Highly Oriented and Crystalline Thermoplastic Filaments and Method of Making Same
A melt-spun highly oriented and crystalline thermoplastic filament or fiber having a tenacity of at least about 10 g/d, an elongation less than about 15%, and a modulus of at least about 130 g/d. A method of making highly oriented and crystalline thermoplastic filaments has been developed that comprises extruding a thermoplastic polymer to form at least one molten filament. The at least one molten filament is introduced into a horizontal liquid isothermal bath. The bath is maintained at a temperature between the glass transition temperature and the melting temperature of the thermoplastic polymer. The bath increases the tension along the molten filament to form at least one partially oriented and low crystalline filament. The partially oriented filament is drawn to form the highly oriented and crystalline filament.
This application is a division of U.S. patent application Ser. No. 13/383,076, filed Jun. 25, 2012, allowed, which itself claims the benefit of International Patent Application No. PCT/US2010/041566 for a Highly Oriented and Crystalline Thermoplastic Filaments and Method of Making Same, filed Jul. 9, 2010, which published Jan. 13, 2011, as International Publication No. WO 2011/006092 A2, and Provisional Patent Application No. 61/224,527, filed Jul. 10, 2009, the entire disclosure of each of which is incorporated herein by reference.
The present invention is related to a method of forming thermoplastic filaments, and particularly to a method for forming melt-spun highly oriented low crystalline precursor filaments and melt-spun highly oriented crystalline filaments produced from same.
BACKGROUNDWith the increasingly fierce competition in the synthetic fiber market, it is important to operate at a high performance to cost ratio. This has been done before by: a) improving the fiber properties (performance) by the development of the dry jet wet-spinning of aramids (e.g., Kevlar™) or gel-spinning of polyethylene (e.g., Spectra™), or b) reducing the production cost via high-speed spinning in the melt-spinning process of thermoplastic polymers. Polyolefins, polyesters, and polyamide fibers have been typically produced using a melt-spinning or the melt spin-draw process. Efforts have been made to improve the fiber performance in this relatively inexpensive process, but the properties of the melt-spun fibers are typically much below those of the wet- or gel-spun fibers.
Melt-spun fibers, however, with physical properties that are comparable to those resulting from wet or gel spinning techniques, have been attempted, but with little success. These processes come with numerous expenses, for example, capital expenditure for appropriate polymer handling, plant space, manpower and storage facilities. Yet despite advances in polymer science to date, melt-spun fibers having a tenacity and modulus typical of, or even intermediate to, the tenacity and modulus of high performance fibers such as Kevlar™ or Spectra™ have not heretofore been obtained.
SUMMARYAn aspect of the invention is a method of making melt-spun highly oriented and crystalline thermoplastic filaments or fibers. The method includes extruding at least one thermoplastic polymer, or a polymer blend, to form molten filaments. The molten filaments are then passed through a liquid bath that maintains the molten filaments at a temperature between the glass transition temperature and the melting temperature of the thermoplastic polymer. The bath includes a guide around which passes the filament, which is redirected toward a first feed driven roller. The bath, guide and feed roller induce some increased tension to form partially oriented, low crystalline precursor filaments. The partially oriented filaments exit the bath and are further drawn to form melt-spun highly oriented crystalline filaments having unexpectedly high values for tenacity and modulus, and relatively low elongation to break values.
Another aspect of the invention is a melt-spun highly oriented and crystalline thermoplastic polymer filaments or fibers having increased tenacity, lower elongation, and increased modulus. The thermoplastic polymers are selected from the group consisting of melt spinable thermoplastic polymers and blends of melt spinable thermoplastic polymers.
Another aspect of the invention is a textile material formed from yarns comprising melt-spun highly oriented and crystalline thermoplastic polymer filaments or fibers each having increased tenacity, lower elongation, and increased modulus compared to conventional melt-spun thermoplastic polymer filaments. The thermoplastic polymer filaments are selected from the group consisting of melt spinable thermoplastic polymers, and blends of melt spinable thermoplastic polymers. The textile material includes, but is not limited to, a woven fabric, knitted fabric, nonwoven fabric, or braided material.
Certain exemplary embodiments of the present invention are described below and illustrated in the accompanying figures. The embodiments described are only for purposes of illustrating the present invention and should not be interpreted as limiting the scope of the invention, which, of course, is limited only by the claims below. Other embodiments of the invention, and certain modifications and improvements of the described embodiments, will occur to those skilled in the art, and all such alternate embodiments, modifications, and improvements are within the scope of the present invention.
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In an embodiment, a single-screw extruder with a four zone temperature control is used to introduce the molten polymer to the spinneret 24. The number of zones may be modified as the need may arise. In an embodiment, a twin-screw extruder with multiple heating zones is used. In alternate embodiments, multiple extruders may be used when spinning more than one polymer or polymer blend. For example, multiple extruders may be used to form bicomponent thermoplastic filaments. In other alternate embodiments, one extruder is used to melt one polymer and a second extruder is used to melt a second polymer. For example, a first extruder is used to form polyester filaments while a second extruder is used to simultaneously form co-polyester filaments.
Referring to
Continuing with
In another exemplary embodiment, the spinneret may be configured with the appropriate spinpacks to form bicomponent filaments. For example, the extruder 20 and spinneret 24 can be configured to form bicomponent filaments such as islands-in-the-sea, segmented pie, side-by-side, sheath-core, or other configurations.
The temperature of the spinneret 24 is dependent on the polymer or polymer blend being used to form the molten filaments. As described above, any thermoplastic polymer or polymer blend may be used. For example, when melt-spinning polyethylene naphthalate is used, the spinneret temperature is between about 275° C. and about 350° C., preferably about 310° C. When polyethylene terephthalate is used, the spinneret temperature is between about 240° C. and about 330° C.
Referring again to
Referring to
Referring now to
During processing, the temperature of the medium 40 is typically between the glass transition temperature (Tg) and the melting temperature (Tm) of the polymer or the polymer blends. In an embodiment, the temperature of the medium or liquid 40 is between about 50° C. and about 400° C. For example, when polyethylene naphthalate is used to form the filaments as described herein, the temperature of the liquid is between about 90° C. and about 250° C., preferably between about 100° C. and about 180° C. In embodiments where polyethylene terephthalate is used to form the filaments, the temperature of the liquid is between about 70° C. and about 200° C., preferably between about 80° C. and about 100° C. In embodiments where blended polymers are used, the temperature of the liquid may be modified accordingly.
Continuing with
The guide 50 is positioned in the HLIB 30 and redirects the filament toward the feed roller 60. As shown in
The depth of liquid 40 in the bath 30 is modified as needed. As shown in
A first driven feed roller 60 redirects the partially oriented filament 130 toward a drawing apparatus 80. The feed roller 60 is positioned externally of the HLIB 30 and at an elevation above the guide 50 in the bath 30. This position draws the filament at least partially around the guide 50 and in an upwardly direction from within the HLIB 30. In the embodiment shown in
The drawing apparatus 80 may be any configuration of rollers and a heat source that imparts thermal energy and extension to the partially oriented filaments to form the highly oriented and crystallized filaments 140. Because the partially oriented filaments have the unique oriented morphology as discussed above, relatively low or modest draw ratios provide a highly oriented and crystalline filaments 140 with the unexpected results described herein. Typically, draw ratios for conventional melt-spun filaments that do not use the HLIB as described herein are the region of 3.5 to 5 and yield physical properties that fall short of those described herein.
An embodiment of a drawing apparatus is shown in
Drawing at the drawing step occurs between the glass transition temperature and the melting temperature of the thermoplastic polymer. In an embodiment, heat source 86 applies heat to the filament while differential speeds between the first 84 and second 88 rolls extend and crystallize the polymer chains. In addition, first 84 and second draw 88 rolls may be heated as the need may arise. The drawing temperatures for PEN are preferably between about 100° C. and 260° C. preferably about 160° C. The drawing temperatures for PET are between about 100° C. and 260° C., preferably about 160° C. The drawing temperatures, however, may range between about 50° C. and about 400° C.
As shown in
As shown in
In other alternate embodiments, the air drawing may be used. For example, high velocity heated air may be used to extend the partially oriented filaments to form highly oriented and crystalline filaments.
Further, the highly oriented and crystalline filaments may be used to form a nonwoven, e.g. melt-spun nonwovens. As shown in
Thermoplastics polymers and blends thereof are used to form the high tenacity, high modulus filaments. Thermoplastic polymers that have a definable glass transition (Tg) and melting (Tm) temperatures are preferable. Polymers that have low, medium, or high intrinsic viscosities (IV) can yield high tenacity and high modulus filaments when melt-spun as described herein. For example, a polymer having an intrinsic viscosity between about 0.75 and about 1.0 dl/g can be used. Preferable thermoplastic polymers include polyethylene terephthalate (PET) and polyethylene naphthalate (PEN). In alternate embodiments, other thermoplastic polymers can be used including, but not limited to, PET, PEN, polytrinethylene terephthalate (PTT), polybutylene terephthalate (PBT), polypropylene (PP), polylactic acid (PLA), polyamide 6 (PA6), polyamide 6,6 (PA66), polyethylene, and co-polymers of PET, PEN and PA or any of the polymers listed above. In other embodiments, recycled polymers may be used.
Blends of polymers may also be used to form the highly oriented and crystalline filaments as described herein. For example, two or more polymers including, but not limited to, PET, PEN, PTT, PBT, PP, PLA, PA6, PA66, PE co-polymers of PET, co-polymers of PEM, and co-polymers of PA may be used to form the highly oriented and crystalline filaments. In other embodiments, one or more polymers may be combined with a recycled polymer. In an embodiment, polymer blends can comprise between about 0.01% and 50% by weight of a first polymer and between about 50% and 99.99% by weight of a second polymer. For example, one blend comprises about 99% by weight of PEN and about 1% by weight of PET. In another embodiment, the blend comprises about 99% by weight of PEN and about 1% by weight of PP.
In other embodiments various additives may be combined with a polymer or polymer blends. Additives may include, but are not limited to, nonionic melt additives, hydrophobic additives, hydrophilic additives, polymer combatablizers, plasticizers, UV enhancers, calcium carbonate, flame retardants, intumescents, fluorochemicals, antibacterial agents, antifungal agents, heat and light stabilizers, delustrants such as titanium dioxide, dyes, pigments, carbon particles, carbon nanoparticles, carbon nanotubes, and other nanoparticles.
The melt-spun highly oriented and crystalline thermoplastic filament or fibers as described herein may have a range of deniers. In an embodiment, the denier of the fiber or filament may by up to about 100 denier. In some exemplary embodiments, the denier per filament (dpf) may range between about 0.01 dpf to 10 dpf and higher. Further, multifilament yarns formed as described herein may have any range of denier and denier per filament as is needed.
The filaments formed as described herein may be used to manufacture a variety of textile materials. The filaments are capable of forming continuous filament yarns, textured continuous filament yarns, core-spun yarns or other yarn structures. In alternate embodiments, the drawn filaments can be collected and cut into staple fibers, crimped and used to form spun yarns, e.g., ring-spun and/or open end spun yarns. In other embodiments, the fibers may be used to form nonwoven fabrics. The filaments or spun yarns may therefor be used to form woven fabrics, weft knit fabrics, warp knit fabrics, three dimensional braids, 3D woven structures, composites and the like.
EXAMPLE 1PEN polymer chips having intrinsic viscosity (IV) of 1.0 dl/g was used to form filaments. The intrinsic viscosity was measured in a 60/40 w/w phenol/tetrachloroethane solution. The PEN polymer chips were vacuum dried at 140° C. for 16 hours. A Fourne single-screw extruder, equipped with a single-hole, hyperbolic spinneret with 0.6 mm orifice diameter was used for melt-extrusion and spinning. The spinneret temperature was set at 310° C. After emergence from the spinneret, the filament was directed into a horizontal liquid isothermal bath and around a guide therein toward take-up. The HLIB was positioned 110 cm below the spinneret (D1). The liquid depth (LD) was fixed at 25 cm. The as-spun speed was 4000 m/min. The temperature of the liquid was 135° C. The fibers were spun and passed through the HLIB to form partially oriented filaments. The filaments were collected and then heat-drawn off line on a modified Instron machine to approximate the drawing step described above. The modified Instron tensile testing machine has two opposing clamps and a 60 cm long heating tube positioned therebetween. The fibers spun with the HLIB were then placed within the 60 cm heating tube and secured to each clamp. The temperature of the heating tube was set to 160° C. One of two clamps traveled at 5 cm/min. The fibers were drawn to a draw ratio of 1.4.
EXAMPLE 2PET polymer chips having an intrinsic viscosity (IV) of 1.0 dl/g were used to form the filaments. The intrinsic viscosity was measured in a 60/40 w/w phenol/tetrachloroethane solution. The PET polymer chips were vacuum dried at 140° C. for 16 hours. A Fourne single-screw extruder, equipped with a single-hole, hyperbolic spinneret with 0.6 mm orifice diameter was used for melt-extrusion and spinning the PET. The spinneret temperature was set at 290° C. After emergence from the spinneret, the filament was directed into a HLIB and around a guide therein toward take-up. The HLIB was positioned 110 cm below the spinneret (D1). The liquid depth (LD) was fixed at 25 cm. The spinning speed (S1) was 2000-3000 m/min. The take-up was 4000 m/min. The temperature of the liquid was 80° C. The fibers were spun and passed through the HLIB to form partially oriented filaments. The filaments were collected and then heat-drawn off line on a modified Instron machine to approximate the drawing step described above. The modified Instron tensile testing machine has two opposing clamps and a 60 cm long heating tube positioned therebetween. The fibers spun with the HLIB were then placed inside the 60 cm heating tube and secured to each clamp. The temperature of the heating tube was set to 120° C. One of the two clamps traveled at 5 cm/min. The fibers were drawn to a draw ratio of 1.4.
Wide-angle X-ray diffraction (WAXD) measurements were performed on PEN polymers using a Siemens type-F diffractometer system with CuKa radiation generated at 30 kV and 20 mA. Measurements were taken on undrawn and drawn filaments. The diffracting intensities were recorded every 0.1° from 20 scans in the range 5-40°. Density of filament samples was measured by using a density gradient column consisting of aqueous sodium bromine maintained at 23+0.1° C. Tensile properties of fibers were measured on an MTS testing machine following ASTM D3822. A gauge length of 25.4 mm and a constant cross-head speed of 15 mm/min were used. The crystallinity, or the weight fraction crystallinity, Xc,wt, is calculated from density by applying the following equation:
Where ρ is the density of the fiber, ρc0 is the density of the crystalline phase and ρa0 is the density of the amorphous phase.
Table 1 shows the properties of the PEN fibers formed with and without the HLIB, and with and without a subsequent drawing step. A draw ratio (DR) of 1.40 resulted in increased tenacity and modulus as well as decreased elongation. However, the HLIB filaments show a greater improvement in fiber properties after drawing. The PEN fibers have high tenacity (10.75 g/d), and high modulus (216.7 g/d) at a low draw ratio (1.40). The data also indicates that the HLIB fibers have a unique morphology. The undrawn HLIB fibers have a low density and appear totally amorphous. The undrawn HLIB reported a crystallinity of zero as shown in Table 1. This is surprising because the undrawn HLIB fibers also have higher tenacity than the undrawn fibers formed without the HLIB.
WAXD profiles of the undrawn and drawn PEN fibers spun with HLIB are shown in
Table 2 summarizes the physical properties of PET and PEN filaments formed using the HLIB compared to commercially available PET and PEN filaments. Sample A is the commercial, non HLIB PET filament (“PET COM”). Sample B is a PET filament that was melt-spun using the HLIB (“PET HLIB”). Sample C is the commercial, non HLIB PEN filament (“PEN COM”). Sample D is a PEN filament that was melt-spun using the HLIB (“PEN HLIB”). Filaments spun using the HLIB (samples B and D) show dramatic improvements in physical properties over the non-HLIB filaments (samples A and C).
Tables 1 and 2 are representative of PET and PEN polymers used to form the highly oriented crystalline filaments as described herein. Other polymers may be used to form highly oriented crystalline filaments having lower tenacity values than those reported in Tables 1 and 2, yet would have increased tenacity and modulus of similar polymer types processed without the HLIB and subsequent drawing step.
Exemplary embodiments of the invention have been described herein, however the invention is not limited to Examples 1 and 2 set forth above. The highly oriented and crystalline filaments as described herein may have a tenacity of at least 10 g/d, an elongation less than about 15%, and a modulus of at least about 130 g/d, when measured as described above. Further, in an embodiment, polyethylene terephthalate filaments may have a tenacity of at least about 11 g/d, an elongation less than about 10%, and a modulus of at least about 130 g/d. Polyethylene terephthalate filaments or fibers have a crystallinity of at least between about 45% and 60%, when measured as described above. In other embodiments, polyethylene naphthalate filaments or fibers have a tenacity of at least about 10 g/d, an elongation less than about 10%, and a modulus of at least about 200 g/d. Further, polyethylene naphthalate filaments have a crystallinity of between about 45% and about 52%, when measured as described above.
Although the present invention has been described with exemplary embodiments, it is to be understood that modifications and variations may be utilized without departing from the spirit and scope of the invention, as those skilled in the art will readily understand. Such modifications and variations are considered to be within the purview and scope of the appended claims and their equivalents.
Claims
1. A melt-spun oriented crystalline filament and/or fiber formed of polyethylene terephthalate (PET) and having a crystallinity of about 45% to about 60%, an elongation of less than about 10%, and a tenacity of at least about 11 g/d.
2. The melt-spun oriented crystalline filament and/or fiber of claim 1, wherein the filament and/or fiber has a modulus of at least about 130 g/d.
3. A melt-spun oriented crystalline filament and/or fiber formed of polyethylene naphthalate (PEN) and having a crystallinity of about 45% to about 52%, an elongation of less than about 10%, and a tenacity of at least about 10 g/d.
4. The melt-spun oriented crystalline filament and/or fiber of claim 3, wherein the filament and/or fiber has a modulus of at least about 200 g/d.
5. A textile material comprising a plurality of melt-spun oriented crystalline filaments and/or fibers formed of polyethylene terephthalate (PET) and having a crystallinity of about 45% to about 60%, an elongation of less than about 10%, and a tenacity of at least about 11 g/d.
6. The textile material of claim 5, wherein the melt-spun oriented crystalline filaments and/or fibers have a modulus of at least about 130 g/d.
7. The textile material of claim 5, wherein the textile material is a woven fabric.
8. The textile material of claim 5, wherein the textile material is a nonwoven material.
9. The textile material of claim 5, wherein the textile material is a knit fabric.
10. The textile material of claim 5, wherein the textile material is a yarn.
11. The textile material of claim 5, wherein the textile material is a braid.
12. The textile material of claim 5, wherein the textile material is a 3D woven structure.
13. A textile material comprising a plurality of melt-spun oriented crystalline filaments and/or fibers formed of polyethylene naphthalate (PEN) and having a crystallinity of about 45% to about 52%, an elongation of less than about 10%, and a tenacity of at least about 10 g/d.
14. The textile material of claim 13, wherein the melt-spun oriented crystalline filaments and/or fibers have a modulus of at least about 200 g/d.
15. The textile material of claim 13, wherein the textile material is a woven fabric.
16. The textile material of claim 13, wherein the textile material is a nonwoven material.
17. The textile material of claim 13, wherein the textile material is a knit fabric.
18. The textile material of claim 13, wherein the textile material is a yarn.
19. The textile material of claim 13, wherein the textile material is a braid.
20. The textile material of claim 13, wherein the textile material is a 3D woven structure.
21. A melt-spun oriented crystalline filament and/or fiber formed a blend comprising about 50% by weight to about 99.9% by weight of polyethylene naphthalate (PEN) and about 0.01% by weight to about 50% by weight of polyethylene terephthalate (PET), the filament or fiber having an elongation of less than about 15%, a tenacity of at least about 10 g/d, and a modulus of at least about 130 g/d.
22. The melt-spun oriented crystalline filament and/or fiber of claim 21, comprising a blend of about 99% by weight PEN and about 1% by weight PET.
23. A textile material comprising a plurality of melt-spun oriented crystalline filaments and/or fibers formed of a blend comprising about 50% by weight to about 99.9% by weight of polyethylene naphthalate (PEN) and about 0.01% by weight to about 50% by weight of polyethylene terephthalate (PET), the filament or fiber having an elongation of less than about 15%, a tenacity of at least about 10 g/d, and a modulus of at least about 130 g/d.
24. The textile material of claim 23, wherein the textile material is a woven fabric.
25. The textile material of claim 23, wherein the textile material is a nonwoven material.
26. The textile material of claim 23, wherein the textile material is a knit fabric.
27. The textile material of claim 23, wherein the textile material is a yarn.
28. The textile material of claim 23, wherein the textile material is a braid.
29. The textile material of claim 23, wherein the textile material is a 3D woven structure.
30. A melt-spun oriented crystalline filament and/or fiber formed of polypropylene and having a tenacity of at least about 10 g/d, an elongation of less than about 15%, and a modulus of at least about 130 g/d.
Type: Application
Filed: Jul 13, 2015
Publication Date: Jan 14, 2016
Inventors: John A. Cuculo (Raleigh, NC), Richard Kotek (Raleigh, NC), Peng Chen (Zhejiang), Mehdi Afshari (Raleigh, NC), Ferdinand Lundberg (Garner, NC)
Application Number: 14/797,684