EP0517693B1 - Chlorfluorkohlenstoffe zum flash-spinnen von polyethylenefasern - Google Patents

Chlorfluorkohlenstoffe zum flash-spinnen von polyethylenefasern Download PDF

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Publication number
EP0517693B1
EP0517693B1 EP90904045A EP90904045A EP0517693B1 EP 0517693 B1 EP0517693 B1 EP 0517693B1 EP 90904045 A EP90904045 A EP 90904045A EP 90904045 A EP90904045 A EP 90904045A EP 0517693 B1 EP0517693 B1 EP 0517693B1
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EP
European Patent Office
Prior art keywords
polyethylene
solution
flash
spinning
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
EP90904045A
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English (en)
French (fr)
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EP0517693A1 (de
Inventor
Hyunkook Shin
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EIDP Inc
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EI Du Pont de Nemours and Co
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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
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/04—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins
    • 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 flash-spinning polyethylene film-fibril strands. More particularly, the invention concerns an improvement in such a process which permits flash-spinning of the strands from a liquid which, if released to the atmosphere, would not detrimentally affect the earth's ozone.
  • EP-A-0 361 684 which is prior art in accordance with Art. 54(3) EPC discloses a process for flash-spinning plexifilamentary film-fibril strands from polyethylene having a melt index of 0.1 to 6.0 and a density of 0.94 to 0.98 g/cm 3 dissolved in 1,1-dichloro-2,2,2-trifluoroethane or 1,2-dichloro-1,2,2-trifluoroethane to form a spin solution of 10 to 20 wt% of polyethylene at a temperature of 130° to 210°C at a pressure of greater than 3000 psi.
  • An object of this invention is to provide an improved process for flash-spinning plexifilamentary film-fibril strands of fiber-forming polyethylene, wherein the solvent should not be a depletion hazard to the earth's ozone.
  • the present invention provides an improved process for flash-spinning plexifilamentary film-fibril strands wherein polyethylene having a melt index of at least 4 and a density of about 0.92-0.98 is dissolved in at least one isomer of dichlorotrifluoroethane, preferably l,l-dichloro-2,2,2-trifluoroethane, to form a spin solution containing 10 to 20 percent of the polyethylene by weight of the solution at a temperature in the range of 130 to 210°C and a pressure that is greater than 2400 psi (16548 kPa) followed by flash-spinning the solution into a region of substantially lower temperature and pressure.
  • dichlorotrifluoroethane preferably l,l-dichloro-2,2,2-trifluoroethane
  • the present invention provides a novel solution consisting essentially of 10 to 20 weight percent of polyethylene having a melt index of at least 4 and a density of about 0.92-0.98 and 90 to 80 weight percent of at least one isomer of dichlorotrifluoroethane, preferably 1,1-dichloro-2,2,2-trifluoroethane.
  • the process and solution defined above are further restricted according to the invention Claimed in that either the solution is a two-phase solution, or the melt index (ASTM D-1238-57T) is greater than 6, or the density is at least 0.92 and less than 0.94 g/cm 3 .
  • Polyethylene as used herein is intended to embrace not only homopolymers of ethylene, but also copolymers wherein at least 85% of the recurring units are ethylene units.
  • One preferred polyethylene is a linear high density 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/cm 3 and a melt index (as defined by ASTM D-1238-57T, Condition E) of greater than 4, and preferably below 100.
  • Another preferred polyethylene is a linear low density polyethylene having a density of about 0.92-0.94 and a melt index of at least 4, preferably also below 100.
  • duplexifilamentary film-fibril strands 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 generally of less than about 4 microns ( ⁇ m) 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.
  • Woodell United States Patent 3,655,498. This test has been used extensively to determine the suitability of alternatives to the trichlorofluoromethane solvent for preparing plexifilamentary strands.
  • a mixture of the polymer plus the amount of solvent calculated to give about a 10 weight percent solution is sealed in a thick-walled glass tube (the mixture occupies about one-third to one-half the tube volume) and the mixture is heated at autogenous pressure.
  • Test temperatures usually range from about 100°C to just below the critical temperature of the liquid being tested. Woodell states that if a singled-phase, flowable solution is not formed in the tube at any temperature below the solvent critical temperature, T c , (or the polymer degradation temperature, which is lower) the solvent power is too low.
  • the halocarbon is 1,1-dichloro-2,2,2-trifluoroethane ("HC-123"), 1,2-dichloro-1,2,2-trifluoroethane ("HC-123a”), or 1,1-dichloro-1,2,2-trifluoroethane ("HC-123b”).
  • the parenthetic designation is used herein as an abbreviation for the chemical formula of the halocarbon.
  • the following table lists the known normal atmospheric boiling points (Tbp), critical temperatures (Tcr) and critical pressures (Pcr) for thesehalocarbons and for some prior art solvents.
  • the halocarbons of the present invention do not dissolve the polyethylene at autogenous pressures, in contrast to the prior art solvent- shown above. In contrast to the flash spinning fluids of the past, they do not form a single phase solution with polyethylene at the required concentrations and temperatures at a pressure of less than 5,000 psia (34475 kPa). Indeed it is not necessary that these halocarbons form a single phase solution even at the mixing temperature.
  • the polyethylenes of this invention can be dissolved in the various HC-123 isomers to form a uniform two phase solution which can be spun directly.
  • a mixture of the components is raised to a temperature in the range of 130 to 210°C.
  • the mixtures described above are held under the required pressure until a homogeneous one phase or two phase solution is formed.
  • maximum pressures of less than 10,000 psi (68950 kPa) are satisfactory.
  • the pressure may optionally be reduced somewhat and the mixture then flash spun to form the desired high quality plexifilamentary strand structure.
  • the spin solution preferably consists of HC-123 or its isomers and fiber-forming polyethylene.
  • conventional flash-spinning additives can be incorporated into the spin mixture by known techniques. These additives can function as ultraviolet-light stabilizers, antioxidants, fillers, dyes, and the like.
  • the quality of the plexifilamentary film-fibril strands produced in the examples was rated subjectively.
  • a rating of "5" indicates that the strand had better fibrillation than is usually achieved in the commercial production of spunbonded sheet made from such flash-spun polyethylene strands.
  • a rating of "4" indicates that the product was as good as commercially flash-spun strands.
  • a rating of "3” indicates that the strands were not quite as good as the commercially flash-spun strands.
  • a “2” indicates a very poorly fibrillated, inadequate strand.
  • a “1” indicates no strand formation.
  • a rating of "3" is the minimum considered satisfactory for use in the process of the present invention.
  • the commercial strand product is produced from solutions of about 12.5% linear polyethylene in trichlorofluoromethane substantially as set forth in Lee, United States patent 4,554,207, column 4, line 63, to column 5, line 10.
  • the surface area of the plexifilamentary film-fibril strand product is another measure of the degree and fineness of fibrillation of the flash-spun product. Surface area is measured by the BET nitrogen absorption method of S. Brunauer, P.H. Emmett and E. Teller, J. Am. Chem Soc., V. 60 p 309-319 (1938) and is reported as m 2 /g.
  • Tenacity of the flash-spun strand is determined with an Instron tensile-testing machine. The strands are conditioned and tested at 70°F (21.1°C) and 65% relative humidity.
  • the denier of the strand is determined from the weight of a 15 cm sample length of strand. The sample is then twisted to 10 turns per inch (3.9 t./cm) and mounted in the jaws of the Instron Tester. A 1-inch (2.54 cm) gauge length and an elongation rate of 60% per minute are used. The tenacity at break is recorded in grams per denier (gpd).
  • the apparatus employed comprises a pair of high pressure cylindrical vessels, each fitted with a piston for applying pressure.
  • the vessels are cylindrical and are connected to each other with a transfer line.
  • the transfer line contains a series of fine mesh screens intended for mixing the contents of the apparatus by forcing the contents through the transfer line from one cylinder to the other.
  • a spinneret assembly having an orifice of 0.030-inch (0.076 cm) diameter is connected to the transfer lines with quick acting means for opening and closing the orifice. Means are included for measuring the pressure and temperature inside the vessel.
  • the spinneret assembly consists of a pressure letdown orifice of 0.03375 inch (8.5X10 -4 m) diameter and a 0.030 inch length (7.62X10 -4 m), a letdown chamber of 0.25 inch (6.3X10 -3 m) diameter and 1.92 inch (4.9 cm) length, and a spinneret orifice of 0.30 inch (7.62X10 -4 m) diameter.
  • the apparatus is charged with polymer and HC-123 and a high pressure is applied to the charge.
  • the contents then are heated at the desired temperature for about an hour and a half during which time a differential pressure of about 50 psi (345 kPa) is alternately established between the two cylinders to repeatedly force the contents through the transfer line from one cylinder to the other to provide mixing and effect formation of a solution.
  • the pressure desired for spinning is then set and the spinneret orifice opened. The resultant flash-spun product is then collected.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Artificial Filaments (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Claims (8)

  1. Verfahren zum Flash-Spinnen von plexifilamentären Folienfibrillensträngen, bei dem Polyethylen, das einen Schmelzindex von wenigstens 4 gemäß ASTM D-1238-57T, Bedingung E, und eine Dichte von etwa 0,92-0,98 besitzt, in einem Isomer von Dichlortrifluorethan unter Bildung einer Spinnlösung, die 10 bis 20 % des Polyethylens, bezogen auf das Gewicht der Lösung, enthält, bei einer Temperatur im Bereich von 130 bis 210 °C und einem Druck, der größer ist als 2 400 psi (16 548 kPa), aufgelöst wird, so daß eine Zwei-Phasen-Lösung gebildet wird, gefolgt vom Flash-Spinnen der Lösung in einen Bereich von im wesentlichen niedrigerer Temperatur und niedrigerem Druck.
  2. Verfahren zum Flash-Spinnen von plexifilamentären Folienfibrillensträngen, bei dem Polyethylen, das einen Schmelzindex von größer als 6 gemäß ASTM D-1238-57T, Bedingung E, und eine Dichte von etwa 0,92-0,98 besitzt, in einem Isomer von Dichlortrifluorethan unter Bildung einer Spinnlösung, die 10 bis 20 % des Polyethylens, bezogen auf das Gewicht der Lösung, enthält, bei einer Temperatur im Bereich von 130 bis 210 °C und einem Druck, der größer ist als 2 400 psi (16 548 kPa), aufgelöst wird, gefolgt vom Flash-Spinnen der Lösung in einen Bereich von im wesentlichen niedrigerer Temperatur und niedrigerem Druck.
  3. Verfahren zum Flash-Spinnen von plexifilamentären Folienfibrillensträngen, bei dem Polyethylen, das einen Schmelzindex von wenigstens 4 gemäß ASTM D-1238-57T, Bedingung E, und eine Dichte von wenigstens 0,92 und weniger als 0,94 besitzt, in einem Isomer von Dichlortrifluorethan unter Bildung einer Spinnlösung, die 10 bis 20 % des Polyethylens, bezogen auf das Gweicht der Lösung, enthält, bei einer Temperatur im Bereich von 130 bis 210 °C und einem Druck, der größer ist als 2 400 psi (16 548kPa), aufgelöst wird, gefolgt vom Flash-Spinnen der Lösung in einen Bereich von im wesentlichen niedrigerer Temperatur und niedrigerem Druck.
  4. Verfahren nach irgendeinem der vorhergehenden Ansprüche, bei dem das Isomer 1,1-Dichlor-2,2,2-trifluorethan ist.
  5. Zwei-Phasen-Lösung, bestehend im wesentlichen aus 10 bis 20 Gew.-% Polyethylen, das einen Schmelzindex von wenigstens 4 gemäß ASTM D-1238-57T, Bedingung E, und eine Dichte von etwa 0,92 - 0,98 besitzt, und 90 bis 80 Gew.-% eines Isomeren von Dichlortrifluorethan.
  6. Lösung, bestehend im wesentlichen aus 10 bis 20 Gew.-% Polyethylen, das einen Schmelzindex von größer als 6 gemäß ASTM D-1238-57T, Bedingung E, und eine Dichte von etwa 0,92 - 0,98 besitzt, und 90 bis 80 Gew.-% eines Isomeren von Dichlortrifluorethan.
  7. Lösung, bestehend im wesentlichen aus 10 bis 20 Gew.-% Polyethylen, das einen Schmelzindex von wenigstens 4 gemäß ASTM D-1238-57T, Bedingung E, und eine Dichte von wenigstens 0,92 und weniger als 0,94 g/cm3 besitzt, und 90 bis 80 Gew.-% eines Isomeren von Dichlortrifluorethan.
  8. Lösung nach irgendeinem der Ansprüche 5 bis 7, in der das Isomer 1,1-Dichlor-2,2,2-trifluorethan ist.
EP90904045A 1990-02-26 1990-02-26 Chlorfluorkohlenstoffe zum flash-spinnen von polyethylenefasern Expired - Lifetime EP0517693B1 (de)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1990/000875 WO1991013193A1 (en) 1990-02-26 1990-02-26 Halocarbons for flash-spinning polyethylene plexifilaments

Publications (2)

Publication Number Publication Date
EP0517693A1 EP0517693A1 (de) 1992-12-16
EP0517693B1 true EP0517693B1 (de) 1997-05-02

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EP90904045A Expired - Lifetime EP0517693B1 (de) 1990-02-26 1990-02-26 Chlorfluorkohlenstoffe zum flash-spinnen von polyethylenefasern

Country Status (7)

Country Link
EP (1) EP0517693B1 (de)
JP (1) JP2851943B2 (de)
KR (1) KR0126548B1 (de)
CA (1) CA2077192C (de)
DE (1) DE69030626T2 (de)
HK (1) HK113797A (de)
WO (1) WO1991013193A1 (de)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
US5833900A (en) * 1995-07-28 1998-11-10 E. I. Du Pont De Nemours And Company Process for modifying porosity in sheet made from flash spinning olefin polymer
US6117801A (en) * 1997-03-27 2000-09-12 E. I. Du Pont De Nemours And Company Properties for flash-spun products
CN116024734A (zh) * 2021-04-16 2023-04-28 江苏青昀新材料科技有限公司 一种闪纺法制备的薄片材料
CN114293322B (zh) * 2021-12-31 2022-12-13 湖北拓盈新材料有限公司 高透湿低渗水复合无纺布的制备方法
KR102691099B1 (ko) * 2022-03-03 2024-08-05 한국생산기술연구원 플래시 방사 장치
CN116623367B (zh) * 2023-07-14 2023-09-22 江苏青昀新材料有限公司 一种低雾度衰减率的闪蒸材料

Family Cites Families (4)

* 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
US3504076A (en) * 1967-04-06 1970-03-31 Du Pont Cooling of flash spinning cell atmosphere
EP0361684B1 (de) * 1988-08-30 1993-10-13 E.I. Du Pont De Nemours And Company Halogenkohlenwasserstoffe für Flash-Spinnen von polymeren Plexifilamenten

Also Published As

Publication number Publication date
WO1991013193A1 (en) 1991-09-05
DE69030626D1 (de) 1997-06-05
HK113797A (en) 1997-08-29
KR930700705A (ko) 1993-03-15
DE69030626T2 (de) 1997-12-18
KR0126548B1 (en) 1998-04-06
CA2077192C (en) 1999-10-19
EP0517693A1 (de) 1992-12-16
CA2077192A1 (en) 1991-08-27
JPH05503552A (ja) 1993-06-10
JP2851943B2 (ja) 1999-01-27

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