WO2015009962A1 - Force spun sub-micrometer fiber and applications - Google Patents
Force spun sub-micrometer fiber and applications Download PDFInfo
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- WO2015009962A1 WO2015009962A1 PCT/US2014/047084 US2014047084W WO2015009962A1 WO 2015009962 A1 WO2015009962 A1 WO 2015009962A1 US 2014047084 W US2014047084 W US 2014047084W WO 2015009962 A1 WO2015009962 A1 WO 2015009962A1
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- Prior art keywords
- filaments
- component
- copolymer
- poly
- polyetherimide
- Prior art date
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Classifications
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- 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
- D04H1/76—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 otherwise than in a plane, e.g. in a tubular way
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- 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
- D01D5/18—Formation of filaments, threads, or the like by means of rotating spinnerets
-
- 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
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
- D01F6/64—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters from polycarbonates
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- 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
- D04H3/07—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 otherwise than in a plane, e.g. in a tubular way
Definitions
- the invention relates generally to a process of forming a non-woven web from a polymeric material including spinning a plurality of continuous polymeric filaments selected from the group consisting of a polycarbonate homopolymer component, a polycarbonate copolymer component, and combinations thereof; a polyetherimide component; and a poly(phenylene ether) component and a poly(phenylene ether)- polysiloxane block copolymer.
- the polymeric component may be chopped prior to forming the non-woven. Forming the non-woven web at a high rate of at least 300 grams/hour/spinneret is disclosed.
- PC Polycarbonate
- PC Copolymers have been converted into fibers using the melt spinning process for some time. This is capable of producing fibers in the range of 10- 20 micrometers. Melt blown has also been used for some PC's producing fibers in the 1 to 10 micrometer range.
- Typical production rates for this process are in the 200 to 300 grams per hour, and 60 meters per minute line speed rates.
- PEI Polyetherimide
- PPE Polyphenylene ether
- PPE / olefin resin blends that offer toughness, a wide range of stiffness, flame retardancy and are available from SABIC, have been converted down to 15 to 20 micrometers in diameter using the melt spinning process, but haven't been used in the melt blown area.
- Polybutylene terephthalate (PBT) has been spun to 10 - 20 micrometer range via melt spinning, and to 1 - 10 micrometers using the melt blown process. Electro-spinning of these resins is possible, but the cost of the resin and the slow throughput rate of this process have made this method commercially
- Typical production rates for this process are in the 200 to 300 grams per hour, and 60 meters per minute line speed rates.
- the above-identified materials can be either melt spun or solution spun into fiber diameters in the sub-micrometer range. Even small decreases in fiber diameters results in substantial increases in the surface area of the resins, thereby increasing the performance benefit that the individual resins bring to the applications.
- Each of these resin families have been converted to sub-micrometer fibers using this process.
- One advantage this process brings is a reasonable throughput of ultra-fine fibers enabling them to be produced in an economically viable method. Throughput rates as high as 200 to 300 thousand grams per hour are possible, with line speeds as high as 250 meters per minute and higher.
- the output of this process is a non-woven web structure of continuous fiber lengths, randomly laid down onto a carrier substrate, or coated onto another functional sheet, film, non-woven or other rolled good product.
- the resulting product is then packaged as a rolled good to be used in further downstream processes, to produce applications such as membranes, battery separators, filtration media, composites, electrical papers, and honeycomb papers.
- FIG. 1 depicts one or more nozzles coupled to one or more openings of a known fiber producing device
- FIG. 2 shows a cross-sectional view of the known fiber producing device
- FIG. 3 is an image showing the fiber morphology obtained according to Example 1 ;
- FIG. 4 is an image showing the fiber morphology obtained according to Example 2.
- FIGs. 5A -5D show force spun polyetherimide fibers
- FIG. 6A is an image showing the fiber morphology obtained according to Example 6;
- FIG. 6B is a histogram showing fiber diameter measurements obtained according to Example 6;
- FIG. 7A is an image showing the fiber morphology obtained according to Example 7.
- FIG. 7B is a histogram showing fiber diameter measurements obtained according to Example 7.
- FIG. 8A is an image showing the fiber morphology obtained according to
- FIG. 8B is a histogram showing fiber diameter measurements obtained according to Example 8.
- FIG. 9A is an image showing the fiber morphology obtained according to Example 9;
- FIG. 9B is a histogram showing fiber diameter measurements obtained according to Example 9;
- FIGs. 10A-10C show force spun poly(phenylene ether) fibers
- FIG. 1 1 A is an image showing the fiber morphology obtained according to Example 15;
- FIG. 1 1 B is a histogram showing fiber diameter measurements obtained according to Example 15;
- FIG. 12A is an image showing the fiber morphology obtained according to Example 1 6;
- FIG. 12B is a histogram showing fiber diameter measurements obtained according to Example 1 6;
- FIG. 13A is an image showing the fiber morphology obtained according to Example 17.
- FIG. 13B is a histogram showing fiber diameter measurements obtained according to Example 17.
- Various embodiments of a process of forming a non-woven web including spinning a plurality of continuous polymeric filaments including a polycarbonate homopolymer component, a polycarbonate copolymer component, and combinations thereof at a high rate of at least 300 grams/hour/spinneret.
- inventions provide a process of forming a non-woven web including spinning a plurality of continuous polymeric filaments including polyetherimide homopolymers, polyetherimide copolymers, aromatic polyester homopolymers, aromatic polyester copolymers, or combinations thereof at a rate of at least 300 grams/hour/spinneret.
- Still other embodiments provide processes of forming a non-woven web including a poly(phenylene ether) component, a poly(phenylene ether)-polysiloxane block copolymer, and combinations thereof at a high rate of at least 300
- FIG. 1 depicts a known fiber producing device 100, as described in WO 2012/109215, the entirety of which is hereby incorporated by reference.
- one or more nozzles 130 may be coupled to one or more openings 122 of fiber producing device 100.
- a "nozzle" is a mechanical device designed to control the direction or characteristics of a fluid flow as it exits (or enters) an enclosed chamber or pipe via an orifice. Nozzles may have an internal cavity 138 running through the longitudinal length of the nozzle, as depicted in FIG. 1 .
- Internal cavity 138 may be substantially aligned with opening 122 when nozzle 130 is coupled to an opening. Spinning of fiber producing device 100 causes material to pass thorough one or more of openings 122 and into one or more nozzles 130. The material is then ejected from one or more nozzles 130 through nozzle orifice 136 to produce fibers.
- Nozzle 130 may include a nozzle tip 134 having an internal diameter smaller than an internal diameter of nozzle internal cavity 138.
- internal cavity 138 of nozzle 130 and/or nozzle orifice 136 may have a size and/or shape that causes the creation of microfibers and/or nanofibers by ejecting of the material through the nozzle.
- the openings may be placed in any position on the body of a fiber producing device.
- the position of the openings may be varied to create different kinds of fibers.
- openings may be placed in different planes of the fiber producing device.
- openings may be clustered in certain locations. Such alternate positioning of the openings may increase the fiber dispersion patterns and/or increase the fiber production rates.
- the openings regardless of the position, may accept an outlet element (e.g., a nozzle or needle).
- FIG. 2 shows a cross-sectional view of fiber producing device of FIG. 2.
- Body 120 includes one or more sidewalls 121 and a bottom 123 which together define an internal cavity 125.
- body 120 is substantially circular or oval and includes a singular continuous sidewall 121 , for example, sidewall and bottom are a single, unitary component of the fiber producing device.
- Openings 122 are formed in sidewall 121 of body 120, extending through the sidewall such that the opening allows transfer of material from internal cavity 125 through the sidewall.
- sidewall 121 is angled from bottom 1 23 toward one or more openings 122.
- sidewall 121 may be rounded from bottom 123 toward one or more openings 122.
- Having an angled or rounded sidewall extending toward one or more openings facilitates flow of material in the body toward the openings when the fiber producing device is being rotated. As the fiber producing device is rotated the material rides up the angled or rounded walls toward the openings. This minimizes the occurrence of regions where material is inhibited from traveling toward the openings.
- Various embodiments relate to a process of forming a non-woven web.
- the process can include spinning a plurality of continuous polymeric filaments including one selected from a polycarbonate homopolymer component, a polycarbonate copolymer component, and combinations thereof.
- the filaments can have a length to diameter ratio that can be more than 1 ,000,000, and a diameter ranging from 50 nanometers to 5 micrometers, preferably from 50 nanometers to 2 micrometers.
- the spinning can include passing a polymer through a spinneret having a plurality of orifices in a non-electrospinning environment.
- the process according to various embodiments can further include: chopping the plurality of continuous filaments and obtaining a plurality of chopped nano-fibers; and forming the nano-fibers into a non- woven web.
- the spinning can be conducted at a rate of at least 300
- none of the plurality of continuous polymeric filaments are bonded to adjacent filaments. According to other embodiments, none of the plurality of continuous polymeric filaments are bonded to adjacent filaments. According to other embodiments,
- a portion of the plurality of continuous polymeric filaments can be at least partially bonded to adjacent filaments.
- each of the plurality of continuous polymeric filaments can be at least partially bonded to adjacent filaments.
- Various embodiments of the process can further include entangling the filaments.
- the non-woven web can contain less than 10 wt% of a material selected from polyvinyl pyrrolidine, polymethyl methacrylate, polyvinylidene fluoride, polypropylene, polyethylene oxide, agarose, polyvinylidene fluoride, polylactic glycolic acid, nylon 6, polycaprolactone, polylactic acid, polybutylene terephthalate, polyetherimide homopolymers, polyetherimide copolymers,
- polyetherether ketones homopolymers, polyetherether ketone copolymers, polyphenylene sulfone homopolymers, polyphenylene sulfone copolymers, poly(phenylene ether) components, poly(phenylene ether)-polysiloxane block copolymer, and combinations thereof.
- the polymeric filaments are free of one or more of the foregoing polymers.
- Various embodiments relate to a process including spinning a plurality of continuous polymeric filaments by passing at least one polymeric component through a spinneret having a plurality of orifices, and producing a non-woven web including the plurality of continuous polymeric filaments.
- the at least one polymeric component can include a polycarbonate homopolymer component, a polycarbonate copolymer component, and combinations thereof.
- Each of the plurality of continuous polymeric filaments can have a length to diameter ratio within a range having a lower limit and/or an upper limit.
- the range can include or exclude the lower limit and/or the upper limit.
- the lower limit and/or upper limit can be selected from 500000, 1000000, 1500000, 2000000, 2500000, 3000000, 3500000, 4000000, 4500000, 5000000, 10000000, 15000000, 20000000, 25000000, 30000000, 35000000, 40000000, 45000000, 50000000, 55000000, 60000000, 65000000, 70000000, 75000000, 80000000, 85000000, 90000000, 95000000, 100000000, 105000000, 1 10000000, 1 15000000, 120000000,
- each of the plurality of continuous polymeric filaments can have a length to diameter ratio that can be more than 1 ,000,000.
- Each of the plurality of continuous polymeric filaments can have a diameter within a range having a lower limit and/or an upper limit.
- the range can include or exclude the lower limit and/or the upper limit.
- the lower limit and/or upper limit can be selected from 25, 50, 75, 100, 125, 150, 175, 200, 225, 250, 275, 300, 325, 350, 375, 400, 425, 450, 475, 500, 525, 550, 575, 600, 625, 650, 675, 700, 725, 750, 775, 800, 825, 850, 875, 900, 925, 950, 975, 1000, 1025, 1050, 1075, 1 100, 1 125, 1 150, 1 175, 1200, 1225, 1250, 1275, 1300, 1325, 1350, 1375, 1400, 1425, 1450, 1475, 1500, 1525, 1550, 1575, 1 600, 1 625, 1 650, 1 675, 1700,
- Table 1 summarizes exemplary length to diameter ratios according to various embodiments.
- the non-woven web can have a width within a range having a lower limit and/or an upper limit.
- the range can include or exclude the lower limit and/or the upper limit.
- the lower limit and/or upper limit can be selected from 100, 105, 1 10, 1 15, 120, 125, 130, 135, 140, 145, 150, 155, 1 60, 1 65, 170, 175, 180, 185, 190, 195, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490, 500, 600, 700, 800, 900, 1000, 1 100, 1200, 1300, 1400, 1500, 1 600, 1700, 1800, 1900, and 2000 millimeters (mm).
- the non-woven web can have a width of
- Producing the non-woven web can include depositing the plurality of continuous filaments onto one selected from a carrier substrate, a functional sheet, a film, a woven or non-woven fabric (i.e., a felt), a rolled good product, and combinations thereof.
- the carrier substrate can be a reciprocating belt.
- the process can further include solidifying the plurality of continuous polymeric filaments before the depositing step.
- the non-woven web can be unconsolidated.
- the process can further include consolidating the non-woven web.
- the process can further include consolidating the non-woven web under pressure.
- the spinning can be conducted in a non-electrospinning environment.
- the spinning can be conducted at a rate within a range having a lower limit and/or an upper limit.
- the range can include or exclude the lower limit and/or the upper limit.
- the lower limit and/or upper limit can be selected from 100, 105, 1 10, 1 15, 120, 125, 130, 135, 140, 145, 150, 155, 1 60, 1 65, 170, 175, 180, 185, 190, 195, 200, 205, 210, 215, 220, 225, 230, 235, 240, 245, 250, 255, 260, 265, 270, 275, 280, 285, 290, 295, 300, 305, 310, 315, 320, 325, 330, 335, 340, 345, 350, 355, 360, 365, 370, 375, 380, 385, 390, 395, 400, 425, 450, 475, 500, 525, 550, 575, 600, 625, 650, 675, 700, 725
- each of the plurality of continuous polymeric filaments can be provided with at least one additional functionality imparting at least one selected from therapeutic activity, catalytic activity
- microelectronic activity microelectronic activity, micro-optoelectronic activity, magnetic activity, biological activity, and combinations thereof.
- none of the plurality of continuous polymeric filaments can be bonded to adjacent filaments.
- a portion of the plurality of continuous polymeric filaments can be at least partially bonded to adjacent filaments.
- each of the plurality of continuous polymeric filaments are at least partially bonded to adjacent filaments.
- the process can further include entangling the filaments.
- the entangling can be one of needle-punching and fluid hydroentanglement.
- the polycarbonate homopolymer component can include a bisphenol A homopolymer.
- the polycarbonate copolymer component can include bisphenol A carbonate units and unit f the formula:
- the polycarbonate copolymer component can include a poly(carbonate-siloxane) including bisphenol A carbonate units and siloxane units of the formulas:
- E can have an average value of 2 to 200, wherein the poly(carbonate-siloxane) can include 0.5 to 55 wt.% of siloxane units based on the total weight of the poly(carbonate-siloxane).
- the polycarbonate homopolymer component, the polycarbonate copolymer component, or the combination thereof can be in the form of a solution of the polycarbonate homopolymer component in a solvent.
- the process can further include at least partially removing the solvent from the filament before the filament can be deposited.
- the solvent can be selected from the group of N-methyl-2-pyrrolidone or chlorinated solvents.
- the chlorinated solvent can be selected from the group of chloroform, methylene chloride, carbon
- the non-woven web can contain less than 10 wt.%, less than 9 wt.%, less than 8 wt.%, less than 7 wt.%, less than 6 wt.%, less than 5 wt.%, less than 4 wt.%, less than 3 wt.%, less than 2 wt.%, less than 1 wt.%, of a material selected from polyvinyl pyrrolidine, polymethyl methacrylate,
- polyvinylidene fluoride polypropylene, polyethylene oxide, agarose, polyvinylidene fluoride, polylactic glycolic acid, nylon 6, polycaprolactone, polylactic acid, polybutylene terephthalate, polyetherimide homopolymers, polyetherimide
- copolymers polyetherether ketones homopolymers, polyetherether ketones copolymers, polyphenylene sulfone homopolymers, polyphenylene sulfone copolymers, poly(phenylene ether) components, poly(phenylene ether)-polysiloxane block copolymer, and combinations thereof.
- the process and the non-woven web can exclude any detectable amount of a material selected form polyvinyl pyrrolidine, polymethyl methacrylate, polyvinylidene fluoride, polypropylene, polycarbonate, polyethylene oxide, agarose, polyvinylidene fluoride, polylactic glycolic acid, nylon 6, polycaprolactone, polylactic acid, polybutylene terephthalate, and combinations thereof.
- the product can be at least one selected from non-woven paper, medical implants, ultra-fine filters, membranes, hospital gowns, electrical insulation paper, honeycomb structures and personal hygiene products, dialyzers, blood, oxygenator filters, intravenous (IV) filters, diagnostic test filters, and
- blood/apheresis filters can be a composite non-woven product including the spun filaments and at least one other fiber.
- the product can be a composite non- woven product adhered to a rolled sheet article.
- the product can be a composite non-woven product adhered to at least one of a sheet or film.
- Various embodiments relate to a process of forming a non-woven web, which include spinning a plurality of continuous polymeric filaments including a
- polyetherimide homopolymer a polyetherimide copolymer, a polyetherether ketone homopolymer, a polyetherether ketone copolymer, a polyphenylene sulfone homopolymer, a polyphenylene sulfone copolymer, an aromatic polyester
- the filaments can have a length to diameter ratio that is more than 1 ,000,000, and a diameter ranging from 50 nanometers to 5 micrometers, preferably from 50 nanometers to 2 micrometers.
- the spinning can include passing a polymer through a spinneret having a plurality of orifices in a non-electrospinning environment.
- the process can further include chopping the plurality of continuous filaments and obtaining a plurality of chopped nano-fibers and forming the nano-fibers into a non-woven web.
- the spinning is conducted at a rate of at least 300 grams/hour/spinneret.
- the process can further include entangling the filaments.
- none of the plurality of continuous polymeric filaments are bonded to adjacent filaments. According to other embodiments, none of the plurality of continuous polymeric filaments are bonded to adjacent filaments. According to other embodiments,
- a portion of the plurality of continuous polymeric filaments can be at least partially bonded to adjacent filaments. According to other embodiments, each of the plurality of continuous polymeric filaments can be at least partially bonded to adjacent filaments.
- the non-woven web can contain less than 10 wt% of a material selected from polyvinyl pyrrolidine, polymethyl methacrylate, polyvinylidene fluoride, polypropylene, polycarbonate, polyethylene oxide, agarose, polyvinylidene fluoride, polylactic glycolic acid, nylon 6, polycaprolactone, polylactic acid, polybutylene terephthalate, polycarbonate homopolymers, polycarbonate copolymers, poly(phenylene ether) polymers, poly(phenylene ether)-polysiloxane block copolymers, and combinations thereof.
- the non-woven web is free of one or more of the foregoing polymers.
- Various embodiments relate to a process including spinning a plurality of continuous polymeric filaments by passing at least one polymeric component through a spinneret having a plurality of orifices, and producing a non-woven web can include the plurality of continuous polymeric filaments.
- the at least one polymeric component can include polyetherimide homopolymers, polyetherimide copolymers, polyetherether ketones homopolymers, polyetherether ketone
- polyetherimide component selected from polyetherimide homopolymers, polyetherimide copolymers, or a combination thereof, aromatic polyester homopolymers, aromatic polyester copolymers, or combinations thereof.
- Each of the plurality of continuous polymeric filaments can have a length to diameter ratio within a range having a lower limit and/or an upper limit.
- the range can include or exclude the lower limit and/or the upper limit.
- the lower limit and/or upper limit can be selected from 500000, 1000000, 1500000, 2000000, 2500000, 3000000, 3500000, 4000000, 4500000, 5000000, 10000000, 15000000, 20000000, 25000000, 30000000, 35000000, 40000000, 45000000, 50000000, 55000000, 60000000, 65000000, 70000000, 75000000, 80000000, 85000000, 90000000, 95000000, 100000000, 105000000, 1 10000000, 1 15000000, 120000000,
- each of the plurality of continuous polymeric filaments can have a length to diameter ratio that can be more than 1 ,000,000, for example 1 ,000,000 to 300000000.
- Each of the plurality of continuous polymeric filaments can have a diameter within a range having a lower limit and/or an upper limit.
- the range can include or exclude the lower limit and/or the upper limit.
- the lower limit and/or upper limit can be selected from 25, 50, 75, 100, 125, 150, 175, 200, 225, 250, 275, 300, 325, 350, 375, 400, 425, 450, 475, 500, 525, 550, 575, 600, 625, 650, 675, 700, 725, 750, 775, 800, 825, 850, 875, 900, 925, 950, 975, 1000, 1025, 1050, 1075, 1 100, 1 125, 1 150, 1 175, 1200, 1225, 1250, 1275, 1300, 1325, 1350, 1375, 1400, 1425, 1450, 1475, 1500, 1525, 1550, 1575, 1 600, 1 625, 1 650, 1 675, 1700,
- each of the plurality of continuous polymeric filaments can have a diameter ranging from 50 nanometers to 5 micrometers, preferably from 50 nanometers to 2 micrometers.
- Table 2 summarizes exemplary length to diameter ratios according to various embodiments.
- the non-woven web can have a width within a range having a lower limit and/or an upper limit.
- the range can include or exclude the lower limit and/or the upper limit.
- the lower limit and/or upper limit can be selected from 100, 105, 1 10, 1 15, 120, 125, 130, 135, 140, 145, 150, 155, 1 60, 1 65, 170, 175, 180, 185, 190, 195, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490, 500, 600, 700, 800, 900, 1000, 1 100, 1200, 1300, 1400, 1500, 1 600, 1700, 1800, 1900, and 2000 mm.
- the non-woven web can have a width of at least 150
- Producing the non-woven web can include depositing the plurality of continuous filaments onto one selected from a carrier substrate, a functional sheet, a film, a woven or non-woven fabric, a rolled good product, and combinations thereof.
- the carrier substrate can be a reciprocating belt.
- the process can further include solidifying the plurality of continuous polymeric filaments before the depositing step.
- the non-woven web can be unconsolidated.
- the process can further include consolidating the non-woven web.
- the process can further include consolidating the non-woven web under pressure.
- the spinning can be conducted in a non-electrospinning environment.
- the spinning can be conducted at a rate within a range having a lower limit and/or an upper limit.
- the range can include or exclude the lower limit and/or the upper limit.
- the lower limit and/or upper limit can be selected from 100, 105, 1 10, 1 15, 120, 125, 130, 135, 140, 145, 150, 155, 1 60, 1 65, 170, 175, 180, 185, 190, 195, 200, 205, 210, 215, 220, 225, 230, 235, 240, 245, 250, 255, 260, 265, 270, 275, 280, 285, 290, 295, 300, 305, 310, 315, 320, 325, 330, 335, 340, 345, 350, 355, 360, 365, 370, 375, 380, 385, 390, 395, 400, 425, 450, 475, 500, 525, 550, 575, 600, 625, 650, 675, 700, 725
- each of the plurality of continuous polymeric filaments can be provided with at least one additional functionality imparting therapeutic activity, catalytic activity microelectronic activity, micro- optoelectronic activity, magnetic activity, and/or biological activity.
- none of the plurality of continuous polymeric filaments are bonded to adjacent filaments. According to other embodiments,
- a portion of the plurality of continuous polymeric filaments are at least partially bonded to adjacent filaments.
- each of the plurality of continuous polymeric filaments are at least partially bonded to adjacent filaments.
- the process can further include entangling the filaments. The entangling can be one of needle-punching and fluid hydroentanglement.
- the polyetherimide component can include a polyetherimide in molten form.
- the polyetherimide component can be selected from a member including (i) the reaction product of 4,4'-bisphenol A dianhydride and meta-phenylene diamine monomers, (ii) the reaction product of 4,4'-bisphenol A dianhydride and para- phenylene diamine monomers, and (iii) the reaction product of 4,4'-bisphenol A dianhydride, aminopropyl-capped polydimethylsiloxane, and meta-phenylene diamine monomers.
- the polyetherimide component can be a thermoplastic resin composition including the polyetherimide, and a phosphorous-containing stabilizer, in an amount that is effective to increase the melt stability of the polyetherimide, wherein the phosphorous-containing stabilizer exhibits a low volatility such that, as measured by thermogravimetric analysis of an initial amount of a sample of the phosphorus-containing stabilizer, greater than or equal to 10 percent by weight of the initial amount of the sample remains unevaporated upon heating of the sample from room temperature to 300°C at a heating rate of 20°C per minute under an inert atmosphere.
- the polyetherimide component can be in the form of a solution of polyetherimide in a solvent.
- the composition can include a phosphorus stabilizer in an amount within a range having a lower limit and/or an upper limit.
- the range can include or exclude the lower limit and/or the upper limit.
- the lower limit and/or upper limit can be selected from 0.01 , 0.05, 0.1 , 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 , 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1 , 12, 13, 14, 15, 1 6, 17, 18, 19 and 20 wt. %.
- the phosphorous stabilizer can be mixed together with the other components of the composition.
- the phosphorous stabilizer can be introduced as a component of a polyetherimide thermoplastic resin composition comprising (a) a polyetherimide resin, and, (b) a phosphorous-containing stabilizer.
- a polyetherimide resin e.g., polyethylene glycol dimethacrylate copolymer
- a phosphorous-containing stabilizer for the polyetherimide resin is described in U.S. Patent 6,001 ,957, the entire disclosure of which is herein incorporated by reference.
- the phosphorus-containing stabilizer is present in an amount effective to increase the melt stability of the polyetherimide resin, wherein the phosphorous-containing stabilizer exhibits a low volatility such that, as measured by gravimetric analysis of an initial amount of a sample of the phosphorous-containing stabilizer, greater than or equal to 10% by weight of the initial amount of the sample remains unevaporated upon heating the sample from room temperature to 300° C at a heating rate of 20° C per minute under an inert atmosphere, wherein the phosphorous-containing compound is a compound according to the structural formula P-R1 a, wherein each R1 is independently H, C1 - 12 alkyl, C1 -12 alkoxyl, C6-12 aryl, C6-12 aryloxy or oxo, and a is 3 or 4.
- the composition can include a phosphorus stabilizer in an amount of between 0.01 -10 wt.%, 0.05 - 10 wt.%, or from 5 to 10 wt.%
- aromatic polyesters can be used alone in in
- the aromatic polyester homopolymers and/or the aromatic polyester copolymers can include liquid crystal polymers.
- Wholly or partially aromatic polyesters include liquid crystal polyesters.
- Illustrative examples of such aromatic polyesters include self-condensed polymers of p-hydroxybenzoic acid, polyesters comprising repeat units derived from terephthalic acid and hydroquinone, polyester fibers comprising repeat units derived from p-hydroxybenzoic acid and 6-hydroxy-2- naphthoic acid, or combinations thereof.
- a specific aromatic liquid crystal polyester can produced by the polycondensation of 4-hydroxybenzoic acid and 6- hydroxynaphthalene-2-carboxylic acid (fibers made from such a product are commercially available from Kuraray Co., Ltd. under the trade name designation VECTRAN).
- Such a polymer can have the followin formula:
- x and y are independently selected positive integers.
- x and y can be independently selected from any positive integer within a range having a lower limit and/or an upper limit.
- the range can include or exclude the lower limit and/or the upper limit.
- the lower limit and/or upper limit can be selected from 1 , 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 1 10, 120, 130, 140, 150, 1 60, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490, 500, 510, 520, 530, 540, 550, 560, 570, 580, 590, 600, 610, 620, 630, 640, 650, 660, 670, 680
- x and y can both be 1000. According to other embodiments, x can be between 500 and 1500 and y can be between 1000 and 2000.
- aromatic polyesters may be produced by any methods known to one skilled in the art. Fibers made from such aromatic polyesters are advantageously made from molten aromatic polymers and can be melt spun.
- the process can further include at least partially removing the solvent from the filament before the filament is deposited.
- the solvent can be selected from meta-cresol, veratrol, ortho-dich!orobenzene (ODCB), N-methyl pyrrolidinone, chloroform, tetrahydrofuran (THF), dimethyl formamide (DMF), dimethyl acetamide (DCM), dichloromethane, trichlorobenzene, benzoic acid, and mixtures thereof.
- the non-woven web can contain less than 10 wt% of a material selected from polyvinyl pyrrolidine, polymethyl methacrylate, polyvinylidene fluoride, polypropylene, polycarbonate, polyethylene oxide, agarose, polyvinylidene fluoride, polylactic glycolic acid, nylon 6, polycaprolactone, polylactic acid, polybutylene terephthalate, polycarbonate homopolymers, polycarbonate copolymers, poly(phenylene ether) polymers, poly(phenylene ether)-polysiloxane block copolymers and combinations thereof.
- a material selected from polyvinyl pyrrolidine, polymethyl methacrylate, polyvinylidene fluoride, polypropylene, polycarbonate, polyethylene oxide, agarose, polyvinylidene fluoride, polylactic glycolic acid, nylon 6, polycaprolactone, polylactic acid, polybutylene terephthalate, polycarbonate homopolymers, polycarbonate copo
- Various embodiments of the process can exclude any detectable amount of a material selected from polyvinyl pyrrolidine, polymethyl methacrylate, polyvinylidene fluoride, polypropylene, polycarbonate, polyethylene oxide, agarose, polyvinylidene fluoride, polylactic glycolic acid, nylon 6, polycaprolactone, polylactic acid, polybutylene terephthalate, polycarbonate homopolymers, polycarbonate copolymers, and combinations thereof.
- the non-woven web is free of any one or more of the foregoing polymers.
- the product can be at least one selected from non- woven paper, medical implants, ultra-fine filters, membranes, hospital gowns, electrical insulation paper, honeycomb structures and personal hygiene products, dialyzers, blood, oxygenator filters, intravenous (IV) filters, diagnostic test filters, and blood/apheresis filters.
- The can be a composite non-woven product including the spun filaments and at least one other fiber.
- the product can be a composite non- woven product adhered to a rolled sheet good (i.e., a rolled sheet article).
- the product can be a composite non-woven product adhered to at least one of a sheet or film.
- Various embodiments relate to a process of forming a non-woven web wherein the process includes spinning a plurality of continuous polymeric filaments comprising a poly(phenylene ether) component, a poly(phenylene ether)- polysiloxane block copolymer, and combinations thereof.
- the filaments can have a length to diameter ratio that is more than 1 ,000,000, and a diameter ranging from 50 nanometers to 5 micrometers, preferably from 50 nanometers to 2 micrometers.
- the spinning can include passing a polymer through a spinneret having a plurality of orifices in a non-electrospinning environment.
- the process can further include chopping the plurality of continuous filaments and obtaining a plurality of chopped nano-fibers and forming the nano-fibers into a non-woven web.
- the spinning can be conducted at a rate of at least 300 grams/hour/spinneret.
- none of the plurality of continuous polymeric filaments are bonded to adjacent filaments. According to other embodiments, none of the plurality of continuous polymeric filaments are bonded to adjacent filaments. According to other embodiments,
- a portion of the plurality of continuous polymeric filaments can be at least partially bonded to adjacent filaments.
- each of the plurality of continuous polymeric filaments can be at least partially bonded to adjacent filaments.
- the process can further include entangling the filaments.
- the non-woven web can contain less than 10 wt% of a material selected from polyvinyl pyrrolidine, polymethyl methacrylate, polyvinylidene fluoride, polypropylene, polycarbonate, polyethylene oxide, agarose, polyvinylidene fluoride, polylactic glycolic acid, nylon 6, polycaprolactone, polylactic acid, polybutylene terephthalate, polyetherimide homopolymers, polyetherimide copolymers, polyetherether ketones homopolymers, polyetherether ketones copolymers, polyphenylene sulfone homopolymers, polyphenylene sulfone copolymers, polycarbonate homopolymers, polycarbonate copolymers, and combinations thereof.
- a material selected from polyvinyl pyrrolidine, polymethyl methacrylate, polyvinylidene fluoride, polypropylene, polycarbonate, polyethylene oxide, agarose, polyvinylidene fluoride, polylactic glycolic acid, nylon
- the non-woven web is free of any one or more of the foregoing polymers.
- Various embodiments relate to a process including spinning a plurality of continuous polymeric filaments by passing at least one polymeric component through a spinneret having a plurality of orifices, and producing a non-woven web comprising the plurality of continuous polymeric filaments.
- the at least one polymeric component can include one selected from a poly(phenylene ether) component, a poly(phenylene ether)-polysiloxane block copolymer, and combinations thereof.
- the non-woven web has a width of at least 150 mm
- Each of the plurality of continuous polymeric filaments can have a length to diameter ratio within a range having a lower limit and/or an upper limit.
- the range can include or exclude the lower limit and/or the upper limit.
- the lower limit and/or upper limit can be selected from 500000, 1000000, 1500000, 2000000, 2500000, 3000000, 3500000, 4000000, 4500000, 5000000, 10000000, 15000000, 20000000, 25000000, 30000000, 35000000, 40000000, 45000000, 50000000, 55000000, 60000000, 65000000, 70000000, 75000000, 80000000, 85000000, 90000000, 95000000, 100000000, 105000000, 1 10000000, 1 15000000, 120000000,
- each of the plurality of continuous polymeric filaments can have a length to diameter ratio that can be more than 1 ,000,000.
- Each of the plurality of continuous polymeric filaments can have a diameter within a range having a lower limit and/or an upper limit.
- the range can include or exclude the lower limit and/or the upper limit.
- the lower limit and/or upper limit can be selected from 25, 50, 75, 100, 125, 150, 175, 200, 225, 250, 275, 300, 325, 350, 375, 400, 425, 450, 475, 500, 525, 550, 575, 600, 625, 650, 675, 700, 725, 750, 775, 800, 825, 850, 875, 900, 925, 950, 975, 1000, 1025, 1050, 1075, 1 100, 1 125, 1 150, 1 175, 1200, 1225, 1250, 1275, 1300, 1325, 1350, 1375, 1400, 1425, 1450, 1475, 1500, 1525, 1550, 1575, 1 600, 1 625, 1 650, 1 675, 1700,
- each of the plurality of continuous polymeric filaments can have a diameter ranging from 50 nanometers to 5 micrometers, preferably from 50 nanometers to 2 micrometers.
- Table 3 summarizes exemplary length to diameter ratios according to various embodiments.
- the non-woven web can have a width within a range having a lower limit and/or an upper limit.
- the range can include or exclude the lower limit and/or the upper limit.
- the lower limit and/or upper limit can be selected from 100, 105, 1 10, 1 15, 120, 125, 130, 135, 140, 145, 150, 155, 1 60, 1 65, 170, 175, 180, 185, 190, 195, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490, 500, 600, 700, 800, 900, 1000, 1 100, 1200, 1300, 1400, 1500, 1 600, 1700, 1800, 1900, and 2000 mm.
- the non-woven web can have a width of at least 150
- Producing the non-woven web can include depositing the plurality of continuous filaments onto one selected from a carrier substrate, a functional sheet, a film, a woven or non-woven fabric, a rolled good product, and combinations thereof.
- the carrier substrate can be a reciprocating belt.
- the process can further include solidifying the plurality of continuous polymeric filaments before the depositing step.
- the non-woven web can be unconsolidated.
- the process can further include consolidating the non-woven web.
- the process can further include consolidating the non-woven web under pressure.
- the spinning can be conducted in a non-electrospinning environment.
- the spinning can be conducted at a rate within a range having a lower limit and/or an upper limit.
- the range can include or exclude the lower limit and/or the upper limit.
- the lower limit and/or upper limit can be selected from 100, 105, 1 10, 1 15, 120, 125, 130, 135, 140, 145, 150, 155, 1 60, 1 65, 170, 175, 180, 185, 190, 195, 200, 205, 210, 215, 220, 225, 230, 235, 240, 245, 250, 255, 260, 265, 270, 275, 280, 285, 290, 295, 300, 305, 310, 315, 320, 325, 330, 335, 340, 345, 350, 355, 360, 365, 370, 375, 380, 385, 390, 395, 400, 425, 450, 475, 500, 525, 550, 575, 600, 625, 650, 675, 700, 725
- each of the plurality of continuous polymeric filaments is provided with at least one additional functionality imparting therapeutic activity, catalytic activity microelectronic activity, micro-optoelectronic activity, magnetic activity, and/or biological activity.
- none of the plurality of continuous polymeric filaments are bonded to adjacent filaments. According to other embodiments,
- a portion of the plurality of continuous polymeric filaments are at least partially bonded to adjacent filaments.
- each of the plurality of continuous polymeric filaments are at least partially bonded to adjacent filaments.
- the process can further include entangling the filaments. The entangling can be one of needle-punching and fluid hydroentanglement.
- the poly(phenylene ether) component can include repeating structural units having the formula:
- halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms; and wherein each occurrence of Z 2 is independently hydrogen, halogen, unsubstituted or substituted C1-C-12 hydrocarbyl provided that the
- hydrocarbyl group is not tertiary hydrocarbyl, C1-C12 hydrocarbylthio, C1 -C12
- hydrocarbyloxy or C2-C12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms.
- the poly(phenylene ether)-polysiloxane block copolymer can be prepared by an oxidative copolymerization method.
- the poly(phenylene ether) component can include a homopolymer or copolymer of monomers selected from the group consisting of 2,6-dimethylphenol, 2,3,6-trimethylphenol, and combinations thereof.
- the polymeric component can be in the form of a solution including the
- the process can further include at least partially removing the solvent from the filament before the filament is deposited.
- the solvent can be a chlorinated solvent.
- the solvent can be at least one selected from benzene, toluene, xylene, chlorobenzene, chloroform, carbon tetrachloride, alcohols, ketones, anisole, veratrole, dichloroethane, trichloroethane and combinations thereof.
- the non-woven web can contain less than 10 wt% of a material selected from polyvinyl pyrrolidine, polymethyl methacrylate, polyvinylidene fluoride, polypropylene, polycarbonate, polyethylene oxide, agarose, polyvinylidene fluoride, polylactic glycolic acid, nylon 6, polycaprolactone, polylactic acid, polybutylene terephthalate, polyetherimide homopolymers, polyetherimide copolymers, polyetherether ketones homopolymers, polyetherether ketones copolymers, polyphenylene sulfone homopolymers, polyphenylene sulfone copolymers, polycarbonate homopolymers, polycarbonate copolymers, and combinations thereof.
- a material selected from polyvinyl pyrrolidine, polymethyl methacrylate, polyvinylidene fluoride, polypropylene, polycarbonate, polyethylene oxide, agarose, polyvinylidene fluoride, polylactic glycolic acid, nylon
- the non-woven web can exclude any detectable amount of a material selected from polyvinyl pyrrolidine, polymethyl methacrylate, polyvinylidene fluoride, polypropylene, polycarbonate, polyethylene oxide, agarose, polyvinylidene fluoride, polylactic glycolic acid, nylon 6, polycaprolactone, polylactic acid, polybutylene terephthalate, and combinations thereof.
- the product can be at least one selected from non- woven paper, medical implants, ultra-fine filters, membranes, hospital gowns, electrical insulation paper, honeycomb structures and personal hygiene products, dialyzers, blood, oxygenator filters, intravenous (IV) filters, diagnostic test filters, and blood/apheresis filters.
- The can be a composite non-woven product including the spun filaments and at least one other fiber.
- the product can be a composite non- woven product adhered to a rolled sheet good.
- the product can be a composite non-woven product adhered to at least one of a sheet or film.
- PC resins were solution spun to average fiber diameters in the sub-micrometer range.
- Table 4 provides a list of materials that were employed in the Examples.
- Fiber diameter analysis software e.g., Fibermetric software is used to measure the sample's images and at least 100 measurements per image, which are randomly selected by the software, are used in determining the average fiber diameter and distribution.
- FIG. 3 is an image showing the fiber morphology obtained according to Example 1 .
- FIG. 4 is an image showing the fiber morphology obtained according to Example 2.
- FIGs. 5A - 5D show Examples of the results of solution force spinning into sub-micrometer fibers.
- Table 5 provides a list of materials used in the Examples.
- Fiber diameter analysis software e.g., Fibermetric software is used to measure the sample's images and at least 100 measurements per image, which are randomly selected by the software, are used in determining the average fiber diameter and distribution.
- a solution comprising of 25 wt. % ULTEM® 1010 dissolved in NMP, with a solution viscosity of about 6,000 centiPoise (cP) was spun through an orifice diameter of 159 ⁇ (30G) at a spinneret speed of 12,000 RPM.
- This Example resulted in fiber diameter between 3.0 ⁇ and 1 15 nm with an average fiber diameter of 1 .1 ⁇ .
- Figure 6A is an image showing the fiber morphology obtained according to
- Example 6B is a histogram showing fiber measurements obtained according to Example 6.
- a solution comprising of 25 wt. % ULTEM® 1010 dissolved in NMP, with a solution viscosity of about 6,000 cP was spun through an orifice diameter of 210 ⁇ (27G) at a spinneret speed of 6,000 RPM.
- This Example resulted in fiber diameter between 1 .4 ⁇ and 32 nm with an average fiber diameter of 650 nm.
- Figure 7A is an image showing the fiber morphology obtained according to Example 7.
- Figure 7B is a histogram showing fiber measurements obtained according to Example 7.
- FIG. 8A is an image showing the fiber morphology obtained according to Example 8.
- Figure 8B is a histogram showing fiber measurements obtained according to Example 8.
- a solution comprising of 35 wt. % ULTEM® 1010 dissolved in NMP, with a solution viscosity of about 1 60,000 cP was spun through an orifice diameter of 1 194 ⁇ (1 6G) at a spinneret speed of 2,000 RPM.
- This Example resulted in fiber diameter between 20 ⁇ and 285 nm with an average fiber diameter of 7.2 ⁇ .
- Figure 9A is an image showing the fiber morphology obtained according to Example 9.
- Figure 9B is a histogram showing fiber measurements obtained according to Example 9.
- a solution comprising of 20 wt. % ULTEM® 1000 dissolved in a NMP, with a solution viscosity of about 2,300 cP was spun through an orifice diameter of 337 ⁇ (23G) at a spinneret speed of 4,000 RPM.
- the Example resulted in no formation of fibers.
- a solution comprising of 16 wt. % ULTEM® 1000 dissolved in a NMP, with a solution viscosity of about 700 cP was spun through an orifice diameter of 210 ⁇ (27G) at a spinneret speed of 1 1 ,000 RPM.
- the Example resulted in no formation of fibers.
- a solution comprising of 16 wt. % ULTEM® 1000 dissolved in a NMP, with a solution viscosity of about 700 cP was spun through an orifice diameter of 210 ⁇ (27G) at a spinneret speed of 1 1 ,000 RPM.
- the Example resulted in no formation of fibers.
- a solution comprising of 25 wt. % ULTEM® 1010 dissolved in a NMP, with a solution viscosity of about 6,000 cP was spun through an orifice diameter of 159 ⁇ (30G) at a spinneret speed of 2,000 RPM.
- the Example resulted in no formation of fibers.
- a solution comprising of 25 wt. % ULTEM® 1010 dissolved in a NMP, with a solution viscosity of about 6,000 cP was spun through an orifice diameter of 159 ⁇ (30G) at a spinneret speed of 2,000 RPM.
- the Example resulted in no formation of fibers.
- FIGS. 10A - 10C show an example of the results of solution force spinning into sub-micrometer fibers.
- Table 6 provides a list of materials used in the examples.
- Fiber diameter analysis software e.g., Fibermetric software
- Fibermetric software is used to measure the sample's images and at least 100 measurements per image, which are randomly selected by the software, are used in determining the average fiber diameter and distribution.
- a solution comprising of 8 wt. % PPO6130 dissolved in Toluene, with a solution viscosity of about 100 cP was spun through an orifice diameter of 337 ⁇ (23G) at a spinneret speed of 6,000 RPM.
- the example resulted in fibers with a diameter of 0.1 to 3.9 ⁇ with an average fiber diameter of about 840 nm.
- Figure 1 1 A is an image showing the fiber morphology obtained according to Example 15.
- Figure 1 1 B is a histogram showing fiber diameter measurements obtained according to Example 15.
- a solution comprising of 8 wt. % PP06130 dissolved in a mixture of 50%
- FIG. 12A is an image showing the fiber morphology obtained according to Example 1 6.
- Figure 12B is a histogram showing fiber diameter measurements obtained according to Example 1 6.
- a solution comprising of 8 wt. % PPO6130 dissolved in Chloroform, with a solution viscosity of about 900 cP was spun through an orifice diameter of 337 ⁇ (23G) at a spinneret speed of 10,000 RPM.
- the example resulted in fibers with a diameter between 275 nm and 23.4 ⁇ with an average fiber diameter of 7.3 ⁇ .
- Figure 13A is an image showing the fiber morphology obtained according to
- Example 17 is a histogram showing fiber diameter measurements obtained according to Example 17.
- a solution comprising of 5 wt. % PPO6130 dissolved in toluene, with a solution viscosity of about 30 cP was spun through an orifice diameter of 210 ⁇ (27G) at a spinneret speed of 2,000 RPM.
- the example resulted in no formation of fibers.
- a solution comprising of 8 wt. % PPO6130 dissolved in Chloroform, with a solution viscosity of about 900 cP was spun through an orifice diameter of 337 ⁇ (23G) at a spinneret speed of 6,000 RPM.
- the example resulted in no formation of fibers.
- a solution comprising of 2.5 wt. % PPO6130 dissolved in a mixture of 50% Chloroform and 50% Toluene, with a solution viscosity of about 10 cP was spun through an orifice diameter of 337 ⁇ (23G) at a spinneret speed of 12,000 RPM.
- the example resulted in no formation of fibers.
- the invention comprises a process, and a product made by a process comprising: spinning a plurality of continuous polymeric filaments by passing at least one polymeric component, in either molten form or as a solution, through a spinneret having a plurality of orifices, wherein the at least one polymeric component comprises a polycarbonate homopolymer component, a polycarbonate copolymer component (preferably a polycarbonate copolymer comprising bisphenol A carbonate units and units of the formula
- R 5 is hydrogen, phenyl optionally substituted with up to five CM O alkyl groups, or Ci -4 alky, or a poly(carbonate-siloxane) comprising bisphenol A carbonate units, and siloxane units of the formula
- E has an average value of 2 to 200
- the poly(carbonate-siloxane) comprises 0.5 to 55 wt.% of siloxane units based on the total weight of the poly(carbonate-siloxane)), or a combination thereof
- each of the plurality of continuous polymeric filaments has a length to diameter ratio that is more than 1 ,000,000, preferably more than 5,000,000, more preferably more than 20,000,000
- each of the plurality of continuous polymeric filaments has a diameter ranging from 50 nanometers to 5 micrometers, preferably from 50 to 1 000 nanometers, more preferably from 1 0 to 500 nanometers
- the spinning is conducted in a non-electrospinning environment, wherein the spinning is conducted by rotating the spinneret at a speed sufficient to spin the filaments under the effect of centrifugal force, preferably at a rate of at least 300 grams/hour/spinneret, more preferably at
- producing the non-woven web can comprise depositing the plurality of continuous filaments onto a carrier substrate, a functional sheet, a film, a woven or non-woven fabric, a rolled goods product, and combinations thereof, preferably wherein the carrier substrate is a reciprocating belt; the process can further comprise solidifying the plurality of continuous polymeric filaments before the depositing step; the process can further comprise consolidating the non-woven web, preferably under pressure, or leaving the non-woven web unconsolidated; each of the plurality of continuous polymeric filaments is provided with at least one additional functionality imparting at least one selected from therapeutic activity, catalytic activity
- the process can further comprise entangling the filaments, for example by needle-punching or fluid hydroentanglement; the process can further comprise at least partially removing any solvent from the filament before the filament is
- the non-woven web contains less than 10 wt.%, and preferably no detectable amount of polyvinyl pyrrolidine, polymethyl methacrylate, polyvinylidene fluoride, polypropylene, polycarbonate, polyethylene oxide, agarose, polyvinylidene fluoride, polylactic glycolic acid, nylon 6, polycaprolactone, polylactic acid, polybutylene terephthalate, polyetherimides, poly(phenylene ether) polymers, poly(phenylene ether)-polysiloxane block copolymers and combinations thereof; optionally wherein the product is a non-woven paper, medical implant, ultra-fine filter, membrane, hospital gown, electrical insulation paper, honeycomb structure, and personal hygiene product, dialyzer, blood, oxygenator filter, intravenous (IV) filter, diagnostic test filter, blood/apheresis filter, optionally in the form of a composite non- woven product comprising the spun filaments and at least one other fiber, or a composite
- the inventions is a process, and product made by a process comprising: spinning a plurality of continuous polymeric filaments by passing at least one polymeric component, in either molten form or as a solution, through a spinneret having a plurality of orifices, wherein the at least one polymeric component comprises a polycarbonate homopolymer component, a polycarbonate copolymer component (preferably a polycarbonate copolymer comprising bisphenol A carbonate units and units of the formula
- R 5 is hydrogen, phenyl optionally substituted with up to five CM 0 alkyl groups, or Ci -4 alky, or a poly(carbonate-siloxane) comprising bisphenol A carbonate units, and siloxane units of the formula
- E has an average value of 2 to 200
- the poly(carbonate-siloxane) comprises 0.5 to 55 wt.% of siloxane units based on the total weight of the poly(carbonate-siloxane)), or a combination thereof, the filaments having a length to diameter ratio that is more than 1 ,000,000, preferably more than 5,000,000, more preferably more than
- said spinning comprising passing a polymer through a spinneret having a plurality of orifices in a non-electrospinning environment and being conducted at a rate of at least 300 grams/hour/spinneret more preferably at a rate of at least 7000
- producing the non-woven web can comprise depositing the plurality of continuous filaments onto a carrier substrate, a functional sheet, a film, a woven or non-woven fabric, a rolled good product, and combinations thereof, preferably wherein the carrier substrate is a reciprocating belt; the process can further comprise solidifying the plurality of continuous polymeric filaments before the depositing step; the process can further comprise consolidating the non-woven web, preferably under pressure, or leaving the non-woven web unconsolidated; each of the plurality of continuous polymeric filaments is provided with at least one additional functionality imparting at least one selected from therapeutic activity, catalytic activity microelectronic activity, micro- optoelectronic activity, magnetic activity, biological activity, and combinations thereof; and none of the plurality of continuous polymeric filaments are
- IV filter intravenous filter
- diagnostic test filter blood/apheresis filter
- blood/apheresis filter optionally in the form of a composite non-woven product comprising the spun filaments and at least one other fiber, or a composite non-woven product adhered to a sheet, a film, or a rolled sheet.
- the invention comprises a process, and a product made by a process comprising: spinning a plurality of continuous polymeric filaments by passing at least one polymer component, in either molten form or as a solution, through a spinneret having a plurality of orifices, wherein the polymer component comprises a polyetherimide homopolymer, polyetherimide copolymer (preferably a reaction product of 4,4'-bisphenol A dianhydride and a meta-phenylene diamine monomer, the reaction product of 4,4'-bisphenol A dianhydride and a para- phenylene diamine monomers, or the reaction product of 4,4'-bisphenol A
- polyphenylene sulfone copolymer aromatic polyester homopolymer, aromatic polyester copolymer, or a combination thereof (preferably wherein the aromatic polyester homopolymer or aromatic polyester copolymer comprises a liquid crystal polymer, preferably a liquid cr stal polymer having the following formula:
- x and y are independently selected positive integers), preferably a
- polyetherimide component comprising a polyetherimide homopolymer, a
- the polyetherimide component further optionally comprises a phosphorus-containing stabilizer, in an amount that is effective to increase the melt stability of the polyetherimide, wherein the phosphorous-containing stabilizer exhibits a low volatility such that, as measured by thermogravimetric analysis of an initial amount of a sample of the phosphorous-containing stabilizer, greater than or equal to 10 percent by weight of the initial amount of the sample remains unevaporated upon heating of the sample from room temperature to 300°C at a heating rate of 20°C per minute under an inert atmosphere, wherein each of the plurality of continuous polymeric filaments has a length to diameter ratio that is more than 1 ,000,000, preferably more than 5,000,000, more preferably more than 20,000,000, wherein each of the plurality of continuous polymeric filaments has a diameter ranging from 50 nanometers to 5 micrometers, preferably from 50 to 1000
- the spinning is conducted in a non-electrospinning environment, wherein the spinning is conducted by rotating the spinneret at a speed sufficient to spin the filaments under the effect of centrifugal force, preferably at a rate of at least 300 grams/hour/spinneret, more preferably at a rate of at least 7000 grams/hour/spinneret; and producing a non- woven web comprising the plurality of continuous polymeric filaments, preferably wherein the non-woven web has a width of at least 150 mm.
- producing the non-woven web can comprise depositing the plurality of continuous filaments onto a carrier substrate, a functional sheet, a film, a woven or non-woven fabric, a rolled good product, and combinations thereof, preferably wherein the carrier substrate is a reciprocating belt; the process can further comprise solidifying the plurality of continuous polymeric filaments before the depositing step; the process can further comprise consolidating the non-woven web, preferably under pressure, or leaving the non-woven web unconsolidated; each of the plurality of continuous polymeric filaments is provided with at least one additional functionality imparting at least one selected from therapeutic activity, catalytic activity microelectronic activity, micro-optoelectronic activity, magnetic activity, biological activity, and combinations thereof; and none of the plurality of continuous polymeric filaments are bonded to adjacent filaments, or a portion of the plurality of continuous polymeric filaments are at least partially bonded to adjacent filaments, or each of the plurality of continuous polymeric filaments are at least partially bonded
- the process can further comprise at least partially removing any solvent from the filament before the filament is deposited; optionally wherein the non- woven web contains less than 10 wt.%, and preferably no detectable amount of polyvinyl pyrrolidine, polymethyl methacrylate, polyvinylidene fluoride, polypropylene, polycarbonate, polyethylene oxide, agarose, polyvinylidene fluoride, polylactic glycolic acid, nylon 6, polycaprolactone, polylactic acid, polybutylene terephthalate, polycarbonate homopolymers, polycarbonate copolymers, poly(phenylene ether) polymers, poly(phenylene ether)-polysiloxane block copolymers and combinations thereof; optionally wherein the product is a non-woven paper, medical implant, ultra- fine filter, membrane, hospital gown, electrical insulation paper, honeycomb structure, and personal hygiene product, dialyzer, blood, oxygenator filter,
- IV filter intravenous filter
- diagnostic test filter blood/apheresis filter
- blood/apheresis filter optionally in the form of a composite non-woven product comprising the spun filaments and at least one other fiber, or a composite non-woven product adhered to a sheet, a film, or a rolled sheet.
- the inventions is a process, and product made by a process comprising: spinning a plurality of continuous polymeric filaments
- polyetherimide component in either molten form or as a solution, comprising a polyetherimide homopolymer, polyetherimide co-polymer (preferably a reaction product of 4,4'-bisphenol A dianhydride and a meta-phenylene diamine monomer, the reaction product of 4,4'-bisphenol A dianhydride and a para-phenylene diamine monomers, or the reaction product of 4,4'-bisphenol A dianhydride, aminopropyl capped polydimethylsiloxane, and a meta-phenylene diamine monomer, or a combination thereof), an aromatic polyester homopolymer, aromatic polyester copolymer, or a combination thereof, (preferably wherein the aromatic polyester homopolymer or aromatic polyester copolymer comprises a liquid crystal polymer, preferably a liquid crystal pol mer having the following formula:
- x and y are independently selected positive integers), preferably a
- polyetherimide component comprising a polyetherimide homopolymer, a
- the polyetherimide component optionally comprises a phosphorus- containing stabilizer, in an amount that is effective to increase the melt stability of the polyetherimide, wherein the phosphorus-containing stabilizer exhibits a low volatility such that, as measured by thermogravimetric analysis of an initial amount of a sample of the phosphorous-containing stabilizer, greater than or equal to 10 percent by weight of the initial amount of the sample remains unevaporated upon heating of the sample from room temperature to 300°C at a heating rate of 20°C per minute under an inert atmosphere, the filaments having a length to diameter ratio that is more than 1 ,000,000, preferably more than 5,000,000, more preferably more than 20,000,000, and a diameter ranging from 50 nanometers to 5 micrometers preferably from 50 to 1000 nanometers, more preferably from 10 to 500 nanometers; said spinning comprising passing a polymer through a spinneret having a plurality of orifices in a non
- producing the non-woven web can comprise depositing the plurality of continuous filaments onto a carrier substrate, a functional sheet, a film, a woven or non-woven fabric, a rolled good, and combinations thereof, preferably wherein the carrier substrate is a reciprocating belt; the process can further comprise solidifying the plurality of continuous polymeric filaments before the depositing step; the process can further comprise consolidating the non-woven web, preferably under pressure, or leaving the non-woven web unconsolidated; each of the plurality of continuous polymeric filaments is provided with at least one additional functionality imparting at least one selected from therapeutic activity, catalytic activity microelectronic activity, micro- optoelectronic activity, magnetic activity, biological activity, and combinations thereof; and none of the plurality of continuous polymeric filaments are
- IV filter intravenous filter
- diagnostic test filter blood/apheresis filter
- blood/apheresis filter optionally in the form of a composite non-woven product comprising the spun filaments and at least one other fiber, or a composite non-woven product adhered to a sheet, a film, or a rolled sheet.
- the invention comprises a process, and a product made by a process comprising: spinning a plurality of continuous polymeric filaments by passing at least one poly(phenylene ether) component or a
- poly(phenylene ether)-polysiloxane block copolymers in either molten form or as a solution, through a spinneret having a plurality of orifices, (preferably a
- poly(phenylene ether) comprising repeating structural units having the formula:
- each occurrence of Z 1 is independently halogen, unsubstituted or substituted C1 -C12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl, C1 -C12 hydrocarbylthio, C1 -C12 hydrocarbyloxy, or C2-C12
- halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms, and wherein each occurrence of Z 2 is independently hydrogen, halogen, unsubstituted or substituted C1-C12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl, C1-C12 hydrocarbylthio, C1 -C12
- each of the plurality of continuous polymeric filaments has a length to diameter ratio that is more than 1 ,000,000, preferably more than 5,000,000, more preferably more than 20,000,000, wherein each of the plurality of continuous polymeric filaments has a diameter ranging from 50 nanometers to 5 micrometers, preferably from 50 to 1000 nanometers, more preferably from 10 to 500 nanometers, wherein the spinning is conducted in a non- electrospinning environment, wherein the spinning is conducted by rotating the spinneret at a speed sufficient to spin the filaments under the effect of centrifugal force, preferably at a rate of at least 300 grams/hour/spinneret, more preferably at a rate of at least 7000 grams/hour/spinneret; and producing a non-woven web comprising the plurality of continuous polymeric filaments, preferably wherein the non
- producing the non-woven web can comprise depositing the plurality of continuous filaments onto a carrier substrate, a functional sheet, a film, a woven or non-woven fabric, a rolled good product, and combinations thereof, preferably wherein the carrier substrate is a reciprocating belt; the process can further comprise solidifying the plurality of continuous polymeric filaments before the depositing step; the process can further comprise consolidating the non-woven web, preferably under pressure, or leaving the non-woven web unconsolidated; each of the plurality of continuous polymeric filaments is provided with at least one additional functionality imparting at least one selected from therapeutic activity, catalytic activity microelectronic activity, micro-optoelectronic activity, magnetic activity, biological activity, and combinations thereof; and none of the plurality of continuous polymeric filaments are bonded to adjacent filaments, or a portion of the plurality of continuous polymeric filaments are at least partially bonded to adjacent filaments, or each of the plurality of continuous polymeric filaments are at least partially bonded
- the inventions is a process, and product made by a process comprising: spinning a plurality of continuous polymeric filaments
- each occurrence of Z 1 is independently halogen, unsubstituted or substituted C1 -C12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl, C1 -C12 hydrocarbylthio, C1 -C12 hydrocarbyloxy, or C2-C12
- halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms, and wherein each occurrence of Z 2 is independently hydrogen, halogen, unsubstituted or substituted C1-C12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl, C1-C12 hydrocarbylthio, C1 -C12
- the filaments having a length to diameter ratio that is more than 1 ,000,000, preferably more than 5,000,000, more preferably more than 20,000,000, and a diameter ranging from 50 nanometers to 5 micrometers preferably from 50 to 1000 nanometers, more preferably from 10 to 500 nanometers; said spinning comprising passing a polymer through a spinneret having a plurality of orifices in a non-electrospinning environment and being conducted at a rate of at least 300 grams/hour/spinneret more preferably at a rate of at least 7000 grams/hour/spinneret; chopping the plurality of continuous filaments and obtaining a plurality of chopped nano-fibers; and forming the nano-fibers into a non-woven web.
- producing the non-woven web can comprise depositing the plurality of continuous filaments onto a carrier substrate, a functional sheet, a film, a woven or non-woven fabric, a rolled good product, and combinations thereof, preferably wherein the carrier substrate is a reciprocating belt; the process can further comprise solidifying the plurality of continuous polymeric filaments before the depositing step; the process can further comprise consolidating the non-woven web, preferably under pressure, or leaving the non-woven web unconsolidated; each of the plurality of continuous polymeric filaments is provided with at least one additional functionality imparting at least one selected from therapeutic activity, catalytic activity microelectronic activity, micro- optoelectronic activity, magnetic activity, biological activity, and combinations thereof; and none of the plurality of continuous polymeric filaments are bonded to adjacent filaments, or a portion of the plurality of continuous polymeric filaments are at least partially bonded to adjacent filaments, or each of the plurality of continuous polymeric filaments are at least partially bonded
- IV filter intravenous filter
- diagnostic test filter blood/apheresis filter
- blood/apheresis filter optionally in the form of a composite non-woven product comprising the spun filaments and at least one other fiber, or a composite non-woven product adhered to a sheet, a film, or a rolled sheet.
- Embodiment 1 A process comprising: spinning a plurality of continuous polymeric filaments by passing at least one polymeric component through a spinneret having a plurality of orifices, wherein the at least one polymeric component comprises (1 ) a poly(phenylene ether) component, a poly(phenylene ether)- polysiloxane block copolymer, or a combination thereof; (2) a polyetherimide component comprising a polyetherimide homopolymer, a polyetherimide copolymer, or a combination thereof, a polyetherether ketone homopolymer, a polyetherether ketone copolymer, a polyphenylene sulfone homopolymer, a polyphenylene sulfone copolymer, an aromatic polyester homopolymer an, aromatic polyester copolymer, or a combination thereof; or (3) a polycarbonate homopolymer component, a
- each of the plurality of continuous polymeric filaments has a length to diameter ratio that is more than 1 ,000,000, preferably more than 5,000,000, preferably more than 20,000,000, wherein each of the plurality of continuous polymeric filaments has a diameter ranging from 50 nanometers to 5 micrometers, preferably from 50 to 1000 nanometers, more preferably from 10 to 500 nanometers, wherein the spinning is conducted in a non-electrospinning environment, wherein the spinning is conducted at a rate of at least 300 grams/hour/ spinneret, preferably at least 7000
- Embodiment 2 The process of Embodiment 1 , wherein producing the non-woven web comprises depositing the plurality of continuous filaments onto a carrier substrate, a functional sheet, a film, a woven or non-woven fabric, a rolled good product, or a combination thereof, preferably wherein the carrier substrate is a reciprocating belt.
- Embodiment 3 The process of any one or more of Embodiments 1 to 2, further comprising solidifying the plurality of continuous polymeric filaments before the depositing step.
- Embodiment 4 A process of forming a non-woven web, said process comprising: spinning a plurality of continuous polymeric filaments from at least one polymeric component comprising at least one of (1 ) a poly(phenylene ether) component, a poly(phenylene ether)-polysiloxane block copolymer, and
- the filaments having a length to diameter ratio that is more than 1 ,000,000, preferably more than 5,000,000, preferably more than 20,000,000, and a diameter ranging from 50 nanometers to 5 micrometers, preferably from 50 to 1000 nanometers, more preferably from 10 to 500 nanometers; said spinning comprising passing a polymer through a spinneret having a plurality of orifices in a non-electrospinning environment; said spinning being conducted at a rate of at least 300 grams/hour/spinneret, preferably at
- Embodiment 5 The process of any one or more of Embodiments 1 to 4, wherein the spinning is conducted by rotating the spinneret at a speed sufficient to spin the filaments under the effect of centrifugal force.
- Embodiment 6 The process of any one or more of Embodiments 1 to 5, wherein each of the plurality of continuous polymeric filaments is provided with at least one additional functionality imparting therapeutic activity, catalytic activity microelectronic activity, micro-optoelectronic activity, magnetic activity, biological activity, or a combination thereof.
- Embodiment 7 The process of any one or more of Embodiments 1 to 6, wherein none of the plurality of continuous polymeric filaments are bonded to adjacent filaments.
- Embodiment 8 The process of any one or more of Embodiments 1 to 7, wherein a portion of the plurality of continuous polymeric filaments are at least partially bonded to adjacent filaments.
- Embodiment 9 The process of any one or more of Embodiments 1 to 8, further comprising entangling the filaments, preferably by needle-punching or fluid hydroentanglement.
- Embodiment 10 The process of any one or more of Embodiments 1 to 9, wherein the polymeric component is in molten form.
- Embodiment 1 1 The process of any one or more of Embodiments 1 to 10, wherein the polymeric component is the poly(phenylene ether) or is the
- poly(phenylene ether)-polysiloxane block copolymer wherein the poly(phenylene ether) or the poly(phenylene ether)-polysiloxane block copolymer comprises repeating structural units having t
- C Ci 2 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl, C1 -C12 hydrocarbylthio, C1 -C12 hydrocarbyloxy, or C2-C12
- halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms; and wherein each occurrence of Z 2 is independently hydrogen, halogen, unsubstituted or substituted C Ci 2 hydrocarbyl provided that the
- hydrocarbyl group is not tertiary hydrocarbyl, C Ci 2 hydrocarbylthio, C Ci 2 hydrocarbyloxy, or C 2 -Ci 2 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms.
- Embodiment 12 The process of Embodiment 1 1 , wherein the polymeric component is the poly(phenylene ether) component comprising a homopolymer or copolymer of 2,6-dimethylphenol, 2,3,6-trimethylphenol, or a combination thereof, or the polymeric component is the poly(phenylene ether)-polysiloxane block copolymer comprising a homopolymer or copolymer of 2,6-dimethylphenol, 2,3,6- trimethylphenol, or a combination thereof.
- the polymeric component is the poly(phenylene ether) component comprising a homopolymer or copolymer of 2,6-dimethylphenol, 2,3,6- trimethylphenol, or a combination thereof.
- Embodiment 13 The process of any one or more of Embodiments 1 1 to 12, wherein the polymeric component is in the form of a solution comprising the poly(phenylene ether) component, the poly(phenylene ether)-polysiloxane block copolymer, or a combination thereof, in a solvent.
- Embodiment 14 The process of any one or more of Embodiments 1 to 10, wherein the polymeric component is the polycarbonate homopolymer component comprising a bisphenol A polycarbonate, the polycarbonate copolymer component comprising a copolymer comprising bisphenol A carbonate units and units of the formula
- R 5 is hydrogen, phenyl optionally substituted with up to five C-M O alkyl groups, or Ci -4 alkyl, or a poly(carbonate-siloxane) comprising bisphenol A carbonate units, and siloxane units of the formula
- E has an average value of 2 to 200, wherein the poly(carbonate-siloxane) comprises 0.5 to 55 wt.% of siloxane units based on the total weight of the poly(carbonate-siloxane), or a combination of the polycarbonate homopolymer component and the polycarbonate copolymer component.
- Embodiment 15 The process of any one or more of Embodiments 1 to 10, wherein the polymeric component is the polyetherimide homopolymer or
- polyetherimide copolymer is (i) the reaction product of 4,4'-bisphenol A dianhydride and meta-phenylene diamine monomers, (ii) the reaction product of 4,4'- bisphenol A dianhydride and para-phenylene diamine monomers, or (iii) the reaction product of 4,4'-bisphenol A dianhydride, aminopropyl-capped polydimethylsiloxane, and meta-phenylene diamine monomers.
- Embodiment 16 The process of any one or more of Embodiments 1 to 10 or 15, wherein the polymeric component the polyetherimide homopolymer or polyetherimide copolymer, and further comprises a phosphorus-containing stabilizer, in an amount that is effective to increase the melt stability of the polyetherimide, wherein the phosphorus-containing stabilizer exhibits a low volatility such that, as measured by thermogravimetric analysis of an initial amount of a sample of the phosphorus-containing stabilizer, greater than or equal to 10 percent by weight of the initial amount of the sample remains unevaporated upon heating of the sample from room temperature to 300°C at a heating rate of 20°C per minute under an inert atmosphere.
- Embodiment 17 A product produced by the process of any one or more of
- Embodiments 1 to 1 6.
- Embodiment 18 The product of Embodiment 17, wherein the product is at least one selected from non-woven paper, medical implants, ultra-fine filters, membranes, hospital gowns, electrical insulation paper, honeycomb structures and personal hygiene products, dialyzers, blood, oxygenator filters, intravenous (IV) filters, diagnostic test filters, and blood/apheresis filters.
- Embodiment 19 The product of any one or more of Embodiments 17 to
- the product is a composite non-woven product comprising the spun filaments and at least one other fiber.
- Embodiment 20 The product of any one or more of Embodiments 17 to
- the product is a composite non-woven product adhered to a sheet, a film, or rolled sheet goods.
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Abstract
A process of forming a non-woven web including spinning a plurality of continuous polymeric filaments from a polymeric component including a polycarbonate homopolymer component, a polycarbonate copolymer component, and combinations thereof; a polyetherimide component selected from polyetherimide homopolymers, polyetherimide copolymers, aromatic polyester homopolymers, aromatic polyester copolymers, and combinations; a polyetherimide component selected from polyetherimide homopolymers, polyetherimide copolymers, aromatic polyester homopolymers, aromatic polyester copolymers, and combinations thereof. The non-woven can be formed from continuous filaments or the filament can be chopped before forming the non-woven. Preferably, the spinning is conducted at a high rate of at least 300 grams/hour/spinneret. The continuous filaments have a diameter from 50 nanometers to 5 micrometers, preferably 50 nanometers to 2 micrometers, and a length to diameter ratio that is more than 1,000,000.
Description
FORCE SPUN SUB-MICROMETER FIBER AND APPLICATIONS
BACKGROUND OF THE INVENTION
1 . Field of the Invention
The invention relates generally to a process of forming a non-woven web from a polymeric material including spinning a plurality of continuous polymeric filaments selected from the group consisting of a polycarbonate homopolymer component, a polycarbonate copolymer component, and combinations thereof; a polyetherimide component; and a poly(phenylene ether) component and a poly(phenylene ether)- polysiloxane block copolymer. In some embodiments, the polymeric component may be chopped prior to forming the non-woven. Forming the non-woven web at a high rate of at least 300 grams/hour/spinneret is disclosed.
2. Description of the related art
Polycarbonate (PC) and PC Copolymers have been converted into fibers using the melt spinning process for some time. This is capable of producing fibers in the range of 10- 20 micrometers. Melt blown has also been used for some PC's producing fibers in the 1 to 10 micrometer range.
Electro-spinning of these resins is possible, but the cost of the resin and the slow throughput rate of this process have made this method commercially
unacceptable. Typical production rates for this process are in the 200 to 300 grams per hour, and 60 meters per minute line speed rates.
Polyetherimide (PEI) has been converted into fibers using the melt spinning process for some time. This is capable of producing fibers in the range of 10 - 20 micrometers. Melt blowing has also been attempted with PEI, and there is currently work being done to make this process amenable to using PEI. If the technical hurdles could be overcome here, this would be capable of producing PEI fibers in the
3 to 10 micrometer range.
Polyphenylene ether (PPE) resins, such as NORYL resins, which are modified
PPE / olefin resin blends that offer toughness, a wide range of stiffness, flame retardancy and are available from SABIC, have been converted down to 15 to 20 micrometers in diameter using the melt spinning process, but haven't been used in the melt blown area. Polybutylene terephthalate (PBT) has been spun to 10 - 20 micrometer range via melt spinning, and to 1 - 10 micrometers using the melt blown process.
Electro-spinning of these resins is possible, but the cost of the resin and the slow throughput rate of this process have made this method commercially
unacceptable. Typical production rates for this process are in the 200 to 300 grams per hour, and 60 meters per minute line speed rates.
These materials would be desirable in many applications and composite structures that require various unique properties of the different resins to perform in the necessary environment. Many of these applications require the resins to be in a fiber size much smaller than currently achievable using conventional methods of fiber production at a reasonable throughput rate. This has been a barrier to the introduction and testing of many of these resins suitability for use in these
applications. It would be desirable to use these materials in nano-fiber form produced from the force spinning process in applications such as electrical paper, battery separator membranes, structural composites and filter papers, etc. BRIEF SUMMARY OF THE INVENTION
According to various embodiments, using a force spinning process, the above-identified materials can be either melt spun or solution spun into fiber diameters in the sub-micrometer range. Even small decreases in fiber diameters results in substantial increases in the surface area of the resins, thereby increasing the performance benefit that the individual resins bring to the applications. Each of these resin families have been converted to sub-micrometer fibers using this process. One advantage this process brings is a reasonable throughput of ultra-fine fibers enabling them to be produced in an economically viable method. Throughput rates as high as 200 to 300 thousand grams per hour are possible, with line speeds as high as 250 meters per minute and higher.
The output of this process is a non-woven web structure of continuous fiber lengths, randomly laid down onto a carrier substrate, or coated onto another functional sheet, film, non-woven or other rolled good product. The resulting product is then packaged as a rolled good to be used in further downstream processes, to produce applications such as membranes, battery separators, filtration media, composites, electrical papers, and honeycomb papers.
BRIEF DESCRIPTION OF THE DRAWINGS
These and other features, aspects, and advantages of the present invention will become better understood with reference to the following description and appended claims, and accompanying drawings where:
FIG. 1 depicts one or more nozzles coupled to one or more openings of a known fiber producing device;
FIG. 2 shows a cross-sectional view of the known fiber producing device;
FIG. 3 is an image showing the fiber morphology obtained according to Example 1 ;
FIG. 4 is an image showing the fiber morphology obtained according to Example 2;
FIGs. 5A -5D: show force spun polyetherimide fibers;
FIG. 6A is an image showing the fiber morphology obtained according to Example 6;
FIG. 6B is a histogram showing fiber diameter measurements obtained according to Example 6;
FIG. 7A is an image showing the fiber morphology obtained according to Example 7;
FIG. 7B is a histogram showing fiber diameter measurements obtained according to Example 7;
FIG. 8A is an image showing the fiber morphology obtained according to
Example 8;
FIG. 8B is a histogram showing fiber diameter measurements obtained according to Example 8;
FIG. 9A: is an image showing the fiber morphology obtained according to Example 9;
FIG. 9B is a histogram showing fiber diameter measurements obtained according to Example 9;
FIGs. 10A-10C show force spun poly(phenylene ether) fibers;
FIG. 1 1 A is an image showing the fiber morphology obtained according to Example 15;
FIG. 1 1 B is a histogram showing fiber diameter measurements obtained according to Example 15;
FIG. 12A is an image showing the fiber morphology obtained according to Example 1 6;
FIG. 12B is a histogram showing fiber diameter measurements obtained according to Example 1 6;
FIG. 13A is an image showing the fiber morphology obtained according to Example 17; and
FIG. 13B is a histogram showing fiber diameter measurements obtained according to Example 17.
It should be understood that the various embodiments are not limited to the arrangements and instrumentality shown in the drawings.
DETAILED DESCRIPTION OF THE INVENTION
Various embodiments of a process of forming a non-woven web including spinning a plurality of continuous polymeric filaments including a polycarbonate homopolymer component, a polycarbonate copolymer component, and combinations thereof at a high rate of at least 300 grams/hour/spinneret.
Other embodiments provide a process of forming a non-woven web including spinning a plurality of continuous polymeric filaments including polyetherimide homopolymers, polyetherimide copolymers, aromatic polyester homopolymers, aromatic polyester copolymers, or combinations thereof at a rate of at least 300 grams/hour/spinneret.
Still other embodiments provide processes of forming a non-woven web including a poly(phenylene ether) component, a poly(phenylene ether)-polysiloxane block copolymer, and combinations thereof at a high rate of at least 300
grams/hour/spinneret.
The present disclosure may be understood more readily by reference to the following detailed description of preferred embodiments of the invention as well as to the examples included therein. All numeric values are herein assumed to be modified by the term "about," whether or not explicitly indicated. The term "about" generally refers to a range of numbers that one of skill in the art would consider equivalent to the recited value (i.e., having the same function or result). In many instances, the term "about" may include numbers that are rounded to the nearest significant figure.
In any of the embodiments below, the spinning can be conducted by rotating the spinneret at a speed sufficient to spin the filaments under the effect of centrifugal force. FIG. 1 depicts a known fiber producing device 100, as described in WO 2012/109215, the entirety of which is hereby incorporated by reference. As shown in
FIG. 1 one or more nozzles 130 may be coupled to one or more openings 122 of fiber producing device 100. As used herein a "nozzle" is a mechanical device designed to control the direction or characteristics of a fluid flow as it exits (or enters) an enclosed chamber or pipe via an orifice. Nozzles may have an internal cavity 138 running through the longitudinal length of the nozzle, as depicted in FIG. 1 . Internal cavity 138 may be substantially aligned with opening 122 when nozzle 130 is coupled to an opening. Spinning of fiber producing device 100 causes material to pass thorough one or more of openings 122 and into one or more nozzles 130. The material is then ejected from one or more nozzles 130 through nozzle orifice 136 to produce fibers. Nozzle 130 may include a nozzle tip 134 having an internal diameter smaller than an internal diameter of nozzle internal cavity 138. In some
embodiments, internal cavity 138 of nozzle 130 and/or nozzle orifice 136 may have a size and/or shape that causes the creation of microfibers and/or nanofibers by ejecting of the material through the nozzle.
It should be understood that while opposing openings are depicted, the openings may be placed in any position on the body of a fiber producing device. The position of the openings may be varied to create different kinds of fibers. In some embodiments, openings may be placed in different planes of the fiber producing device. In other embodiments, openings may be clustered in certain locations. Such alternate positioning of the openings may increase the fiber dispersion patterns and/or increase the fiber production rates. In some embodiments, the openings, regardless of the position, may accept an outlet element (e.g., a nozzle or needle).
FIG. 2 shows a cross-sectional view of fiber producing device of FIG. 2. Body 120 includes one or more sidewalls 121 and a bottom 123 which together define an internal cavity 125. In some embodiments, body 120 is substantially circular or oval and includes a singular continuous sidewall 121 , for example, sidewall and bottom are a single, unitary component of the fiber producing device. Openings 122 are formed in sidewall 121 of body 120, extending through the sidewall such that the opening allows transfer of material from internal cavity 125 through the sidewall. In an embodiment, sidewall 121 is angled from bottom 1 23 toward one or more openings 122. Alternatively, sidewall 121 may be rounded from bottom 123 toward one or more openings 122. Having an angled or rounded sidewall extending toward one or more openings facilitates flow of material in the body toward the openings when the fiber producing device is being rotated. As the fiber producing device is
rotated the material rides up the angled or rounded walls toward the openings. This minimizes the occurrence of regions where material is inhibited from traveling toward the openings.
Polycarbonate Woven Webs
Various embodiments relate to a process of forming a non-woven web. The process can include spinning a plurality of continuous polymeric filaments including one selected from a polycarbonate homopolymer component, a polycarbonate copolymer component, and combinations thereof. The filaments can have a length to diameter ratio that can be more than 1 ,000,000, and a diameter ranging from 50 nanometers to 5 micrometers, preferably from 50 nanometers to 2 micrometers. The spinning can include passing a polymer through a spinneret having a plurality of orifices in a non-electrospinning environment. The process according to various embodiments can further include: chopping the plurality of continuous filaments and obtaining a plurality of chopped nano-fibers; and forming the nano-fibers into a non- woven web. The spinning can be conducted at a rate of at least 300
grams/hour/spinneret.
According to various embodiments, none of the plurality of continuous polymeric filaments are bonded to adjacent filaments. According to other
embodiments, a portion of the plurality of continuous polymeric filaments can be at least partially bonded to adjacent filaments. According to other embodiments, each of the plurality of continuous polymeric filaments can be at least partially bonded to adjacent filaments. Various embodiments of the process can further include entangling the filaments. The non-woven web can contain less than 10 wt% of a material selected from polyvinyl pyrrolidine, polymethyl methacrylate, polyvinylidene fluoride, polypropylene, polyethylene oxide, agarose, polyvinylidene fluoride, polylactic glycolic acid, nylon 6, polycaprolactone, polylactic acid, polybutylene terephthalate, polyetherimide homopolymers, polyetherimide copolymers,
polyetherether ketones homopolymers, polyetherether ketone copolymers, polyphenylene sulfone homopolymers, polyphenylene sulfone copolymers, poly(phenylene ether) components, poly(phenylene ether)-polysiloxane block copolymer, and combinations thereof. In some embodiments the polymeric filaments are free of one or more of the foregoing polymers.
Various embodiments relate to a process including spinning a plurality of continuous polymeric filaments by passing at least one polymeric component
through a spinneret having a plurality of orifices, and producing a non-woven web including the plurality of continuous polymeric filaments. The at least one polymeric component can include a polycarbonate homopolymer component, a polycarbonate copolymer component, and combinations thereof.
Each of the plurality of continuous polymeric filaments can have a length to diameter ratio within a range having a lower limit and/or an upper limit. The range can include or exclude the lower limit and/or the upper limit. The lower limit and/or upper limit can be selected from 500000, 1000000, 1500000, 2000000, 2500000, 3000000, 3500000, 4000000, 4500000, 5000000, 10000000, 15000000, 20000000, 25000000, 30000000, 35000000, 40000000, 45000000, 50000000, 55000000, 60000000, 65000000, 70000000, 75000000, 80000000, 85000000, 90000000, 95000000, 100000000, 105000000, 1 10000000, 1 15000000, 120000000,
125000000, 130000000, 135000000, 140000000, 145000000, 150000000,
155000000, 1 60000000, 1 65000000, 170000000, 175000000, 180000000,
185000000, 190000000, 195000000, 200000000, 205000000, 210000000,
215000000, 220000000, 225000000, 230000000, 235000000, 240000000,
245000000, 250000000, 255000000, 260000000, 265000000, 270000000,
275000000, 280000000, 285000000, 290000000, 295000000, and 300000000 . For example, according to certain preferred embodiments, each of the plurality of continuous polymeric filaments can have a length to diameter ratio that can be more than 1 ,000,000.
Each of the plurality of continuous polymeric filaments can have a diameter within a range having a lower limit and/or an upper limit. The range can include or exclude the lower limit and/or the upper limit. The lower limit and/or upper limit can be selected from 25, 50, 75, 100, 125, 150, 175, 200, 225, 250, 275, 300, 325, 350, 375, 400, 425, 450, 475, 500, 525, 550, 575, 600, 625, 650, 675, 700, 725, 750, 775, 800, 825, 850, 875, 900, 925, 950, 975, 1000, 1025, 1050, 1075, 1 100, 1 125, 1 150, 1 175, 1200, 1225, 1250, 1275, 1300, 1325, 1350, 1375, 1400, 1425, 1450, 1475, 1500, 1525, 1550, 1575, 1 600, 1 625, 1 650, 1 675, 1700, 1725, 1750, 1775, 1800, 1825, 1850, 1875, 1900, 1925, 1950, 1975, 2000, 2025, 2050, 2075, 2100, 2125, 2150, 2175, 2200, 2225, 2250, 2275, 2300, 2325, 2350, 2375, 2400, 2425, 2450, 2475, 2500, 2525, 2550, 2575, 2600, 2625, 2650, 2675, 2700, 2725, 2750, 2775, 2800, 2825, 2850, 2875, 2900, 2925, 2950, 2975, 3000, 3025, 3050, 3075, 3100, 3125, 3150, 3175, 3200, 3225, 3250, 3275, 3300, 3325, 3350, 3375, 3400, 3425,
3450, 3475, 3500, 3525, 3550, 3575, 3600, 3625, 3650, 3675, 3700, 3725, 3750, 3775, 3800, 3825, 3850, 3875, 3900, 3925, 3950, 3975, 4000, 4025, 4050, 4075, 4100, 4125, 4150, 4175, 4200, 4225, 4250, 4275, 4300, 4325, 4350, 4375, 4400, 4425, 4450, 4475, 4500, 4525, 4550, 4575, 4600, 4625, 4650, 4675, 4700, 4725, 4750, 4775, 4800, 4825, 4850, 4875, 4900, 4925, 4950, 4975, and 5000 nanometers (nm). For example, according to certain preferred embodiments, each of the plurality of continuous polymeric filaments can have a diameter ranging from 50 nanometers to 5 micrometers, more preferably of from 50 nanometers to 2 micrometers.
Table 1 summarizes exemplary length to diameter ratios according to various embodiments.
The non-woven web can have a width within a range having a lower limit and/or an upper limit. The range can include or exclude the lower limit and/or the upper limit. The lower limit and/or upper limit can be selected from 100, 105, 1 10, 1 15, 120, 125, 130, 135, 140, 145, 150, 155, 1 60, 1 65, 170, 175, 180, 185, 190, 195, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490, 500, 600, 700, 800, 900, 1000, 1 100, 1200, 1300, 1400, 1500, 1 600, 1700, 1800, 1900, and 2000 millimeters (mm). For example, according to certain preferred embodiments, the non-woven web can have a width of at least 150 mm, for example 150 to 2000 mm.
Producing the non-woven web can include depositing the plurality of continuous filaments onto one selected from a carrier substrate, a functional sheet, a
film, a woven or non-woven fabric (i.e., a felt), a rolled good product, and combinations thereof.
The carrier substrate can be a reciprocating belt. The process can further include solidifying the plurality of continuous polymeric filaments before the depositing step. The non-woven web can be unconsolidated. The process can further include consolidating the non-woven web. The process can further include consolidating the non-woven web under pressure.
The spinning can be conducted in a non-electrospinning environment.
The spinning can be conducted at a rate within a range having a lower limit and/or an upper limit. The range can include or exclude the lower limit and/or the upper limit. The lower limit and/or upper limit can be selected from 100, 105, 1 10, 1 15, 120, 125, 130, 135, 140, 145, 150, 155, 1 60, 1 65, 170, 175, 180, 185, 190, 195, 200, 205, 210, 215, 220, 225, 230, 235, 240, 245, 250, 255, 260, 265, 270, 275, 280, 285, 290, 295, 300, 305, 310, 315, 320, 325, 330, 335, 340, 345, 350, 355, 360, 365, 370, 375, 380, 385, 390, 395, 400, 425, 450, 475, 500, 525, 550, 575, 600, 625, 650, 675, 700, 725, 750, 775, 800, 825, 850, 875, 900, 925, 950, 975, 1000, 1500, 2000, 2500, 3000, 3500, 4000, 4500, 5000, 5500, 6000, 6500, 7000, 7500, 8000, 8500, 9000, 9500, 10000, 10500, 1 1000, 1 1500, 12000, 12500, 13000, 13500, 14000, 14500, and 15000 grams/hour/spinneret. For example, according to certain preferred embodiments, the spinning can be conducted at a rate of at least 300 grams/hour/ spinneret, for example 300 to 15000 grams/hour/spinneret.
According to various embodiments, each of the plurality of continuous polymeric filaments can be provided with at least one additional functionality imparting at least one selected from therapeutic activity, catalytic activity
microelectronic activity, micro-optoelectronic activity, magnetic activity, biological activity, and combinations thereof.
According to various embodiments of the process, none of the plurality of continuous polymeric filaments can be bonded to adjacent filaments. A portion of the plurality of continuous polymeric filaments can be at least partially bonded to adjacent filaments. According to various embodiments of the process, each of the plurality of continuous polymeric filaments are at least partially bonded to adjacent filaments.
The process can further include entangling the filaments. The entangling can be one of needle-punching and fluid hydroentanglement.
The polycarbonate homopolymer component can include a bisphenol A homopolymer. The polycarbonate copolymer component can include bisphenol A carbonate units and unit f the formula:
wherein R5 can be hydrogen, phenyl optionally substituted with up to five Ci-10 alkyl groups, or Ci-4 alkyl. The polycarbonate copolymer component can include a poly(carbonate-siloxane) including bisphenol A carbonate units and siloxane units of the formulas:
or a combination including at least one of the foregoing, wherein E can have an average value of 2 to 200, wherein the poly(carbonate-siloxane) can include 0.5 to 55 wt.% of siloxane units based on the total weight of the poly(carbonate-siloxane).
The polycarbonate homopolymer component, the polycarbonate copolymer component, or the combination thereof can be in the form of a solution of the polycarbonate homopolymer component in a solvent.
The process can further include at least partially removing the solvent from the filament before the filament can be deposited. The solvent can be selected from the group of N-methyl-2-pyrrolidone or chlorinated solvents. The chlorinated solvent can be selected from the group of chloroform, methylene chloride, carbon
tetrachloride, tetrachloroethane, tetrachioroethylene, dichiorobenzene,
chlorobenzene, trichlorobenzene, and combinations thereof.
According to various embodiments, the non-woven web can contain less than 10 wt.%, less than 9 wt.%, less than 8 wt.%, less than 7 wt.%, less than 6 wt.%, less than 5 wt.%, less than 4 wt.%, less than 3 wt.%, less than 2 wt.%, less than 1 wt.%, of a material selected from polyvinyl pyrrolidine, polymethyl methacrylate,
polyvinylidene fluoride, polypropylene, polyethylene oxide, agarose, polyvinylidene fluoride, polylactic glycolic acid, nylon 6, polycaprolactone, polylactic acid, polybutylene terephthalate, polyetherimide homopolymers, polyetherimide
copolymers, polyetherether ketones homopolymers, polyetherether ketones copolymers, polyphenylene sulfone homopolymers, polyphenylene sulfone copolymers, poly(phenylene ether) components, poly(phenylene ether)-polysiloxane block copolymer, and combinations thereof.
According to various embodiments, the process and the non-woven web can exclude any detectable amount of a material selected form polyvinyl pyrrolidine, polymethyl methacrylate, polyvinylidene fluoride, polypropylene, polycarbonate, polyethylene oxide, agarose, polyvinylidene fluoride, polylactic glycolic acid, nylon 6, polycaprolactone, polylactic acid, polybutylene terephthalate, and combinations thereof.
Other embodiments relate to a product produced by the process according to any of the embodiments. The product can be at least one selected from non-woven paper, medical implants, ultra-fine filters, membranes, hospital gowns, electrical insulation paper, honeycomb structures and personal hygiene products, dialyzers, blood, oxygenator filters, intravenous (IV) filters, diagnostic test filters, and
blood/apheresis filters. They can be a composite non-woven product including the spun filaments and at least one other fiber. The product can be a composite non- woven product adhered to a rolled sheet article. The product can be a composite non-woven product adhered to at least one of a sheet or film.
Polyetherimide and other High Temperature Polymer Woven Webs
Various embodiments relate to a process of forming a non-woven web, which include spinning a plurality of continuous polymeric filaments including a
polyetherimide homopolymer, a polyetherimide copolymer, a polyetherether ketone homopolymer, a polyetherether ketone copolymer, a polyphenylene sulfone homopolymer, a polyphenylene sulfone copolymer, an aromatic polyester
homopolymer an aromatic polyester copolymer, or a combination thereof; preferably a polyetherimide component selected from polyetherimide homopolymers,
polyetherimide copolymers, or a combination thereof, optionally where the polyetherimide component is in combination with aromatic polyester homopolymers, aromatic polyester copolymers, and combinations thereof. The filaments can have a length to diameter ratio that is more than 1 ,000,000, and a diameter ranging from 50 nanometers to 5 micrometers, preferably from 50 nanometers to 2 micrometers. The spinning can include passing a polymer through a spinneret having a plurality of orifices in a non-electrospinning environment. The process can further include chopping the plurality of continuous filaments and obtaining a plurality of chopped nano-fibers and forming the nano-fibers into a non-woven web. The spinning is conducted at a rate of at least 300 grams/hour/spinneret. According to various embodiments, the process can further include entangling the filaments.
According to various embodiments, none of the plurality of continuous polymeric filaments are bonded to adjacent filaments. According to other
embodiments, a portion of the plurality of continuous polymeric filaments can be at least partially bonded to adjacent filaments. According to other embodiments, each of the plurality of continuous polymeric filaments can be at least partially bonded to adjacent filaments.
The non-woven web can contain less than 10 wt% of a material selected from polyvinyl pyrrolidine, polymethyl methacrylate, polyvinylidene fluoride, polypropylene, polycarbonate, polyethylene oxide, agarose, polyvinylidene fluoride, polylactic glycolic acid, nylon 6, polycaprolactone, polylactic acid, polybutylene terephthalate, polycarbonate homopolymers, polycarbonate copolymers, poly(phenylene ether) polymers, poly(phenylene ether)-polysiloxane block copolymers, and combinations thereof. In some embodiments the non-woven web is free of one or more of the foregoing polymers.
Various embodiments relate to a process including spinning a plurality of continuous polymeric filaments by passing at least one polymeric component through a spinneret having a plurality of orifices, and producing a non-woven web can include the plurality of continuous polymeric filaments. The at least one polymeric component can include polyetherimide homopolymers, polyetherimide copolymers, polyetherether ketones homopolymers, polyetherether ketone
copolymers, polyphenylene sulfone homopolymers, polyphenylene sulfone
copolymers, aromatic polyester homopolymers, aromatic polyester copolymers, and combinations thereof, preferably a polyetherimide component selected from
polyetherimide homopolymers, polyetherimide copolymers, or a combination thereof, aromatic polyester homopolymers, aromatic polyester copolymers, or combinations thereof.
Each of the plurality of continuous polymeric filaments can have a length to diameter ratio within a range having a lower limit and/or an upper limit. The range can include or exclude the lower limit and/or the upper limit. The lower limit and/or upper limit can be selected from 500000, 1000000, 1500000, 2000000, 2500000, 3000000, 3500000, 4000000, 4500000, 5000000, 10000000, 15000000, 20000000, 25000000, 30000000, 35000000, 40000000, 45000000, 50000000, 55000000, 60000000, 65000000, 70000000, 75000000, 80000000, 85000000, 90000000, 95000000, 100000000, 105000000, 1 10000000, 1 15000000, 120000000,
125000000, 130000000, 135000000, 140000000, 145000000, 150000000,
155000000, 1 60000000, 1 65000000, 170000000, 175000000, 180000000,
185000000, 190000000, 195000000, 200000000, 205000000, 210000000,
215000000, 220000000, 225000000, 230000000, 235000000, 240000000,
245000000, 250000000, 255000000, 260000000, 265000000, 270000000,
275000000, 280000000, 285000000, 290000000, 295000000, and 300000000 . For example, according to certain preferred embodiments, each of the plurality of continuous polymeric filaments can have a length to diameter ratio that can be more than 1 ,000,000, for example 1 ,000,000 to 300000000.
Each of the plurality of continuous polymeric filaments can have a diameter within a range having a lower limit and/or an upper limit. The range can include or exclude the lower limit and/or the upper limit. The lower limit and/or upper limit can be selected from 25, 50, 75, 100, 125, 150, 175, 200, 225, 250, 275, 300, 325, 350, 375, 400, 425, 450, 475, 500, 525, 550, 575, 600, 625, 650, 675, 700, 725, 750, 775, 800, 825, 850, 875, 900, 925, 950, 975, 1000, 1025, 1050, 1075, 1 100, 1 125, 1 150, 1 175, 1200, 1225, 1250, 1275, 1300, 1325, 1350, 1375, 1400, 1425, 1450, 1475, 1500, 1525, 1550, 1575, 1 600, 1 625, 1 650, 1 675, 1700, 1725, 1750, 1775, 1800, 1825, 1850, 1875, 1900, 1925, 1950, 1975, 2000, 2025, 2050, 2075, 2100, 2125, 2150, 2175, 2200, 2225, 2250, 2275, 2300, 2325, 2350, 2375, 2400, 2425, 2450, 2475, 2500, 2525, 2550, 2575, 2600, 2625, 2650, 2675, 2700, 2725, 2750, 2775, 2800, 2825, 2850, 2875, 2900, 2925, 2950, 2975, 3000, 3025, 3050, 3075, 3100, 3125, 3150, 3175, 3200, 3225, 3250, 3275, 3300, 3325, 3350, 3375, 3400, 3425, 3450, 3475, 3500, 3525, 3550, 3575, 3600, 3625, 3650, 3675, 3700, 3725, 3750,
3775, 3800, 3825, 3850, 3875, 3900, 3925, 3950, 3975, 4000, 4025, 4050, 4075, 4100, 4125, 4150, 4175, 4200, 4225, 4250, 4275, 4300, 4325, 4350, 4375, 4400, 4425, 4450, 4475, 4500, 4525, 4550, 4575, 4600, 4625, 4650, 4675, 4700, 4725, 4750, 4775, 4800, 4825, 4850, 4875, 4900, 4925, 4950, 4975, and 5000
nanometers. For example, according to certain preferred embodiments, each of the plurality of continuous polymeric filaments can have a diameter ranging from 50 nanometers to 5 micrometers, preferably from 50 nanometers to 2 micrometers.
Table 2 summarizes exemplary length to diameter ratios according to various embodiments.
The non-woven web can have a width within a range having a lower limit and/or an upper limit. The range can include or exclude the lower limit and/or the upper limit. The lower limit and/or upper limit can be selected from 100, 105, 1 10, 1 15, 120, 125, 130, 135, 140, 145, 150, 155, 1 60, 1 65, 170, 175, 180, 185, 190, 195, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490, 500, 600, 700, 800, 900, 1000, 1 100, 1200, 1300, 1400, 1500, 1 600, 1700, 1800, 1900, and 2000 mm. For example, according to certain preferred embodiments, the non-woven web can have a width of at least 150 mm.
Producing the non-woven web can include depositing the plurality of continuous filaments onto one selected from a carrier substrate, a functional sheet, a film, a woven or non-woven fabric, a rolled good product, and combinations thereof.
The carrier substrate can be a reciprocating belt. The process can further include solidifying the plurality of continuous polymeric filaments before the depositing step. The non-woven web can be unconsolidated. The process can further include consolidating the non-woven web. The process can further include consolidating the non-woven web under pressure.
The spinning can be conducted in a non-electrospinning environment.
The spinning can be conducted at a rate within a range having a lower limit and/or an upper limit. The range can include or exclude the lower limit and/or the upper limit. The lower limit and/or upper limit can be selected from 100, 105, 1 10, 1 15, 120, 125, 130, 135, 140, 145, 150, 155, 1 60, 1 65, 170, 175, 180, 185, 190, 195, 200, 205, 210, 215, 220, 225, 230, 235, 240, 245, 250, 255, 260, 265, 270, 275, 280, 285, 290, 295, 300, 305, 310, 315, 320, 325, 330, 335, 340, 345, 350, 355, 360, 365, 370, 375, 380, 385, 390, 395, 400, 425, 450, 475, 500, 525, 550, 575, 600, 625, 650, 675, 700, 725, 750, 775, 800, 825, 850, 875, 900, 925, 950, 975, 1000, 1500, 2000, 2500, 3000, 3500, 4000, 4500, 5000, 5500, 6000, 6500, 7000, 7500, 8000, 8500, 9000, 9500, 10000, 10500, 1 1000, 1 1500, 12000, 12500, 13000, 13500, 14000, 14500, and 15000 grams/hour/spinneret. For example, according to certain preferred embodiments, the spinning can be conducted at a rate of at least 300 grams/hour/ spinneret, for example 300 to 15000 grams/hour/ spinneret.
According to various embodiments, each of the plurality of continuous polymeric filaments can be provided with at least one additional functionality imparting therapeutic activity, catalytic activity microelectronic activity, micro- optoelectronic activity, magnetic activity, and/or biological activity.
According to some embodiments, none of the plurality of continuous polymeric filaments are bonded to adjacent filaments. According to other
embodiments, a portion of the plurality of continuous polymeric filaments are at least partially bonded to adjacent filaments. According to other embodiments, each of the plurality of continuous polymeric filaments are at least partially bonded to adjacent filaments. The process can further include entangling the filaments. The entangling can be one of needle-punching and fluid hydroentanglement.
The polyetherimide component can include a polyetherimide in molten form. The polyetherimide component can be selected from a member including (i) the reaction product of 4,4'-bisphenol A dianhydride and meta-phenylene diamine monomers, (ii) the reaction product of 4,4'-bisphenol A dianhydride and para-
phenylene diamine monomers, and (iii) the reaction product of 4,4'-bisphenol A dianhydride, aminopropyl-capped polydimethylsiloxane, and meta-phenylene diamine monomers. The polyetherimide component can be a thermoplastic resin composition including the polyetherimide, and a phosphorous-containing stabilizer, in an amount that is effective to increase the melt stability of the polyetherimide, wherein the phosphorous-containing stabilizer exhibits a low volatility such that, as measured by thermogravimetric analysis of an initial amount of a sample of the phosphorus-containing stabilizer, greater than or equal to 10 percent by weight of the initial amount of the sample remains unevaporated upon heating of the sample from room temperature to 300°C at a heating rate of 20°C per minute under an inert atmosphere. The polyetherimide component can be in the form of a solution of polyetherimide in a solvent.
The composition can include a phosphorus stabilizer in an amount within a range having a lower limit and/or an upper limit. The range can include or exclude the lower limit and/or the upper limit. The lower limit and/or upper limit can be selected from 0.01 , 0.05, 0.1 , 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 , 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1 , 12, 13, 14, 15, 1 6, 17, 18, 19 and 20 wt. %. The phosphorous stabilizer can be mixed together with the other components of the composition. Alternatively, the phosphorous stabilizer can be introduced as a component of a polyetherimide thermoplastic resin composition comprising (a) a polyetherimide resin, and, (b) a phosphorous-containing stabilizer. A preferred phosphorous-containing stabilizer for the polyetherimide resin is described in U.S. Patent 6,001 ,957, the entire disclosure of which is herein incorporated by reference. The phosphorus-containing stabilizer is present in an amount effective to increase the melt stability of the polyetherimide resin, wherein the phosphorous-containing stabilizer exhibits a low volatility such that, as measured by gravimetric analysis of an initial amount of a sample of the phosphorous-containing stabilizer, greater than or equal to 10% by weight of the initial amount of the sample remains unevaporated upon heating the sample from room temperature to 300° C at a heating rate of 20° C per minute under an inert atmosphere, wherein the phosphorous-containing compound is a compound according to the structural formula P-R1 a, wherein each R1 is independently H, C1 - 12 alkyl, C1 -12 alkoxyl, C6-12 aryl, C6-12 aryloxy or oxo, and a is 3 or 4. For example, according to certain preferred embodiments, the composition can include a
phosphorus stabilizer in an amount of between 0.01 -10 wt.%, 0.05 - 10 wt.%, or from 5 to 10 wt.%.
In some embodiments, aromatic polyesters can be used alone in in
combination. The aromatic polyester homopolymers and/or the aromatic polyester copolymers can include liquid crystal polymers. Wholly or partially aromatic polyesters include liquid crystal polyesters. Illustrative examples of such aromatic polyesters include self-condensed polymers of p-hydroxybenzoic acid, polyesters comprising repeat units derived from terephthalic acid and hydroquinone, polyester fibers comprising repeat units derived from p-hydroxybenzoic acid and 6-hydroxy-2- naphthoic acid, or combinations thereof. A specific aromatic liquid crystal polyester can produced by the polycondensation of 4-hydroxybenzoic acid and 6- hydroxynaphthalene-2-carboxylic acid (fibers made from such a product are commercially available from Kuraray Co., Ltd. under the trade name designation VECTRAN). Such a polymer can have the followin formula:
where x and y are independently selected positive integers. For example, x and y can be independently selected from any positive integer within a range having a lower limit and/or an upper limit. The range can include or exclude the lower limit and/or the upper limit. The lower limit and/or upper limit can be selected from 1 , 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 1 10, 120, 130, 140, 150, 1 60, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490, 500, 510, 520, 530, 540, 550, 560, 570, 580, 590, 600, 610, 620, 630, 640, 650, 660, 670, 680, 690, 700, 710, 720, 730, 740, 750, 760, 770, 780, 790, 800, 810, 820, 830, 840, 850, 860, 870, 880, 890, 900, 910, 920, 930, 940, 950, 960, 970, 980, 990, 1000, 1010, 1020, 1030, 1040, 1050, 1060, 1070, 1080, 1090, 1 100, 1 1 10, 1 120, 1 130, 1 140, 1 150, 1 160, 1 170, 1 180, 1 190, 1200, 1210, 1220, 1230, 1240, 1250, 1260, 1270, 1280, 1290, 1300, 1310, 1320, 1330, 1340, 1350, 1360, 1370, 1380, 1390, 1400, 1410, 1420, 1430, 1440, 1450, 1460, 1470, 1480, 1490, 1500, 151 0, 1520, 1530, 1540, 1550, 1560, 1570, 1580, 1590, 1600, 1610, 1 620, 1630, 1 640, 1 650, 1 660, 1 670, 1 680,
1 690, 1700, 1710, 1720, 1730, 1740, 1750, 1760, 1770, 1780, 1790, 1800, 1810, 1820, 1830, 1840, 1850, 1860, 1870, 1880, 1890, 1900, 1910, 1920, 1930, 1940, 1950, 1960, 1970, 1980, 1990, 2000, 2010, 2020, 2030, 2040, 2050, 2060, 2070, 2080, 2090, 2100, 21 10, 2120, 2130, 2140, 2150, 21 60, 2170, 2180, 2190, 2200, 2210, 2220, 2230, 2240, 2250, 2260, 2270, 2280, 2290, 2300, 2310, 2320, 2330, 2340, 2350, 2360, 2370, 2380, 2390, 2400, 2410, 2420, 2430, 2440, 2450, 2460, 2470, 2480, 2490, and 2500 . For example, according to certain preferred
embodiments, x and y can both be 1000. According to other embodiments, x can be between 500 and 1500 and y can be between 1000 and 2000. Such aromatic polyesters may be produced by any methods known to one skilled in the art. Fibers made from such aromatic polyesters are advantageously made from molten aromatic polymers and can be melt spun.
The process can further include at least partially removing the solvent from the filament before the filament is deposited. The solvent can be selected from meta-cresol, veratrol, ortho-dich!orobenzene (ODCB), N-methyl pyrrolidinone, chloroform, tetrahydrofuran (THF), dimethyl formamide (DMF), dimethyl acetamide (DCM), dichloromethane, trichlorobenzene, benzoic acid, and mixtures thereof.
According to various embodiments, the non-woven web can contain less than 10 wt% of a material selected from polyvinyl pyrrolidine, polymethyl methacrylate, polyvinylidene fluoride, polypropylene, polycarbonate, polyethylene oxide, agarose, polyvinylidene fluoride, polylactic glycolic acid, nylon 6, polycaprolactone, polylactic acid, polybutylene terephthalate, polycarbonate homopolymers, polycarbonate copolymers, poly(phenylene ether) polymers, poly(phenylene ether)-polysiloxane block copolymers and combinations thereof. Various embodiments of the process can exclude any detectable amount of a material selected from polyvinyl pyrrolidine, polymethyl methacrylate, polyvinylidene fluoride, polypropylene, polycarbonate, polyethylene oxide, agarose, polyvinylidene fluoride, polylactic glycolic acid, nylon 6, polycaprolactone, polylactic acid, polybutylene terephthalate, polycarbonate homopolymers, polycarbonate copolymers, and combinations thereof. In some embodiments, the non-woven web is free of any one or more of the foregoing polymers.
Other embodiments relate to a product produced by the process according to any of other embodiments. The product can be at least one selected from non- woven paper, medical implants, ultra-fine filters, membranes, hospital gowns,
electrical insulation paper, honeycomb structures and personal hygiene products, dialyzers, blood, oxygenator filters, intravenous (IV) filters, diagnostic test filters, and blood/apheresis filters. The can be a composite non-woven product including the spun filaments and at least one other fiber. The product can be a composite non- woven product adhered to a rolled sheet good (i.e., a rolled sheet article). The product can be a composite non-woven product adhered to at least one of a sheet or film.
Polyfphenylene ether) Woven Webs
Various embodiments relate to a process of forming a non-woven web wherein the process includes spinning a plurality of continuous polymeric filaments comprising a poly(phenylene ether) component, a poly(phenylene ether)- polysiloxane block copolymer, and combinations thereof. The filaments can have a length to diameter ratio that is more than 1 ,000,000, and a diameter ranging from 50 nanometers to 5 micrometers, preferably from 50 nanometers to 2 micrometers. The spinning can include passing a polymer through a spinneret having a plurality of orifices in a non-electrospinning environment. The process can further include chopping the plurality of continuous filaments and obtaining a plurality of chopped nano-fibers and forming the nano-fibers into a non-woven web. The spinning can be conducted at a rate of at least 300 grams/hour/spinneret.
According to various embodiments, none of the plurality of continuous polymeric filaments are bonded to adjacent filaments. According to other
embodiments, a portion of the plurality of continuous polymeric filaments can be at least partially bonded to adjacent filaments. According to other embodiments, each of the plurality of continuous polymeric filaments can be at least partially bonded to adjacent filaments. The process can further include entangling the filaments.
The non-woven web can contain less than 10 wt% of a material selected from polyvinyl pyrrolidine, polymethyl methacrylate, polyvinylidene fluoride, polypropylene, polycarbonate, polyethylene oxide, agarose, polyvinylidene fluoride, polylactic glycolic acid, nylon 6, polycaprolactone, polylactic acid, polybutylene terephthalate, polyetherimide homopolymers, polyetherimide copolymers, polyetherether ketones homopolymers, polyetherether ketones copolymers, polyphenylene sulfone homopolymers, polyphenylene sulfone copolymers, polycarbonate homopolymers, polycarbonate copolymers, and combinations thereof. In some embodiments, the non-woven web is free of any one or more of the foregoing polymers.
Various embodiments relate to a process including spinning a plurality of continuous polymeric filaments by passing at least one polymeric component through a spinneret having a plurality of orifices, and producing a non-woven web comprising the plurality of continuous polymeric filaments.
The at least one polymeric component can include one selected from a poly(phenylene ether) component, a poly(phenylene ether)-polysiloxane block copolymer, and combinations thereof. In certain embodiment, the non-woven web has a width of at least 150 mm
Each of the plurality of continuous polymeric filaments can have a length to diameter ratio within a range having a lower limit and/or an upper limit. The range can include or exclude the lower limit and/or the upper limit. The lower limit and/or upper limit can be selected from 500000, 1000000, 1500000, 2000000, 2500000, 3000000, 3500000, 4000000, 4500000, 5000000, 10000000, 15000000, 20000000, 25000000, 30000000, 35000000, 40000000, 45000000, 50000000, 55000000, 60000000, 65000000, 70000000, 75000000, 80000000, 85000000, 90000000, 95000000, 100000000, 105000000, 1 10000000, 1 15000000, 120000000,
125000000, 130000000, 135000000, 140000000, 145000000, 150000000,
155000000, 1 60000000, 1 65000000, 170000000, 175000000, 180000000,
185000000, 190000000, 195000000, 200000000, 205000000, 210000000,
215000000, 220000000, 225000000, 230000000, 235000000, 240000000,
245000000, 250000000, 255000000, 260000000, 265000000, 270000000,
275000000, 280000000, 285000000, 290000000, 295000000, and 300000000 . For example, according to certain preferred embodiments, each of the plurality of continuous polymeric filaments can have a length to diameter ratio that can be more than 1 ,000,000.
Each of the plurality of continuous polymeric filaments can have a diameter within a range having a lower limit and/or an upper limit. The range can include or exclude the lower limit and/or the upper limit. The lower limit and/or upper limit can be selected from 25, 50, 75, 100, 125, 150, 175, 200, 225, 250, 275, 300, 325, 350, 375, 400, 425, 450, 475, 500, 525, 550, 575, 600, 625, 650, 675, 700, 725, 750, 775, 800, 825, 850, 875, 900, 925, 950, 975, 1000, 1025, 1050, 1075, 1 100, 1 125, 1 150, 1 175, 1200, 1225, 1250, 1275, 1300, 1325, 1350, 1375, 1400, 1425, 1450, 1475, 1500, 1525, 1550, 1575, 1 600, 1 625, 1 650, 1 675, 1700, 1725, 1750, 1775, 1800, 1825, 1850, 1875, 1900, 1925, 1950, 1975, 2000, 2025, 2050, 2075, 2100, 2125,
2150, 2175, 2200, 2225, 2250, 2275, 2300, 2325, 2350, 2375, 2400, 2425, 2450, 2475, 2500, 2525, 2550, 2575, 2600, 2625, 2650, 2675, 2700, 2725, 2750, 2775, 2800, 2825, 2850, 2875, 2900, 2925, 2950, 2975, 3000, 3025, 3050, 3075, 3100, 3125, 3150, 3175, 3200, 3225, 3250, 3275, 3300, 3325, 3350, 3375, 3400, 3425, 3450, 3475, 3500, 3525, 3550, 3575, 3600, 3625, 3650, 3675, 3700, 3725, 3750, 3775, 3800, 3825, 3850, 3875, 3900, 3925, 3950, 3975, 4000, 4025, 4050, 4075, 4100, 4125, 4150, 4175, 4200, 4225, 4250, 4275, 4300, 4325, 4350, 4375, 4400, 4425, 4450, 4475, 4500, 4525, 4550, 4575, 4600, 4625, 4650, 4675, 4700, 4725, 4750, 4775, 4800, 4825, 4850, 4875, 4900, 4925, 4950, 4975, and 5000
nanometers. For example, according to certain preferred embodiments, each of the plurality of continuous polymeric filaments can have a diameter ranging from 50 nanometers to 5 micrometers, preferably from 50 nanometers to 2 micrometers.
Table 3 summarizes exemplary length to diameter ratios according to various embodiments.
The non-woven web can have a width within a range having a lower limit and/or an upper limit. The range can include or exclude the lower limit and/or the upper limit. The lower limit and/or upper limit can be selected from 100, 105, 1 10, 1 15, 120, 125, 130, 135, 140, 145, 150, 155, 1 60, 1 65, 170, 175, 180, 185, 190, 195, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490, 500, 600, 700, 800, 900, 1000, 1 100, 1200, 1300, 1400, 1500, 1 600, 1700, 1800, 1900, and 2000 mm.
For example, according to certain preferred embodiments, the non-woven web can have a width of at least 150 mm, for example, 150 to 2000 mm.
Producing the non-woven web can include depositing the plurality of continuous filaments onto one selected from a carrier substrate, a functional sheet, a film, a woven or non-woven fabric, a rolled good product, and combinations thereof.
The carrier substrate can be a reciprocating belt. The process can further include solidifying the plurality of continuous polymeric filaments before the depositing step. The non-woven web can be unconsolidated. The process can further include consolidating the non-woven web. The process can further include consolidating the non-woven web under pressure.
The spinning can be conducted in a non-electrospinning environment.
The spinning can be conducted at a rate within a range having a lower limit and/or an upper limit. The range can include or exclude the lower limit and/or the upper limit. The lower limit and/or upper limit can be selected from 100, 105, 1 10, 1 15, 120, 125, 130, 135, 140, 145, 150, 155, 1 60, 1 65, 170, 175, 180, 185, 190, 195, 200, 205, 210, 215, 220, 225, 230, 235, 240, 245, 250, 255, 260, 265, 270, 275, 280, 285, 290, 295, 300, 305, 310, 315, 320, 325, 330, 335, 340, 345, 350, 355, 360, 365, 370, 375, 380, 385, 390, 395, 400, 425, 450, 475, 500, 525, 550, 575, 600, 625, 650, 675, 700, 725, 750, 775, 800, 825, 850, 875, 900, 925, 950, 975, 1000, 1500, 2000, 2500, 3000, 3500, 4000, 4500, 5000, 5500, 6000, 6500, 7000, 7500, 8000, 8500, 9000, 9500, 10000, 10500, 1 1000, 1 1500, 12000, 12500, 13000, 13500, 14000, 14500, and 15000 grams/hour/spinneret. For example, according to certain preferred embodiments, the spinning can be conducted at a rate of at least 300 grams/hour/ spinneret, for example 300 to 15000 grams/hour/spinneret.
According to various embodiments, each of the plurality of continuous polymeric filaments is provided with at least one additional functionality imparting therapeutic activity, catalytic activity microelectronic activity, micro-optoelectronic activity, magnetic activity, and/or biological activity.
According to some embodiments, none of the plurality of continuous polymeric filaments are bonded to adjacent filaments. According to other
embodiments, a portion of the plurality of continuous polymeric filaments are at least partially bonded to adjacent filaments. According to other embodiments, each of the plurality of continuous polymeric filaments are at least partially bonded to adjacent
filaments. The process can further include entangling the filaments. The entangling can be one of needle-punching and fluid hydroentanglement.
The poly(phenylene ether) component can include repeating structural units having the formula:
wherein each occurrence of Z is independently halogen, unsubstituted or
substituted C1-C-12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl, C1 -C12 hydrocarbylthio, C1 -C12 hydrocarbyloxy, or C2-Ci2
halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms; and wherein each occurrence of Z2 is independently hydrogen, halogen, unsubstituted or substituted C1-C-12 hydrocarbyl provided that the
hydrocarbyl group is not tertiary hydrocarbyl, C1-C12 hydrocarbylthio, C1 -C12
hydrocarbyloxy, or C2-C12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms.
The poly(phenylene ether)-polysiloxane block copolymer can be prepared by an oxidative copolymerization method. The poly(phenylene ether) component can include a homopolymer or copolymer of monomers selected from the group consisting of 2,6-dimethylphenol, 2,3,6-trimethylphenol, and combinations thereof. The polymeric component can be in the form of a solution including the
poly(phenylene ether) component in a solvent.
According to various embodiments, the process can further include at least partially removing the solvent from the filament before the filament is deposited. The solvent can be a chlorinated solvent. The solvent can be at least one selected from benzene, toluene, xylene, chlorobenzene, chloroform, carbon tetrachloride, alcohols, ketones, anisole, veratrole, dichloroethane, trichloroethane and combinations thereof.
The non-woven web can contain less than 10 wt% of a material selected from polyvinyl pyrrolidine, polymethyl methacrylate, polyvinylidene fluoride, polypropylene, polycarbonate, polyethylene oxide, agarose, polyvinylidene fluoride, polylactic glycolic acid, nylon 6, polycaprolactone, polylactic acid, polybutylene terephthalate,
polyetherimide homopolymers, polyetherimide copolymers, polyetherether ketones homopolymers, polyetherether ketones copolymers, polyphenylene sulfone homopolymers, polyphenylene sulfone copolymers, polycarbonate homopolymers, polycarbonate copolymers, and combinations thereof. The non-woven web can exclude any detectable amount of a material selected from polyvinyl pyrrolidine, polymethyl methacrylate, polyvinylidene fluoride, polypropylene, polycarbonate, polyethylene oxide, agarose, polyvinylidene fluoride, polylactic glycolic acid, nylon 6, polycaprolactone, polylactic acid, polybutylene terephthalate, and combinations thereof.
Other embodiments relate to a product produced by the process according to any of other embodiments. The product can be at least one selected from non- woven paper, medical implants, ultra-fine filters, membranes, hospital gowns, electrical insulation paper, honeycomb structures and personal hygiene products, dialyzers, blood, oxygenator filters, intravenous (IV) filters, diagnostic test filters, and blood/apheresis filters. The can be a composite non-woven product including the spun filaments and at least one other fiber. The product can be a composite non- woven product adhered to a rolled sheet good. The product can be a composite non-woven product adhered to at least one of a sheet or film.
The invention is further described in the following illustrative examples in which all parts and percentages are by weight unless otherwise indicated.
EXAMPLES EXAMPLES 1 - 5
Several variations of PC resins were solution spun to average fiber diameters in the sub-micrometer range. Table 4 provides a list of materials that were employed in the Examples.
Distributions of fiber diameters were measured by imaging the sample using a Phenom Pro Desktop, scanning electron microscope (SEM). A minimum magnification of 140X was used. A minimum of 4 images are retained for fiber diameter analysis. Fiber diameter analysis software (e.g., Fibermetric software) is
used to measure the sample's images and at least 100 measurements per image, which are randomly selected by the software, are used in determining the average fiber diameter and distribution.
Example 1
As an example a solution comprising of 10 wt. % LEXAN® dissolved in methylene chloride was spun through an orifice diameter of 159 micrometer (μηπ) (30G) at a spinneret speed of 12,000 revolutions per minute (RPM). This example resulted in fibers with an average diameter of 2.1 μηπ. Figure 3 is an image showing the fiber morphology obtained according to Example 1 .
Example 2
As an example a solution comprising of 10 wt. % LEXAN® dissolved in methylene chloride was spun through an orifice diameter of 210 μιτι (27G) at a spinneret speed of 12,000 RPM. This example resulted in fibers with an average diameter of 1 .1 μιτι. Figure 4 is an image showing the fiber morphology obtained according to Example 2.
Example 3
As an example a solution comprising of 5 wt. % LEXAN® dissolved in methylene chloride was spun through an orifice diameter of 159 μιτι (30G) at a spinneret speed of 2,000 RPM. The example resulted in no formation of fibers.
Example 4
As an example a solution comprising of 5 wt. % LEXAN® dissolved in methylene chloride was spun through an orifice diameter of 210 μιτι (27G) at a spinneret speed of 6,000 RPM. The example resulted in no formation of fibers.
Example 5
As an example a solution comprising of 15 wt. % LEXAN® dissolved in chloroform was spun through an orifice diameter of 159 μιτι (30G) at a spinneret speed of 6,000 RPM. The example resulted in no formation of fibers.
EXAMPLES 6 - 14
Several variations of PEI resins, were solution spun to average fiber diameters in the sub-micrometer range. FIGs. 5A - 5D show Examples of the results of solution force spinning into sub-micrometer fibers.
Table 5 provides a list of materials used in the Examples.
Table 5
Component Chemical Description Source
ULTEM® 1000 Polyetherimide SABIC
ULTEM® 1010 Polyetherimide SABIC
NMP N-methyl pyrrolidone (99% extra pure) Acros Organics
Distributions of fiber diameters were measured by imaging the sample using a Phenom Pro Desktop, scanning electron microscope (SEM). A minimum magnification of 140X was used. A minimum of 4 images are retained for fiber diameter analysis. Fiber diameter analysis software (e.g., Fibermetric software) is used to measure the sample's images and at least 100 measurements per image, which are randomly selected by the software, are used in determining the average fiber diameter and distribution.
Example 6
A solution comprising of 25 wt. % ULTEM® 1010 dissolved in NMP, with a solution viscosity of about 6,000 centiPoise (cP) was spun through an orifice diameter of 159 μηπ (30G) at a spinneret speed of 12,000 RPM. This Example resulted in fiber diameter between 3.0 μηπ and 1 15 nm with an average fiber diameter of 1 .1 μηπ.
Figure 6A is an image showing the fiber morphology obtained according to
Example 6. Figure 6B is a histogram showing fiber measurements obtained according to Example 6.
Example 7
A solution comprising of 25 wt. % ULTEM® 1010 dissolved in NMP, with a solution viscosity of about 6,000 cP was spun through an orifice diameter of 210 μηπ (27G) at a spinneret speed of 6,000 RPM. This Example resulted in fiber diameter between 1 .4 μηπ and 32 nm with an average fiber diameter of 650 nm.
Figure 7A is an image showing the fiber morphology obtained according to Example 7. Figure 7B is a histogram showing fiber measurements obtained according to Example 7.
Example 8
A solution comprising of 25 wt. % ULTEM® 1000 dissolved in NMP, with a solution viscosity of about 10,000 cP was spun through an orifice diameter of 210 μηπ (27G) at a spinneret speed of 1 1 ,000 RPM. This Example resulted in fiber diameter between 2.8 μηπ and 150 nm with an average fiber diameter of 850 nm.
Figure 8A is an image showing the fiber morphology obtained according to Example 8. Figure 8B is a histogram showing fiber measurements obtained according to Example 8.
Example 9
A solution comprising of 35 wt. % ULTEM® 1010 dissolved in NMP, with a solution viscosity of about 1 60,000 cP was spun through an orifice diameter of 1 194 μηπ (1 6G) at a spinneret speed of 2,000 RPM. This Example resulted in fiber diameter between 20 μηπ and 285 nm with an average fiber diameter of 7.2 μηπ.
Figure 9A is an image showing the fiber morphology obtained according to Example 9. Figure 9B is a histogram showing fiber measurements obtained according to Example 9.
Example 10
A solution comprising of 20 wt. % ULTEM® 1000 dissolved in a NMP, with a solution viscosity of about 2,300 cP was spun through an orifice diameter of 337 μηπ (23G) at a spinneret speed of 4,000 RPM. The Example resulted in no formation of fibers.
Example 1 1
A solution comprising of 16 wt. % ULTEM® 1000 dissolved in a NMP, with a solution viscosity of about 700 cP was spun through an orifice diameter of 210 μηπ (27G) at a spinneret speed of 1 1 ,000 RPM. The Example resulted in no formation of fibers.
Example 12
A solution comprising of 16 wt. % ULTEM® 1000 dissolved in a NMP, with a solution viscosity of about 700 cP was spun through an orifice diameter of 210 μηπ (27G) at a spinneret speed of 1 1 ,000 RPM. The Example resulted in no formation of fibers.
Example 13
A solution comprising of 25 wt. % ULTEM® 1010 dissolved in a NMP, with a solution viscosity of about 6,000 cP was spun through an orifice diameter of 159 μηπ (30G) at a spinneret speed of 2,000 RPM. The Example resulted in no formation of fibers.
Example 14
A solution comprising of 25 wt. % ULTEM® 1010 dissolved in a NMP, with a solution viscosity of about 6,000 cP was spun through an orifice diameter of 159 μηπ
(30G) at a spinneret speed of 2,000 RPM. The Example resulted in no formation of fibers.
EXAMPLES 15 - 20
Several variations of PPE resins, were solution spun to average fiber diameters in the sub-micrometer range. FIGS. 10A - 10C show an example of the results of solution force spinning into sub-micrometer fibers. Table 6 provides a list of materials used in the examples.
Distributions of fiber diameters were measured by imaging the sample using a Phenom Pro Desktop, scanning electron microscope (SEM). A minimum
magnification of 140X was used. A minimum of 4 images are retained for fiber diameter analysis. Fiber diameter analysis software (e.g., Fibermetric software) is used to measure the sample's images and at least 100 measurements per image, which are randomly selected by the software, are used in determining the average fiber diameter and distribution.
Example 15
A solution comprising of 8 wt. % PPO6130 dissolved in Toluene, with a solution viscosity of about 100 cP was spun through an orifice diameter of 337 μηπ (23G) at a spinneret speed of 6,000 RPM. The example resulted in fibers with a diameter of 0.1 to 3.9 μηπ with an average fiber diameter of about 840 nm.
Figure 1 1 A is an image showing the fiber morphology obtained according to Example 15. Figure 1 1 B is a histogram showing fiber diameter measurements obtained according to Example 15.
Example 1 6
A solution comprising of 8 wt. % PP06130 dissolved in a mixture of 50%
Toluene and 50% Chloroform, with a solution viscosity of about 400 cP was spun through an orifice diameter of 159 μηπ (30G) at a spinneret speed of 12,000 RPM. The example resulted in fibers with a diameter between 70 nm and 6.2 μηπ with an average fiber diameter of 1 .6 μηπ.
Figure 12A is an image showing the fiber morphology obtained according to Example 1 6. Figure 12B is a histogram showing fiber diameter measurements obtained according to Example 1 6.
Example 17
A solution comprising of 8 wt. % PPO6130 dissolved in Chloroform, with a solution viscosity of about 900 cP was spun through an orifice diameter of 337 μηπ (23G) at a spinneret speed of 10,000 RPM. The example resulted in fibers with a diameter between 275 nm and 23.4 μηπ with an average fiber diameter of 7.3 μηπ. Fig.
Figure 13A is an image showing the fiber morphology obtained according to
Example 17. Figure 13B is a histogram showing fiber diameter measurements obtained according to Example 17.
Example 18
A solution comprising of 5 wt. % PPO6130 dissolved in toluene, with a solution viscosity of about 30 cP was spun through an orifice diameter of 210 μηπ (27G) at a spinneret speed of 2,000 RPM. The example resulted in no formation of fibers.
Example 19
A solution comprising of 8 wt. % PPO6130 dissolved in Chloroform, with a solution viscosity of about 900 cP was spun through an orifice diameter of 337 μηπ (23G) at a spinneret speed of 6,000 RPM. The example resulted in no formation of fibers.
Example 20
A solution comprising of 2.5 wt. % PPO6130 dissolved in a mixture of 50% Chloroform and 50% Toluene, with a solution viscosity of about 10 cP was spun through an orifice diameter of 337 μηπ (23G) at a spinneret speed of 12,000 RPM. The example resulted in no formation of fibers.
In summary, the invention comprises a process, and a product made by a process comprising: spinning a plurality of continuous polymeric filaments by passing at least one polymeric component, in either molten form or as a solution, through a spinneret having a plurality of orifices, wherein the at least one polymeric component comprises a polycarbonate homopolymer component, a polycarbonate
copolymer component (preferably a polycarbonate copolymer comprising bisphenol A carbonate units and units of the formula
wherein R5 is hydrogen, phenyl optionally substituted with up to five CM O alkyl groups, or Ci-4 alky, or a poly(carbonate-siloxane) comprising bisphenol A carbonate units, and siloxane units of the formula
or a combination comprising at least one of the foregoing, wherein E has an average value of 2 to 200, wherein the poly(carbonate-siloxane) comprises 0.5 to 55 wt.% of siloxane units based on the total weight of the poly(carbonate-siloxane)), or a combination thereof, wherein each of the plurality of continuous polymeric filaments has a length to diameter ratio that is more than 1 ,000,000, preferably more than 5,000,000, more preferably more than 20,000,000, wherein each of the plurality of continuous polymeric filaments has a diameter ranging from 50 nanometers to 5 micrometers, preferably from 50 to 1 000 nanometers, more preferably from 1 0 to 500 nanometers, wherein the spinning is conducted in a non-electrospinning environment, wherein the spinning is conducted by rotating the spinneret at a speed sufficient to spin the filaments under the effect of centrifugal force, preferably at a rate of at least 300 grams/hour/spinneret, more preferably at a rate of at least 7000 grams/hour/spinneret; and producing a non-woven web comprising the plurality of continuous polymeric filaments, preferably wherein the non-woven web has a width of at least 1 50 mm. Optionally in this embodiment, one or more of the following can apply: producing the non-woven web can comprise depositing the plurality of continuous filaments onto a carrier substrate, a functional sheet, a film, a woven or non-woven fabric, a rolled goods product, and combinations thereof, preferably wherein the carrier substrate is a reciprocating belt; the process can further comprise solidifying the plurality of continuous polymeric filaments before the depositing step;
the process can further comprise consolidating the non-woven web, preferably under pressure, or leaving the non-woven web unconsolidated; each of the plurality of continuous polymeric filaments is provided with at least one additional functionality imparting at least one selected from therapeutic activity, catalytic activity
microelectronic activity, micro-optoelectronic activity, magnetic activity, biological activity, and combinations thereof; and none of the plurality of continuous polymeric filaments are bonded to adjacent filaments, or a portion of the plurality of continuous polymeric filaments are at least partially bonded to adjacent filaments, or each of the plurality of continuous polymeric filaments are at least partially bonded to adjacent filaments; the process can further comprise entangling the filaments, for example by needle-punching or fluid hydroentanglement; the process can further comprise at least partially removing any solvent from the filament before the filament is
deposited; optionally wherein the non-woven web contains less than 10 wt.%, and preferably no detectable amount of polyvinyl pyrrolidine, polymethyl methacrylate, polyvinylidene fluoride, polypropylene, polycarbonate, polyethylene oxide, agarose, polyvinylidene fluoride, polylactic glycolic acid, nylon 6, polycaprolactone, polylactic acid, polybutylene terephthalate, polyetherimides, poly(phenylene ether) polymers, poly(phenylene ether)-polysiloxane block copolymers and combinations thereof; optionally wherein the product is a non-woven paper, medical implant, ultra-fine filter, membrane, hospital gown, electrical insulation paper, honeycomb structure, and personal hygiene product, dialyzer, blood, oxygenator filter, intravenous (IV) filter, diagnostic test filter, blood/apheresis filter, optionally in the form of a composite non- woven product comprising the spun filaments and at least one other fiber, or a composite non-woven product adhered to a sheet, a film, or a rolled sheet.
In another embodiment, the inventions is a process, and product made by a process comprising: spinning a plurality of continuous polymeric filaments by passing at least one polymeric component, in either molten form or as a solution, through a spinneret having a plurality of orifices, wherein the at least one polymeric component comprises a polycarbonate homopolymer component, a polycarbonate copolymer component (preferably a polycarbonate copolymer comprising bisphenol A carbonate units and units of the formula
wherein R5 is hydrogen, phenyl optionally substituted with up to five CM 0 alkyl groups, or Ci-4 alky, or a poly(carbonate-siloxane) comprising bisphenol A carbonate units, and siloxane units of the formula
or a combination comprising at least one of the foregoing, wherein E has an average value of 2 to 200, wherein the poly(carbonate-siloxane) comprises 0.5 to 55 wt.% of siloxane units based on the total weight of the poly(carbonate-siloxane)), or a combination thereof, the filaments having a length to diameter ratio that is more than 1 ,000,000, preferably more than 5,000,000, more preferably more than
20,000,000, and a diameter ranging from 50 nanometers to 5 micrometers preferably from 50 to 1 000 nanometers, more preferably from 1 0 to 500 nanometers; said spinning comprising passing a polymer through a spinneret having a plurality of orifices in a non-electrospinning environment and being conducted at a rate of at least 300 grams/hour/spinneret more preferably at a rate of at least 7000
grams/hour/spinneret; chopping the plurality of continuous filaments and obtaining a plurality of chopped nano-fibers; and forming the nano-fibers into a non-woven web. Optionally in this embodiment, one or more of the following can apply: producing the non-woven web can comprise depositing the plurality of continuous filaments onto a carrier substrate, a functional sheet, a film, a woven or non-woven fabric, a rolled good product, and combinations thereof, preferably wherein the carrier substrate is a reciprocating belt; the process can further comprise solidifying the plurality of continuous polymeric filaments before the depositing step; the process can further comprise consolidating the non-woven web, preferably under pressure, or leaving the non-woven web unconsolidated; each of the plurality of continuous polymeric filaments is provided with at least one additional functionality imparting at least one selected from therapeutic activity, catalytic activity microelectronic activity, micro-
optoelectronic activity, magnetic activity, biological activity, and combinations thereof; and none of the plurality of continuous polymeric filaments are bonded to adjacent filaments, or a portion of the plurality of continuous polymeric filaments are at least partially bonded to adjacent filaments, or each of the plurality of continuous polymeric filaments are at least partially bonded to adjacent filaments; the process can further comprise entangling the filaments, for example by needle-punching or fluid hydroentanglement; the process can further comprise at least partially removing any solvent from the filament before the filament is deposited; optionally wherein the non-woven web contains less than 10 wt.%, and preferably no detectable amount of polyvinyl pyrrolidine, polymethyl methacrylate, polyvinylidene fluoride, polypropylene, polycarbonate, polyethylene oxide, agarose, polyvinylidene fluoride, polylactic glycolic acid, nylon 6, polycaprolactone, polylactic acid, polybutylene terephthalate, polycarbonate homopolymers, polycarbonate copolymers, poly(phenylene ether) polymers, poly(phenylene ether)-polysiloxane block copolymers and combinations thereof; optionally wherein the product is a non-woven paper, medical implant, ultra- fine filter, membrane, hospital gown, electrical insulation paper, honeycomb structure, and personal hygiene product, dialyzer, blood, oxygenator filter,
intravenous (IV) filter, diagnostic test filter, blood/apheresis filter, optionally in the form of a composite non-woven product comprising the spun filaments and at least one other fiber, or a composite non-woven product adhered to a sheet, a film, or a rolled sheet.
In another embodiment, the invention comprises a process, and a product made by a process comprising: spinning a plurality of continuous polymeric filaments by passing at least one polymer component, in either molten form or as a solution, through a spinneret having a plurality of orifices, wherein the polymer component comprises a polyetherimide homopolymer, polyetherimide copolymer (preferably a reaction product of 4,4'-bisphenol A dianhydride and a meta-phenylene diamine monomer, the reaction product of 4,4'-bisphenol A dianhydride and a para- phenylene diamine monomers, or the reaction product of 4,4'-bisphenol A
dianhydride, aminopropyl capped polydimethylsiloxane, and a meta-phenylene diamine monomer, or a combination thereof), a polyetherether ketone homopolymer, polyetherether ketone copolymer, polyphenylene sulfone homopolymer,
polyphenylene sulfone copolymer, aromatic polyester homopolymer, aromatic polyester copolymer, or a combination thereof (preferably wherein the aromatic
polyester homopolymer or aromatic polyester copolymer comprises a liquid crystal polymer, preferably a liquid cr stal polymer having the following formula:
where x and y are independently selected positive integers), preferably a
polyetherimide component comprising a polyetherimide homopolymer, a
polyetherimide copolymer, a combination thereof, an aromatic polyester
homopolymer an aromatic polyester copolymer or a combination thereof, more preferably wherein the polyetherimide component further optionally comprises a phosphorus-containing stabilizer, in an amount that is effective to increase the melt stability of the polyetherimide, wherein the phosphorous-containing stabilizer exhibits a low volatility such that, as measured by thermogravimetric analysis of an initial amount of a sample of the phosphorous-containing stabilizer, greater than or equal to 10 percent by weight of the initial amount of the sample remains unevaporated upon heating of the sample from room temperature to 300°C at a heating rate of 20°C per minute under an inert atmosphere, wherein each of the plurality of continuous polymeric filaments has a length to diameter ratio that is more than 1 ,000,000, preferably more than 5,000,000, more preferably more than 20,000,000, wherein each of the plurality of continuous polymeric filaments has a diameter ranging from 50 nanometers to 5 micrometers, preferably from 50 to 1000
nanometers, more preferably from 10 to 500 nanometers, wherein the spinning is conducted in a non-electrospinning environment, wherein the spinning is conducted by rotating the spinneret at a speed sufficient to spin the filaments under the effect of centrifugal force, preferably at a rate of at least 300 grams/hour/spinneret, more preferably at a rate of at least 7000 grams/hour/spinneret; and producing a non- woven web comprising the plurality of continuous polymeric filaments, preferably wherein the non-woven web has a width of at least 150 mm. Optionally in this embodiment, one or more of the following can apply: producing the non-woven web can comprise depositing the plurality of continuous filaments onto a carrier substrate, a functional sheet, a film, a woven or non-woven fabric, a rolled good product, and combinations thereof, preferably wherein the carrier substrate is a reciprocating belt; the process can further comprise solidifying the plurality of continuous polymeric
filaments before the depositing step; the process can further comprise consolidating the non-woven web, preferably under pressure, or leaving the non-woven web unconsolidated; each of the plurality of continuous polymeric filaments is provided with at least one additional functionality imparting at least one selected from therapeutic activity, catalytic activity microelectronic activity, micro-optoelectronic activity, magnetic activity, biological activity, and combinations thereof; and none of the plurality of continuous polymeric filaments are bonded to adjacent filaments, or a portion of the plurality of continuous polymeric filaments are at least partially bonded to adjacent filaments, or each of the plurality of continuous polymeric filaments are at least partially bonded to adjacent filaments; the process can further comprise entangling the filaments, for example by needle-punching or fluid
hydroentanglement; the process can further comprise at least partially removing any solvent from the filament before the filament is deposited; optionally wherein the non- woven web contains less than 10 wt.%, and preferably no detectable amount of polyvinyl pyrrolidine, polymethyl methacrylate, polyvinylidene fluoride, polypropylene, polycarbonate, polyethylene oxide, agarose, polyvinylidene fluoride, polylactic glycolic acid, nylon 6, polycaprolactone, polylactic acid, polybutylene terephthalate, polycarbonate homopolymers, polycarbonate copolymers, poly(phenylene ether) polymers, poly(phenylene ether)-polysiloxane block copolymers and combinations thereof; optionally wherein the product is a non-woven paper, medical implant, ultra- fine filter, membrane, hospital gown, electrical insulation paper, honeycomb structure, and personal hygiene product, dialyzer, blood, oxygenator filter,
intravenous (IV) filter, diagnostic test filter, blood/apheresis filter, optionally in the form of a composite non-woven product comprising the spun filaments and at least one other fiber, or a composite non-woven product adhered to a sheet, a film, or a rolled sheet.
In another embodiment, the inventions is a process, and product made by a process comprising: spinning a plurality of continuous polymeric filaments
comprising a polyetherimide component in either molten form or as a solution, comprising a polyetherimide homopolymer, polyetherimide co-polymer (preferably a reaction product of 4,4'-bisphenol A dianhydride and a meta-phenylene diamine monomer, the reaction product of 4,4'-bisphenol A dianhydride and a para-phenylene diamine monomers, or the reaction product of 4,4'-bisphenol A dianhydride, aminopropyl capped polydimethylsiloxane, and a meta-phenylene diamine monomer,
or a combination thereof), an aromatic polyester homopolymer, aromatic polyester copolymer, or a combination thereof, (preferably wherein the aromatic polyester homopolymer or aromatic polyester copolymer comprises a liquid crystal polymer, preferably a liquid crystal pol mer having the following formula:
where x and y are independently selected positive integers), preferably a
polyetherimide component comprising a polyetherimide homopolymer, a
polyetherimide copolymer, a combination thereof, an aromatic polyester
homopolymer, an aromatic polyester copolymer or a combination thereof, and further wherein the polyetherimide component optionally comprises a phosphorus- containing stabilizer, in an amount that is effective to increase the melt stability of the polyetherimide, wherein the phosphorus-containing stabilizer exhibits a low volatility such that, as measured by thermogravimetric analysis of an initial amount of a sample of the phosphorous-containing stabilizer, greater than or equal to 10 percent by weight of the initial amount of the sample remains unevaporated upon heating of the sample from room temperature to 300°C at a heating rate of 20°C per minute under an inert atmosphere, the filaments having a length to diameter ratio that is more than 1 ,000,000, preferably more than 5,000,000, more preferably more than 20,000,000, and a diameter ranging from 50 nanometers to 5 micrometers preferably from 50 to 1000 nanometers, more preferably from 10 to 500 nanometers; said spinning comprising passing a polymer through a spinneret having a plurality of orifices in a non-electrospinning environment and being conducted at a rate of at least 300 grams/hour/spinneret more preferably at a rate of at least 7000
grams/hour/spinneret; chopping the plurality of continuous filaments and obtaining a plurality of chopped nano-fibers; and forming the nano-fibers into a non-woven web. Optionally in this embodiment, one or more of the following can apply: producing the non-woven web can comprise depositing the plurality of continuous filaments onto a carrier substrate, a functional sheet, a film, a woven or non-woven fabric, a rolled good, and combinations thereof, preferably wherein the carrier substrate is a reciprocating belt; the process can further comprise solidifying the plurality of continuous polymeric filaments before the depositing step; the process can further
comprise consolidating the non-woven web, preferably under pressure, or leaving the non-woven web unconsolidated; each of the plurality of continuous polymeric filaments is provided with at least one additional functionality imparting at least one selected from therapeutic activity, catalytic activity microelectronic activity, micro- optoelectronic activity, magnetic activity, biological activity, and combinations thereof; and none of the plurality of continuous polymeric filaments are bonded to adjacent filaments, or a portion of the plurality of continuous polymeric filaments are at least partially bonded to adjacent filaments, or each of the plurality of continuous polymeric filaments are at least partially bonded to adjacent filaments; the process can further comprise entangling the filaments, for example by needle-punching or fluid hydroentanglement; the process can further comprise at least partially removing any solvent from the filament before the filament is deposited; optionally wherein the non-woven web contains less than 10 wt.%, and preferably no detectable amount of polyvinyl pyrrolidine, polymethyl methacrylate, polyvinylidene fluoride, polypropylene, polycarbonate, polyethylene oxide, agarose, polyvinylidene fluoride, polylactic glycolic acid, nylon 6, polycaprolactone, polylactic acid, polybutylene terephthalate, polycarbonate homopolymers, polycarbonate copolymers, poly(phenylene ether) polymers, poly(phenylene ether)-polysiloxane block copolymers, and combinations thereof; optionally wherein the product is a non-woven paper, medical implant, ultra- fine filter, membrane, hospital gown, electrical insulation paper, honeycomb structure, and personal hygiene product, dialyzer, blood, oxygenator filter,
intravenous (IV) filter, diagnostic test filter, blood/apheresis filter, optionally in the form of a composite non-woven product comprising the spun filaments and at least one other fiber, or a composite non-woven product adhered to a sheet, a film, or a rolled sheet.
In still another embodiment, the invention comprises a process, and a product made by a process comprising: spinning a plurality of continuous polymeric filaments by passing at least one poly(phenylene ether) component or a
poly(phenylene ether)-polysiloxane block copolymers, in either molten form or as a solution, through a spinneret having a plurality of orifices, (preferably a
wherein each occurrence of Z1 is independently halogen, unsubstituted or substituted C1 -C12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl, C1 -C12 hydrocarbylthio, C1 -C12 hydrocarbyloxy, or C2-C12
halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms, and wherein each occurrence of Z2 is independently hydrogen, halogen, unsubstituted or substituted C1-C12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl, C1-C12 hydrocarbylthio, C1 -C12
hydrocarbyloxy, or C2-Ci2 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms), wherein each of the plurality of continuous polymeric filaments has a length to diameter ratio that is more than 1 ,000,000, preferably more than 5,000,000, more preferably more than 20,000,000, wherein each of the plurality of continuous polymeric filaments has a diameter ranging from 50 nanometers to 5 micrometers, preferably from 50 to 1000 nanometers, more preferably from 10 to 500 nanometers, wherein the spinning is conducted in a non- electrospinning environment, wherein the spinning is conducted by rotating the spinneret at a speed sufficient to spin the filaments under the effect of centrifugal force, preferably at a rate of at least 300 grams/hour/spinneret, more preferably at a rate of at least 7000 grams/hour/spinneret; and producing a non-woven web comprising the plurality of continuous polymeric filaments, preferably wherein the non-woven web has a width of at least 150 mm. Optionally in this embodiment, one or more of the following can apply: producing the non-woven web can comprise depositing the plurality of continuous filaments onto a carrier substrate, a functional sheet, a film, a woven or non-woven fabric, a rolled good product, and combinations thereof, preferably wherein the carrier substrate is a reciprocating belt; the process can further comprise solidifying the plurality of continuous polymeric filaments before the depositing step; the process can further comprise consolidating the non-woven web, preferably under pressure, or leaving the non-woven web unconsolidated; each of the plurality of continuous polymeric filaments is provided with at least one additional functionality imparting at least one selected from therapeutic activity,
catalytic activity microelectronic activity, micro-optoelectronic activity, magnetic activity, biological activity, and combinations thereof; and none of the plurality of continuous polymeric filaments are bonded to adjacent filaments, or a portion of the plurality of continuous polymeric filaments are at least partially bonded to adjacent filaments, or each of the plurality of continuous polymeric filaments are at least partially bonded to adjacent filaments; the process can further comprise entangling the filaments, for example by needle-punching or fluid hydroentanglement; the process can further comprise at least partially removing any solvent from the filament before the filament is deposited; optionally wherein the non-woven web contains less than 10 wt.%, and preferably no detectable amount of polyvinyl pyrrolidine, polymethyl methacrylate, polyvinylidene fluoride, polypropylene, polycarbonate, polyethylene oxide, agarose, polyvinylidene fluoride, polylactic glycolic acid, nylon 6, polycaprolactone, polylactic acid, polybutylene terephthalate, polycarbonate homopolymers, polycarbonate copolymers, a polyetherimide homopolymer, a polyetherimide copolymer, a polyetherether ketone homopolymer, a polyetherether ketone copolymer, a polyphenylene sulfone homopolymer, a polyphenylene sulfone copolymer, an aromatic polyester homopolymer an, aromatic polyester copolymer, or combinations thereof; optionally wherein the product is a non-woven paper, medical implant, ultra-fine filter, membrane, hospital gown, electrical insulation paper, honeycomb structure, and personal hygiene product, dialyzer, blood, oxygenator filter, intravenous (IV) filter, diagnostic test filter, blood/apheresis filter, optionally in the form of a composite non-woven product comprising the spun filaments and at least one other fiber, or a composite non-woven product adhered to a sheet, a film, or a rolled sheet.
In another embodiment, the inventions is a process, and product made by a process comprising: spinning a plurality of continuous polymeric filaments
comprising at least one poly(phenylene ether) component or a poly(phenylene ether)-polysiloxane block copolymer, in either molten form or as a solution, through a spinneret having a plurality of orifices, (preferably a poly(phenylene ether)
wherein each occurrence of Z1 is independently halogen, unsubstituted or substituted C1 -C12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl, C1 -C12 hydrocarbylthio, C1 -C12 hydrocarbyloxy, or C2-C12
halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms, and wherein each occurrence of Z2 is independently hydrogen, halogen, unsubstituted or substituted C1-C12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl, C1-C12 hydrocarbylthio, C1 -C12
hydrocarbyloxy, or C2-Ci2 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms), wherein the filaments having a length to diameter ratio that is more than 1 ,000,000, preferably more than 5,000,000, more preferably more than 20,000,000, and a diameter ranging from 50 nanometers to 5 micrometers preferably from 50 to 1000 nanometers, more preferably from 10 to 500 nanometers; said spinning comprising passing a polymer through a spinneret having a plurality of orifices in a non-electrospinning environment and being conducted at a rate of at least 300 grams/hour/spinneret more preferably at a rate of at least 7000 grams/hour/spinneret; chopping the plurality of continuous filaments and obtaining a plurality of chopped nano-fibers; and forming the nano-fibers into a non-woven web. Optionally in this embodiment, one or more of the following can apply: producing the non-woven web can comprise depositing the plurality of continuous filaments onto a carrier substrate, a functional sheet, a film, a woven or non-woven fabric, a rolled good product, and combinations thereof, preferably wherein the carrier substrate is a reciprocating belt; the process can further comprise solidifying the plurality of continuous polymeric filaments before the depositing step; the process can further comprise consolidating the non-woven web, preferably under pressure, or leaving the non-woven web unconsolidated; each of the plurality of continuous polymeric filaments is provided with at least one additional functionality imparting at least one selected from therapeutic activity, catalytic activity microelectronic activity, micro- optoelectronic activity, magnetic activity, biological activity, and combinations thereof; and none of the plurality of continuous polymeric filaments are bonded to
adjacent filaments, or a portion of the plurality of continuous polymeric filaments are at least partially bonded to adjacent filaments, or each of the plurality of continuous polymeric filaments are at least partially bonded to adjacent filaments; the process can further comprise entangling the filaments, for example by needle-punching or fluid hydroentanglement; the process can further comprise at least partially removing any solvent from the filament before the filament is deposited; optionally wherein the non-woven web contains less than 10 wt.%, and preferably no detectable amount of polyvinyl pyrrolidine, polymethyl methacrylate, polyvinylidene fluoride, polypropylene, polycarbonate, polyethylene oxide, agarose, polyvinylidene fluoride, polylactic glycolic acid, nylon 6, polycaprolactone, polylactic acid, polybutylene terephthalate, polycarbonate homopolymers, polycarbonate copolymers, poly(phenylene ether) polymers, poly(phenylene ether)-polysiloxane block copolymers and combinations thereof; optionally wherein the product is a non-woven paper, medical implant, ultra- fine filter, membrane, hospital gown, electrical insulation paper, honeycomb structure, and personal hygiene product, dialyzer, blood, oxygenator filter,
intravenous (IV) filter, diagnostic test filter, blood/apheresis filter, optionally in the form of a composite non-woven product comprising the spun filaments and at least one other fiber, or a composite non-woven product adhered to a sheet, a film, or a rolled sheet.
Other embodiments of the invention can be summarized as follows.
Embodiment 1 . A process comprising: spinning a plurality of continuous polymeric filaments by passing at least one polymeric component through a spinneret having a plurality of orifices, wherein the at least one polymeric component comprises (1 ) a poly(phenylene ether) component, a poly(phenylene ether)- polysiloxane block copolymer, or a combination thereof; (2) a polyetherimide component comprising a polyetherimide homopolymer, a polyetherimide copolymer, or a combination thereof, a polyetherether ketone homopolymer, a polyetherether ketone copolymer, a polyphenylene sulfone homopolymer, a polyphenylene sulfone copolymer, an aromatic polyester homopolymer an, aromatic polyester copolymer, or a combination thereof; or (3) a polycarbonate homopolymer component, a
polycarbonate copolymer component, or a combination thereof; wherein each of the plurality of continuous polymeric filaments has a length to diameter ratio that is more than 1 ,000,000, preferably more than 5,000,000, preferably more than 20,000,000, wherein each of the plurality of continuous polymeric filaments has a diameter
ranging from 50 nanometers to 5 micrometers, preferably from 50 to 1000 nanometers, more preferably from 10 to 500 nanometers, wherein the spinning is conducted in a non-electrospinning environment, wherein the spinning is conducted at a rate of at least 300 grams/hour/ spinneret, preferably at least 7000
grams/hour/spinneret; and producing a non-woven web comprising the plurality of continuous polymeric filaments, wherein the non-woven web has a width of at least 150 mm.
Embodiment 2. The process of Embodiment 1 , wherein producing the non-woven web comprises depositing the plurality of continuous filaments onto a carrier substrate, a functional sheet, a film, a woven or non-woven fabric, a rolled good product, or a combination thereof, preferably wherein the carrier substrate is a reciprocating belt.
Embodiment 3. The process of any one or more of Embodiments 1 to 2, further comprising solidifying the plurality of continuous polymeric filaments before the depositing step.
Embodiment 4. A process of forming a non-woven web, said process comprising: spinning a plurality of continuous polymeric filaments from at least one polymeric component comprising at least one of (1 ) a poly(phenylene ether) component, a poly(phenylene ether)-polysiloxane block copolymer, and
combinations thereof; (2) a polyetherimide homopolymer, polyetherimide copolymer, polyetherether ketones homopolymer, polyetherether ketones copolymers, polyphenylene sulfone homopolymer, polyphenylene sulfone copolymer, aromatic polyester homopolymer, aromatic polyester copolymer, or a combination thereof; and (3) a polycarbonate homopolymer component, a polycarbonate copolymer component, or a combination thereof; the filaments having a length to diameter ratio that is more than 1 ,000,000, preferably more than 5,000,000, preferably more than 20,000,000, and a diameter ranging from 50 nanometers to 5 micrometers, preferably from 50 to 1000 nanometers, more preferably from 10 to 500 nanometers; said spinning comprising passing a polymer through a spinneret having a plurality of orifices in a non-electrospinning environment; said spinning being conducted at a rate of at least 300 grams/hour/spinneret, preferably at least 7000
grams/hour/spinneret; chopping the plurality of continuous filaments and obtaining a plurality of chopped nano-fibers; and forming the nano-fibers into a non-woven web.
Embodiment 5. The process of any one or more of Embodiments 1 to 4, wherein the spinning is conducted by rotating the spinneret at a speed sufficient to spin the filaments under the effect of centrifugal force.
Embodiment 6. The process of any one or more of Embodiments 1 to 5, wherein each of the plurality of continuous polymeric filaments is provided with at least one additional functionality imparting therapeutic activity, catalytic activity microelectronic activity, micro-optoelectronic activity, magnetic activity, biological activity, or a combination thereof.
Embodiment 7. The process of any one or more of Embodiments 1 to 6, wherein none of the plurality of continuous polymeric filaments are bonded to adjacent filaments.
Embodiment 8. The process of any one or more of Embodiments 1 to 7, wherein a portion of the plurality of continuous polymeric filaments are at least partially bonded to adjacent filaments.
Embodiment 9. The process of any one or more of Embodiments 1 to 8, further comprising entangling the filaments, preferably by needle-punching or fluid hydroentanglement.
Embodiment 10. The process of any one or more of Embodiments 1 to 9, wherein the polymeric component is in molten form.
Embodiment 1 1 . The process of any one or more of Embodiments 1 to 10, wherein the polymeric component is the poly(phenylene ether) or is the
poly(phenylene ether)-polysiloxane block copolymer, wherein the poly(phenylene ether) or the poly(phenylene ether)-polysiloxane block copolymer comprises repeating structural units having t
wherein each occurrence of Z is independently halogen, unsubstituted or
substituted C Ci2 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl, C1 -C12 hydrocarbylthio, C1 -C12 hydrocarbyloxy, or C2-C12
halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms; and wherein each occurrence of Z2 is independently hydrogen,
halogen, unsubstituted or substituted C Ci2 hydrocarbyl provided that the
hydrocarbyl group is not tertiary hydrocarbyl, C Ci2 hydrocarbylthio, C Ci2 hydrocarbyloxy, or C2-Ci2 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms.
Embodiment 12. The process of Embodiment 1 1 , wherein the polymeric component is the poly(phenylene ether) component comprising a homopolymer or copolymer of 2,6-dimethylphenol, 2,3,6-trimethylphenol, or a combination thereof, or the polymeric component is the poly(phenylene ether)-polysiloxane block copolymer comprising a homopolymer or copolymer of 2,6-dimethylphenol, 2,3,6- trimethylphenol, or a combination thereof.
Embodiment 13. The process of any one or more of Embodiments 1 1 to 12, wherein the polymeric component is in the form of a solution comprising the poly(phenylene ether) component, the poly(phenylene ether)-polysiloxane block copolymer, or a combination thereof, in a solvent.
Embodiment 14. The process of any one or more of Embodiments 1 to 10, wherein the polymeric component is the polycarbonate homopolymer component comprising a bisphenol A polycarbonate, the polycarbonate copolymer component comprising a copolymer comprising bisphenol A carbonate units and units of the formula
wherein R5 is hydrogen, phenyl optionally substituted with up to five C-MO alkyl groups, or Ci-4 alkyl, or a poly(carbonate-siloxane) comprising bisphenol A carbonate units, and siloxane units of the formula
or a combination comprising at least one of the foregoing, wherein E has an average value of 2 to 200, wherein the poly(carbonate-siloxane) comprises 0.5 to 55 wt.% of siloxane units based on the total weight of the poly(carbonate-siloxane), or a
combination of the polycarbonate homopolymer component and the polycarbonate copolymer component.
Embodiment 15. The process of any one or more of Embodiments 1 to 10, wherein the polymeric component is the polyetherimide homopolymer or
polyetherimide copolymer, and is (i) the reaction product of 4,4'-bisphenol A dianhydride and meta-phenylene diamine monomers, (ii) the reaction product of 4,4'- bisphenol A dianhydride and para-phenylene diamine monomers, or (iii) the reaction product of 4,4'-bisphenol A dianhydride, aminopropyl-capped polydimethylsiloxane, and meta-phenylene diamine monomers.
Embodiment 16. The process of any one or more of Embodiments 1 to 10 or 15, wherein the polymeric component the polyetherimide homopolymer or polyetherimide copolymer, and further comprises a phosphorus-containing stabilizer, in an amount that is effective to increase the melt stability of the polyetherimide, wherein the phosphorus-containing stabilizer exhibits a low volatility such that, as measured by thermogravimetric analysis of an initial amount of a sample of the phosphorus-containing stabilizer, greater than or equal to 10 percent by weight of the initial amount of the sample remains unevaporated upon heating of the sample from room temperature to 300°C at a heating rate of 20°C per minute under an inert atmosphere.
Embodiment 17. A product produced by the process of any one or more of
Embodiments 1 to 1 6.
Embodiment 18. The product of Embodiment 17, wherein the product is at least one selected from non-woven paper, medical implants, ultra-fine filters, membranes, hospital gowns, electrical insulation paper, honeycomb structures and personal hygiene products, dialyzers, blood, oxygenator filters, intravenous (IV) filters, diagnostic test filters, and blood/apheresis filters.
Embodiment 19. The product of any one or more of Embodiments 17 to
18, wherein the product is a composite non-woven product comprising the spun filaments and at least one other fiber.
Embodiment 20. The product of any one or more of Embodiments 17 to
19, wherein the product is a composite non-woven product adhered to a sheet, a film, or rolled sheet goods.
Although the present invention has been described in considerable detail with reference to certain preferred versions thereof, other versions are possible.
Therefore, the spirit and scope of the appended claims should not be limited to the description of the preferred versions contained herein. All the features disclosed in this specification (including any accompanying claims, abstract, and drawings) may be replaced by alternative features serving the same, equivalent or similar purpose, unless expressly stated otherwise. Thus, unless expressly stated otherwise, each feature disclosed is one example only of a generic series of equivalent or similar features.
Claims
1 . A process comprising:
spinning a plurality of continuous polymeric filaments by passing at least one polymeric component through a spinneret having a plurality of orifices,
wherein the at least one polymeric component comprises (1 ) a poly(phenylene ether) component, a poly(phenylene ether)-polysiloxane block copolymer, or a combination thereof; (2) a polyetherimide
component comprising a polyetherimide homopolymer, a polyetherimide copolymer, or a combination thereof, a polyetherether ketone homopolymer, a polyetherether ketone copolymer, a polyphenylene sulfone homopolymer, a polyphenylene sulfone copolymer, an aromatic polyester homopolymer an, aromatic polyester copolymer, or a combination thereof; or (3) a polycarbonate homopolymer component, a polycarbonate copolymer component, or a combination thereof;
wherein each of the plurality of continuous polymeric filaments has a length to diameter ratio that is more than 1 ,000,000, preferably more than 5,000,000, preferably more than 20,000,000,
wherein each of the plurality of continuous polymeric filaments has a diameter ranging from 50 nanometers to 5 micrometers, preferably from 50 to 1000 nanometers, more preferably from 10 to 500 nanometers, wherein the spinning is conducted in a non-electrospinning environment,
wherein the spinning is conducted at a rate of at least 300 grams/hour/ spinneret, preferably at least 7000 grams/hour/spinneret; and producing a non-woven web comprising the plurality of continuous polymeric filaments,
wherein the non-woven web has a width of at least 150 mm.
2. The process of Claim 1 , wherein producing the non-woven web comprises depositing the plurality of continuous filaments onto a carrier substrate, a functional
sheet, a film, a woven or non-woven fabric, a rolled good product, or a combination thereof, preferably wherein the carrier substrate is a reciprocating belt.
3. The process of any one or more of Claims 1 to 2, further comprising solidifying the plurality of continuous polymeric filaments before the depositing step.
4. A process of forming a non-woven web, said process comprising:
spinning a plurality of continuous polymeric filaments from at least one polymeric component comprising at least one of (1 ) a poly(phenylene ether) component, a poly(phenylene ether)-polysiloxane block copolymer, and combinations thereof; (2) a polyetherimide homopolymer, polyetherimide copolymer, polyetherether ketones homopolymer, polyetherether ketones copolymers, polyphenylene sulfone
homopolymer, polyphenylene sulfone copolymer, aromatic polyester homopolymer, aromatic polyester copolymer, or a combination thereof; and (3) a polycarbonate homopolymer component, a polycarbonate copolymer component, or a combination thereof;
the filaments having a length to diameter ratio that is more than 1 ,000,000, preferably more than 5,000,000, preferably more than
20,000,000, and a diameter ranging from 50 nanometers to 5 micrometers, preferably from 50 to 1000 nanometers, more preferably from 10 to 500 nanometers;
said spinning comprising passing a polymer through a spinneret having a plurality of orifices in a non-electrospinning environment;
said spinning being conducted at a rate of at least 300
grams/hour/spinneret, preferably at least 7000 grams/hour/spinneret; chopping the plurality of continuous filaments and obtaining a plurality of chopped nano-fibers; and
forming the nano-fibers into a non-woven web;
5. The process of any one or more of Claims 1 to 4, wherein the spinning is conducted by rotating the spinneret at a speed sufficient to spin the filaments under the effect of centrifugal force.
6. The process of any one or more of Claims 1 to 5, wherein each of the plurality of continuous polymeric filaments is provided with at least one additional
functionality imparting therapeutic activity, catalytic activity microelectronic activity, micro-optoelectronic activity, magnetic activity, biological activity, or a combination thereof.
7. The process of any one or more of Claims 1 to 6, wherein none of the plurality of continuous polymeric filaments are bonded to adjacent filaments.
8. The process of any one or more of Claims 1 to 7, wherein a portion of the plurality of continuous polymeric filaments are at least partially bonded to adjacent filaments.
9. The process of any one or more of Claims 1 to 8, further comprising entangling the filaments, preferably by needle-punching or fluid hydroentanglement.
10. The process of any one or more of Claims 1 to 9, wherein the polymeric component is in molten form.
1 1 . The process of any one or more of Claims 1 to 10, wherein the polymeric component is the poly(phenylene ether) or is the poly(phenylene ether)-polysiloxane block copolymer, wherein the poly(phenylene ether) or the poly(phenylene ether)- polysiloxane block copolymer comprises repeating structural units having the formula:
wherein each occurrence of Z is independently halogen, unsubstituted or substituted C1 -C12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl, C1 -C12 hydrocarbylthio, C1 -C12 hydrocarbyloxy, or C2-Ci 2
halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms; and
wherein each occurrence of Z2 is independently hydrogen, halogen,
unsubstituted or substituted C1 -C-12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl, C1 -C12 hydrocarbylthio, C1 -C12 hydrocarbyloxy, or C2-Ci2 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms.
12. The process of Claim 1 1 , wherein the polymeric component is the poly(phenylene ether) component comprising a homopolymer or copolymer of 2,6- dimethylphenol, 2,3,6-trimethylphenol, or a combination thereof, or the polymeric component is the poly(phenylene ether)-polysiloxane block copolymer comprising a homopolymer or copolymer of 2,6-dimethylphenol, 2,3,6-trimethylphenol, or a
combination thereof.
13. The process of any one or more of Claims 1 1 to 12, wherein the polymeric component is in the form of a solution comprising the poly(phenylene ether) component, the poly(phenylene ether)-polysiloxane block copolymer, or a combination thereof, in a solvent.
14. The process of any one or more of Claims 1 to 10, wherein the polymeric component is
the polycarbonate homopolymer component comprising a bisphenol A
polycarbonate,
the polycarbonate copolymer component comprising
a copolymer comprising bisphenol A carbonate units and units of the formula
wherein R5 is hydrogen, phenyl optionally substituted with up to five CMO alkyl groups, or C-i -4 alkyl, or
a poly(carbonate-siloxane) comprising bisphenol A carbonate units, and
or a combination comprising at least one of the foregoing, wherein E has an average value of 2 to 200, wherein the poly(carbonate-siloxane) comprises 0.5 to 55 wt.% of siloxane units based on the total weight of the poly(carbonate-siloxane),
or a combination of the polycarbonate homopolymer component and the polycarbonate copolymer component.
15. The process of any one or more of Claims 1 to 10, wherein the polymeric component is the polyetherimide homopolymer or polyetherimide copolymer, and is (i) the reaction product of 4,4'-bisphenol A dianhydride and meta-phenylene diamine monomers, (ii) the reaction product of 4,4'-bisphenol A dianhydride and para-phenylene diamine monomers, or (iii) the reaction product of 4,4'-bisphenol A dianhydride, aminopropyl-capped polydimethylsiloxane, and meta-phenylene diamine monomers.
1 6. The process of any one or more of Claims 1 to 10 or 15, wherein the polymeric component the polyetherimide homopolymer or polyetherimide copolymer, and further comprises a phosphorus-containing stabilizer, in an amount that is effective to increase the melt stability of the polyetherimide, wherein the phosphorus-containing stabilizer exhibits a low volatility such that, as measured by thermogravimetric analysis of an initial amount of a sample of the phosphorus-containing stabilizer, greater than or equal to 10 percent by weight of the initial amount of the sample remains unevaporated upon heating of the sample from room temperature to 300°C at a heating rate of 20°C per minute under an inert atmosphere.
17. A product produced by the process of any one or more of Claims 1 to 1 6.
18. The product of Claim 17, wherein the product is at least one selected from non-woven paper, medical implants, ultra-fine filters, membranes, hospital gowns, electrical insulation paper, honeycomb structures and personal hygiene products, dialyzers, blood, oxygenator filters, intravenous (IV) filters, diagnostic test filters, and blood/apheresis filters.
19. The product of any one or more of Claims 17 to 18, wherein the product is a composite non-woven product comprising the spun filaments and at least one other fiber.
20. The product of any one or more of Claims 17 to 19, wherein the product is a composite non-woven product adhered to a sheet, a film, or rolled sheet goods.
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3015586A4 (en) * | 2013-06-28 | 2017-01-25 | Kuraray Co., Ltd. | Flame-retardant nonwoven fabric, molded article, and composite laminate |
CN108149336A (en) * | 2017-12-21 | 2018-06-12 | 义乌华鼎锦纶股份有限公司 | A kind of preparation method of the fat or thin fiber of 6 extraordinary splendor of polyamide fibre |
DE202018100242U1 (en) | 2017-11-28 | 2018-12-07 | BLüCHER GMBH | Air-permeable surface filter material |
US11958308B1 (en) | 2023-05-31 | 2024-04-16 | G13 Innovation In Production Ltd | Thermal paper, and methods and systems for forming the same |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6001957A (en) | 1997-12-23 | 1999-12-14 | General Electric Company | Stabilized polyetherimide resin composition |
US20050032450A1 (en) * | 2003-06-04 | 2005-02-10 | Jeff Haggard | Methods and apparatus for forming ultra-fine fibers and non-woven webs of ultra-fine spunbond fibers |
US20100129628A1 (en) * | 2008-11-25 | 2010-05-27 | E. I. Du Pont De Nemours And Company | Non-Woven Polymeric Webs |
US20120074612A1 (en) * | 2010-09-29 | 2012-03-29 | Scrivens Walter A | Process of Forming a Nanofiber Non-Woven Containing Particles |
WO2012109215A2 (en) | 2011-02-07 | 2012-08-16 | Fiberio Technology Corporation | Apparatuses and methods for the production of microfibers and nanofibers |
US20130078882A1 (en) * | 2011-09-27 | 2013-03-28 | Samsung Electro-Mechanics Co., Ltd. | Porous sheet and method for manufacturing the porous sheet |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4963909B2 (en) * | 2006-09-14 | 2012-06-27 | 旭化成せんい株式会社 | Polyphenylene ether microfiber and its fiber aggregate |
US9834865B2 (en) * | 2007-12-17 | 2017-12-05 | E I Du Pont De Nemours And Company | Centrifugal solution spun nanofiber process |
US8512432B2 (en) * | 2008-08-01 | 2013-08-20 | David Charles Jones | Composite filter media |
US7922959B2 (en) * | 2008-08-01 | 2011-04-12 | E. I. Du Pont De Nemours And Company | Method of manufacturing a composite filter media |
JP6190274B2 (en) * | 2011-02-07 | 2017-08-30 | クラーコア インコーポレーテッドCLARCOR Inc. | Apparatus and method for depositing microfibers and nanofibers on a substrate |
-
2014
- 2014-07-17 WO PCT/US2014/047084 patent/WO2015009962A1/en active Application Filing
- 2014-07-17 JP JP2016527110A patent/JP2016530406A/en active Pending
- 2014-07-17 EP EP14748394.5A patent/EP3022347A1/en not_active Withdrawn
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6001957A (en) | 1997-12-23 | 1999-12-14 | General Electric Company | Stabilized polyetherimide resin composition |
US20050032450A1 (en) * | 2003-06-04 | 2005-02-10 | Jeff Haggard | Methods and apparatus for forming ultra-fine fibers and non-woven webs of ultra-fine spunbond fibers |
US20100129628A1 (en) * | 2008-11-25 | 2010-05-27 | E. I. Du Pont De Nemours And Company | Non-Woven Polymeric Webs |
US20120074612A1 (en) * | 2010-09-29 | 2012-03-29 | Scrivens Walter A | Process of Forming a Nanofiber Non-Woven Containing Particles |
WO2012109215A2 (en) | 2011-02-07 | 2012-08-16 | Fiberio Technology Corporation | Apparatuses and methods for the production of microfibers and nanofibers |
US20130078882A1 (en) * | 2011-09-27 | 2013-03-28 | Samsung Electro-Mechanics Co., Ltd. | Porous sheet and method for manufacturing the porous sheet |
Cited By (7)
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