EP0357364B1 - Verfahren zum Flash-Spinnen von trocknen polymeren Tauen aus plexifilamentaren Film-Fibrillen - Google Patents

Verfahren zum Flash-Spinnen von trocknen polymeren Tauen aus plexifilamentaren Film-Fibrillen Download PDF

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Publication number
EP0357364B1
EP0357364B1 EP89308700A EP89308700A EP0357364B1 EP 0357364 B1 EP0357364 B1 EP 0357364B1 EP 89308700 A EP89308700 A EP 89308700A EP 89308700 A EP89308700 A EP 89308700A EP 0357364 B1 EP0357364 B1 EP 0357364B1
Authority
EP
European Patent Office
Prior art keywords
flash
carbon dioxide
polyolefin
methylene chloride
pressure
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP89308700A
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English (en)
French (fr)
Other versions
EP0357364A3 (en
EP0357364A2 (de
Inventor
Don Mayo Coates
Hyunkook Shin
Gary Stephen Huvard
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
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Filing date
Publication date
Priority claimed from US07/382,092 external-priority patent/US5043109A/en
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of EP0357364A2 publication Critical patent/EP0357364A2/de
Publication of EP0357364A3 publication Critical patent/EP0357364A3/en
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Publication of EP0357364B1 publication Critical patent/EP0357364B1/de
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Classifications

    • 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
    • D01D5/42—Formation of filaments, threads, or the like by cutting films into narrow ribbons or filaments or by fibrillation of films or filaments
    • 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
    • D01D5/11—Flash-spinning

Definitions

  • This invention relates to a process for flash-spinning substantially dry polymeric plexifilamentary film-fibril strands. More particularly, the invention concerns an improved process in which a substantially dry strand is flash-spun from mixtures of fiber-forming polyolefin, methylene chloride and carbon dioxide.
  • the following liquids are useful in the flash-spinning process: aromatic hydrocarbons such as benzene, toluene, etc.; aliphatic hydrocarbons such as butane, pentane, hexane, heptane, octane, and their isomers and homologs; alicyclic hydrocarbons such as cyclohexane; unsaturated hydrocarbons; halogenated hydrocarbons such as methylene chloride, carbon tetrachloride, chloroform, ethyl chloride, methyl chloride; alcohols; esters; ethers; ketones; nitriles; amides; fluorocarbons; sulfur dioxide; carbon disulfide; nitromethane; water; and mixtures of the above liquids.
  • aromatic hydrocarbons such as benzene, toluene, etc.
  • aliphatic hydrocarbons such as butane, pentane, hexane, heptane
  • the flash-spinning solution additionally may contain a dissolved gas, such as nitrogen, carbon dioxide, helium, hydrogen, methane, propane, butane, ethylene, propylene, butane, etc.
  • a dissolved gas such as nitrogen, carbon dioxide, helium, hydrogen, methane, propane, butane, ethylene, propylene, butane, etc.
  • Preferred for improving plexifilament fibrillation are the less soluble gases, i.e., those that dissolve to a less than 7% concentration in the polymer solution under the spinning conditions.
  • Trichlorofluoromethane (Freon-11) has been a very useful solvent for commercial manufacture of plexifilamentary film-fibril strands of polyethylene.
  • escape of such a halocarbon into the atmosphere has been implicated as a serious source of depletion of the earth's ozone.
  • a general discussion of the ozone-depletion problem is presented, for example, by P. S. Zurer, "Search Intensifies for Alternatives to Ozone-Depleting Halocarbons", Chemical & Engineering News , pages 17-20 (February 8, 1988).
  • the substitution of methylene chloride for trichlorofluoromethane in the commercial flash-spinning process should avoid the ozone depletion problem.
  • This invention provides a process for flash-spinning substantially dry polymeric plexifilamentary film-fibril strands from spin mixtures of methylene chloride, carbon dioxide and fiber-forming polyolefin.
  • the present invention provides an improved process for flash-spinning polymeric plexifilamentary film-fibril strands, wherein a spin mixture is formed comprising methylene chloride, fiber-forming polyolefin and carbon dioxide which is then flash-spun at a pressure that is greater than the autogenous pressure of the spin mixture into a region of substantially lower temperature and pressure, the improvement for producing substantially dry strands comprising, in combination, the carbon dioxide amounting to 9 to 25 percent by weight of the spin mixture, the polyolefin amounting to 18 to 33 percent by weight of the spin mixture and the methylene chloride amounting to 42 to 73 percent by weight of the spin mixture, the mixing of the polyolefin and the flash-spinning being performed at a temperature in the range of 130 to 220°C.
  • the present invention also includes novel solutions comprising 18 to 33 percent fiber-forming polyolefin by weight of the spin mixture, 42 to 73 percent methylene chloride by weight of the spin mixture and 9 to 25 percent carbon dioxide by weight of the spin mixture.
  • polyolefin as used herein, is intended to mean any of a series of largely saturated open chain polymeric hydrocarbons composed only of carbon and hydrogen.
  • Typical polyolefins include, but are not limited to, polyethylene, polypropylene, polymethylpentene and various combinations of the monomers ethylene, propylene, methylpentene.
  • polyethylene is intended to embrace not only homopolymers of ethylene, but also copolymers wherein at least 85% of the recurring units are ethylene units.
  • the preferred polyethylene is a homopolymeric linear polyethylene which has an upper limit of melting range of about 130 to 135°C, a density in the range of 0.94 to 0.98 g/cm3 and a melt index (as defined by ASTM D-1238-57T, Condition E) of 0.1 to 6.0.
  • polypropylene is intended to embrace not only homopolymers of propylene but also copolymers wherein at least 85% of the recurring units are propylene units.
  • duplexifilamentary film-fibril strand means a strand which is characterized as a three-dimensional integral network of a multitude of thin, ribbon-like, film-fibril elements of random length and of less than about 4 microns average thickness, generally coextensively aligned with the longitudinal axis of the strand.
  • the film-fibril elements intermittently unite and separate at irregular intervals in various places throughout the length, width and thickness of the strand to form the three-dimensional network.
  • Such strands are described in further detail by Blades and White, United States Patent 3,081,519 and by Anderson and Romano, United States Patent 3,227,794.
  • the present invention provides an improvement in the known process disclosed for producing plexifilamentary film-fibril strands by flash-spinning a spin mixture of fiber-forming polyolefin in methylene chloride and carbon dioxide to produce substantially dry polymeric plexifilimentary film-fibril strands.
  • the process of the present invention requires the flash-spinning to be performed with a spin mixture comprising 18 to 33 weight percent of the total spin mixture of fiber-forming polyolefin, 42 to 73 weight percent of the total spin mixture of methylene chloride and 9 to 25 weight percent of the total spin mixture of carbon dioxide.
  • the flash-spun strand is dry or substantially dry as it emerges from the spinneret. That is, the "as-spun" strand is substantially free of methylene chloride. This is particularly so in comparison with U.S. Patent 3,081,519.
  • Example VI referenced above wherein a strand spun from a mixture of with 3.7% carbon dioxide, 13% polyethylene and methylene chloride is wet to the touch with methylene chloride when spun.
  • the preferred fiber-forming polyolefins for use in the present invention are polyethylene and polypropylene as disclosed in U.S. Patent 3,081,519. Polyolefin concentrations of 18 to 33 percent by weight of the spin mixture are employed.
  • Carbon dioxide is present in the spin mixture in concentrations ranging from 9 to 25 percent. Generally, in order to spin dry strands from the spin mixtures of this invention, lower concentrations of polyolefin require more carbon dioxide in the spin mixture.
  • the practice of this invention requires a reasonable combination of methylene chloride, carbon dioxide and polyolefin depending on the composition of the mixture, and temperature and pressure.
  • the required temperatures for preparing the spin mixture and for flash-spinning the mixture are usually about the same and usually are in the range of 130 to 220°C.
  • the mixing and the flash-spinning are performed at a pressure that is higher than the autogenous pressure of the mixture.
  • the pressure during the spin mixture preparation is usually at least 5516 kPa (800 psia) and usually no higher than 17237 kPa (2,500) psia, though pressures as high as about 55160 kPa (8,000 psia) can be used.
  • the flash-spinning pressure is usually at least 4137 kPa (600 psia) though somewhat higher spin pressures are often employed.
  • the spin mixture preferably comprises fiber-forming polyolefin, methylene chloride and carbon dioxide.
  • conventional flash-spinning additives can be incorporated into the spin mixtures by known techniques. These additives can function as ultraviolet-light stabilizers, antioxidants, fillers, dyes, and the like.
  • novel solutions of this invention comprise 18 to 33 weight percent fiber-forming polyolefin, 42 to 73 weight percent methylene chloride and 9 to 25 weight percent carbon dioxide.
  • the preferred fiber-forming polyolefins are polyethylene and polypropylene.
  • the plexifilamentary strands for Examples 1, 2, 3 and 4 were prepared in equipment that comprises an autoclave of 5-gallon capacity which is equipped with a motor-driven, close fitting, spiral blade agitator, temperature and pressure measuring devices, heating means and inlets for loading the necessary ingredients into the autoclave.
  • An exit line from the autoclave is connected through a quick-acting valve to a spin assembly of the type disclosed by Marshall, United States Patent 4,352,650, the entire disclosure of which is hereby incorporated herein by reference.
  • the spin assembly included a pressure let-down orifice of 0.072, 0.068 or 0.062-inch (1.8, 1.7 or 1.6 mm) diameter, which leads to a let-down chamber of 5.5 inch (14 cm) length followed by spin orifice of 0.064, 0.058 or 0.046-inch (1.6, 1.5 or 1.2 mm) diameter, and then a "tunnel" of 0.27-inch (6.9 mm) length, 0.33-inch (8.4 mm) entrance diameter and 0.45-inch (11.4 mm) exit diameter.
  • the autoclave was loaded with high density linear polyethylene of 0.76 melt index and methylene chloride.
  • the autoclave was closed, evacuated and moderate-speed agitation was begun. Carbon dioxide was added to the autoclave and heating was begun.
  • the temperature of the contents of the autoclave reached 140°C, the internal pressure was increased to 1,500 psia (10343 kPa) by adding more carbon dioxide.
  • the addition of the carbon dioxide caused significant pressure and temperature fluctuations and accordingly pressure was allowed to stabilize for 15 minutes after each carbon dioxide addition. The pressure dropped as the carbon dioxide dissolved in the methylene chloride polyethylene mixture.
  • the autoclave was then repeatedly re-pressurized to 1,800 psia (12411 kPa) with carbon dioxide until saturation was judged to have been achieved. This was indicated by a steady pressure of 1,800 psia (12411 kPa) being maintained in the autoclave.
  • the temperature of the autoclave was then maintained at 150°C. The total time of heating and mixing, counting from the time the autoclave temperature reached 140°C, was about one hour.
  • Example 4 the autoclave was loaded with high density linear polyethylene of the type used before. The autoclave was closed, evacuated and the methylene chloride added. Then the desired amount of carbon dioxide was added under pressure by use of a pump. The agitation was started using moderate speed and the heating begun. The mixture was held at goal temperature of 170°C for one hour, timed when first at 150°C. The mixer was slowed to about 1/3 of its initial speed and the autoclave pressure rapidly adjusted as needed to 1,800 psi (12411 kPa) with nitrogen or venting. Finally, prompt opening of the exit valve to the spin assembly allowed spinning of the mixture.
  • 1,800 psi 12411 kPa
  • the autoclave was first loaded with a pre-weighed quantity of high density, linear polyethylene pellets of 0.76 melt index.
  • the autoclave was closed and air was evacuated to a final pressure below 1 psia (6.9 kPa) (typically 0.5 psia - 3.4 kPa).
  • Methylene chloride was charged to the vessel at room temperature and moderate agitation begun to suspend the polyethylene pellets.
  • the total charge of carbon dioxide was then charged to the autoclave at room temperature and heating of the autoclave contents started.
  • the autoclave was heated to about 150°C over about 45 minutes and then held at the temperature with agitation for another 30 minutes. During this period, the polyethylene melted and dissolved in the methylene chloride/carbon dioxide mixture.
  • the polymer solution thus formed was then heated to the final desired temperature and again held for approximately 30 minutes with agitation to insure homogeneity.
  • the total charge of polyethylene, methylene chloride and carbon dioxide was chosen such that a pressure of between 1800 and 1900psia (12411 and 13100 kPa) was hydraulically generated by the polymer solution upon heating the vessel contents to the final desired temperature. At this hydraulically full condition and pressure range, the polyethylene, methylene chloride and carbon dioxide form a single, homogeneous solution in which all components are intimately and thoroughly mixed. No gas or vapor bubbles exist in the solution.

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Textile Engineering (AREA)
  • Artificial Filaments (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)

Claims (6)

  1. Verfahren zum Flash-Spinnen von polymeren, plexifilamentaren, im wesentlichen trockenen Film-Fibrillen-Strängen, bei dem ein Spinngemisch gebildet wird, welches Methylenchlorid, faserbildendes Polyolefin und Kohlendioxid aufweist, das dann bei einem Druck flash gesponnen wird, welcher größer als der autogene Druck des Spinngemisches ist, in einen Bereich mit wesentlich niedrigerer Temperatur und niedrigerem Druck ist, bei dem in Kombination das Kohlendioxid 9 bis 25 Gewichtsprozent des Spinngemisches ausmacht, das Polyolefin 18 bis 33 Gewichtsprozent des Spinngemisches ausmacht und das Methylenchlorid 42 bis 73 Gewichtsprozent des Spinngemisches ausmacht, und bei dem das Mischen des Polyolefins und das Flash-Spinnen bei einer Temperatur in einem Bereich von 130 bis 220°C durchgeführt werden.
  2. Verfahren nach Anspruch 1, bei dem das faser-bildende Olefin Polyethylen ist.
  3. Verfahren nach Anspruch 1, bei dem das faser-bildende Polyolefin Polypropylen ist.
  4. Lösung, welche 18 bis 33 Gewichtsprozent faser-bildendes Olefin, 42 bis 73 Gewichtsprozent Ethylenchlorid und 9 bis 25 Gewichtsprozent Kohlendioxid aufweist.
  5. Lösung nach Anspruch 4, bei der das Polyolefin Polyethylen ist.
  6. Lösung nach Anspruch 4, bei der das Polyolefin Polypropylen ist.
EP89308700A 1988-08-30 1989-08-29 Verfahren zum Flash-Spinnen von trocknen polymeren Tauen aus plexifilamentaren Film-Fibrillen Expired - Lifetime EP0357364B1 (de)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US23863988A 1988-08-30 1988-08-30
US238639 1988-08-30
US37817789A 1989-07-14 1989-07-14
US382092 1989-07-24
US07/382,092 US5043109A (en) 1988-08-30 1989-07-24 Process for flash-spinning dry polymeric plexifilamentary film-fibril strands

Publications (3)

Publication Number Publication Date
EP0357364A2 EP0357364A2 (de) 1990-03-07
EP0357364A3 EP0357364A3 (en) 1990-03-28
EP0357364B1 true EP0357364B1 (de) 1993-07-28

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EP89308700A Expired - Lifetime EP0357364B1 (de) 1988-08-30 1989-08-29 Verfahren zum Flash-Spinnen von trocknen polymeren Tauen aus plexifilamentaren Film-Fibrillen

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EP (1) EP0357364B1 (de)
KR (1) KR0132668B1 (de)
CA (1) CA1335917C (de)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5147586A (en) 1991-02-22 1992-09-15 E. I. Du Pont De Nemours And Company Flash-spinning polymeric plexifilaments
EP0527019B1 (de) * 1991-08-03 1999-04-21 Asahi Kasei Kogyo Kabushiki Kaisha Halogen-enthaltendes Lösungsmittel und Lösung und Verfahren zur Herstellung von dreidimensionalen Fasern
US5643524A (en) * 1994-12-30 1997-07-01 E. I. Du Pont De Nemours And Company Corona charging of flash spun plexifilamentary film-fibril webs in poor charging environments
BR9809895A (pt) * 1997-07-01 2000-08-01 Pfizer Prod Inc Formas de dosagem da sertralina de liberação retardada
CN114908478B (zh) * 2021-03-18 2023-11-24 江苏青昀新材料有限公司 一种轻薄型闪蒸聚合物无纺布
CN115537959B (zh) * 2021-09-28 2023-05-05 江苏青昀新材料有限公司 一种复合材料

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3081519A (en) * 1962-01-31 1963-03-19 Fibrillated strand
NL300881A (de) * 1962-11-23

Also Published As

Publication number Publication date
EP0357364A3 (en) 1990-03-28
EP0357364A2 (de) 1990-03-07
KR910003168A (ko) 1991-02-27
CA1335917C (en) 1995-06-13
KR0132668B1 (ko) 1998-04-16

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