tools
US9295482B2 (en) 2001-05-25 2016-03-29 Conformis, Inc. Patient selectable joint arthroplasty devices and surgical tools
EP2292189A2 (fr) 2002-11-27 2011-03-09 Conformis, Inc. Outils chirurgicaux pouvant etre selectionnes en fonction du patient
EP2292188A2 (fr) 2002-11-27 2011-03-09 Conformis, Inc. Outils chirurgicaux pouvant etre selectionnes en fonction du patient
US9198766B2 (en) 2003-05-14 2015-12-01 Gmedelaware 2 Llc Prostheses, tools, and methods for replacement of natural facet joints with artificial facet joint surfaces
US8409254B2 (en) 2003-05-14 2013-04-02 Gmedelaware 2 Llc Prostheses, tools and methods for replacement of natural facet joints with artificial facet joint surfaces
US8231655B2 (en) 2003-07-08 2012-07-31 Gmedelaware 2 Llc Prostheses and methods for replacement of natural facet joints with artificial facet joint surfaces
US8523907B2 (en) 2003-07-08 2013-09-03 Gmedelaware 2 Llc Prostheses, tools and methods for replacement of natural facet joints with artificial facet joint surfaces
EP2335654A1 (fr) 2003-11-25 2011-06-22 Conformis, Inc. Dispositifs d'arthroplastie d'articulation du genou selectionnables selon le patient
US9056016B2 (en) 2003-12-15 2015-06-16 Gmedelaware 2 Llc Polyaxial adjustment of facet joint prostheses
US8425557B2 (en) 2004-04-22 2013-04-23 Gmedelaware 2 Llc Crossbar spinal prosthesis having a modular design and related implantation methods
US8675930B2 (en) 2004-04-22 2014-03-18 Gmedelaware 2 Llc Implantable orthopedic device component selection instrument and methods
US8187303B2 (en) 2004-04-22 2012-05-29 Gmedelaware 2 Llc Anti-rotation fixation element for spinal prostheses
US8491635B2 (en) 2004-04-22 2013-07-23 Gmedelaware 2 Llc Crossbar spinal prosthesis having a modular design and related implantation methods
US8496687B2 (en) 2004-04-22 2013-07-30 Gmedelaware 2 Llc Crossbar spinal prosthesis having a modular design and related implantation methods
US7674293B2 (en) 2004-04-22 2010-03-09 Facet Solutions, Inc. Crossbar spinal prosthesis having a modular design and related implantation methods
US7775968B2 (en) 2004-06-14 2010-08-17 Pneumrx, Inc. Guided access to lung tissues
US7670282B2 (en) 2004-06-14 2010-03-02 Pneumrx, Inc. Lung access device
US7766938B2 (en) 2004-07-08 2010-08-03 Pneumrx, Inc. Pleural effusion treatment device, method and material
US7766891B2 (en) 2004-07-08 2010-08-03 Pneumrx, Inc. Lung device with sealing features
US8398681B2 (en) 2004-08-18 2013-03-19 Gmedelaware 2 Llc Adjacent level facet arthroplasty devices, spine stabilization systems, and methods
US8221461B2 (en) 2004-10-25 2012-07-17 Gmedelaware 2 Llc Crossbar spinal prosthesis having a modular design and systems for treating spinal pathologies
US10034999B2 (en) 2004-11-23 2018-07-31 Pneumrx, Inc. Steerable device for accessing a target site and methods
US9125639B2 (en) 2004-11-23 2015-09-08 Pneumrx, Inc. Steerable device for accessing a target site and methods
EP2324799A2 (fr) 2004-11-24 2011-05-25 Conformis, Inc. Dispositifs d'arthroplastie de l'articulation du genou, sélectionnables selon le patient
US7914556B2 (en) 2005-03-02 2011-03-29 Gmedelaware 2 Llc Arthroplasty revision system and method
US8496686B2 (en) 2005-03-22 2013-07-30 Gmedelaware 2 Llc Minimally invasive spine restoration systems, devices, methods and kits
US8961516B2 (en) 2005-05-18 2015-02-24 Sonoma Orthopedic Products, Inc. Straight intramedullary fracture fixation devices and methods
US7942875B2 (en) 2005-05-18 2011-05-17 Sonoma Orthopedic Products, Inc. Methods of using minimally invasive actuable bone fixation devices
US7914533B2 (en) 2005-05-18 2011-03-29 Sonoma Orthopedic Products, Inc. Minimally invasive actuable bone fixation devices
US9060820B2 (en) 2005-05-18 2015-06-23 Sonoma Orthopedic Products, Inc. Segmented intramedullary fracture fixation devices and methods
US8287539B2 (en) 2005-05-18 2012-10-16 Sonoma Orthopedic Products, Inc. Fracture fixation device, tools and methods
US7846162B2 (en) 2005-05-18 2010-12-07 Sonoma Orthopedic Products, Inc. Minimally invasive actuable bone fixation devices
US8287541B2 (en) 2005-05-18 2012-10-16 Sonoma Orthopedic Products, Inc. Fracture fixation device, tools and methods
EP3187153A2 (fr) 2005-09-30 2017-07-05 Conformis, Inc. Implant porteur
EP2520255A1 (fr) 2005-11-21 2012-11-07 Vertegen, Inc. Dispositifs et procédés de traitement de facettes articulaires lombaires, d'articulations uncovertébrales, d'articulations costovertébrales et d'autres articulations
EP1813292A1 (fr) * 2006-01-25 2007-08-01 Inion Oy Implant chirurgical et procédé de fabrication
US9326780B2 (en) 2006-02-06 2016-05-03 Conformis, Inc. Patient selectable joint arthroplasty devices and surgical tools incorporating anatomical relief
EP2671520A2 (fr) 2006-02-06 2013-12-11 ConforMIS, Inc. Dispositifs d'arthroplastie articulaire et outils chirurgicaux selectionnables par le patient
US9308053B2 (en) 2006-02-06 2016-04-12 Conformis, Inc. Patient-specific joint arthroplasty devices for ligament repair
EP2649951A2 (fr) 2006-02-06 2013-10-16 ConforMIS, Inc. Dispositifs d'arthroplastie articulaire et outils chirurgicaux selectionnables par le patient
US9220517B2 (en) 2006-02-06 2015-12-29 Conformis, Inc. Patient selectable joint arthroplasty devices and surgical tools
EP2671521A2 (fr) 2006-02-06 2013-12-11 ConforMIS, Inc. Dispositifs d'arthroplastie articulaire et outils chirurgicaux selectionnables par le patient
US9220516B2 (en) 2006-02-06 2015-12-29 Conformis, Inc. Patient selectable joint arthroplasty devices and surgical tools
EP2710967A2 (fr) 2006-02-06 2014-03-26 ConforMIS, Inc. Dispositifs d'arthroplastie articulaire et outils chirurgicaux selectionnables par le patient
EP2671522A2 (fr) 2006-02-06 2013-12-11 ConforMIS, Inc. Dispositifs d'arthroplastie articulaire et outils chirurgicaux selectionnables par le patient
US8157837B2 (en) 2006-03-13 2012-04-17 Pneumrx, Inc. Minimally invasive lung volume reduction device and method
US9801637B2 (en) 2006-03-13 2017-10-31 Pneumrx, Inc. Genetically-associated chronic obstructive pulmonary disease treatment
EP3167821A1 (fr) 2006-03-13 2017-05-17 PneumRx, Inc. Dispositifs de réduction du volume pulmonaire
US10226257B2 (en) 2006-03-13 2019-03-12 Pneumrx, Inc. Lung volume reduction devices, methods, and systems
US9474533B2 (en) 2006-03-13 2016-10-25 Pneumrx, Inc. Cross-sectional modification during deployment of an elongate lung volume reduction device
US10188397B2 (en) 2006-03-13 2019-01-29 Pneumrx, Inc. Torque alleviating intra-airway lung volume reduction compressive implant structures
EP3143962A1 (fr) 2006-03-13 2017-03-22 Pneumrx, Inc. Dispositifs, procédés et systèmes de réduction du volume pulmonaire invasif minimal
EP2842501A1 (fr) 2006-03-13 2015-03-04 Pneumrx, Inc. Dispositifs, procédés et systèmes de réduction du volume pulmonaire invasif minimal
DE202007019683U1 (de) 2006-03-13 2015-09-16 PNEUMRX. lnc. Minimalinvasive Lungenvolumenreduktionsvorrichtungen und -systeme
US8888800B2 (en) 2006-03-13 2014-11-18 Pneumrx, Inc. Lung volume reduction devices, methods, and systems
US9402632B2 (en) 2006-03-13 2016-08-02 Pneumrx, Inc. Lung volume reduction devices, methods, and systems
US9402633B2 (en) 2006-03-13 2016-08-02 Pneumrx, Inc. Torque alleviating intra-airway lung volume reduction compressive implant structures
US9402971B2 (en) 2006-03-13 2016-08-02 Pneumrx, Inc. Minimally invasive lung volume reduction devices, methods, and systems
US9782558B2 (en) 2006-03-13 2017-10-10 Pneumrx, Inc. Minimally invasive lung volume reduction devices, methods, and systems
US8932310B2 (en) 2006-03-13 2015-01-13 Pneumrx, Inc. Minimally invasive lung volume reduction devices, methods, and systems
US9155574B2 (en) 2006-05-17 2015-10-13 Sonoma Orthopedic Products, Inc. Bone fixation device, tools and methods
US8702755B2 (en) 2006-08-11 2014-04-22 Gmedelaware 2 Llc Angled washer polyaxial connection for dynamic spine prosthesis
US7909825B2 (en) 2006-11-22 2011-03-22 Sonoma Orthepedic Products, Inc. Fracture fixation device, tools and methods
US9259250B2 (en) 2006-11-22 2016-02-16 Sonoma Orthopedic Products, Inc. Fracture fixation device, tools and methods
US8013076B2 (en) 2008-03-17 2011-09-06 Sabic Innovative Plastics Ip B.V. Aromatic polyketone and polysiloxane/polyimide block copolymer composition
US8013251B2 (en) 2008-03-17 2011-09-06 Sabic Innovative Plastics Ip B.V. Electrical wire comprising an aromatic polyketone and polysiloxane/polyimide block copolymer composition
EP2848208A2 (fr) 2008-09-12 2015-03-18 Pneumrx, Inc. Dispositifs mini-invasifs de réduction du volume pulmonaire et leur administration
WO2010030993A1 (fr) 2008-09-12 2010-03-18 Pneumrx, Inc. Modèles améliorés et/ou rallongés de dispositifs de réduction de volume pulmonaire à effraction minimale et leur mise en place
US10058331B2 (en) 2008-09-12 2018-08-28 Pneumrx, Inc. Enhanced efficacy lung volume reduction devices, methods, and systems
US9192403B2 (en) 2008-09-12 2015-11-24 Pneumrx, Inc. Elongated lung volume reduction devices, methods, and systems
EP3305234A1 (fr) 2008-09-12 2018-04-11 PneumRx, Inc. Dispositifs de réduction du volume pulmonaire minimalement invasifs et methodes de planification de telles procédures
US9173669B2 (en) 2008-09-12 2015-11-03 Pneumrx, Inc. Enhanced efficacy lung volume reduction devices, methods, and systems
US10285707B2 (en) 2008-09-12 2019-05-14 Pneumrx, Inc. Enhanced efficacy lung volume reduction devices, methods, and systems
US9675365B2 (en) 2009-02-24 2017-06-13 Microport Orthopedics Holdings Inc. System and method for anterior approach for installing tibial stem
US11389177B2 (en) 2009-02-24 2022-07-19 Microport Orthopedics Holdings Inc. Method for forming a patient specific surgical guide mount
US11779347B2 (en) 2009-02-24 2023-10-10 Microport Orthopedics Holdings Inc. System for forming a patient specific surgical guide mount
US9089342B2 (en) 2009-02-24 2015-07-28 Microport Orthopedics Holdings Inc. Patient specific surgical guide locator and mount
US9642632B2 (en) 2009-02-24 2017-05-09 Microport Orthopedics Holdings Inc. Orthopedic surgical guide
US9649117B2 (en) 2009-02-24 2017-05-16 Microport Orthopedics Holdings, Inc. Orthopedic surgical guide
US11779356B2 (en) 2009-02-24 2023-10-10 Microport Orthopedics Holdings, Inc. Orthopedic surgical guide
US11534186B2 (en) 2009-02-24 2022-12-27 Microport Orthopedics Holdings Inc. Orthopedic surgical guide
US9113914B2 (en) 2009-02-24 2015-08-25 Microport Orthopedics Holdings Inc. Method for forming a patient specific surgical guide mount
US9017334B2 (en) 2009-02-24 2015-04-28 Microport Orthopedics Holdings Inc. Patient specific surgical guide locator and mount
US11464527B2 (en) 2009-02-24 2022-10-11 Microport Orthopedics Holdings Inc. Systems and methods for installing an orthopedic implant
US9566075B2 (en) 2009-02-24 2017-02-14 Microport Orthopedics Holdings Inc. Patient specific surgical guide locator and mount
US11154305B2 (en) 2009-02-24 2021-10-26 Microport Orthopedics Holdings Inc. Patient specific surgical guide locator and mount
US10973536B2 (en) 2009-02-24 2021-04-13 Microport Orthopedics Holdings, Inc. Orthopedic surgical guide
US10660654B2 (en) 2009-02-24 2020-05-26 Microport Orthopedics Holdings Inc. Method for forming a patient specific surgical guide mount
US9883870B2 (en) 2009-02-24 2018-02-06 Microport Orthopedics Holdings Inc. Method for forming a patient specific surgical guide mount
US9901353B2 (en) 2009-02-24 2018-02-27 Microport Holdings Inc. Patient specific surgical guide locator and mount
US11911046B2 (en) 2009-02-24 2024-02-27 Microport Orthopedics Holdings, Inc. Patient specific surgical guide locator and mount
US9949747B2 (en) 2009-02-24 2018-04-24 Microport Orthopedics Holdings, Inc. Systems and methods for installing an orthopedic implant
US10646238B2 (en) 2009-02-24 2020-05-12 Microport Orthopedics Holdings, Inc. Systems and methods for installing an orthopedic implant
US10039557B2 (en) 2009-02-24 2018-08-07 Micorport Orthopedics Holdings, Inc. Orthopedic surgical guide
US10512476B2 (en) 2009-02-24 2019-12-24 Microport Orthopedics Holdings, Inc. Orthopedic surgical guide
WO2010135352A1 (fr) 2009-05-18 2010-11-25 Pneumrx, Inc. Modification de section transversale durant le déploiement d'un dispositif allongé de réduction du volume pulmonaire
WO2011082149A1 (fr) 2009-12-31 2011-07-07 Sabic Innovative Plastics Ip B.V. Fil électrique comprenant une polycétone aromatique et une composition de copolymère séquencé polysiloxane/polyimide
EP2754419A2 (fr) 2011-02-15 2014-07-16 Conformis, Inc. Implants orthopédiques améliorés et adaptés au patient, conceptions et outils associés
CN102492132A (zh) * 2011-12-09 2012-06-13 中橡集团炭黑工业研究设计院 含氰基聚芳醚酮类共聚物及其制备方法
WO2013131066A1 (fr) 2012-03-02 2013-09-06 Conformis, Inc. Implants du genou stabilisés postérieurs adaptés au patient, conceptions et procédés et outils associés
WO2013148943A2 (fr) 2012-03-30 2013-10-03 Sabic Innovative Plastics Ip B.V. Compresseurs incluant des composants polymères
EP3255279A1 (fr) 2012-03-30 2017-12-13 SABIC Global Technologies B.V. Compresseurs incluant des composants polymères
US9486226B2 (en) 2012-04-18 2016-11-08 Conformis, Inc. Tibial guides, tools, and techniques for resecting the tibial plateau
US9675471B2 (en) 2012-06-11 2017-06-13 Conformis, Inc. Devices, techniques and methods for assessing joint spacing, balancing soft tissues and obtaining desired kinematics for joint implant components
EP3632375A1 (fr) 2013-03-15 2020-04-08 PneumRx Inc. Atténuation du couple dans des structures d'implant de compression de réduction du volume pulmonaire à l'intérieur des voies respiratoires
EP3357455A2 (fr) 2013-03-15 2018-08-08 PneumRx, Inc. Atténuation du couple dans des structures d'implant de compression de réduction du volume pulmonaire à l'intérieur des voies respiratoires
WO2014151557A2 (fr) 2013-03-15 2014-09-25 Pneumrx, Inc. Structures d'implant compressif à réduction de volume pulmonaire dans les voies aériennes à soulagement de couple
US10537334B2 (en) 2013-10-25 2020-01-21 Pneumrx, Inc. Genetically-associated chronic obstructive pulmonary disease treatment
US9770278B2 (en) 2014-01-17 2017-09-26 Arthrex, Inc. Dual tip guide wire
WO2015114427A1 (fr) 2014-01-31 2015-08-06 Sabic Global Technologies B.V. Composite fibre
US10390838B1 (en) 2014-08-20 2019-08-27 Pneumrx, Inc. Tuned strength chronic obstructive pulmonary disease treatment
US10548648B2 (en) 2014-09-30 2020-02-04 Arthrex, Inc. Intramedullary fracture fixation devices and methods
US9814499B2 (en) 2014-09-30 2017-11-14 Arthrex, Inc. Intramedullary fracture fixation devices and methods
CN105175714A (zh) * 2015-09-23 2015-12-23 中橡集团炭黑工业研究设计院 一种制备氰基聚芳醚酮树脂的工艺方法
RU2716677C1 (ru) * 2018-12-03 2020-03-13 Федеральное государственное бюджетное образовательное учреждение высшего образования Санкт-Петербургская государственная академия ветеринарной медицины ФГБОУ ВО СПбГАВМ Способ изготовления анатомических копий костей методом отливки в силиконовой форме
US12108959B2 (en) 2019-05-29 2024-10-08 Wright Medical Technology, Inc. Preparing a tibia for receiving tibial implant component of a replacement ankle
WO2022230934A1 (fr) * 2021-04-27 2022-11-03 出光興産株式会社 Polyétheréthercétone, et procédé de fabrication de celui-ci

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