Classifications

• • 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
  • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
  • D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
  • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
  • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
• • 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
  • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
  • D01F6/90—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides

Definitions

• Thermoplastics may be melt spun at exceptionally high speeds, while maintaining desirable properties that are obtained at lower spinning speeds, by adding a small amount of a liquid crystalline polymer containing repeat units derived from specified monomers.
• Fibers made from thermoplastics are important items of commerce. These fibers are used for apparel, luggage, thread, and industrial uses. Oftentimes these fibers are formed by melt spinning, that is by melting the thermoplastic, forcing (extruding) the molten polymer through a small orifice (spinneret), cooling, and then using that extrudate, perhaps after having undergone other treatments such as drawing, as a fiber, see for example H. Mark, et al., Ed., Encyclopedia of Polymer Science and Engineering, Nol. 6, John Wiley & Sons, New York, 1986, p. 802-839, and W.
• U.S. Patent 4,442,057 describes the addition of small amounts of liquid crystalline polymers (LCP) to thermoplastics to allow high speed fiber spinning while maintaining desirable polymer properties. LCPs of the composition described herein are not mentioned.
• U.S. Patent 4,518,744 describes the use of various polymers as additives in thermoplastics to allow high speed fiber spinning while maintaining desirable polymer properties. LCPs are not mentioned in this patent.
• European Patent Application 80,273 describes the use of thermoplastic blends with other polymers, including LCPs, to make bulked fibers using melt spinning.
• LCPs thermoplastic blends with other polymers, including LCPs
• This invention concerns a process for the melt spinning of one or more thermoplastics at windup speeds of about 1000 m/minute or more, wherein the improvement comprises, spinning said thermoplastic or thermoplastics as a blend which contains about 0.1 to about 10 percent by weight of a liquid crystalline polymer, said percentage based on a total amount of said thermoplastic or thermoplastics plus said liquid crystalline present, and provided that said liquid crystalline polymer consists essentially of repeat units of the formula:
• a molar ratio of (II) to (III) ranges from about 25 :75 to about 90: 10; a molar ratio of (I) to [(II)+(III)] is substantially 1:1; a molar ratio of (IV) to (V) ranges from about 97:3 to about 50:50; a number of moles of (IV) plus (V) ranges from about 100 to about 600 per 100 moles of (I); and wherein (I), (II), (III), (IV), (V) and (VI) are in units of moles.
• the number of moles of (I) is the total moles of (I A) plus (IB) plus (IC) and the total number of moles of (III) is the total moles of (IIIA) plus (IIIB).
• This invention also concerns a composition, comprising: (a) from about 99.9 to about 90 percent by weight of a thermoplastic;
• a molar ratio of (II) to (III) ranges from about 25:75 to about 90:10; a molar ratio of (I) to [(II)+(III)] is substantially 1:1; a molar ratio of (IV) to (V) ranges from about 97:3 to about 50:50; a number of moles of (IV) plus (V) ranges from about 100 to about 600 per 100 moles of (I); and wherein (I), (II), (III), (IV), (V) and (VI) are in units of moles, and said percent by weight of (a) and said percent by weight of (b) are based on the total amount of (a) and (b) present.
• FIGURE Figure 1 shows a quench apparatus used in spinning the fiber of Examples 17-
• the LCPs used herein are described in U.S. Patent 5,525,700, which is hereby included by reference, and methods of making such polymers are described therein.
• the molar ratio of repeat units (I A) to (IB) to (IC) ranges from 0:0:100 to 0:100:0 to 100:0:0.
• repeat units (IA) and (IB) are present, with the molar ratio of (IA) to (IB) ranging from about 1 :99 to about 99: 1.
• repeat units (IA) and (IB) are present, with the molar ratio of (IA) to (IB) ranging from about 75:25 to about 25:75, and/or the molar ratio of (II):(III) ranges from about 30:70 to about 85:15, and/or the molar ratio of (IV):(V) is from about 50:50 to about 90: 10, and/or the number of moles of (IV) plus (V), per 100 moles of (I), ranges from about 200 to about 500.
• the molar ratio of the diols [i.e., (IA), (IB) and/or (IC)] to the diacids [i.e., (II) and (IIIA) and/or (IIIB)] present in the polymerization of monomers to form an LCP should be about 1:1. Small deviations from this ratio are not critical, but large deviations are normally to be avoided, since it usually prevents or slows polymerization to relatively high molecular weight.
• thermoplastic polymers such as polyesters, polyamides, copolyesters, copolyamides or polyolefms, for example poly(ethylene terephthalate) and its copolyesters, polycaprolactam, poly(hexamethylene adipamide), polypropylene, polyethylene, acrylic polymers, vinyl chloride and vinylidene-chloride-based polymers, polystyrene, polyphenylene oxide/polystyrene blends, polysulphones and polyethersulfones, polyketones and polyetherketones, polyfluoroolefins, polyoxymethylenes, thermoplastic cellulosic polymers, and other biologically produced polymers, such as poly(hydroxybutyrate).
• thermoplastic polymers such as polyesters, polyamides, copolyesters, copolyamides or polyolefms, for example poly(ethylene terephthalate) and its copolyesters, polycaprolactam, poly(hexamethylene
• thermoplastics are polyesters such as poly(l,3-propylene terephthalate), poly(ethylene terephthalate) (PET), and poly(l,4- butylene terephthalate), and polyamides such as polyhexamethylene adipamide (nylon-6,6) and polycaprolactam (nylon-6).
• the mixture of the LCP and the thermoplastic contains about 99.5 to about 95 percent by weight of the thermoplastic and about 0.5 to about 5.0 percent by weight of the LCP.
• the polymer mixture and the resulting fiber may also contain the usual amounts of other materials found in thermoplastic fibers, such as pigments, dyes, antioxidants, lubricants, antistatics, antimicrobials, and flame retardants.
• the mixture of the LCP and thermoplastic may be made by a number of standard methods, for example they may be melt mixed in a single or twin screw extruder, formed into pellets, and then be remelted for melt spinning.
• a mixture of LCP and thermoplastic particles may be made by pellet blending and then melt mixed just before being melt spun, in other words the melt mixing may take place in the melting step for melt spinning.
• the blend of the LCP and thermoplastic be relatively uniform, so that consistent quality fiber may be produced, and thus preferred that melt mixing take place under the relatively high shear conditions found in melt polymer apparatus such as single and twin screw extruders.
• melt polymer apparatus such as single and twin screw extruders.
• the LCP has a particle size in the melt of about 0.5 to 3 ⁇ m prior to the actual spinning of the fiber.
• the melt spinning is carried out under conditions that are normal for melt spinning the thermoplastic being used, except that higher fiber production speeds may be used.
• thermoplastic By fiber production speed is meant the final length of fiber produced per unit time, synonymous herein with WUS.
• the normal spinning temperature of a thermoplastic will usually be above its glass transition temperature and melting point (if it has a melting point), but below a temperature at which sufficient thermal degradation takes place to affect fiber properties significantly.
• the LCP should be melt processible, that is molten, at that temperature.
• An advantage of the present LCPs is that by varying their composition within the limits described above, LCPs with a wide range of melting points can be made. Thus both the thermoplastic and LCP used should be melt processible at the spinning temperature.
• the WUS is about 1000 m/min or more, preferably about 2000 rn/min or more, and especially preferably about 3000 m/min or more.
• LCPs described herein higher production speeds are possible than with other LCPs while maintaining good fiber properties and/or being able to use lesser amounts of LCP to obtain similar production rates. Since LCPs are generally more expensive than most thermoplastics used for fibers, this is an advantage. At lower LCP amounts there is also less risk the LCP will adversely affect other fiber properties, such as dyeability.
• the Examples herein demonstrate the unexpected advantages of the current LCPs over other LCPs in high speed spinning of thermoplastics.
• Examples 1-9 and Comparative Example A-F Pellets of the LCP (where used) and a commercial grade poly(ethylene terephthalate) were compounded in a Baker-Perkins twin-screw extruder.
• the diameter of the screw flight was 4.921 cm (1.9375 in) and the screws operated at 100 rpm.
• the feed zone of the extruded was at 230°C, and the barrel temperatures were 230°C, 270°C and 290°C.
• a spinning block was attached which housed a melt filter-pack and a spinneret plate with 34 holes.
• the melt spinning temperatures are reported in Table 1.
• the diameter of each hole was 0.38 mm (0.015 in) and the melt throughput was 40 g per hour per hole.
• the freshly spun filaments were cooled in ambient air without any forced air flow or any special quenching apparatus.
• the throughput per hole remained constant and, consequently, finer filaments were produced as the windup speed increased.
• the intrinsic viscosity of the control PET after spinning was 0.65.
• each hole was 0.23 mm (0.009 in) and the melt throughput was 98 g per hour per hole.
• the freshly spun filaments were cooled in ambient air without any forced air flow or any special quenching apparatus.
• the cooled filaments, after finish application, were wound up at the speeds shown in Table 2.
• the throughput per hole remained constant and, consequently, finer filaments were produced as the windup speed increased.
• the intrinsic viscosity of the control PET after spinning was 0.65.
• the results as well as the productivity increase in every case are shown in Table 2.
• the data labeled "Brody" are taken from Table 3 of U.S. Patent 4,442,057, and in show that the present LCP is superior to the LCP used in Table 3 of this issued patent.
• the productivity increase was computed using the formula shown at column 4, line 55 of U.S. Patent 4,442,057.
• the throughput was 1.63 grams per minute per hole in all cases.
• the dpf was 7.35 at 2000 m/min and it decreased as the spinning speed increased.
• Examples 17-22 and Comparative Example N-P Pellets of the LCP and a commercial grade nylon-66 were compounded in a Baker-Perkins twin-screw extruder.
• the diameter of the screw flight was 4.921 cm (1.9375 in) and the screws operated at 100 rpm.
• the feed zone of the extruded was at 230°C, and the barrel temperatures were 230°C, 270°C and 290°C.
• a spinning block was attached which housed a melt filter-pack and a spinneret plate with 34 holes. The melt spinning temperatures are reported in Table 3.
• the diameter of each hole was 0.254 mm (0.010 in) and the melt throughput was adjusted proportionally to the windup speed, as shown in Table 3, so that the produced yarn decitex was 139 or 4.08 decitex per filament at all speeds.
• the freshly spun filaments were quenched in an apparatus shown in Figure 1.
• the quench apparatus included a housing 50 which forms a chamber 52, i.e., an enclosed zone supplied with pressurized gas Q at a rate of 0.85 mVmin (30 standard cubic feet per min) through inlet conduit 54 which was formed in the side wall 51 of the housing.
• a cylindrical screen 55 was positioned in chamber 52 to uniformly distribute gas flowing into the chamber.
• the diameter of the cylindrical screen 55 was 7.62 cm (3.0 in) and its length 38.1 cm (15 in).
• a spinning pack 16 was positioned centrally and directly above the housing which abuts the surface 16a of the pack.
• a spinneret (not shown) was attached to the bottom surface of the spinneret pack for extruding filaments 20 into a path from molten polymer supplied to the pack.
• a molten polymer was metered into the spinning pack 16 and extruded as filaments 20.
• the filaments were pulled from the spinneret into a path by withdrawal roll 34. Finish is applied above roll 34.
• Yam was wound up at 4118, 4575, 5032 and 5490 m/min. Table 3 summarizes the draw tension for the control nylon-66 fibers as well as for the blend of nylon-66 with 0.5 weight % of LCP HX-8000-270.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• General Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Artificial Filaments (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
• Multicomponent Fibers (AREA)

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• 2000
  • 2000-02-23 ID IDW00200101831A patent/ID30113A/id unknown
  • 2000-02-23 CN CN00804267A patent/CN1131345C/zh not_active Expired - Lifetime
  • 2000-02-23 JP JP2000601232A patent/JP4480898B2/ja not_active Expired - Fee Related
  • 2000-02-23 AU AU33752/00A patent/AU3375200A/en not_active Abandoned
  • 2000-02-23 BR BRPI0010117-6A patent/BR0010117B1/pt not_active IP Right Cessation
  • 2000-02-23 DE DE60015938T patent/DE60015938T2/de not_active Expired - Lifetime
  • 2000-02-23 EP EP00911939A patent/EP1163382B1/en not_active Expired - Lifetime
  • 2000-02-23 WO PCT/US2000/004650 patent/WO2000050674A1/en not_active Ceased
  • 2000-02-23 TR TR2001/02486T patent/TR200102486T2/xx unknown
  • 2000-02-23 US US09/511,042 patent/US6432340B1/en not_active Expired - Lifetime
  • 2000-02-23 KR KR1020017010919A patent/KR100609801B1/ko not_active Expired - Fee Related
  • 2000-02-25 TW TW089103366A patent/TW557316B/zh not_active IP Right Cessation
• 2002
  • 2002-05-31 US US10/161,391 patent/US20030042650A1/en not_active Abandoned

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