CN104178926B - 利用高粘度材料对ptfe进行电纺丝 - Google Patents

利用高粘度材料对ptfe进行电纺丝 Download PDF

Info

Publication number
CN104178926B
CN104178926B CN201410312160.XA CN201410312160A CN104178926B CN 104178926 B CN104178926 B CN 104178926B CN 201410312160 A CN201410312160 A CN 201410312160A CN 104178926 B CN104178926 B CN 104178926B
Authority
CN
China
Prior art keywords
ptfe
spinning
dispersion
cylinderical surface
pad described
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN201410312160.XA
Other languages
English (en)
Other versions
CN104178926A (zh
Inventor
布鲁斯·L·阿诺
罗伯特·巴拉德
大卫·P·加纳
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zeus Industrial Products Inc
Original Assignee
Zeus Industrial Products Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zeus Industrial Products Inc filed Critical Zeus Industrial Products Inc
Publication of CN104178926A publication Critical patent/CN104178926A/zh
Application granted granted Critical
Publication of CN104178926B publication Critical patent/CN104178926B/zh
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
    • D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
    • D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/007—Processes for applying liquids or other fluent materials using an electrostatic field
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B11/00—Making preforms
    • B29B11/06—Making preforms by moulding the material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B13/00—Conditioning or physical treatment of the material to be shaped
    • B29B13/02—Conditioning or physical treatment of the material to be shaped by heating
    • B29B13/023—Half-products, e.g. films, plates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • 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
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/04—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B1/00—Layered products having a general shape other than plane
    • B32B1/08—Tubular products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/085—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/022—Non-woven fabric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/005—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F114/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F114/18—Monomers containing fluorine
    • C08F114/26—Tetrafluoroethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/005—Processes for mixing polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/05—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from solid polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/22—After-treatment of expandable particles; Forming foamed products
    • C08J9/228—Forming foamed products
    • C08J9/232—Forming foamed products by sintering expandable particles
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
    • D01D10/02—Heat treatment
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0015—Electro-spinning characterised by the initial state of the material
    • D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0015—Electro-spinning characterised by the initial state of the material
    • D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
    • D01D5/0038—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion the fibre formed by solvent evaporation, i.e. dry electro-spinning
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/08—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of halogenated hydrocarbons
    • D01F6/12—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of halogenated hydrocarbons from polymers of fluorinated hydrocarbons
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/48—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of halogenated hydrocarbons
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/413—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties containing granules other than absorbent substances
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4282—Addition polymers
    • D04H1/4318—Fluorine series
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4326—Condensation or reaction polymers
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/54—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
    • D04H1/74—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being orientated, e.g. in parallel (anisotropic fleeces)
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/02—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of forming fleeces or layers, e.g. reorientation of yarns or filaments
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N7/00—Flexible sheet materials not otherwise provided for, e.g. textile threads, filaments, yarns or tow, glued on macromolecular material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • 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
    • B29K2027/00—Use of polyvinylhalogenides or derivatives thereof as moulding material
    • B29K2027/12—Use of polyvinylhalogenides or derivatives thereof as moulding material containing fluorine
    • B29K2027/18—PTFE, i.e. polytetrafluorethene, e.g. ePTFE, i.e. expanded polytetrafluorethene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • 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
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0094—Condition, form or state of moulded material or of the material to be shaped having particular viscosity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • 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
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037—Other properties
    • B29K2995/0063—Density
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • 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
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037—Other properties
    • B29K2995/0077—Yield strength; Tensile strength
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/755—Membranes, diaphragms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2471/02—Polyalkylene oxides
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2321/00—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D10B2321/04—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polymers of halogenated hydrocarbons
    • D10B2321/042—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polymers of halogenated hydrocarbons polymers of fluorinated hydrocarbons, e.g. polytetrafluoroethene [PTFE]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/131—Glass, ceramic, or sintered, fused, fired, or calcined metal oxide or metal carbide containing [e.g., porcelain, brick, cement, etc.]
    • Y10T428/1314—Contains fabric, fiber particle, or filament made of glass, ceramic, or sintered, fused, fired, or calcined metal oxide, or metal carbide or other inorganic compound [e.g., fiber glass, mineral fiber, sand, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
    • Y10T428/1355—Elemental metal containing [e.g., substrate, foil, film, coating, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
    • Y10T428/1362—Textile, fabric, cloth, or pile containing [e.g., web, net, woven, knitted, mesh, nonwoven, matted, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
    • Y10T442/654—Including a free metal or alloy constituent
    • Y10T442/656—Preformed metallic film or foil or sheet [film or foil or sheet had structural integrity prior to association with the nonwoven fabric]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
    • Y10T442/674—Nonwoven fabric with a preformed polymeric film or sheet
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
    • Y10T442/681—Spun-bonded nonwoven fabric

Abstract

本发明涉及利用高粘度材料对PTFE进行电纺丝，其中描述了一种制备PTFE垫的改进方法。该方法包括：提供含有PTFE、成纤聚合物和溶剂的分散体，其中所述分散体的粘度为至少50,000cP。提供一种装置，该装置包括电荷源和与该电荷源相距一定距离的靶。提供电压源，该电压源在所述电荷源处建立第一电荷，而在所述靶处建立相反的电荷。通过使所述分散体与所述电荷源接触从而使所述分散体带上静电荷。在所述靶上收集所述带静电荷的分散体以形成垫前体，加热该垫前体以除去所述溶剂和所述成纤聚合物，从而形成所述PTFE垫。

Description

利用高粘度材料对PTFE进行电纺丝
本专利申请是申请号为201080004845.8、申请日为2010年1月19日、发明名称为“利用高粘度材料对PTFE进行电纺丝”的专利申请的分案申请。
相关申请的交叉引用
本申请要求于2009年1月16日提交的待审的美国临时专利申请No.61/145,309、以及于2009年10月30日提交的待审的美国临时专利申请No.61/256,349的优先权，它们的全部内容以引用方式并入本文。
背景技术
本发明涉及聚四氟乙烯(PTFE)的电纺丝方法。更具体来说，本发明涉及对高粘度PTFE分散体进行电纺丝，以及利用该方法所制备的制品。
静电纺丝工艺在本技术领域内是公知的，如在美国专利No.2,158,416、No.4,043,331、No.4,143,196、No.4,287,139、No.4,432,916、No.4,689,186、No.6,641,773和No.6,743,273中所描述的工艺，它们的内容以引用方式并入本文。以引用方式并入本文的美国专利No.4,323,525、No.4,127,706和No.4,044,404提供了有关从水性分散体或者其它分散体对PTFE进行加工和静电纺丝的信息。
静电纺丝(在本技术领域中也被称为电纺丝)涉及带电聚合物向带电表面的移动。在一个实施方案中，将聚合物通过小的带电喷孔(例如针)排至靶，其中，针和靶带有相反的电荷。需要认识到的是，聚合物的性质至关重要。在本技术领域中，人们长期以来一直认为有必要保持小于约150泊的相对低的粘度，其中对于较低分子量的聚合物来说，其粘度应相对较高，而对于较高分子量的聚合物来说，其粘度应相对较低。如果过高的粘度和过高的分子量相组合，则认为不能充分成纤。
因为触变性限制(导致喷孔堵塞、成纤性差等)，因此长期以来人们一直认为使聚合物溶液的粘度提高至超过约150泊是不可取的。此外，当使用带电喷孔时，聚合物纤维在飞行过程中会发生排斥，人们长期以来认为这会限制给定喷射体积内的纤维数量。通过辛勤的研究，本发明人已经发现，与现有认知相反，将粘度大大增加至远超过以前认为可行的程度，实际上会改善所得材料，并且会提供其它以前认为不可能获得的性能和优点。
发明内容
本发明的目的在于，提供一种对PTFE进行电纺丝的改进方法。
本发明的另一个目的在于，提供一种基于电纺丝PTFE来制备优良制品的方法。
本发明的独特的特征在于，能够利用现有的电纺丝技术和设备来提供改善的制品。
一种制备PTFE垫的方法提供了这些优点，以及将会被认识到的其它优点。该方法包括提供含有PTFE、成纤聚合物和溶剂的分散体，其中，所述分散体的粘度至少为50,000cP。提供包括电荷源和与该电荷源相距一定距离的靶的装置。提供电压源，该电压源在所述电荷源处建立第一电荷，而在所述靶处建立相反的电荷。通过使所述分散体与所述电荷源接触而使分散体带上静电荷。在所述靶上收集带静电荷的分散体以形成垫前体，加热该垫前体以除去所述溶剂和所述成纤聚合物，从而形成所述PTFE垫。
一种制备PTFE垫的方法还提供了另外的优点。该方法包括提供含有下述成分的分散体：粒度为至少0.1微米至不大于0.8微米的PTFE；1重量％至不大于10重量％且分子量为至少50,000至不大于4,000,000的聚环氧乙烷；以及溶剂，其中，所述分散体的粘度为至少50,000cP。提供包括喷孔和与该喷孔相距一定距离的靶的装置。提供电压源以在所述喷孔处建立第一电荷，而在所述靶处建立相反的电荷。迫使所述分散体通过所述喷孔，其中，通过使所述分散体与所述喷孔接触而使分散体带上静电荷。在所述靶上收集所述带静电荷的分散体以形成垫前体，加热该垫前体以除去所述溶剂和所述成纤聚合物，从而形成所述PTFE垫。
附图说明
图1示意性示出电沉积。
图2示意性示出本发明的方法。
具体实施方式
本发明涉及将聚四氟乙烯(PTFE)静电纺丝成为连续纤维以用于制成无纺布片、薄膜、管状物和覆层且有潜力用于多种其它用途和形式的方法。具体来说，与以前认为可行的粘度直接相比，本发明涉及在相对于现有技术来说非常高的粘度下对PTFE进行电纺丝。
图1示意性示出静电纺丝装置。在图1中，将如本文进一步描述的高粘度分散体装入贮存器10中。输送系统11将所述分散体自所述贮存器输送至电荷源12(可以为喷孔)。相距该电荷源12一定距离布置靶15。电源16(例如直流电源)在所述电荷源和靶之间建立电荷差，从而使聚合物材料14带上与所述靶相反的电荷。所述聚合物材料被静电吸引至所述靶，并且沉积在其上。所述靶可以静止、运动，或者可以为连续的或者近似连续的材料，其可通过在传送辊17(或者类似的物体)上移动，从而移动穿过聚合物所撞击的区域。在一个实施方案中，将电荷施加到与所述靶导电接触的辊上(或者如图所示接地)。所述靶可以是连续的环状物，或者其可以起始于传送装置(例如供卷筒(supply spool))，并且收纳于收集装置(例如接收卷筒(receiver spool))。在可供选择的实施方案中，可以将所述电荷源和靶置于共同的分散体浴中。
本方法需要具有足够PTFE固体百分比的分散体或者悬浮液，以有助于将所收集的纤维垫后加工成具有一定机械完整性的形式。如果分散体中的PTFE固体含量过低，则所得材料将不具有或具有差的机械完整性。第二，必须仔细选择用于提高溶液、悬浮液或者分散体粘度的、待纺的聚合物(也称为成纤聚合物)。我们发现，加入所述PTFE中的成纤聚合物的分子量过低将导致低劣的性能和加工特性。还据信，分子量过高将导致粘度增加，使得在电纺丝和固化过程中，没有足够的聚合物将PTFE粉末真正结合到一起。此外，必须精确控制用于将所述PTFE粉末烧结到一起的工艺，从而使所得制品具有良好的机械完整性。
优选的是，所述PTFE的分子量为106至108。
优选的是，所述PTFE的粒度为至少0.1微米至不大于0.8微米。更优选的是，所述PTFE的粒度为至少0.2微米至不大于0.6微米。粒度小于0.1微米时，所述材料难以制备。粒度大于0.8微米时，该粒度接近目标纤维直径，从而在纤维中成为缺陷。对于其它用途来说，较大的粒度可能适于使用。
参照图2对制备非织造PTFE材料的方法进行说明。制备粒度分布窄的PTFE粉末的水性分散体，20。将成纤聚合物加入所述分散体中，22。所述成纤聚合物的加入量优选在1重量％至10重量％之间，更优选为约2重量％至7重量％，最优选为约4重量％至5重量％。所述成纤聚合物优选在溶剂(优选为水)中具有高溶解度，溶解度大于约0.5重量％是优选的。当在约400℃下烧结时，所述成纤聚合物的灰分优选小于约5重量％，甚至更低的灰分更为优选。
特别优选的成纤聚合物包括：葡聚糖、藻酸盐、壳聚糖、瓜尔胶化合物、淀粉、聚乙烯基吡啶化合物、纤维素化合物、纤维素醚、水解聚丙烯酰胺、聚丙烯酸酯、聚羧酸酯、聚乙烯醇、聚环氧乙烷、聚乙二醇、聚乙烯亚胺、聚乙烯吡咯烷酮、聚丙烯酸、聚(甲基丙烯酸)、聚(衣康酸)、聚(丙烯酸2-羟乙酯)、聚(甲基丙烯酸2-(二甲氨基)乙酯-co-丙烯酰胺)、聚(N-异丙基丙烯酰胺)、聚(2-丙烯酰胺基-2-甲基-1-丙磺酸)、聚(乙烯基甲醚)、聚(乙烯醇)、12％乙酰化聚(乙烯醇)、聚(2,4-二甲基-6-三嗪基乙烯)、聚(3-吗啉基乙烯)、聚(N-1,2,4-三唑基乙烯)、聚(乙烯基亚砜)、聚(乙烯胺)、聚(N-乙烯基吡咯烷酮-co-乙酸乙烯酯)、聚(g-谷氨酸)、聚(N-丙酰亚氨基乙烯)、聚(4-氨基-磺基-苯胺)、聚[N-(对磺基苯基)氨基-3-羟甲基-1,4-亚苯基亚氨基-1,4-苯撑)]、异丙基纤维素、羟乙基、羟丙基纤维素、乙酸纤维素、硝酸纤维素、藻酸铵盐、i-卡拉胶、N-[(3’-羟基-2’,3’-二羧基)乙基]壳聚糖、魔芋葡甘聚糖、支链淀粉、黄原胶、聚(烯丙基氯化铵)、聚(烯丙基磷酸铵)、聚(二烯丙基二甲基氯化铵)、聚(苄基三甲基氯化铵)、聚(二甲基十二烷基(2-丙烯酰胺基乙基)溴化铵)、聚(4-N-丁基吡啶亚乙基碘)(poly(4-N-butylpyridiniumethylene iodine))、聚(2-N-甲基吡啶亚甲基碘)(poly(2-N-methylpridiniummethylene iodine))、聚(N-甲基吡啶-2,5-二基亚乙烯基)(poly(N methylpyridinium-2,5-diylethenylene))、聚乙二醇聚合物及共聚物、纤维素乙醚、纤维素乙基羟乙基醚、纤维素甲基羟乙基醚、聚(甲基丙烯酸1-甘油酯)、聚(2-乙基-2-唑啉)、聚(甲基丙烯酸2-羟乙酯/甲基丙烯酸)90:10、聚(甲基丙烯酸2-羟丙酯)、聚(2-甲基丙烯酰氧乙基三甲基溴化铵)、聚(2-乙烯基-1-甲基溴化吡啶)、聚(2-乙烯基吡啶氮氧化物)、聚(2-乙烯基吡啶)、聚(3-氯-2-羟丙基-2-甲基丙烯酰氧乙基三甲基氯化铵)、聚(4-乙烯基吡啶氮氧化物)、聚(4-乙烯基吡啶)、聚(丙烯酰胺/2-甲基丙烯酰氧乙基三甲基溴化铵)80:20、聚(丙烯酰胺/丙烯酸)、聚(烯丙胺盐酸盐)、聚(丁二烯/马来酸)、聚(二烯丙基二甲基氯化铵)、聚(丙烯酸乙酯/丙烯酸)、聚(乙二醇)双(2-氨乙基)(poly(ethylene glycol)bis(2-aminoethyl))、聚(乙二醇)单甲醚、聚(乙二醇)-双酚A二缩水甘油醚加合物、聚(环氧乙烷-b-环氧丙烷)、聚(乙烯/丙烯酸)92:8、聚(1-赖氨酸氢溴酸盐)、聚(1-赖氨酸氢溴酸盐)、聚(马来酸)、聚(丙烯酸正丁酯/2-甲基丙烯酰氧乙基三甲基溴化铵)、聚(N-异丙基丙烯酰胺)、聚(N-乙烯基吡咯烷酮/甲基丙烯酸2-二甲氨基乙酯)硫酸二甲酯季铵盐(poly(N-vinylpyrrolidone/2-dimethylaminoethyl methacrylate),dimethyl sulfatequaternary)、聚(N-乙烯吡咯烷酮/乙酸乙烯酯)、聚(氧乙烯)失水山梨醇单月桂酸酯(Tween)、聚(苯乙烯磺酸)、聚(乙烯醇)N-甲基-4(4’-甲酰苯乙烯基)吡啶甲基硫酸酯缩醛(poly(vinyl alcohol),N-methyl-4(4'-formylstyryl) pyridinium,methosulfate acetal)、聚(乙烯基甲基醚)、聚(乙烯胺)盐酸盐、聚(乙烯基膦酸)、聚(乙烯基磺酸)钠盐和聚苯胺。
特别优选的成纤聚合物为分子量是50,000至4,000,000的聚环氧乙烷(PEO)，更优选的分子量为约250,000至350,000，并且最优选的分子量为约300,000。
进一步参照图2，在混合后，优选将PTFE与成纤聚合物的分散体均质化，24。在特别优选的方法中，允许在不搅拌的情况下缓慢形成所述聚合物分散体，之后将其转移至瓶罐转辊(jar roller)，该瓶罐转辊以恒定的速率使分散体转动若干天。优选形成在所得高粘度混合物中没有或者只有少量夹带气体的均匀分散体。一旦所述分散体具有均匀的稠度，优选将其过滤以去除任何块状物或凝胶。之后，将已经过滤的具有所需粘度的分散体装入具有固定导电元件(用作电荷源)的受控泵送装置中，26。特别优选的导电元件为喷孔，例如被切钝并且经砂磨以去除任何毛刺的16号针。将所述泵送装置的喷射量设定为预定的速率，所述预定的速率取决于所制备的形式和所需的纤维直径。优选将所述电荷源与精密直流电源的正极相连。优选将所述电源的负极与收集表面或靶相连。可以将极性反转，但这不是优选的。
所述靶的表面可以为圆筒、机件(device)或平板。该表面可以为金属、陶瓷或者聚合物材料，特别优选选自以下的材料：不锈钢、钴铬合金、镍钛(镍钛合金)、镁合金、聚交酯(polyactide)、聚乙交酯、聚羟基丁酸酯、聚羟基烷基酸酯(polyhydroxyalkynoate)、聚二烷酮(polydioxinine)、聚醚醚酮(PEEK)、聚氨酯、聚碳酸酯和聚环氧乙烷。将电源上的电压增加至所需电压，从而均匀地吸取出聚合物/PTFE分散体。
所施加的电压通常为2,000至80,000伏。通过连接电源所诱导的电荷使带电的聚合物被排斥离开电荷源，并且将其吸引至所述收集表面。
优选将所述收集靶相对于所述泵和喷孔系统垂直放置，并且使其在至少一个方向上运动，从而使吸向靶的纤维均匀地覆盖整个表面，28。一旦充分覆盖所述收集表面，优选将所述材料固化/烧结，30，可以将整个收集表面置于烘箱中而原地进行固化/烧结，也可以将片状物、管状物或者其它的形式从所述收集表面移除，而后在烘箱中进行烧结。
电纺丝得到的PTFE织物在烧结过程中发生收缩。不被任何理论所束缚，据信，所述收缩以两步骤进行。一开始，所述纤维和织物(初纺纤维和织物)包含水分和成纤聚合物(优选为聚环氧乙烷)。完成纺丝之后，将所述样品干燥并且进行低程度的纤维重整。将所述纤维和织物置于550℉至900℉的温度下持续一段时间，对所述样品进行烧结，从而消除所述水分和成纤聚合物。推断在该消除过程中发生第二次更显著的收缩。据信，在未使所述织物松弛的情况下，在所述第二次收缩中发生织物的开裂和纤维的断裂。
为了适应收缩，可以将所述纤维和织物纺在膨胀的结构上。之后可以将该结构移除或者使其收缩。这样可以使得织物在烧结过程中收缩而不发生开裂。另一种方法涉及，将所述纤维和织物纺在这样的结构上，该结构之后(在烧结之前)可以膨胀或收缩。收缩或者膨胀和收缩的程度优选大约为3％至100％，并且取决于电沉积织物垫的厚度和尺寸。
对于片状织物来说，如果将沉积方向设定为垂直于该织物平面，则必须在所述织物平面中的至少一个或更多个方向上发生收缩或者膨胀/收缩。对于沉积在圆筒形表面上的织物来说，必须使所述织物沿径向和/或纵向收缩或者收缩/膨胀。对于球形表面来说，必须使所述织物沿径向收缩或者收缩/膨胀。无论基于何种形状的表面来进行纺丝，都可以将这些收缩和/或膨胀/收缩的基本原则应用在任何电纺丝织物上。因此，基于PTFE织物的非常复杂的织物形状成为可能。
在特别优选的实施方案中，使用了高粘度材料。出乎意料地发现，通过将粘度为至少50,000cP至不大于300,000cP的材料进行电纺丝，能够观察到优越的性能。更优选的是，所述粘度为至少100,000cP至不大于250,000cP，最优选的是，所述粘度为至少150,000cP至不大于200,000cP。当粘度超过300,000cP时，则该材料会逐渐变得难以形成纤维。
在一个实施方案中，电纺丝分散体基于Daikin D210PTFE和Sigma Aldrich公司的分子量为300,000的聚环氧乙烷。Daikin D210PTFE为适于示范本发明的代表材料。DaikinD210PTFE具有约59重量％至62重量％的固体、6.0重量％至7.2重量％的表面活性剂、8.5至10.5的pH、1.5至1.53的比重、以及35cP的最大布氏粘度。
所述分散体的PTFE固体％优选为50重量％至80重量％，更优选为55重量％至65重量％，甚至更优选为59重量％至61重量％。比重优选为1.5至1.54，并且更优选为1.51。例如，1000ml分散体的重量范围应当为1500g至1530g，其中含有885g至933.3g的PTFE。
特别优选的实施方案为固体PTFE为60％，比重为1.51，每1000ml分散体中含有909gm PTFE。
在特别优选的例子中，每1000ml Daikin D210分散体中优选含有32gm至52gm成纤聚合物(最优选为PEO)，这样，成纤聚合物固体与PTFE分散体的比例(例如PEO/PTFE)为：在1000ml分散体中，PEO为0.032gm/ml至0.052gm/ml。当成纤聚合物的重量比例低于0.03gm/ml时，导致形成非常劣质的且不均一的纤维垫。劣质被定义为纤维断裂程度高(>20％)，并且形成在本技术领域中也被称为“形成小珠(beading)”的不均一的纤维直径。断裂纤维以及/或者不均一纤维的存在会导致纤维垫中出现不均一的孔隙。由于不连续的原纤从垫中被拉出，因此断裂的原纤(尤其是短原纤)的存在会导致效率随时间而降低。
典型的PTFE分散体中含有60％的PTFE固体和介于200,000Mw至4,000,000Mw之间的PEO。特别典型的是，成纤聚合物是分子量为300,000的PEO，它与PTFE的比值为0.03至0.06。
采用布氏LV粘度计，在25℃下、在设定为2.5的恒定转速(#25转子)下测量不同的PEO/PTFE配制物的粘度，结果在表1中示出。
表1
样品 扭矩(％) 粘度(cp)
0.052gm/ml PEO 88.5 171,000
0.048gm/ml PEO 76.8 147,000
0.044gm/ml PEO 79.2 152,000
0.040gm/ml PEO 58.5 112,000
0.036gm/ml PEO 40.1 77,000
0.032gm/ml PEO 34.5 66,000
假设1000ml Diakin D210分散体中含有909gm PTFE，优选的PEO/PTFE分散体的百分比范围为0.032至0.060gm/ml。为示范本发明，特别优选为约0.048gm/ml。
对于沉积而言，除非另外指明，否则本发明在此优选并依赖带电的针和接地的靶。部分由于安全因素，这在工业领域已被认可为标准做法。也可以使用接地的针和带电的靶，但由于结果形成较差的材料，因此并不优选。
为了方便说明本文所述的样品，利用11kV、14kV或17kV的电压，相应的针尖与靶顶端(TTT)之间的距离为4.5"、5.5"和6.5"。根据所采用的试验装置来设计选择电压和距离，这对于本技术领域的技术人员来说是公知的。出于示范的目的，将样品沉积于金属箔上，干燥，并且之后在725℉下烧结5分钟，之后利用SEM进行检测。通过此方法，制备了平滑、厚重、宽幅的网状物，这表明在材料迁移效率方面得到显著改善。使用相反极性的试验结果较差。沉积得到约5"宽度的垫。
目测观察显示，在通过相反的极性而制备的样品中出现不同程度的劣化。此外，显微照片显示出纤维的断裂、以及纤维扭曲形成了纤维束。纤维直径和纤维束直径也分布广泛。所有这些纤维特征将导致形成不均一且劣质的纤维垫。这些纤维特征与我们尝试由低PEO/PTFE浓度的分散体进行电纺丝所观察到的劣等纤维垫的品质是一致的。在高压并且针尖至靶的距离为5.5"和6.5"的情况下，显示出最大程度的纤维断裂，而在TTT距离为4.5"的情况下，显示出最大程度的成束现象。
当在高放大倍率下检测“正常”的电纺PTFE时，没有明显的纤维断裂，所有纤维的直径均一，并且纤维垫能够经得住烧结过程。
代表性的结果在表2至表4中示出，括号中给出标准偏差。在这些表中，用毛细管流动孔径分析仪(型号CFP-1100-AEXL，Porous Materials公司制造)，采用“干燥/润湿”测试类型来检测气流、孔径和泡点。使用气体比重计，采用标准ISO1183-3检测密度。在模冲的ASTM D638V型犬骨形样品几何形状下采用标准ASTM D882来检测拉伸性能、伸长率和模量。采用布氏LV粘度计，在25℃下、在所列的对于#25转子设定的恒定转速下测量不同的PEO/PTFE配制物的粘度。
本方法所提供的独特的优点在于，与现有技术的样品相比，本发明所得材料经烧结之后，具有明显减少的断裂的原纤。原纤断裂的减少会减少劣质材料，因此提高了制备生产率。这不需要损失产品特性即可实现。
已参照所述优选实施方案对本发明进行了说明，但并不仅限于此。本技术领域的技术人员可以实现本发明的目的和范围内的其它的实施方案和改进形式，这在所附的权利要求书中更加具体地阐明。
表2：PTFE膜(60％PTFE，0.048gm/ml PEO/1000ml PTFE分散体)的物理性能。
表3：PTFE膜(67％PTFE，0.015gm/ml至0.040gm/ml PEO/1000ml PTFE分散体)的物理性能。
表4：PTFE膜(72％PTFE，0.020gm/ml至0.030gm/ml PEO/1000ml PTFE分散体)的物理性能。

Claims (35)

1.由金属、陶瓷或者聚合物材料形成的圆筒形表面和在所述圆筒形表面的至少一部分上的纺丝聚四氟乙烯(PTFE)覆层的组合，其中所述纺丝PTFE是由粘度至少为50,000cP的分散体静电纺丝得到的，并且所述分散体包含PTFE、成纤聚合物、以及溶剂。
2.权利要求1所述的组合，其中所述圆筒形表面是由选自不锈钢、钴铬合金、镍钛(镍钛合金)、和镁合金的金属材料形成的部件，并且覆层在所述部件上原地烧结。
3.权利要求1或2所述的组合，其中所述纺丝PTFE是由所述分散体电纺丝得到的电纺PTFE。
4.一种纺丝方法，包括以下步骤：由粘度至少为50,000cP的分散体将聚四氟乙烯(PTFE)静电纺丝到圆筒形表面上，之后在所述圆筒形表面上原地烧结所得到的纺丝PTFE，其中所述分散体包含PTFE、成纤聚合物、以及溶剂。
5.权利要求4所述的方法，其中所述烧结的步骤包括将其上具有所述纺丝PTFE的整个所述圆筒形表面置于烘箱中。
6.权利要求4所述的方法，还包括使所述纺丝PTFE覆盖整个所述圆筒形表面，并且一旦所述圆筒形表面被充分覆盖，就通过将整个被覆盖的圆筒形表面置于烘箱中而原地烧结所述纺丝PTFE。
7.权利要求4所述的方法，其中将PTFE纺丝到所述圆筒形表面上的步骤包括以下步骤：
施加电压，以在电荷源和所述圆筒形表面之间建立电荷差；
使分散体带上静电荷，其中通过电荷源使所述分散体带上静电荷，并且其中所述分散体包含PTFE、成纤聚合物、以及溶剂；和
在所述圆筒形表面上收集带静电荷的所述分散体。
8.权利要求4-7中的任一项所述的方法，其中将PTFE纺丝到圆筒形表面上的步骤包括：对包含PTFE、成纤聚合物、以及溶剂的分散体进行纺丝，其中所述分散体的粘度为至少50,000cP。
9.一种无纺垫，其包括多根纺丝聚四氟乙烯纤维，其中所述多根聚四氟乙烯纤维表现出均一的直径，其中所述纺丝聚四氟乙烯是由粘度至少为50,000cP的分散体静电纺丝得到的，并且所述分散体包含PTFE、成纤聚合物、以及溶剂。
10.权利要求9所述的垫，其以覆层的形式设置在圆筒形表面上，并在所述圆筒形表面上原地烧结。
11.权利要求10所述的垫，其中所述圆筒形表面是金属、陶瓷或聚合物材料的部件。
12.权利要求10所述的垫，其中所述圆筒形表面由选自不锈钢、钴铬合金、镍钛(镍钛合金)、和镁合金的金属材料形成的部件。
13.权利要求9所述的垫，其呈片的形式。
14.权利要求9所述的垫，其呈膜的形式。
15.权利要求9所述的垫，其呈管的形式。
16.权利要求9所述的垫，其中当对所述垫在放大倍率下进行目测观察时，所述纺丝聚四氟乙烯纤维未观察到形成小珠。
17.权利要求9所述的垫，其中少于20％的所述多根纺丝聚四氟乙烯纤维呈断裂纤维的形式。
18.权利要求9-17中的任一项所述的垫，其中所述纺丝聚四氟乙烯纤维为电纺聚四氟乙烯纤维。
19.一种无纺垫，其包括多根纺丝聚四氟乙烯纤维，其中少于20％的所述多根纺丝聚四氟乙烯纤维呈断裂纤维的形式，其中所述纺丝聚四氟乙烯是由粘度至少为50,000cP的分散体静电纺丝得到的,并且所述分散体包含PTFE、成纤聚合物、以及溶剂。
20.权利要求19所述的垫，其中所述聚四氟乙烯的平均分子量为106Da至108Da。
21.权利要求19所述的垫，其以覆层的形式设置在圆筒形表面上，并在所述圆筒形表面上烧结。
22.权利要求21所述的垫，其中所述圆筒形表面是金属、陶瓷或聚合物材料的部件。
23.权利要求21所述的垫，其中所述圆筒形表面由选自不锈钢、钴铬合金、镍钛(镍钛合金)、和镁合金的金属材料形成的部件。
24.权利要求19所述的垫，其呈片的形式。
25.权利要求19所述的垫，其呈膜的形式。
26.权利要求19所述的垫，其呈管的形式。
27.权利要求19-26中的任一项所述的垫，其中所述纺丝聚四氟乙烯纤维为电纺聚四氟乙烯纤维。
28.一种无纺垫，其包括多根纺丝聚四氟乙烯(PTFE)纤维，其中所述纺丝PTFE纤维是由粘度至少为50,000cP的分散体静电纺丝得到的，并且所述分散体包含PTFE、成纤聚合物、以及溶剂。
29.权利要求28所述的垫，其以覆层的形式设置在圆筒形表面上，并在所述圆筒形表面上烧结。
30.权利要求29所述的垫，其中所述圆筒形表面是金属、陶瓷或聚合物材料的部件。
31.权利要求29所述的垫，其中所述圆筒形表面由选自不锈钢、钴铬合金、镍钛(镍钛合金)、和镁合金的金属材料形成的部件。
32.权利要求28所述的垫，其呈片的形式。
33.权利要求28所述的垫，其呈膜的形式。
34.权利要求28所述的垫，其呈管的形式。
35.权利要求28-34中的任一项所述的垫，其中所述纺丝聚四氟乙烯纤维为电纺聚四氟乙烯纤维。
CN201410312160.XA 2009-01-16 2010-01-19 利用高粘度材料对ptfe进行电纺丝 Expired - Fee Related CN104178926B (zh)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US14530909P 2009-01-16 2009-01-16
US61/145,309 2009-01-16
US25634909P 2009-10-30 2009-10-30
US61/256,349 2009-10-30
CN201080004845.8A CN102282301B (zh) 2009-01-16 2010-01-19 利用高粘度材料对ptfe进行电纺丝

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
CN201080004845.8A Division CN102282301B (zh) 2009-01-16 2010-01-19 利用高粘度材料对ptfe进行电纺丝

Publications (2)

Publication Number Publication Date
CN104178926A CN104178926A (zh) 2014-12-03
CN104178926B true CN104178926B (zh) 2018-02-09

Family

ID=42340323

Family Applications (2)

Application Number Title Priority Date Filing Date
CN201080004845.8A Expired - Fee Related CN102282301B (zh) 2009-01-16 2010-01-19 利用高粘度材料对ptfe进行电纺丝
CN201410312160.XA Expired - Fee Related CN104178926B (zh) 2009-01-16 2010-01-19 利用高粘度材料对ptfe进行电纺丝

Family Applications Before (1)

Application Number Title Priority Date Filing Date
CN201080004845.8A Expired - Fee Related CN102282301B (zh) 2009-01-16 2010-01-19 利用高粘度材料对ptfe进行电纺丝

Country Status (7)

Country Link
US (9) US8178030B2 (zh)
EP (1) EP2384375B1 (zh)
JP (2) JP5300987B2 (zh)
CN (2) CN102282301B (zh)
DK (1) DK2384375T3 (zh)
PL (1) PL2384375T3 (zh)
WO (1) WO2010083530A2 (zh)

Families Citing this family (71)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8856782B2 (en) 2007-03-01 2014-10-07 George Mason Research Foundation, Inc. On-demand disposable virtual work system
US8795577B2 (en) 2007-11-30 2014-08-05 Cook Medical Technologies Llc Needle-to-needle electrospinning
US9098698B2 (en) 2008-09-12 2015-08-04 George Mason Research Foundation, Inc. Methods and apparatus for application isolation
US20130268062A1 (en) * 2012-04-05 2013-10-10 Zeus Industrial Products, Inc. Composite prosthetic devices
CN102282301B (zh) 2009-01-16 2014-07-30 Zeus工业品公司 利用高粘度材料对ptfe进行电纺丝
US8257640B2 (en) * 2009-08-07 2012-09-04 Zeus Industrial Products, Inc. Multilayered composite structure with electrospun layer
US8637109B2 (en) * 2009-12-03 2014-01-28 Cook Medical Technologies Llc Manufacturing methods for covering endoluminal prostheses
CN101942709B (zh) * 2010-09-26 2012-01-04 东华大学 一种含多壁碳纳米管的cs/pva 复合纳米纤维及其制备方法
EP2563956A4 (en) * 2010-10-14 2013-09-18 Zeus Ind Products Inc ANTIMICROBIAL SUBSTRATE
RU2581871C2 (ru) 2011-01-28 2016-04-20 Мерит Медикал Системз, Инк. Стент, покрытый электроспряденным птфэ, и способ применения
CA2829612C (en) 2011-03-09 2020-08-11 Board Of Regents Of The University Of Texas System Apparatuses and methods for the production of fibers
US20120328885A1 (en) * 2011-06-21 2012-12-27 Applied Materials, Inc. Deposition of polymer films by electrospinning
US9163333B2 (en) 2011-07-15 2015-10-20 Cook Medical Technologies Llc Method for electrospinning a graft layer
DE102011109767A1 (de) 2011-08-09 2013-02-14 Mann + Hummel Gmbh Verfahren zur Herstellung von Polyamid-Nanofasern mittels Elektrospinnen, Polyamid-Nanofasern, ein Filtermedium mit Polyamid-Nanofasern sowie ein Filterelement mit ei-nem solchen Filtermedium
US9175427B2 (en) 2011-11-14 2015-11-03 Cook Medical Technologies Llc Electrospun patterned stent graft covering
US9081959B2 (en) 2011-12-02 2015-07-14 Invincea, Inc. Methods and apparatus for control and detection of malicious content using a sandbox environment
EP2804637B1 (en) 2012-01-16 2019-09-25 Merit Medical Systems, Inc. Rotational spun material covered medical appliances and methods of manufacture
DK2809433T3 (en) 2012-01-27 2018-01-15 Zeus Ind Products Inc ELECTROSPUNDED POROST MEDIA
CN102764171B (zh) * 2012-07-31 2015-08-19 上海交通大学 一种静电纺丝复合血管支架及其制备方法
US9890498B2 (en) 2012-07-31 2018-02-13 Nippon Valqua Industries, Ltd. Hydrophilic sheet and process for producing the same
US11541154B2 (en) * 2012-09-19 2023-01-03 Merit Medical Systems, Inc. Electrospun material covered medical appliances and methods of manufacture
US9198999B2 (en) 2012-09-21 2015-12-01 Merit Medical Systems, Inc. Drug-eluting rotational spun coatings and methods of use
CN104756213A (zh) 2012-10-31 2015-07-01 日本华尔卡工业株式会社 压电层叠体
US9486940B2 (en) * 2012-12-18 2016-11-08 Autoliv Asp, Inc. Radiation curable resin systems for composite materials and methods for use thereof
US10154918B2 (en) 2012-12-28 2018-12-18 Cook Medical Technologies Llc Endoluminal prosthesis with fiber matrix
CN103111122B (zh) * 2013-01-21 2014-10-08 苏州经贸职业技术学院 一种多孔吸附膜及其制备方法
US20140205781A1 (en) * 2013-01-23 2014-07-24 Zeus Industrial Products, Inc. Silicone espun ptfe composites
US9827703B2 (en) 2013-03-13 2017-11-28 Merit Medical Systems, Inc. Methods, systems, and apparatuses for manufacturing rotational spun appliances
WO2014159710A1 (en) * 2013-03-13 2014-10-02 Merit Medical Systems, Inc. Serially deposited fiber materials and associated devices and methods
US20140277467A1 (en) 2013-03-14 2014-09-18 Spinal Stabilization Technologies, Llc Prosthetic Spinal Disk Nucleus
US9066425B2 (en) * 2013-04-01 2015-06-23 Rohm And Haas Electronic Materials Llc Method of manufacturing a patterned transparent conductor
US20150024185A1 (en) * 2013-07-17 2015-01-22 Sabic Global Technologies B.V. Force spun sub-micron fiber and applications
US10119214B2 (en) 2013-07-17 2018-11-06 Sabic Global Technologies B.V. Force spun sub-micron fiber and applications
US9422642B2 (en) * 2013-07-29 2016-08-23 Toray Fluorofibers (America), Inc. Wear polytetrafluoroethylene (PTFE) fiber and method of making same
CN105579913B (zh) * 2013-09-27 2018-02-16 佳能株式会社 电子照相用导电性构件、处理盒和电子照相设备
CN103614860A (zh) * 2013-11-26 2014-03-05 东华大学 一种葡萄糖壬二酸二乙烯脂/异丙基丙烯酰胺共聚物纳米纤维膜的制备方法
CN103614859A (zh) * 2013-11-26 2014-03-05 东华大学 一种葡萄糖癸二酸二乙烯脂/异丙基丙烯酰胺共聚物纳米纤维膜的制备方法
KR20160093016A (ko) * 2013-12-03 2016-08-05 닛폰 바루카 고교 가부시키가이샤 전기화학소자용 복합 막
DE102014201756A1 (de) 2014-01-31 2015-08-06 Evonik Degussa Gmbh Reinigung chlorverschmutzter Organophosphorverbindungen
CN107837691B (zh) * 2014-04-22 2020-02-14 成都百途医药科技有限公司 一种超疏水聚四氟乙烯膜的制备方法
JPWO2015167013A1 (ja) * 2014-05-01 2017-04-20 日本バルカー工業株式会社 音波・衝撃検知素子
JPWO2015167014A1 (ja) * 2014-05-01 2017-06-08 日本バルカー工業株式会社 音波検知素子
US10314714B2 (en) 2014-11-04 2019-06-11 Spinal Stabilization Technologies Llc Percutaneous implantable nuclear prosthesis
US10786360B2 (en) 2014-11-04 2020-09-29 Spinal Stabilization Technologies Llc Percutaneous implantable nuclear prosthesis
CN104389106A (zh) * 2014-11-12 2015-03-04 无锡中科光远生物材料有限公司 一种聚四氟乙烯超细纤维膜及其制备方法
KR20160075170A (ko) * 2014-12-19 2016-06-29 주식회사 아모그린텍 방수 음향 장치
EP3261589B1 (en) 2015-02-26 2020-09-16 Merit Medical Systems, Inc. Layered medical appliances
WO2016194707A1 (ja) * 2015-05-29 2016-12-08 日本バルカー工業株式会社 機能性複合膜の製造方法
CN105031735B (zh) * 2015-06-24 2018-01-19 东华大学 一种三层复合结构小口径人工血管及其制备方法
CN104963098A (zh) * 2015-06-29 2015-10-07 天津工业大学 一种静电纺丝全氟聚合物纳米纤维膜的制备方法
CN105058786B (zh) * 2015-07-14 2017-05-24 大连理工大学 一种同轴聚焦电射流打印方法
US10108033B2 (en) 2015-08-04 2018-10-23 Rogers Corporation Subassemblies comprising a compressible pressure pad, methods for reducing ripple effect in a display device, and methods for improving impact absorption in a display device
JP6891176B2 (ja) 2015-09-01 2021-06-18 スパイナル スタビライゼーション テクノロジーズ リミテッド ライアビリティ カンパニー 埋込み可能な髄核プロテーゼ
CN108137997A (zh) * 2015-09-23 2018-06-08 阿克伦大学 用于制造干粘合剂产品的卷对卷方法
CN105133080A (zh) * 2015-10-16 2015-12-09 天津工业大学 一种聚四氟乙烯静电纺丝溶液
US9486323B1 (en) 2015-11-06 2016-11-08 Spinal Stabilization Technologies Llc Nuclear implant apparatus and method following partial nuclectomy
SE540918C2 (en) * 2016-01-15 2018-12-18 Scania Cv Ab A method for controlling a cooling system delivering coolant to heat exchanger in a vehicle
SG10202011609VA (en) 2016-05-16 2020-12-30 Edwards Lifesciences Corp System and method for applying material to a stent
CN105862256B (zh) * 2016-05-27 2018-01-30 江西先材纳米纤维科技有限公司 通过peo模板牺牲法制备聚四氟乙烯纳米纤维多孔膜的方法
US20170362740A1 (en) * 2016-06-16 2017-12-21 Eurekite Holding BV Flexible ceramic fibers and polymer composite and method of making the same
JP7457712B2 (ja) 2018-09-04 2024-03-28 スパイナル スタビライゼーション テクノロジーズ リミテッド ライアビリティ カンパニー 植込み可能な髄核補綴物、キット、および関連する方法
EP3921284A1 (en) 2019-02-08 2021-12-15 W.L. Gore & Associates Inc. Ultraviolet light disinfecting systems
CN109893680B (zh) * 2019-03-07 2021-10-08 宁波光远致信生物科技有限公司 一种修复纤维膜、修复套接管及其制备方法和用途
CN114126541A (zh) 2019-08-02 2022-03-01 爱德华兹生命科学公司 对医疗装置旋转施加纤维材料
CN110578208A (zh) * 2019-09-10 2019-12-17 江苏盛纺纳米材料科技股份有限公司 一种纳米纤维多组分复合丝柔非织造布及其制造方法
CN110558769A (zh) * 2019-09-18 2019-12-13 福建农林大学 一种魔芋葡甘聚糖功能型床垫及其制备方法
CA3158135A1 (en) 2019-10-28 2021-05-06 Edwards Lifesciences Corporation Sensor integration in cardiac implant devices
CN111388763B (zh) * 2020-03-25 2021-12-10 南通纺织丝绸产业技术研究院 基于ptfe的血管支架的制备方法及其应用
JP2023523998A (ja) 2020-04-28 2023-06-08 エドワーズ ライフサイエンシーズ コーポレイション 埋め込みシステムおよび埋め込みデバイスのための絹に基づいて静電紡糸された材料
WO2022177737A1 (en) 2021-02-16 2022-08-25 Edwards Lifesciences Corporation Implant devices with shunt channel sensors
JP2023036352A (ja) 2021-09-02 2023-03-14 株式会社バルカー 導電層付き基材

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1241224A (zh) * 1996-12-20 2000-01-12 纳幕尔杜邦公司 聚(四氟乙烯)及相关聚合物的分散体纺丝法

Family Cites Families (165)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2158416A (en) 1937-07-28 1939-05-16 Richard Schrelber Gastell Method and apparatus for the production of artificial fibers
US4143196A (en) * 1970-06-29 1979-03-06 Bayer Aktiengesellschaft Fibre fleece of electrostatically spun fibres and methods of making same
US4096227A (en) 1973-07-03 1978-06-20 W. L. Gore & Associates, Inc. Process for producing filled porous PTFE products
GB1530990A (en) 1974-08-05 1978-11-01 Ici Ltd Electrostatically spun tubular product
GB1527592A (en) * 1974-08-05 1978-10-04 Ici Ltd Wound dressing
GB1522605A (en) 1974-09-26 1978-08-23 Ici Ltd Preparation of fibrous sheet product
US6436135B1 (en) 1974-10-24 2002-08-20 David Goldfarb Prosthetic vascular graft
CH620483A5 (zh) * 1977-12-22 1980-11-28 Battelle Memorial Institute
DE2806030C2 (de) 1978-02-14 1984-02-02 B. Braun Melsungen Ag, 3508 Melsungen Verfahren zur Herstellung einer schlauchförmigen Blutgefäßprothese
DE2960875D1 (en) * 1978-04-19 1981-12-10 Ici Plc A method of preparing a tubular product by electrostatic spinning
EP0009941B2 (en) 1978-10-10 1987-05-27 Imperial Chemical Industries Plc Production of electrostatically spun products
US4432916A (en) 1982-01-15 1984-02-21 Morrison-Knudsen Forest Products Company, Inc. Method and apparatus for the electrostatic orientation of particulate materials
GB2121286B (en) 1982-06-02 1985-11-06 Ethicon Inc Improvements in synthetic vascular grafts, and methods of manufacturing such grafts
JP2571379B2 (ja) 1987-03-06 1997-01-16 東レ・ファインケミカル株式会社 ポリテトラフロロエレン系繊維の製造方法
US5162074A (en) 1987-10-02 1992-11-10 Basf Corporation Method of making plural component fibers
JP3000654B2 (ja) * 1990-10-19 2000-01-17 ダイキン工業株式会社 ポリテトラフルオロエチレン微粒子および粉末
CA2074349C (en) 1991-07-23 2004-04-20 Shinji Tamaru Polytetrafluoroethylene porous film and preparation and use thereof
US5328946A (en) 1991-08-29 1994-07-12 E. I. Du Pont De Nemours And Company Solvents for tetrafluoroethylene polymers
DE4130356C2 (de) 1991-09-12 1995-01-26 Bitterfeld Wolfen Chemie Fasermaterial aus PTFE und Verfahren zu seiner Herstellung
TR28790A (tr) * 1992-12-23 1997-03-25 Du Pont Düzgün alt-tabakalar icin yapismayan merdane kaplamasi.
WO1994023098A1 (en) 1993-04-05 1994-10-13 Daikin Industries, Ltd. Polytetrafluoroethylene fiber, cottony material containing the same, and process for producing the same
WO1995022359A1 (en) 1994-02-17 1995-08-24 W.L. Gore & Associates, Inc. A carvable ptfe implant material
US6133165A (en) 1994-06-30 2000-10-17 Daikin Industries, Ltd. Bulky polytetrafluoroethylene filament and split yarn, method of producting thereof, method of producing cotton-like materials by using said filament or split yarn and filter cloth for dust collection
US6175571B1 (en) 1994-07-22 2001-01-16 Network Peripherals, Inc. Distributed memory switching hub
US5509902A (en) 1994-07-25 1996-04-23 Raulerson; J. Daniel Subcutaneous catheter stabilizing devices and methods for securing a catheter using the same
EP0785302B1 (en) 1994-10-04 2003-03-26 Daikin Industries, Ltd. Mixed cotton-like material, nonwoven cloth obtained from the material and method of manufacturing these materials
US5476589A (en) 1995-03-10 1995-12-19 W. L. Gore & Associates, Inc. Porpous PTFE film and a manufacturing method therefor
BE1009278A3 (fr) 1995-04-12 1997-01-07 Corvita Europ Tuteur auto-expansible pour dispositif medical a introduire dans une cavite d'un corps, et dispositif medical muni d'un tel tuteur.
US5665428A (en) 1995-10-25 1997-09-09 Macromed, Inc. Preparation of peptide containing biodegradable microspheres by melt process
US5806633A (en) 1995-12-22 1998-09-15 Macuga; Henry J. Elevator safety system incorporating false pit
US5800512A (en) * 1996-01-22 1998-09-01 Meadox Medicals, Inc. PTFE vascular graft
US5702658A (en) 1996-02-29 1997-12-30 Owens-Corning Fiberglas Technology, Inc. Bicomponent polymer fibers made by rotary process
US5928279A (en) * 1996-07-03 1999-07-27 Baxter International Inc. Stented, radially expandable, tubular PTFE grafts
JPH11204114A (ja) 1998-01-20 1999-07-30 Daikin Ind Ltd 電極材料
DE69933545T2 (de) 1998-02-24 2007-06-21 Asahi Glass Co., Ltd. Wässrige Polytetrafluorethylendispersionszusammensetzung
US6488701B1 (en) 1998-03-31 2002-12-03 Medtronic Ave, Inc. Stent-graft assembly with thin-walled graft component and method of manufacture
EP0950421B1 (en) 1998-04-14 2006-10-18 Tranquil Prospects Ltd. Implantable material and method for its preparation
US6265333B1 (en) * 1998-06-02 2001-07-24 Board Of Regents, University Of Nebraska-Lincoln Delamination resistant composites prepared by small diameter fiber reinforcement at ply interfaces
US20030069343A1 (en) * 1998-08-06 2003-04-10 Paul Smith Melt-processible poly(tetrafluoroethylene)
US6737165B1 (en) 1998-08-06 2004-05-18 Omlidon Technologies Llc Melt-processible poly(tetrafluoroethylene)
US7235096B1 (en) 1998-08-25 2007-06-26 Tricardia, Llc Implantable device for promoting repair of a body lumen
US7815763B2 (en) 2001-09-28 2010-10-19 Abbott Laboratories Vascular Enterprises Limited Porous membranes for medical implants and methods of manufacture
EP1121066B1 (en) 1999-01-22 2006-05-17 Gore Enterprise Holdings, Inc. Covered endoprosthesis
US7018401B1 (en) 1999-02-01 2006-03-28 Board Of Regents, The University Of Texas System Woven intravascular devices and methods for making the same and apparatus for delivery of the same
US6364903B2 (en) 1999-03-19 2002-04-02 Meadox Medicals, Inc. Polymer coated stent
US6547915B2 (en) 1999-04-15 2003-04-15 Kimberly-Clark Worldwide, Inc. Creep resistant composite elastic material with improved aesthetics, dimensional stability and inherent latency and method of producing same
US6652570B2 (en) 1999-07-02 2003-11-25 Scimed Life Systems, Inc. Composite vascular graft
US7947069B2 (en) 1999-11-24 2011-05-24 University Of Washington Medical devices comprising small fiber biomaterials, and methods of use
US7300662B2 (en) 2000-05-12 2007-11-27 Cordis Corporation Drug/drug delivery systems for the prevention and treatment of vascular disease
AU2001286731A1 (en) 2000-08-25 2002-03-04 Kensey Nash Corporation Covered stents, systems for deploying covered stents
US6743273B2 (en) 2000-09-05 2004-06-01 Donaldson Company, Inc. Polymer, polymer microfiber, polymer nanofiber and applications including filter structures
US7416559B2 (en) 2000-10-27 2008-08-26 Poly-Med, Inc. Micromantled drug-eluting stent
US7244272B2 (en) 2000-12-19 2007-07-17 Nicast Ltd. Vascular prosthesis and method for production thereof
US20020084178A1 (en) 2000-12-19 2002-07-04 Nicast Corporation Ltd. Method and apparatus for manufacturing polymer fiber shells via electrospinning
US20040030377A1 (en) 2001-10-19 2004-02-12 Alexander Dubson Medicated polymer-coated stent assembly
US20070031607A1 (en) 2000-12-19 2007-02-08 Alexander Dubson Method and apparatus for coating medical implants
US6641773B2 (en) * 2001-01-10 2003-11-04 The United States Of America As Represented By The Secretary Of The Army Electro spinning of submicron diameter polymer filaments
CN1239542C (zh) * 2001-03-13 2006-02-01 纳幕尔杜邦公司 厚涂层分散体
US7105124B2 (en) * 2001-06-19 2006-09-12 Aaf-Mcquay, Inc. Method, apparatus and product for manufacturing nanofiber media
JP2005500642A (ja) * 2001-08-13 2005-01-06 スリーエム イノベイティブ プロパティズ カンパニー 光記録媒体用の物品およびその固定方法
US6827737B2 (en) 2001-09-25 2004-12-07 Scimed Life Systems, Inc. EPTFE covering for endovascular prostheses and method of manufacture
US20030100944A1 (en) 2001-11-28 2003-05-29 Olga Laksin Vascular graft having a chemicaly bonded electrospun fibrous layer and method for making same
US6752826B2 (en) 2001-12-14 2004-06-22 Thoratec Corporation Layered stent-graft and methods of making the same
JP4332329B2 (ja) 2002-02-26 2009-09-16 三菱レイヨン株式会社 中空糸膜モジュールの製造装置並びに製造方法
US8367570B2 (en) 2002-04-04 2013-02-05 The University Of Akron Mechanically strong absorbent non-woven fibrous mats
US20040051201A1 (en) 2002-04-11 2004-03-18 Greenhalgh Skott E. Coated stent and method for coating by treating an electrospun covering with heat or chemicals
US20030211135A1 (en) 2002-04-11 2003-11-13 Greenhalgh Skott E. Stent having electrospun covering and method
US20050187605A1 (en) 2002-04-11 2005-08-25 Greenhalgh Skott E. Electrospun skin capable of controlling drug release rates and method
US20030195611A1 (en) 2002-04-11 2003-10-16 Greenhalgh Skott E. Covering and method using electrospinning of very small fibers
US7351256B2 (en) * 2002-05-10 2008-04-01 Cordis Corporation Frame based unidirectional flow prosthetic implant
US7485141B2 (en) 2002-05-10 2009-02-03 Cordis Corporation Method of placing a tubular membrane on a structural frame
AU2003225291A1 (en) * 2002-05-10 2003-11-11 Cordis Corporation Method of making a medical device having a thin wall tubular membrane over a structural frame
US6863852B1 (en) 2002-05-30 2005-03-08 Zeus Industrial Products, Inc. Fluoropolymer extrusions based on novel combinations of process parameters and clay minerals
JP2004028261A (ja) 2002-06-27 2004-01-29 Fuji Koki Corp 膨張弁
FR2843975B1 (fr) * 2002-09-04 2008-11-14 Kermel Fibres et fibrides, leur procede d'obtention, articles obtenus a partir de ces fibres et/ou fibrides.
US7083697B2 (en) * 2002-12-30 2006-08-01 Boston Scientific Scimed, Inc. Porous spun polymeric structures and method of making same
US7744792B2 (en) 2003-03-27 2010-06-29 Robert Roberts Methods for continuous processing polytetrafluoroethylene (PTFE) resin
US7524527B2 (en) 2003-05-19 2009-04-28 Boston Scientific Scimed, Inc. Electrostatic coating of a device
US7790135B2 (en) * 2003-07-02 2010-09-07 Physical Sciences, Inc. Carbon and electrospun nanostructures
WO2005018600A2 (en) 2003-08-22 2005-03-03 Cube Medical A/S Method of treating a patient suffering from a solid tumour
US20050053782A1 (en) * 2003-09-04 2005-03-10 Ayusman Sen Process for forming polymeric micro and nanofibers
JP2007508121A (ja) 2003-10-14 2007-04-05 キューブ メディカル エーエス 血管形成術用バルーン
WO2005055834A1 (en) 2003-11-20 2005-06-23 Nmt Medical, Inc. Device, with electrospun fabric, for a percutaneous transluminal procedure, and methods thereof
US20050113886A1 (en) * 2003-11-24 2005-05-26 Fischell David R. Implantable medical system with long range telemetry
US7347960B2 (en) * 2003-12-31 2008-03-25 E. I. Du Pont De Nemours And Company Dispersion spinning core-shell fluoropolymers
FR2865480B1 (fr) * 2004-01-22 2006-02-24 Rhodia Polyamide Intermediates Procede de fabrication de surfaces non tissees
US8057841B2 (en) 2004-02-12 2011-11-15 University Of Akron Mechanically attached medical device coatings
US7108912B2 (en) 2004-03-09 2006-09-19 Yeu Ming Tai Chemical Industrial Co., Ltd. Polytetrafluoroethylene fiber and method for manufacturing the same
WO2005095684A1 (en) * 2004-03-25 2005-10-13 Massachusetts Institute Of Technology Production of submicron diameter fibers by two-fluid electrospinning process
US7550444B2 (en) 2004-03-26 2009-06-23 Surmodics, Inc. Composition and method for preparing biocompatible surfaces
EP1730332B1 (en) 2004-04-01 2012-08-08 E.I. Du Pont De Nemours And Company Rotary process for forming uniform material
US7297158B2 (en) 2004-06-14 2007-11-20 Thoratec Corporation Multilayer composite vascular access graft
US20080296808A1 (en) * 2004-06-29 2008-12-04 Yong Lak Joo Apparatus and Method for Producing Electrospun Fibers
US7413575B2 (en) 2004-08-30 2008-08-19 Phaneuf Matthew D Nanofibrous biocomposite prosthetic vascular graft
JP2006152479A (ja) * 2004-11-29 2006-06-15 Toray Ind Inc 極細繊維の製造装置およびそれを用いた製造方法
DE102005008926A1 (de) 2005-02-24 2006-11-16 Philipps-Universität Marburg Verfahren zur Herstellung von Nano- und Mesofasern durch Elektrospinning von kolloidalen Dispersionen
US8771582B2 (en) 2005-03-04 2014-07-08 BioScurfaces, Inc. Electrospinning process for making a textile suitable for use as a medical article
US8691543B2 (en) 2009-11-25 2014-04-08 Worcester Polytechnic Institute Nanofibrous scaffold comprising immobilized cells
US20060200232A1 (en) 2005-03-04 2006-09-07 Phaneuf Matthew D Nanofibrous materials as drug, protein, or genetic release vehicles
US20070043428A1 (en) 2005-03-09 2007-02-22 The University Of Tennessee Research Foundation Barrier stent and use thereof
US20060213829A1 (en) * 2005-03-25 2006-09-28 Rutledge Gregory C Production of submicron diameter fibers by two-fluid electrospinning process
JP5037034B2 (ja) 2005-04-26 2012-09-26 日東電工株式会社 フィルタ濾材とその製造方法および使用方法ならびにフィルタユニット
US7799262B1 (en) 2005-05-02 2010-09-21 Industrial Cooperation Foundation Chonbuk National University Method of manufacturing a continuous filament by electrospinning
KR20080008364A (ko) 2005-05-05 2008-01-23 헤모텍 아게 관 스텐트의 전면 코팅
EP1885282A4 (en) 2005-05-17 2010-05-05 Nicast Ltd IMPLANTABLE MEDICAL DEVICE WITH ELECTRIC CHARGE
US7306729B2 (en) 2005-07-18 2007-12-11 Gore Enterprise Holdings, Inc. Porous PTFE materials and articles produced therefrom
KR100785378B1 (ko) * 2005-09-05 2007-12-14 주식회사 바이오레인 다층구조의 유착방지제
US8689985B2 (en) * 2005-09-30 2014-04-08 E I Du Pont De Nemours And Company Filtration media for liquid filtration
JP2009513842A (ja) * 2005-10-31 2009-04-02 ザ、トラスティーズ オブ プリンストン ユニバーシティ 電気流体力学的印刷および製造
US7981353B2 (en) 2005-12-12 2011-07-19 University Of Washington Method for controlled electrospinning
JP4890049B2 (ja) 2006-02-24 2012-03-07 日本バイリーン株式会社 極細繊維集合体
US8585753B2 (en) 2006-03-04 2013-11-19 John James Scanlon Fibrillated biodegradable prosthesis
ES2405945T3 (es) 2006-03-28 2013-06-04 Lnk Chemsolutions, Llc. Método de manufactura de apósitos hemostáticos fibrosos
US8303874B2 (en) 2006-03-28 2012-11-06 E I Du Pont De Nemours And Company Solution spun fiber process
US8048150B2 (en) 2006-04-12 2011-11-01 Boston Scientific Scimed, Inc. Endoprosthesis having a fiber meshwork disposed thereon
US7790273B2 (en) 2006-05-24 2010-09-07 Nellix, Inc. Material for creating multi-layered films and methods for making the same
JP5049519B2 (ja) 2006-06-15 2012-10-17 日本ゴア株式会社 伸縮性複合生地、及び延伸多孔質ポリテトラフルオロエチレンフィルム
CN1876926A (zh) * 2006-07-04 2006-12-13 薛占强 一种可生物降解防止术后粘连的纳米纤维无纺织物及制备
US9139940B2 (en) 2006-07-31 2015-09-22 3M Innovative Properties Company Bonded nonwoven fibrous webs comprising softenable oriented semicrystalline polymeric fibers and apparatus and methods for preparing such webs
KR100845239B1 (ko) 2006-08-07 2008-07-10 한국과학기술연구원 내열성 초극세 섬유층을 지닌 분리막 및 이를 이용한이차전지
KR100820162B1 (ko) 2006-08-07 2008-04-10 한국과학기술연구원 내열성 초극세 섬유상 분리막 및 그 제조 방법과, 이를 이용한 이차전지
WO2008022993A2 (de) * 2006-08-21 2008-02-28 Basf Se Verfahren zur herstellung von nano- und mesofasern durch elektrospinnen von kolloidalen dispersionen
US9622888B2 (en) 2006-11-16 2017-04-18 W. L. Gore & Associates, Inc. Stent having flexibly connected adjacent stent elements
US20100190254A1 (en) 2006-12-05 2010-07-29 Nanyang Technological University Three-dimensional porous hybrid scaffold and manufacture thereof
US7857608B2 (en) 2006-12-08 2010-12-28 Spindynamics, Inc. Fiber and nanofiber spinning apparatus
CN101003917A (zh) 2007-01-19 2007-07-25 中国民航大学 一种正负极同电场复合型静电纺丝方法及其应用
US9237945B2 (en) 2007-01-30 2016-01-19 University of Pittsburgh—of the Commonwealth System of Higher Education Bioerodible wraps and uses therefor
US20080208325A1 (en) 2007-02-27 2008-08-28 Boston Scientific Scimed, Inc. Medical articles for long term implantation
US8257459B2 (en) 2007-02-28 2012-09-04 Hollingsworth & Vose Company Waved filter media and elements
US8765255B2 (en) 2007-03-06 2014-07-01 E I Du Pont De Nemours And Company Breathable waterproof garment
US8277711B2 (en) 2007-03-29 2012-10-02 E I Du Pont De Nemours And Company Production of nanofibers by melt spinning
US8303693B2 (en) 2007-04-26 2012-11-06 The Hong Kong Polytechnic University Nanofiber filter facemasks and cabin filters
AU2008261691A1 (en) 2007-06-11 2008-12-18 Nanovasc, Inc. Stents
KR100932688B1 (ko) 2007-07-06 2009-12-21 한국과학기술연구원 인공혈관용 이중막 구조의 튜브형 다공성 스캐폴드 및 그의제조방법
CZ300345B6 (cs) * 2007-07-17 2009-04-22 Elmarco, S. R. O. Zpusob zvláknování kapalné matrice, zarízení pro výrobu nanovláken elektrostatickým zvláknováním kapalné matrice a zvláknovací elektroda pro takové zarízení
US8978899B2 (en) 2007-08-01 2015-03-17 Donaldson Company, Inc. Fluoropolymer fine fiber
US9040646B2 (en) 2007-10-04 2015-05-26 W. L. Gore & Associates, Inc. Expandable TFE copolymers, methods of making, and porous, expanded articles thereof
US8637144B2 (en) 2007-10-04 2014-01-28 W. L. Gore & Associates, Inc. Expandable TFE copolymers, method of making, and porous, expended articles thereof
CN101182650A (zh) * 2007-10-30 2008-05-21 中国科学院上海硅酸盐研究所 一种可控图案化电纺丝纤维聚集体的制备方法
WO2009061787A1 (en) 2007-11-05 2009-05-14 Nanocopoeia, Inc. Coated devices and method of making coated devices that reduce smooth muscle cell proliferation and platelet activity
US7799261B2 (en) 2007-11-30 2010-09-21 Cook Incorporated Needle-to-needle electrospinning
US9834865B2 (en) 2007-12-17 2017-12-05 E I Du Pont De Nemours And Company Centrifugal solution spun nanofiber process
WO2009086015A2 (en) 2007-12-21 2009-07-09 Boston Scientific Scimed, Inc. Flexible stent-graft device having patterned polymeric coverings
EP2271796A4 (en) 2008-03-17 2012-01-04 Univ Texas FIBER SUPERFIN CREATION SECTOR AND USES THEREOF
US20090248131A1 (en) 2008-03-31 2009-10-01 Medtronic Vascular, Inc. Covered Stent and Method of Making Same
CZ2008226A3 (cs) 2008-04-15 2009-10-29 Elmarco S.R.O. Zpusob výroby nanovláken z fluorovaných kopolymeru a terpolymeru elektrostatickým zvláknováním, nanovlákna a textilie
CN101350413B (zh) * 2008-07-22 2010-09-15 山东东岳神舟新材料有限公司 一种纤维增强的多层含氟交联离子膜及其制备方法
CN102084043B (zh) 2008-10-02 2013-04-10 松下电器产业株式会社 纳米纤维制造装置
US8257640B2 (en) 2009-08-07 2012-09-04 Zeus Industrial Products, Inc. Multilayered composite structure with electrospun layer
CN102282301B (zh) 2009-01-16 2014-07-30 Zeus工业品公司 利用高粘度材料对ptfe进行电纺丝
US8206481B2 (en) 2009-02-27 2012-06-26 Bha Group, Inc. HEPA (H-10) performance synthetic nonwoven and nanofiber composite filter media
US9139669B2 (en) 2009-03-24 2015-09-22 W. L. Gore & Associates, Inc. Expandable functional TFE copolymer fine powder, the expandable functional products obtained therefrom and reaction of the expanded products
US8658707B2 (en) 2009-03-24 2014-02-25 W. L. Gore & Associates, Inc. Expandable functional TFE copolymer fine powder, the expanded functional products obtained therefrom and reaction of the expanded products
CN101530750A (zh) 2009-04-20 2009-09-16 浙江理工大学 聚四氟乙烯超细纤维多孔膜的制备方法
WO2010132636A1 (en) 2009-05-13 2010-11-18 President And Fellows Of Harvard College Methods and devices for the fabrication of 3d polymeric fibers
US8637109B2 (en) 2009-12-03 2014-01-28 Cook Medical Technologies Llc Manufacturing methods for covering endoluminal prostheses
DE102010010553A1 (de) 2010-03-05 2011-09-08 Carl Freudenberg Kg Verfahren zur Herstellung von Fasern aus Polymerdispersionen
EP2563956A4 (en) 2010-10-14 2013-09-18 Zeus Ind Products Inc ANTIMICROBIAL SUBSTRATE
RU2581871C2 (ru) 2011-01-28 2016-04-20 Мерит Медикал Системз, Инк. Стент, покрытый электроспряденным птфэ, и способ применения
KR101268447B1 (ko) 2011-04-13 2013-06-04 (주)시지바이오 이중코팅 스텐트 및 그 제조방법
EP2804637B1 (en) 2012-01-16 2019-09-25 Merit Medical Systems, Inc. Rotational spun material covered medical appliances and methods of manufacture
US20140012304A1 (en) 2012-07-03 2014-01-09 Merit Medical Systems, Inc. Multilayered balloon
US11541154B2 (en) 2012-09-19 2023-01-03 Merit Medical Systems, Inc. Electrospun material covered medical appliances and methods of manufacture
US9198999B2 (en) 2012-09-21 2015-12-01 Merit Medical Systems, Inc. Drug-eluting rotational spun coatings and methods of use
WO2014159710A1 (en) 2013-03-13 2014-10-02 Merit Medical Systems, Inc. Serially deposited fiber materials and associated devices and methods

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1241224A (zh) * 1996-12-20 2000-01-12 纳幕尔杜邦公司 聚(四氟乙烯)及相关聚合物的分散体纺丝法

Also Published As

Publication number Publication date
EP2384375A4 (en) 2012-04-18
US20160060797A1 (en) 2016-03-03
DK2384375T3 (en) 2017-10-16
US8178030B2 (en) 2012-05-15
CN104178926A (zh) 2014-12-03
JP2012515850A (ja) 2012-07-12
US20170096755A1 (en) 2017-04-06
US20130316103A1 (en) 2013-11-28
US20160002430A1 (en) 2016-01-07
JP5738928B2 (ja) 2015-06-24
US9856588B2 (en) 2018-01-02
US20100193999A1 (en) 2010-08-05
JP2013231269A (ja) 2013-11-14
US20130023175A1 (en) 2013-01-24
WO2010083530A2 (en) 2010-07-22
US20150183940A1 (en) 2015-07-02
US20160032505A1 (en) 2016-02-04
CN102282301B (zh) 2014-07-30
PL2384375T3 (pl) 2017-12-29
WO2010083530A3 (en) 2010-10-21
CN102282301A (zh) 2011-12-14
EP2384375A2 (en) 2011-11-09
JP5300987B2 (ja) 2013-09-25
EP2384375B1 (en) 2017-07-05
US20150011139A1 (en) 2015-01-08

Similar Documents

Publication Publication Date Title
CN104178926B (zh) 利用高粘度材料对ptfe进行电纺丝
McKee et al. Solution rheological behavior and electrospinning of cationic polyelectrolytes
Hu et al. Electrospun sodium alginate/polyethylene oxide fibers and nanocoated yarns
Okutan et al. Affecting parameters on electrospinning process and characterization of electrospun gelatin nanofibers
Chunder et al. Fabrication of ultrathin polyelectrolyte fibers and their controlled release properties
Ojha et al. Fabrication and characterization of electrospun chitosan nanofibers formed via templating with polyethylene oxide
Saquing et al. Alginate–polyethylene oxide blend nanofibers and the role of the carrier polymer in electrospinning
Hendrick et al. Increasing surface hydrophilicity in poly (lactic acid) electrospun fibers by addition of PLA-b-PEG co-polymers
Lin et al. Reducing electrospun nanofiber diameter and variability using cationic amphiphiles
Yuan et al. Regulating drug release from pH-and temperature-responsive electrospun CTS-g-PNIPAAm/poly (ethylene oxide) hydrogel nanofibers
CN102782196A (zh) 抗微生物基材
Stubbe et al. Aqueous electrospinning of poly (2-ethyl-2-oxazoline): Mapping the parameter space
Jia et al. Electrospun nano-fiber mats containing cationic cellulose derivatives and poly (vinyl alcohol) with antibacterial activity
Talwar et al. Associative polymer facilitated electrospinning of nanofibers
Akinalan Balik et al. Role of rheology on the formation of Nanofibers from pectin and polyethylene oxide blends
Zhang et al. Dual‐functional electrospun poly (2‐hydroxyethyl methacrylate)
WO2021006813A1 (en) An apparatus and a method of drawing a fibre
Zha et al. Effects of surface condition of conductive electrospun nanofiber mats on cell behavior for nerve tissue engineering
Shadi et al. Preparation of electroactive nanofibers of star-shaped polycaprolactone/polyaniline blends
Shadi et al. Preparation of electrospun nanofibers of star-shaped polycaprolactone and its blends with polyaniline
Zhang et al. Electrospun Ribbon‐Like Microfiber Films of a Novel Guanidine‐Based ABA Triblock Copolymer: Fabrication, Antibacterial Activity, and Cytotoxicity
Přádný et al. Electrospinning of the hydrophilic poly (2-hydroxyethyl methacrylate) and its copolymers with 2-ethoxyethyl methacrylate
Malpani et al. Rheology and Electrospinnability of Supramolecular Comb Polymer Networks Formed via Coordination Interactions
Alizadeh et al. Electroactive nanofibers of poly (2-hydroxyethyl methacrylate-graft-aniline) copolymers and their blends with polycaprolactone
Kadham et al. Preparation and characterization of Poly vinyl alcohol blends nanofibers for bio-super hydrophilic applications

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20180209

Termination date: 20210119

CF01 Termination of patent right due to non-payment of annual fee