EP0361684B1 - Hydrocarbures halogénés pour le filage-éclair de plexifilaments de polymères - Google Patents

Hydrocarbures halogénés pour le filage-éclair de plexifilaments de polymères Download PDF

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Publication number
EP0361684B1
EP0361684B1 EP89308701A EP89308701A EP0361684B1 EP 0361684 B1 EP0361684 B1 EP 0361684B1 EP 89308701 A EP89308701 A EP 89308701A EP 89308701 A EP89308701 A EP 89308701A EP 0361684 B1 EP0361684 B1 EP 0361684B1
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dichloro
halocarbon
solution
flash
pressure
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EP0361684A1 (fr
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Hyunkook Shin
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EIDP Inc
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EI Du Pont de Nemours and Co
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    • 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
    • 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

Definitions

  • This invention relates to flash-spinning polymeric film-fibril strands. More particularly, the invention concerns an improvement in such a process which permits flash-spinning of the strands from liquids which, if released to the atmosphere, would not detrimentally affect the earth's ozone.
  • a suitable liquid for the flash spinning (a) has a boiling point that is at least 25°C below the melting point of the polymer, (b) is substantially unreactive with the polymer at the extrusion temperature; (c) should be a solvent for the polymer under the pressure and temperature set forth in the patent (i.e., these extrusion temperatures and pressures are respectively in the ranges of 165 to 225°C and 545 to 1490 psia - 3757 to 10273 kPa); (d) should dissolve less than 1% of the polymer at or below its normal boiling point; and should form a solution that will undergo rapid phase separation upon extrusion to form a polymer phase that contains insufficient solvent to plasticize the polymer.
  • 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 patent also diagrammatically illustrates certain principles helpful in establishing optimum spinning conditions to obtain plexifilamentary strands.
  • Blades and White states that the flash-spinning solution additionally may contain a dissolved gas, such as nitrogen, carbon dioxide, helium, hydrogen, methane, propane, butane, ethylene, propylene, butene, etc.
  • a dissolved gas such as nitrogen, carbon dioxide, helium, hydrogen, methane, propane, butane, ethylene, propylene, butene, etc.
  • Preferred for improving plexifilament fibrillation are the less soluble gasses, i.e., those that are dissolved to a less than 7% concentration in the polymer solution under the spinning conditions.
  • Common additives, such as antioxidants, UV stabilizers, dyes, pigments and the like also can be added to the solution prior to extrusion.
  • An object of this invention is to provide an improved process for flash-spinning plexifilamentary film-fibril strands of fiber-forming polyolefin, 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 is dissolved in a halocarbon spin liquid to form a spin solution containing 10 to 20 percent of polyethylene by weight of the solution at a temperature in the range of 130 to 210°C and a pressure that is greater than 3000 psi (20685 kPa) which solution is flash-spun into a region of substantially lower temperature and pressure, the improvement comprising the halocarbon being selected from 1,1-dichloro-2,2,2-trifluoroethane and 1,2-dichloro-1,2,2-trifluoroethane.
  • the present invention provides an improved process for flash-spinning plexifilamentary film-fibril strands wherein polyethylene is dissolved in a halocarbon spin liquid to form a spin solution containing 10 to 20 percent of polyethylene by weight of the solution at a temperature in the range of 130 to 210°C and a pressure that is greater than 1,800 psi (12411 kPa) which solution is flash-spun into a region of substantially lower temperature and pressure, the improvement comprising the halocarbon being selected from 1,1-dichloro-2,2-difluoroethane and 1,2-dichloro-1,1-difluoroethane.
  • the present invention provides an improved process for flash-spinning plexifilamentary film-fibril strands wherein polyethylene is dissolved in a halocarbon spin liquid to form a spin solution containing 10 to 20 percent of polyethylene by weight of the solution at a temperature in the range of 130 to 210°C and a pressure that is greater than 2,000 psi (13790 kPa) which solution is flash-spun into a region of substantially lower temperature and pressure, the improvement comprising the halocarbon being 1,1-dichloro-1-fluoroethane.
  • the present invention provides an improved process for flash-spinning plexifilamentary film-fibril strands wherein polypropylene is dissolved in a halocarbon spin liquid to form a spin solution containing 10 to 20 percent of polypropylene by weight of the solution at a temperature in the range of 130 to 210°C and a pressure that is greater than 1,500 psi (10343 kPa) which solution is flash-spun into a region of substantially lower temperature and pressure, the improvement comprising the halocarbon being selected from 1,1-dichloro-2,2,2-trifluoroethane, 1,2-dichloro-1,2,2-trifluoroethane, 1,1-dichloro-2,2-difluoroethane, 1,2-dichloro-1,1-difluoroethane and 1,1-dichloro-1-fluoroethane.
  • the present invention provides an improved process for flash-spinning plexifilamentary film-fibril strands wherein a fiber-forming polyolefin is dissolved in a halocarbon spin liquid at a temperature in the range of 130 to 210°C and a pressure that is greater than 1000 psi (6895 kPa) wherein the spin liquid further contains a co-solvent, either a hydrocarbon which amounts to 2 to 25 percent of the total weight of spin liquid or methylene chloride which amounts to 5 to 50 percent of the total weight of spin liquid, to form a spin solution containing 10 to 20 percent of fiber-forming polyolefin by weight of the solution and then is flash-spun into a region of substantially lower temperature and pressure, the improvement comprising the halocarbon being selected from 1,1-dichloro-2,2,2-trifluoroethane, 1,2-dichloro-1,2,2-trifluoroethane, 1,1-dichloro-2,2-difluoroethane,
  • the present invention provides a novel solution consisting essentially of 10 to 20 weight percent of a fiber-forming polyolefin and 90 to 80 weight percent of a liquid containing a halocarbon selected from 1,1-dichloro-2,2,2-trifluoroethane, 1,2-dichloro-1,2,2-trifluoroethane, 1,1-dichloro-2,2-difluoroethane, 1,2-dichloro-1,1-difluoroethane and 1,1-dichloro-1-fluoroethane.
  • a halocarbon selected from 1,1-dichloro-2,2,2-trifluoroethane, 1,2-dichloro-1,2,2-trifluoroethane, 1,1-dichloro-2,2-difluoroethane, 1,2-dichloro-1,1-difluoroethane and 1,1-dichloro-1-fluoroethane.
  • the present invention provides a novel solution consisting essentially of 10 to 20 weight percent of a fiber-forming polyolefin and 90 to 80 weight percent of a halocarbon liquid selected from 1,1-dichloro-2,2,2-trifluoroethane, 1,2-dichloro-1,2,2-trifluoroethane, 1,1-dichloro-2,2-difluoroethane, 1,2-dichloro-1,1-difluoroethane and 1,1-dichloro-1-fluoroethane.
  • a halocarbon liquid selected from 1,1-dichloro-2,2,2-trifluoroethane, 1,2-dichloro-1,2,2-trifluoroethane, 1,1-dichloro-2,2-difluoroethane, 1,2-dichloro-1,1-difluoroethane and 1,1-dichloro-1-fluoroethane.
  • 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 and polymethylpentene. Conveniently, polyethylene and polypropylene are the preferred polyolefins for use in the process of the present invention.
  • 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.
  • 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 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 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 through 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 for producing plexifilamentary film-fibril strands of fiber-forming polyolefins from a halocarbon spin solution that contains 10 to 20 weight percent of the fiber-forming polyolefin.
  • a fiber-forming polyolefin e.g. linear polyethylene
  • a spin liquid that includes a halocarbon to form a spin solution containing 10 to 20 percent of the linear polyethylene by weight of the solution and then is flash-spun at a temperature in the range of 130 to 210°C and a pressure that is greater than the autogenous pressure of the spin liquid into a region of substantially lower temperature and pressure.
  • halocarbon to be selected from 1,1-dichloro-2,2,2-trifluoroethane ("HC-123”) 1,2-dichloro-1,2,2-trifluoroethane ("HC-123a”) 1,1-dichloro-2,2-difluoroethane (HC-132a”) 1,2-dichloro-1,1-difluoroethane ("HC-132b”) and 1,1-dichloro-1-fluoroethane ("HC-141b”).
  • HC-123 1,1-dichloro-2,2,2-trifluoroethane
  • HC-123a 1,2-dichloro-1,2,2-trifluoroethane
  • HC-132a 1,1-dichloro-1,1-difluoroethane
  • HC-141b 1,1-dichloro-1-fluoroethane
  • 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 the selected halocarbons and for some prior art solvents.
  • Tbp normal atmospheric boiling points
  • Tcr critical temperatures
  • Pcr critical pressures
  • Solubility the Table also lists whether a 10% polyethylene solution can be formed in the halocarbon at temperatures between 130 and about 225°C under autogenous pressures.
  • halocarbons listed above represent a very particular and small group of halocarbons that are suitable for use in the present invention. There are hundreds of halocarbons to select from.
  • the conventional method of screening liquids i.e., by means of the autogenous pressure polyethylene solubility test, described above
  • the halocarbons discovered to be useful for the present invention do not dissolve the polyethylene at autogenous pressures, in contrast to the prior art solvents shown above that would have been selected for further study because they do form solutions with the polyethylene at autogenous pressure.
  • halocarbons of the present invention form a single phase solution with polyethylene at the required concentrations and temperatures at a pressure of less than 1,500 psia (10345 kPa).
  • These halocarbons do, of course, have certain characteristics that are also possessed by the known fiber-forming polyolefin flash-spinning liquids. For example, these halocarbons also are substantially unreactive with the polymer at the extrusion temperature.
  • halocarbons are solvents for the fiber-forming polyolefin under certain conditions, dissolve less than 1% of the polymer at or below their normal boiling points and form solutions that undergo rapid phase separation upon extrusion to form a polymer phase that contains insufficient solvent to plasticize the polymer.
  • halocarbons suitable for use in the process and solutions of the present invention (1) have boiling points in the range of 0 to 80°C, (2) are incompletely fluorinated and/or chlorinated, (3) have low flammability, (4) have adequate heat of vaporization to permit rapid cooling of the plexifilament when it is formed upon flash spinning, (5) have adequate thermal and hydrolytic stability for use in the flash spinning process, (6) have a sufficiently high electrostatic breakdown potential in the gaseous state so that they can be used in conventional spunbonded processes for forming sheets of the plexifilament (e.g., Steuber, United States Patent 3,169,899) without exhibiting excessive decomposition of the halocarbon and (7) cannot form a single phase 10 weight percent solution of polyethylene in the liquid at temperatures in the range of 130 to 225°C at any pressure less than 1,500 psia (10345 kPa).
  • such solutions of polyethylene can be formed in the halocarbon liquid only at pressures greater than 3,000 psi (20685 kPa); with HC-132a and HC-132b, such solutions of polyethylene can be formed in the halocarbon liquid only at pressures greater than 1,800 psi (12411 kPa) and with HC-141b, such solutions of polyethylene can be formed in the halocarbon liquid only at pressures greater than 2,000 psi (13790 kPa).
  • Such solutions of polypropylene can be formed in the halocarbon spin liquids of this invention only at pressures greater than 1,500 psi (10343 kPa).
  • Satisfactory solutions of polymer and halocarbon can be formed at pressures greater than 1,000 psi (6895 kPa), only when co-solvents of high solvent power are present in the halocarbon spin liquid.
  • halocarbon characteristics have been discovered to be met substantially by only the five halocarbons, listed above.
  • another halocarbon would also have to meet substantially all of these characteristics in order to be suitable for flash-spinning high quality, plexifilamentary film-fibril strands of fiber-forming polyolefin.
  • halocarbons suitable for use in the process of the invention care must be taken with these halocarbons to avoid certain disadvantageous characteristics which may be present. For example, excessive heating times are avoided with HC-123a, HC-132a, HC-132b and HC-141b to minimize decomposition that can arise from dehydrohalogenation or hydrolysis of the halocarbon. Care must also be taken with HC-132b, because there have been some indications that this chemical may be a male-animal-reproductive toxin. Because of its relative freedom from all of these stability and toxicity problems, HC-123 is the preferred halocarbon for use in the process of the invention.
  • a mixture of the fiber-forming polyolefin and halocarbon are raised to a temperature in the range of 130 to 210°C. If polyethylene is the polyolefin; the mixture is under a pressure of greater than 2,000 psi (13790 kPa) if the halocarbon is HC-141b, greater than 3,000 psi (20685 kPa) if the halocarbon is HC-123 or HC-123a and greater than 1,800 psi (12411 kPa) if the halocarbon is HC-132a or HC-132b.
  • the pressure is greater than 1,500 psi (10345 kPa) regardless of the halocarbon chosen.
  • the mixtures described above are held under the required pressure until a solution of the fiber-forming polyolefin is formed in the liquid. Usually, maximum pressures of less than 10,000 psi (68950 kPa) are satisfactory. After the fiber-forming polyolefin has dissolved, the pressure may be reduced somewhat and the mixture is then flash spun to form the desired high quality plexifilamentary strand structure.
  • the concentration of fiber-forming polyolefin in the spin liquid usually is in the range of 10-20 percent, based on the total weight of the liquid and the fiber-forming polyolefin.
  • the spin solution preferably consists of halocarbon liquid and fiber-forming polyolefin, but if lower pressures are desired for solution preparation and spinning, the spin solution can contain a second liquid, or co-solvent, for the fiber-forming polyolefin.
  • the co-solvent is a hydrocarbon solvent, such as cyclohexane, toluene, chlorobenzene, hexane, pentane, 3-methyl pentane and the like
  • the concentration of the co-solvent in the mixture of halocarbon and co-solvent generally amounts to 2 to 25 weight percent and preferably less than 15 weight percent to minimize potential flammability problems.
  • concentrations of the methylene chloride in the halocarbon/co-solvent mixture generally amounts to 5 to 50 weight percent.
  • 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.
  • Solubility of the polyethylene and polypropylene under autogenous conditions were measured by the convenient sealed-tube test of Woodell, United States Patent 3,655,498, that was also described in the next to last paragraph of the "Description of the Prior Art" section of this document.
  • the quality of the plexifilamentary film-fibril strands produced in the examples were 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 tichlorofluoromethane substantially as set forth in Lee, United States patent 4,554,207, column 4, line 63, through column 5, line 10, which disclosure is hereby incorporated by reference.
  • 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 m2/g.
  • Tenacity of the flash-spun strand is determined with an Instron tensile-testing machine. The strands are conditioned and tested at 21.1°C (70°F) 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 and mounted in the jaws of the Instron Tester. A 1-inch (25.4 mm) gauge length and an elongation rate of 60% per minute are used. The tenacity at break is recorded in grams per denier (gpd).
  • the invention is illustrated in the Examples which follow with a batch process in equipment of relatively small size. Such batch processes can be scaled-up and converted to continuous flash-spinning processes that can be performed, for example, in the type of equipment disclosed by Anderson and Romano, United States Patent 3,227,794.
  • processes of the invention are identified with Arabic numerals. Processes identified with uppercase letters are comparison processes that are outside the invention.
  • Apparatus “I” is a high pressure apparatus comprising a cylindrical vessel of 50 cm3 volume, fitted at one end with a cylindrical piston which is adapted to apply pressure to the contents of the vessel.
  • the other end of the vessel is fitted with a spinneret assembly having an orifice of 0.030-inch (0.76 mm) diameter and 0.060-inch (1.5 mm) length and a quick-acting means for opening and closing the orifice.
  • Means are included for measuring the pressure and temperature inside the vessel.
  • the vessel is charged with fiber-forming polyolefin and halocarbon.
  • a high pressure e.g., 4,500 psi - 31028 kPa
  • the contents are heated at the desired temperature (e.g., 140°C) for about an hour to effect the formation of a solution which is then "mixed" by cycling the pressure about ten times.
  • the pressure is then reduced to that desired for spinning and the spinneret orifice valve opened.
  • the resultant flash-spun product is then collected.
  • Apparatus “II” comprises a pair of high pressure cylindrical vessels, each fitted with a piston for applying pressure.
  • the vessels are each similar to the cylindrical vessel of apparatus “I”, but rather than having an orifice assembly in each vessel, the two 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 (0.76 mm) 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. In operation, the apparatus is charged with fiber-forming polyolefin and halocarbon 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.
  • Examples 1-7 illustrate the use of different halocarbons suitable for the process and solutions of the invention. Comparisons A and B show the use of some of the same halocarbons but under conditions that do not permit production of satisfactory strand.
  • Examples 8-25 illustrate the use of various co-solvents with the halocarbons.
  • Example 26 shows that well fibrillated plexifilaments can be obtained from other types of polyolefins using this invention.
  • the apparatus and methodology used in this example were the same as the examples in Table II except polyethylene was substituted with isotactic polypropylene with a Melt Flow Rate of 0.4, available commercially under the tradename "Profax 6823" by Hercules, Inc. Wilmington, De.
  • higher mixing temperature was used to compensate for the higher melting point of the polymer.
  • the conditions used and the properties of the resultant fiber are summarized in Table III.
  • the polymer mix contained 3.6 wt% based on polymer of Irganox R 1010 (Trademark of Ciba-Geigy Corp. for a high-molecular weight hindered polyphenol) as an antioxidant.

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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)

Claims (14)

  1. Un procédé pour le filage-éclair de faisceaux de fibrilles pelliculaires plexifilamentaires dans lequel du polyéthylène est dissous dans un liquide à filer du type hydrocarbure halogéné pour constituer une solution à filer contenant 10 à 20 pour cent de polyéthylène par rapport au poids de la solution à une température de l'ordre de 130 à 210° C et une pression superatmosphérique, cette solution étant soumise à un filage-éclair dans une région de température et de pression considérablement inférieures, dans lequel pour une pression superatmosphérique supérieure à 20685 kPa l'hydrocarbure halogéné est choisi parmi
       le 1,1-dichloro-2,2,2-trifluoroéthane et
       le 1,2-dichloro-1,2,2-trifluoroéthane ;
       pour une pression superatmosphérique supérieure à 12410 kpa, l'hydrocarbure halogéné est choisi parmi le 1,1-dichloro-2,2-difluoroéthane et le 1,2-dichloro-1,1-difluoroéthane ; et pour une pression superatmosphérique supérieure à 13790 kPa, l'hydrocarbure halogéné est du 1,1-dichloro-1-fluoroéthane.
  2. Un procédé pour le filage-éclair de faisceaux de fibrilles pelliculaires plexifilamentaires dans lequel du polyéthylène est dissous dans un liquide à filer du type hydrocarbure halogéné pour constituer une solution à filer contenant 10 à 20 pour cent de polypropylène par rapport au poids de la solution à une température de l'ordre de 130 à 210° C et une pression supérieure à 10343 kPa, cette solution étant soumise à un filage-éclair dans une région de température et de pression considérablement inférieures, dans lequel l'hydrocarbure halogéné est choisi parmi
       le 1,1-dichloro-2,2,2-trifluoroéthane,
       le 1,2-dichloro-1,2,2-trifluoroéthane,
       le 1,1-dichloro-2,2-difluoroéthane,
       le 1,2- dichloro-1,1-difluoroéthane et
       le 1,1-dichloro-1-fluoroéthane.
  3. Un procédé pour le filage-éclair de faisceaux de fibrilles pelliculaire plexifilamentaires dans lequel une polyoléfine fibrogène est dissoute dans un liquide à filer du type hydrocarbure halogéné à une température de l'ordre de 130 à 210° C et à une pression supérieure à 6895 kpa, dans lequel le liquide à filer contient un cosolvant pour constituer une solution à filer contenant 10 à 20 pour cent de polyoléfine fibrogène par rapport au poids de la solution, et est ensuite soumise à un filage-éclair dans une région de température et de pression considérablement inférieures, dans lequel ledit cosolvant est soit un hydrocarbure représentant 2 à 25 pour cent du poids total du liquide à filer soit du chlorure de méthylène représentant 5 à 50 pour cent du poids total du liquide à filer et dans lequel l'hydrocarbure halogéné est choisi parmi
       le 1,1-dichloro-2,2,2-trifluoroéthane,
       le 1,2-dichloro-1,2,2-trifluoroéthane,
       le 1,1-dichloro-2,2-difluoroéthane,
       le 1,2- dichloro-1,1-difluoroéthane et
       le 1,1-dichloro-1-fluoroéthane.
  4. Un procédé selon la revendication 3 dans lequel le cosolvant est choisi parmi le 3-méthyl-pentane, le cyclohexane, le toluène, le pentane, l'hexane et le chlorobenzène.
  5. Un procédé selon la revendication 4 dans lequel le cosolvant ne représente pas plus de 15 pour cent du poids total du liquide à filer.
  6. Un procédé selon les revendications 1, 2, 3, 4 ou 5, dans lequel l'hydrocarbure halogéné est du 1,1-dichloro-2,2,2-trifluoroéthane.
  7. Un procédé selon les revendications 3, 4 ou 5, dans lequel la polyoléfine est du polyéthylène.
  8. Un procédé selon les revendications 3, 4 ou 5, dans lequel la polyoléfine est du polypropylène.
  9. Une solution comportant essentiellement 10 à 20 pour cent en poids d'une polyoléfine fibrogène et 80 à 90 pour cent en poids d'un liquide comprenant un hydrocarbure halogéné choisi parmi
       le 1,1-dichloro-2,2,2-trifluoroéthane,
       le 1,2-dichloro-1,2,2-trifluoroéthane,
       le 1,1-dichloro-2,2-difluoroéthane,
       le 1,2- dichloro-1,1-difluoroéthane et
       le 1,1-dichloro-1-fluoroéthane.
  10. Une solution selon la revendication 9 dans laquelle le liquide contient un cosolvant hydrocarbure représentant 2 à 25 pour cent du poids total de l'hydrocarbure halogéné et du cosolvant.
  11. Une solution selon la revendication 9 dans laquelle le liquide contient aussi du chlorure de méthylène comme cosolvant représentant 5 à 50 pour cent du poids de l'hydrocarbure halogéné et du chlorure de méthylène.
  12. Une solution selon l'une quelconque des revendications 9 à 11 dans laquelle l'hydrocarbure halogéné est du 1,1-dichloro-2,2,2-trifluoroéthane.
  13. Une solution selon l'une quelconque des revendications 9 à 12 dans laquelle la polyoléfine est du polyéthylène.
  14. Une solution selon l'une quelconque des revendications 9 à 12 dans laquelle la polyoléfine est du polypropylène.
EP89308701A 1988-08-30 1989-08-29 Hydrocarbures halogénés pour le filage-éclair de plexifilaments de polymères Expired - Lifetime EP0361684B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US23844288A 1988-08-30 1988-08-30
US238442 1988-08-30
US37929189A 1989-07-18 1989-07-18
US379291 1989-07-18

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EP0361684A1 EP0361684A1 (fr) 1990-04-04
EP0361684B1 true EP0361684B1 (fr) 1993-10-13

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EP89308701A Expired - Lifetime EP0361684B1 (fr) 1988-08-30 1989-08-29 Hydrocarbures halogénés pour le filage-éclair de plexifilaments de polymères

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EP (1) EP0361684B1 (fr)
JP (1) JP2756489B2 (fr)
KR (1) KR0136110B1 (fr)
CN (1) CN1041190A (fr)
AU (1) AU627488B2 (fr)
CA (1) CA1338407C (fr)
DE (1) DE68909880T2 (fr)
MX (1) MX171962B (fr)
RU (1) RU2002861C1 (fr)

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU643386B2 (en) * 1988-08-30 1993-11-11 E.I. Du Pont De Nemours And Company Non-ozone depleting halocarbons for flash-spinning polymeric plexifilaments
US5032326A (en) * 1988-08-31 1991-07-16 E. I. Du Pont De Nemours And Company Flash-spinning of polymeric plexifilaments
TW204377B (fr) * 1989-07-12 1993-04-21 Asahi Chemical Ind
JP2851943B2 (ja) * 1990-02-26 1999-01-27 イー・アイ・デユポン・ドウ・ヌムール・アンド・カンパニー ポリエチレン・プレクシフイラメントのフラシユ紡糸用ハロゲン化炭素
US5459188A (en) * 1991-04-11 1995-10-17 Peach State Labs, Inc. Soil resistant fibers
US5286422A (en) * 1991-08-03 1994-02-15 Asahi Kasei Kogyo Kabushiki Kaisha Process for producing three-dimensional fiber using a halogen group solvent
US5279776A (en) * 1991-09-17 1994-01-18 E. I. Du Pont De Nemours And Company Method for making strong discrete fibers
US5672307A (en) * 1996-03-08 1997-09-30 E. I. Du Pont De Nemours And Company Flash spinning process
US5977237A (en) * 1996-03-08 1999-11-02 E. I. Du Pont De Nemours And Company Flash-spinning solution
US5874036A (en) * 1996-03-08 1999-02-23 E. I. Du Pont De Nemours And Company Flash-spinning process
US5985196A (en) * 1998-01-20 1999-11-16 E. I. Du Pont De Nemours And Company Flash spinning process and flash spinning solution
US6524492B2 (en) 2000-12-28 2003-02-25 Peach State Labs, Inc. Composition and method for increasing water and oil repellency of textiles and carpet
US11261543B2 (en) * 2015-06-11 2022-03-01 Dupont Safety & Construction, Inc. Flash spinning process
CN111286790B (zh) * 2020-03-05 2021-08-03 上海青昀新材料科技有限公司 一种安全的溶液纺丝方法
CN112609334B (zh) * 2020-11-30 2022-06-28 江苏青昀新材料科技有限公司 闪蒸无纺布及其制备方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3018519A (en) 1958-03-06 1962-01-30 Coats & Clark Apparatus for molding plastic insert in threaded lock nut blanks
US3081519A (en) * 1962-01-31 1963-03-19 Fibrillated strand
NL300881A (fr) * 1962-11-23
US4528300A (en) * 1984-01-31 1985-07-09 The Dow Chemical Company Process for producing dimensionally stable polyolefin foams using environmentally acceptable blowing agent systems

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JPH02160909A (ja) 1990-06-20
KR900003435A (ko) 1990-03-26
MX171962B (es) 1993-11-25
CN1041190A (zh) 1990-04-11
JP2756489B2 (ja) 1998-05-25
RU2002861C1 (ru) 1993-11-15
DE68909880T2 (de) 1994-05-05
AU4085389A (en) 1990-03-08
CA1338407C (fr) 1996-06-18
AU627488B2 (en) 1992-08-27
KR0136110B1 (ko) 1998-04-28
EP0361684A1 (fr) 1990-04-04
DE68909880D1 (de) 1993-11-18

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