# US 9,040,646 B2 · Expandable TFE copolymers, methods of making, and porous, expanded articles thereof > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 9,040,646 B2 - Document ID: US9040646B2 - Status: Granted - Kind: B2 - Application number: 12/408,153 - Filed: 2009-03-20 - Published: 2009-10-15 - Granted: 2015-05-26 - Earliest claimed: 2007-10-04 - Assignees: W. L. Gore & Associates, Inc. - Applicants: Lawrence A. Ford - Inventors: Lawrence A. Ford - Web page: https://patentgrep.com/patent/US9040646B2 ## CPC - C08J 9/16: Making expandable particles - A61F 2/06: Blood vessels - A61F 2/82: Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents (stent-grafts for tubular structures of the body other than blood vessels A61F2/04; stent-grafts for blood vessels A61F2/07) - A61L 27/16: obtained by reactions only involving carbon-to-carbon unsaturated bonds - A61L 27/507: {for artificial blood vessels (apparatus for applying cells on a blood vessel prosthesis A61F2/062)} - A61L 27/56: Porous materials, {e.g. foams or sponges} - A61L 31/048: {obtained by reactions only involving carbon-to-carbon unsaturated bonds (A61L31/041 takes precedence)} - A61L 31/146: {Porous materials, e.g. foams or sponges} - B29C 55/005: {characterised by the choice of materials} - C08F 14/26: Tetrafluoroethene - C08F 214/26: Tetrafluoroethene - C08F 214/262: {with fluorinated vinyl ethers} - C08F 214/265: {with non-fluorinated comonomers} - C08F 259/08: on to polymers containing fluorine - C08J 9/00: Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof (mechanical aspects of shaping of plastics or substances in a plastic state for the production of porous or cellular articles B29C) - B29K 2027/18: PTFE, i.e. polytetrafluoroethylene {, e.g. ePTFE, i.e. expanded polytetrafluoroethylene} - B29K 2105/04: cellular or porous - C08J 2207/02: Adhesive - C08J 2327/18: Homopolymers or copolymers of tetrafluoroethylene - Y10T 428/1376: Foam or porous material containing - C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29) - A61F: FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS (dental prosthetics A61C) - 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 (preservation of bodies or disinfecting characterised by the agents employed A01N; preserving, e.g. sterilising, food or foodstuffs A23; preparations for medical, dental or toiletry purposes A61K) - B29C: SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING (making preforms B29B11/00; making laminated products by combining previously unconnected layers which become one product whose layers will remain together B32B37/00 - B32B41/00) - C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS - B29K: INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR {MOULDS, } REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS - Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION ## Abstract A true tetrafluoroethylene (TFE) copolymer of the fine powder type is provided, wherein the copolymer contains polymerized comonomer units of at least one comonomer other than TFE in concentrations of at least or exceeding 1.0 weight percent, and which can exceed 5.0 weight percent, wherein the copolymer is expandable, that is, the copolymer may be expanded to produce strong, useful, expanded TFE copolymeric articles having a microstructure of nodes interconnected by fibrils. Articles made from the expandable copolymer may include tapes, membranes, films, fibers, and are suitable in a variety of end applications, including medical devices. ## Claims ### Claim 1 An expandable core-shell tetrafluoroethylene (TFE) copolymer, said copolymer comprising: (a) a first, core portion comprising a polymer chain of TFE monomers and at least one comonomer; and (b) a second, shell portion consisting of a polymer chain consisting of TFE monomers, wherein said expandable core-shell tetrafluoroethylene copolymer comprises at least 3.0% by weight polymerized units of said at least one comonomer based on total weight of said copolymer, wherein said copolymer exhibits adhesion, and wherein said copolymer comprises a first melt transition temperature and a second melt transition temperature. ### Claim 2 (depends on 1) The expandable tetrafluoroethylene (TFE) copolymer of claim 1, wherein said adhesion is exhibited after subjecting the copolymer to a temperature at or below about 290° C. ### Claim 3 (depends on 1) The expandable tetrafluoroethylene (TFE) copolymer of claim 1, wherein said copolymer exhibits adhesion after subjecting the copolymer to its first melt transition temperature or above. ### Claim 4 (depends on 1) The expandable tetrafluoroethylene (TFE) copolymer of claim 1, wherein said copolymer exhibits adhesion after subjecting the copolymer to a temperature between said first melt transition temperature and about 290° C. ### Claim 5 (depends on 1) The copolymer of claim 1, wherein said at least one comonomer is an olefin selected from the group consisting of ethylene, propylene and isobutylene. ### Claim 6 (depends on 1) The copolymer of claim 1, wherein said at least one comonomer is a fluorinated monomer selected from the group consisting of chlorotrifluoroethylene (CTFE), hexafluoro-propylene (HFP), vinylidene fluoride (CFH═CH2), vinylidene difluoride (CF2=CH2), hexafluoroisobutylene(HFIB), trifluoroethylene (CF2=CFH), a fluorodioxole and a fluorodioxalane. ### Claim 7 (depends on 1) The copolymer of claim 1, wherein said at least one comonomer is a perfluoroalkyl ethylene monomer. ### Claim 8 (depends on 7) The copolymer of claim 7, wherein said perfluoroalkyl ethylene monomer is selected from the group consisting of perfluorobutylethylene (PFBE), perfluorohexyl ethylene (PFHE) and perfluorooctylethylene (PFOE). ### Claim 9 (depends on 1) The copolymer of claim 1, including more than one comonomer. ### Claim 10 (depends on 1) The copolymer of claim 1, having at least 5.0% by weight polymerized units of said at least one comonomer. ### Claim 11 (depends on 1) The copolymer of claim 1, in the form of fine particles dispersed within an aqueous medium. ### Claim 12 (depends on 1) The copolymer of claim 1, in the form of fine powder. ### Claim 13 A medical device comprising: an expanded core-shell tetrafluoroethylene (TFE) copolymer comprising: (a) a first, core portion comprising a polymer chain of TFE monomers and at least one comonomer; and (b) a second, shell portion consisting of a polymer chain consisting of TFE monomers, wherein said expanded core-shell tetrafluoroethylene copolymer comprises at least 3.0% by weight polymerized units of said at least one comonomer based on total weight of said copolymer, and wherein said copolymer comprises a first melt transition temperature and a second melt transition temperature. ### Claim 14 (depends on 13) The medical device of claim 13 in the form of an implantable medical device. ### Claim 15 (depends on 13) The medical device of claim 13 in the form of a vascular graft. ### Claim 16 (depends on 13) The medical device of claim 13 in the form of an endoluminal prosthesis. ### Claim 17 (depends on 13) The medical device of claim 13, said expanded core-shell tetrafluoroethylene copolymer having a matrix tensile strength in at least one direction exceeding 13,000 psi. ### Claim 18 (depends on 17) The medical device of claim 17, said expanded core-shell tetrafluoroethylene copolymer having a matrix tensile strength in at least one direction exceeding 15,000 psi. ### Claim 19 (depends on 17) The medical device of claim 17, said expanded core-shell tetrafluoroethylene copolymer having a matrix tensile strength in at least one direction exceeding 25,000 psi. ### Claim 20 (depends on 17) The medical device of claim 17, said expanded core-shell tetrafluoroethylene copolymer having a matrix tensile strength in at least one direction exceeding 30,000 psi. ### Claim 21 (depends on 13) The medical device of claim 13 in the form of an implantable medical device.