Patent Application
20190382921
The present invention relates to polyamide materials, and in particular, to gel spinning techniques for producing fibers from polyamides.
Typical polyamide, or nylon, textiles are produced using melt spinning techniques, in which the polyamide resin is heated to a melt state prior to extruding the resin through a spinneret to form the textile fiber. Such nylon resins typically have a molecular weight in the range of about 14,000 Dalton (Da) to 20,000 Da, and produce fibers having a tenacity of about 6-10 grams/denier. This mechanical strength is not sufficient for some high-performance textile fiber applications.
Some pre-fiber gel compositions, methods of manufacture, and uses thereof are disclosed, for example, in U.S. Pat. Nos. 7,258,048, 8,106,116, and International Patent Publication WO 2005/049694, the disclosures of which are hereby incorporated by reference in their entireties.
Improvements in the foregoing pre-fiber gel compositions and methods of manufacture are desired in order to produce mechanically stronger polyamide textile fibers suitable for a broader range of textile applications.
The present disclosure provides a composition for gel spinning of polyamide fibers. The spun fibers may be useful in producing high-performance textiles.
Various embodiments concern a composition for forming a fiber. The composition includes at least one polyamide and caprolactam. The at least one polyamide has a number average molecular weight between 38,000 Da and 100,000 Da derived from formic acid viscosity (FAV) as determined according to ASTM 789. The polyamide is at least partially dissolved in the caprolactam. The caprolactam comprises between 20 wt. % and 90 wt. % of the composition. In some embodiments, the at least one polyamide of the composition is polyamide-6. In some embodiments, the caprolactam comprises between 50 wt. % and 90 wt. % of the total weight of the composition. In some embodiments, the polyamide has a number average molecular weight between 41,000 Da and 68,000 Da derived from formic acid viscosity (FAV) as determined according to ASTM 789.
Various embodiments include a method of producing a fiber. The method includes dissolving at least one polyamide into caprolactam to form a spinnable solution and spinning the spinnable solution by extruding the spinnable solution through a spinneret to form the fiber. The at least one polyamide has a number average molecular weight between 38,000 Da and 100,000 Da derived from formic acid viscosity (FAV) as determined according to ASTM 789. In some embodiments, dissolving the at least one polyamide is performed at a temperature of 150° C. to 270° C. In further embodiments, dissolving the at least one polyamide is performed at a temperature of 150° C. to 200° C. In some embodiments, the at least one polyamide is polyamide-6. In some embodiments, the spinnable solution includes between 20 wt. % and 90 wt. % caprolactam. In further embodiments, the spinnable solution includes between 50 wt. % to 90 wt. % caprolactam. In some embodiments, the polyamide has a number average molecular weight between 41,000 Da and 68,000 Da derived from formic acid viscosity (FAV) as determined according to ASTM 789. In some embodiments, the method further includes quenching the spun fibers in a quench bath containing a quenching liquid. In some embodiments, an air gap is defined between the spinneret and the quenching liquid in the quench bath, the air gap from 0.25 inches to 11 inches in length. In some embodiments, the air gap is from 0.5 inches to 2 inches in length. In some embodiments, quenching the spun fibers includes pulling the fiber through the quenching bath in a first direction and flowing the quenching liquid in a second direction. The second direction being substantially opposite to the first direction. In some embodiments, the quenching liquid has a dynamic viscosity of between 1,000 and 26,000 centipoise. In some embodiments, the quenching liquid is at a temperature from 50° C. to 150° C.
Various embodiments include a polyamide fiber. The polyamide fiber includes a plurality of polyamide polymer chains. The polyamide polymer chains have a number average molecular weight between 38,000 Da and 100,000 Da derived from formic acid viscosity (FAV) as determined according to ASTM 789. In some embodiments, a tenacity of the polyamide fiber is greater than 10 grams/denier.
The above mentioned and other features of the invention, and the manner of attaining them, will become more apparent and the invention itself will be better understood by reference to the following description of embodiments of the invention taken in conjunction with the accompanying drawings.
Embodiments of the disclosure can employ high molecular weight polyamide to form stronger polyamide fibers. For the purposes of this disclosure, high molecular weight polyamide has a number average molecular weight (Mn) greater than about 38,000 Da. As noted above, the molecular weight of the polyamides used in melt spinning has in the past been generally limited to no more than about 20,000 Da. Higher molecular weight polyamide may be too viscous to process through typical industrial extruders unless the extrusion temperature is increased, though a significant increase of the extrusion temperature may thermally degrade the polyamide.
However, it has now been found that high molecular weight polyamide can be partially dissolved in a gelling agent to form a spinnable solution in the form of a gel. The spinnable solution or gel can be extruded to form a polyamide fiber, as described below. It has been found that the strength of the polyamide fiber increases as the number average molecular weight of the polyamide used in the gel increases. Without wishing to be bound by any theory, it is believed that the greater strength of such polyamide fibers may be the result of fewer chain end defects.
In some embodiments, the polyamide fiber produced according to the present disclosure can have a tenacity greater than 10 grams/denier (gpd). In some embodiments, the polyamide fiber can have a tenacity as low as 10.5 gpd, 11 gpd, or 12 gpd, or as high as 14 gpd, 15 gpd, or 16 gpd, or within any range between any two of the foregoing values, such as 10.5 gpd to 16 gpd, 11 gpd to 15 gpd, or 12 gpd to 14 gpd, for example.
The polyamide may be provided in the form of a resin. In some embodiments, the polyamide includes at least one of polyamide-6 (PA-6), polyamide-6,6 (PA-6,6), and polyamide-9,6 (PA-9,6). In one embodiment the polyamide is polyamide-6 or polyamide-6,6. In a more particular embodiment, the polyamide is polyamide-6.
The polyamide can have a number average molecular weight greater than about 38,000 Da. In some embodiments, the polyamide can have a number average molecular weight as low as 38,000 Da, 41,000 Da, 46,000 Da, or 53,000 Da, or as high as 68,000 Da, 77,000 Da, 88,000 Da, or 100,000 Da, or within any range defined between any two of the forgoing values, for example, in some embodiments, the polyamide can have an number average molecular weight ranging from 38,000 Da to 100,000 Da, 41,000 Da to 88,000 Da, 46,000 Da to 77,000 Da, and 53,000 Da to 68,000 Da. In some embodiments, the polyamide can have a number average molecular weight of about 60,000 Da.
The molecular weight is typically related to the viscosity of the resin. Viscosity can be reported as the formic acid viscosity (FAV). The FAV is the viscosity of a 10 vol. % solution in 90 vol. % formic acid according to ASTM 789. The number average molecular weight (Mn) can be estimated from a measured FAV according to the relationship:
M
n=4791.8×(log(FAV))24056. Equation 1:
Accordingly, an FAV of 205 corresponds to a Mn of about 36,000, an FAV of 230 corresponds to a Mn of about 38,000, an FAV of 280 corresponds to a Mn of about 41,000, an FAV of 365 corresponds to a Mn of about 46,000, an FAV of 520 corresponds to a Mn of about 53,000, an FAV of 725 corresponds to a Mn of about 60,000, an FAV of 1,030 corresponds to a Mn of about 68,000, an FAV of 1,500 corresponds to a Mn of about 77,000, an FAV of 2,260 corresponds to a Mn of about 88,000, and an FAV of 3,440 corresponds to a Mn of about 100,000.
In this connection, the polyamide may have an FAV as little as 205, 230, 280, 365, or 520, or as great as 725, 1,030, or 1,500, 2,260 or 3,440, or may have an FAV within any range defined between any pair of the foregoing values, such as 205 to 3,440, 230 to 2,260, 280 to 1,500, 365 to 1,030, or 520 to 725, for example.
In one exemplary embodiment, the polyamide has an extractable content according to ISO 6427 as low as 0.2 wt. %, 0.5 wt. %, or 1 wt. %, or as high as 2 wt. %, 5 wt. %, or 10 wt. %, or an extractable content within any range defined between any two of the foregoing values, such as 0.2 wt. % to 10 wt. %, 0.2 wt. % to 2 wt. %, or 0.2 wt. % to 1 wt. %, for example. The extractable content can include, for example, caprolactam and various oligomers.
The gelling agent is capable of at least partially dissolving the polyamide to form a viscous solution or gel which is capable of being spun. Typical gelling agents have relatively low molecular weights, and may be monomers or oligomers. In some embodiments, the gelling agents include lactams. In some embodiments, the lactams can include caprolactam, caprolactam-based amides such as N-methyl caprolactam and N-ethyl caprolactam, and caprolactam-based amide-esters such as:
Caprolactam illustratively provides advantages as a gelling agent of the polyamide. In some embodiments, these advantages include one or more of: partial solvation of the polyamide to form the spinnable solution of a viscous solution or gel, low toxicity, relatively low cost, low odor, and relatively easy extraction from a spun fiber using water as a solvent.
The spinnable solution can be formed from the polyamide and range of concentrations of the gelling agent, such as caprolactam. In some embodiments, the spinnable solution has a caprolactam concentration as low as 20 wt. %, 30 wt. %, 40 wt. %, or 50 wt. %, or as high as 60 wt. %, 70 wt. %, 80 wt. %, or 90 wt. %, or within any range defined between any two of the foregoing values, for example, in some embodiments, the caprolactam concentration of the spinnable solution can range from 20 wt. % to 90 wt. %, 30 wt. % to 80 wt. %, 40 wt. % to 70 wt. %, 50 wt. % to 90 wt. %, 50 wt. % to 80 wt. %, 50 wt. % to 70 wt. %, or 50 wt. % to 60 wt. %. All caprolactam concentrations are based on the total weight of the spinnable solution.
In some embodiments, the spinnable solution has a polyamide concentration as low as 10 wt. %, 20 wt. %, 30 wt. %, or 40 wt. %, or as high as 50 wt. %, 60 wt. %, 70 wt. %, or 80 wt. %, or within any range defined between any two of the foregoing values, for example, in some embodiments, the polyamide concentration of the spinnable solution can range from 10 wt. % to 80 wt. %, 20 wt. % to 70 wt. %, 30 wt. % to 60 wt. %, or 40 wt. % to 50 wt. %. All polyamide concentrations are based on the total weight of the spinnable solution.
In some embodiments, the spinnable solution may further include one or more additives, such as a heat stabilizer, an anti-oxidant, a colorant, or a processing aid. In some embodiments, the total concentration of all additives does not exceed 5 wt. % of the total weight of the spinnable solution.
Higher number average molecular weight polyamides require generally higher concentrations of caprolactam to produce a spinnable solution that is not too viscous to process through typical industrial extruders. It has also been found that higher concentrations of caprolactam in the spinnable solution can produce stronger fibers. Without wishing to be bound by any theory, it is believed that the higher caprolactam concentrations, or loadings, help to reduce the entanglement density of the polymer chains of the polyamide (i.e., increase the molecular weight between entanglements (Me)), which can improve the drawing ability, or drawability, of the fibers and the longitudinal orientation of the polymer chains to produce stronger fibers. See, e.g., R. Schaller et al., “High-Performance Polyethylene Fibers ‘Al Dente’: Improved Gel-Spinning of Ultrahigh Molecular Weight Polyethylene Using Vegetable Oils,” Macromolecules, 2015, 48 (24), pp 8877-8884.
In some embodiments, the spinnable solution 46 is formed at a temperature as low as 150° C., 160° C., 170° C., 175° C., 180° C., 185° C., or 190° C., or as high as 200° C., 225° C., 250° C., 255° C., 260° C., 270° C., or 275° C., or within any range defined between any two of the foregoing values, such as 150° C. to 200° C., 170° C. to 190° C., 175° C. to 185° C., 250° C. to 270° C., or 255° C. to 265° C., for example.
Referring to block 106, the spinnable solution 46 is provided to the spin block 14 where it is spun by extrusion through the holes of the spinneret 22 to form a plurality of fibers 48. The speed of the fibers 48 exiting the spinneret 22 is referred to as a gel speed. In some embodiments, the gel speed may be as low as 0.4 meters/minute (m/min.), 0.8 m/min., 1 m/min., or 3 m/min., as high as 10 m/min., 14 m/min., 20 m/min., or 30 m/min., or within any range defined between any two of the foregoing values, such as 0.4 m/min. to 30 m/min., 0.8 m/min. to 20 m/min, or 3 m/min. to 14 m/min.
In some embodiments, the spin block 14 may heat the spinnable solution 46 during spinning. In some embodiments, the spinnable solution 46 is spun at a temperature as low as 150° C., 160° C., 180° C., or 200° C., or as high as 220° C., 240° C., 260° C., 265° C., or 270° C., or within any range defined between any two of the foregoing values, such as 150° C. to 270° C., 180° C. to 265° C., or 200° C. to 265° C., for example.
As noted above, higher number average molecular weight polyamides 42 require generally higher concentrations of the gelling agent 44, such as caprolactam, to produce the spinnable solution 46 that is not too viscous to process through typical industrial extruders. Also, higher concentrations of caprolactam in the spinnable solution 46 can produce stronger fibers.
However, in some embodiments, the high caprolactam loading can result in the fibers 48 having a low melt strength as extruded from the spinneret 22. Fibers having too low a melt strength may break while being pulled into fiber form during subsequent drawing processes. Thus, in block 108, the fibers 48 are provided to the quench system 18. As shown in
In some embodiments, the quenching liquid 34 is maintained at a temperature as low as 2° C., 4° C., 8° C., 15° C., 25° C. or 40° C., or as high as 50° C., 75° C., 100° C., 120° C., or 150° C., or within any range defined between any two of the foregoing values, such as 2° C. to 150° C., 4° C. to 120° C., 8° C. to 100° C., 15° C. to 75° C., 25° C. to 50° C., 40° C. to 50° C., 50° C. to 75° C., or 25° C. to 75° C., for example. In some embodiments, the quenching liquid 34 is maintained at a temperature greater than a glass transition temperature of the fibers 48, for example, 50° C. to 150° C. Without wishing to be bound by any theory, it is believed that a higher temperature of the quenching liquid 34 delays polymer crystallization and that delaying crystallization provides for more successful spinning of polyamide having a number average molecular weight greater than about 38,000 Da.
A distance between the spinneret 22 and a surface 50 of the quenching liquid 34 in the quench bath 32 defines an air gap 52, as shown in
Referring to block 110, after quenching has begun, the fibers 48 are provided to the fiber drawing apparatus 16 to draw the fibers 48. As shown in
As the fibers 48 are subsequently pulled over the plurality of rollers 26 by the draw rollers 28, the speed of the fibers 48 can increase, further drawing the fibers 48. For example, in some embodiments, the ratio of the speed of the fibers 48 leaving the quenching liquid 34 to the gel speed can be as low as 15:1, 30:1, 50:1, 70:1, or 100:1, or as high as 160:1, 200:1, 250:1, 300:1, or 350:1, or within any range defined by any two of the foregoing values, such as 15:1 to 350:1, 30:1 to 300:1, 50:1 to 250:1, 70:1 to 200:1, or 100:1 to 160:1, for example. The ratio of the speed of the fibers 48 leaving the quenching liquid 34 to the gel speed is the spinning draw ratio.
In some embodiments, the speed of the fibers 48 leaving the quenching liquid 34 can be as low as 200 meters per minute (mpm), 300 mpm, 400 mpm, 500 mpm, 600 mpm, 700 mpm, or 800 mpm, or as high as 1,000 mpm, 1,100 mpm, 1,200 mpm, 1,300 mpm, 1,400 mpm, 1,500 mpm, or 1,600 mpm, or can be within any range defined by any two forgoing values, such as 200 mpm to 1,600 mpm, 300 mpm to 1,500 mpm, 400 mpm to 1,400 mpm, 500 mpm to 1,300 mpm, 600 mpm to 1,200 mpm, 700 mpm to 1,100 mpm, and 800 mpm to 1,000 mpm, for example. The speed of the fibers 48 leaving the quenching liquid 34 is called the take-up speed (T.U. Speed).
As shown in
Alternatively, or in addition to, the flow circulation system 36, drag on the fibers 48 can be increased by increasing the dynamic viscosity of the quenching liquid 34. In some embodiments, the dynamic viscosity of the quenching liquid 34 can be as low as 1,000 centipoise (cp), 5,000 cp, 10,000 cp, 12,000 cp, or 14,000 cp, or as high as 18,000 cp, 20,000 cp, 22,000 cp, 24,000 cp, or 26,000 cp, or within any range defined between any two of the foregoing values, such as 1,000 cp to 26,000 cp, 5,000 cp to 24,000 cp, 10,000 cp to 22,000 cp, 12,000 cp to 20,000 cp, 14,000 cp to 18,000 cp, or 18,000 cp to 24,000 cp, for example.
In some embodiments, the desired level of dynamic viscosity of the quenching liquid 34 can be obtained by lowering the temperature of the quenching liquid 34 or by adding thickening agents to the quenching liquid 34. For example, in some embodiments, the quenching liquid 34 is maintained at a temperature as low as 2° C., 4° C., 6° C., or 8° C., or as high as 10° C., 12° C., 14° C., or 16° C., or within any range defined between any two of the foregoing values, such as 2° C. to 16° C., 4° C. to 14° C., 6° C. to 12° C., or 8° C. to 10° C., for example. In some embodiments, the quenching liquid 34 is maintained at a temperature of about 4.4° C. Additionally or alternatively, in some embodiments, the quenching liquid 34 can further include a thickening agent, such as corn starch or polymeric acrylic acid ester.
In block 112, the fibers 48 are wound on the winder 30. In some embodiments, the ratio of the speed of the fibers 48 as they are wound on the winder 30 to the gel speed can be as low as 1.0:1, 1.5:1, or 2.0:1, or as high as 200:1, 1000:1, or 3000:1, or within any range defined between any two of the foregoing values, such as 1.0:1 to 200:1, 1.5:1 to 1000:1, or 2.0:1 to 3000:1, for example.
In some embodiments in which the quenching liquid 34 consists essentially of water, the quenching liquid 34 can extract a significant portion of the caprolactam from the fibers 48, possibly reducing the extent to which the higher caprolactam concentration is able to reduce the entanglement density of the polymer chains of the polyamide and improve longitudinal orientation of the polymer chains to produce stronger fibers. Thus, in some other embodiments, the quenching liquid 34 can include caprolactam in addition to water. The concentration of caprolactam in the quenching liquid 34 can be maintained as desired to prevent extraction of the caprolactam from the fibers 48, or to controllably reduce the extent to which the caprolactam is extracted from the fibers 48 during quenching. In some embodiments, the quenching liquid 34 can have a caprolactam concentration as low as 10 wt. %, 20 wt. %, 30 wt. %, 40 wt. %, or as high as 60 wt. %, 70 wt. %, 80 wt. %, or 90 wt. %, or within any range defined between any two of the foregoing values, such as 10 wt. % to 90 wt. %, 30 wt. % to 70 wt. %, or 40 wt. % to 60 wt. %, for example.
In some embodiments, the fibers 48 have a strength according to ASTM D2256 as low as 8 grams per denier (gpd), 9 gpd, 10, gpd, or 12 gpd, or as high as 14 gpd, 16 gpd, 18 gpd, or 20 gpd, or within any range defined between any two of the foregoing values, such as 8 gpd to 20 gpd, 9 gpd to 18 gpd, 10 gpd to 16 gpd, or 12 gpd to 14 gpd, for example.
In some embodiments, the fibers 48 have an ultimate elongation UE (%) according to ASTM D2256 as little as 1%, 2,%, or 5% or as great as 10%, 20%, or 50%, or within any range defined between any two of the foregoing values, such as 1% to 50%, 2% to 50%, or 1% to 20%, for example.
As used herein, the phrase “within any range defined between any two of the foregoing values” literally means that any range may be selected from any two of the values listed prior to such phrase regardless of whether the values are in the lower part of the listing or in the higher part of the listing. For example, a pair of values may be selected from two lower values, two higher values, or a lower value and a higher value.
While the present disclosure is primarily directed to applications such as textile spinning, it should be understood that the features disclosed herein may have application to other spinning and extrusion processes, including carpet fiber spinning, conventional spinning, and gel spinning such as used for ultra-high molecular weight polyethylene used in high performance fiber applications.
While this invention has been described as relative to exemplary designs, the present invention may be further modified within the spirit and scope of this disclosure. Further, this application is intended to cover such departures from the present disclosure as come within known or customary practice in the art to which this invention pertains.
Compositions of varying amounts of PA-6 and caprolactam were formed by dissolving the PA-6 into the caprolactam at an elevated temperature to form a viscous solution or gel. The compositions were then fed to an extruder including a spinneret including a plurality of outlet holes to spin the composition into fibers.
For Comparative Example A, a composition of 100% PA-6 having a formic acid viscosity of 280 (0% caprolactam) was fed to a spinneret having a 72 filament count, each of a 0.4 mm diameter. Fibers were unable to be formed as the pack pressure exceeded the 3000 psi operating limit of the system at a throughput of 10-11 pounds per hour. Comparative Example A is shown in the lightly shaded region of
For Example B, a composition of 20% caprolactam and 80% PA-6 having a formic acid viscosity of 280 was formed by dissolving the PA-6 into the caprolactam at a temperature in the range of 255° C. to 265° C., and then provided to the same spinneret as Comparative Example A. Fibers were successfully spun at a throughput of 12 pounds per hour. Comparative Example B is shown in the unshaded region of
In
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/US2018/017959 | 2/13/2018 | WO | 00 |
| Number | Date | Country | |
|---|---|---|---|
| 62469038 | Mar 2017 | US |
