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WO2012013167A2 - Procédé de filage électrostatique d'un polymère fondu - Google Patents

Procédé de filage électrostatique d'un polymère fondu Download PDF

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Publication number
WO2012013167A2
WO2012013167A2 PCT/CZ2011/000070 CZ2011000070W WO2012013167A2 WO 2012013167 A2 WO2012013167 A2 WO 2012013167A2 CZ 2011000070 W CZ2011000070 W CZ 2011000070W WO 2012013167 A2 WO2012013167 A2 WO 2012013167A2
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WO
WIPO (PCT)
Prior art keywords
polymer
weight
melting
temperature
spinning
Prior art date
Application number
PCT/CZ2011/000070
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English (en)
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WO2012013167A3 (fr
Inventor
Lukas Plistil
Michal Komarek
Original Assignee
Elmarco S.R.O,
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Elmarco S.R.O, filed Critical Elmarco S.R.O,
Publication of WO2012013167A2 publication Critical patent/WO2012013167A2/fr
Publication of WO2012013167A3 publication Critical patent/WO2012013167A3/fr

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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
    • D01D5/0007—Electro-spinning
    • D01D5/0015—Electro-spinning characterised by the initial state of the material
    • D01D5/0023—Electro-spinning characterised by the initial state of the material the material being a polymer melt
    • 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
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • 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
    • 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
    • D01F6/06—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 from polypropylene
    • 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
    • D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/30—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising olefins as the major constituent
    • 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
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
    • D01F6/625—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters derived from hydroxy-carboxylic acids, e.g. lactones

Definitions

  • the invention relates to a method of electrostatic spinning of polymer melt, at which prepared polymer melt is supplied into an electric field induced between a spinning electrode and a collecting electrode.
  • Another disadvantage of electrostatic spinning of polymer solutions is necessity of continual removal of vapours of the solvent, which evaporate from produced nanofibres, and in some cases also from free surface of polymer solution in a reservoir, from the space in which electrostatic spinning is performed. Even slightly increased concentration of these vapours negatively influences output of electrostatic spinning and also quality and morphology of nanofibres being produced. At higher concentrations of vapours of some solvents there even exists danger of their ignition or explosion. Usually it is necessary to neutralise and/or to recycle removed vapours due to their nature, and so there is an increase in acquisition costs as well as in operational costs of the device on which the process of electrostatic spinning of polymer solutions is performed.
  • the goal of the invention is to remedy or at least to minimise the disadvantages of the background art and to propose a method of electrostatic spinning of polymer melts, especially of polyethylene, polypropylene, polycaprolactone and copolymer of polyethylene-acrylic acid with 5% content of acrylic acid, which could be applicable in industrial scale.
  • the goal of the invention is achieved by a method of electrostatic spinning of polymer melt in an electric field induced between a spinning electrode and a collecting electrode, whose principle consists in that, before and/or during and/or after preparation of the polymer melt 1 to 25% by weight of a conducting agent is added to the polymer, by which electrical conductivity of the polymer melt is increased.
  • the polymer melt is before supplying into the electric field homogenised by mixing.
  • the most suitable conducting agent for spinning of polyethylene melt is tetraalkylammonium halogenide with four identical alkyls and temperature of melting up to 250°C, like e.g. tetrabutylammonium iodide or tetrabutylammonium bromide, in quantity of 3 to 25% by weight, or tetraalkylammonium halogenide with three identical alkyls and temperature of melting up to 250°C, like for example triethylhexylammonium bromide in quantity of 3 to 25% by weight, or their mixture.
  • tetraalkylammonium halogenide with four identical alkyls and temperature of melting up to 250°C, like e.g. tetrabutylammonium iodide or tetrabutylammonium bromide, in quantity of 3 to 25% by weight, or their mixture.
  • the same conducting agents may be used, whose quantity varies in case of copolymer of ethylene-acrylic acid with 5% content of acrylic acid in the range from 5 to 20% by weight, in case of polycaprolactone in the range from 1 to 10% by weight, and in the case of polypropylene in the range from 3 to 15% by weight.
  • nanofibres of polypropylene tetraalkylphosphonium salt with four identical alkyls, where the anion is halogenide, tosylate or bistriflamide, or tetraalkylphosphonium salt with three identical alkyls, where the anion is halogenide, tosylate or bistriflamide, or their mixture in quantity of 1 to 5% by weight can be used as the conducting agent.
  • tetraalkylphosphonium salt with four identical alkyles is tetraoctylphosphonium bromide or tetraoctylphosphonium iodide, in case of tetraalkylphosphonium salt with three identical alkyls it is then tributhylhexadecylphosphonium bromide, tributhylhexadecylphosphonium chloride, trihexyltetradecylphosphonium chloride, tributhylhexadecylphosphonium tosylate or triisobuthyl(methyl)phosphonium tosylate.
  • sodium salt of higher fatty acid or mixture of sodium salts of higher fatty acid in quantity from 5 to 15% by weight may be used.
  • sodium stearate or sodium octanoate is suitable salt.
  • FIG. 1 shows a cross-section of one of variants of a device for electrostatic spinning of polymer melt
  • Fig. 1a a SEM picture of fibres produced through electrostatic spinning of polyethylene melt according to the invention
  • Fig. 1b shows distribution of diameters of these fibres
  • Fig. 2a a SEM picture of fibres produced through electrostatic spinning of polyethylene melt of another composition
  • Fig. 2b shows distribution of diameters of these fibres
  • Fig. 3a a SEM picture of fibres produced through electrostatic spinning of copolymer melt of ethylene-acrylic acid with 5% content of acrylic acid
  • Fig. 3b shows distribution of diameters of these fibres
  • Fig. 1 shows a cross-section of one of variants of a device for electrostatic spinning of polymer melt
  • Fig. 1a shows distribution of diameters of these fibres
  • Fig. 2a a SEM picture of fibres produced through electrostatic spinning of polyethylene melt of another composition
  • Fig. 2b shows distribution of diameters of
  • FIG. 4a a SEM picture of fibres produced through electrostatic spinning of polycaprolactone melt according to the invention
  • Fig. 4b shows distribution of diameters of these fibres
  • Fig. 5a, 6a, 7a, 8a, 9a, 10a, 11a SEM pictures of fibres produced through electrostatic spinning of polypropylene melt of various compositions according to the invention
  • Fig. 5b, 6b, 7b, 8b, 9b, 10b, 11b shows distribution of diameters of these fibres.
  • a method of electrostatic spinning of polymer melt according to the invention will be explained on examples of electrostatic spinning of melt of polyethylene, melt of copolymer of polyethylene-acrylic acid with 5% content of acrylic acid, melt of polycaprolactone and melt of polypropylene performed on the device represented in Fig. 1.
  • This device comprises in its spinning chamber static cylindric collecting electrode 2 according to the international patent application WO 2008011840, and against it rotatably arranged spinning electrode 3 according to EP patent application 2059630 or CZ PV 2009-525 with electrically conducting faces 31 , between which the spinning elements 32 formed of electrically conducting wire are led.
  • the spinning electrode 3 is coupled with not represented drive for rotating motion around its longitudinal axis 30, which is parallel with longitudinal axis 20 of collecting electrode 2, while extends by its lower section and respective spinning elements 32 into the polymer melt 4 contained in the reservoir 5.
  • Spinning elements 32 of the spinning electrode 3 and the collecting electrode 2 are connected with opposite poles of source 6 of high direct voltage positioned outside the spinning chamber ⁇ , by which an electric field of high intensity is induced between them.
  • this electric field may be induced also by grounding the spinning electrode 3 or the collecting electrode 2, while to the second of electrodes high voltage of positive or negative polarity is supplied.
  • substrate 7 may be according to the considered application both electrically conducting as well as electrically non-conducting, while most frequently planar or linear textile formations of various types, plastic or metallic foils, various types of paper, filtration paper etc., are used. If an electrically non-conducting substrate 7 is used, it may be advantageous to use a corona discharger according to the international patent application WO 2008098526, which deposits an electric charge on the substrate 7, so that it behaves thanks to this as the collecting electrode.
  • the substrate 7 is coupled with not represented drive, and according to the requirements moves in the spinning chamber 1 either in an interrupted manner, or non-interrupted manner in direction of arrow A, thus in direction from the picture plane of Fig. 1.
  • the substrate 7 may in the spinning chamber ⁇ move, if there is such a need, also reversibly.
  • the device for performance the method according to the invention is in the spinning chamber 1 and/or outside it provided with not represented elements to increase temperature in the spinning chamber 1 and/or to maintain it on the required value. Their construction, principle, number and positioning may be at the same time totally individual, depending on inner arrangement of other elements of this device, and/or on the polymer being subject to spinning, and due to the fact, that they do not influence principle of the invention, will not be further described.
  • the spinning elements 32 of the rotating spinning electrode 3 carry out on their surface the polymer melt 4 from reservoir 5 into the electric field, which is induced between the given spinning element 32 and the collecting electrode 2, and in which due to its action of force this melt 4 is transformed into nanofibres.
  • These nanofibres move after their creation towards the collecting electrode 2 and are caught on the impact side 71 of the substrate 7, where they deposit into a layer.
  • the layer of nanofibres is after then used according to the requirements and type of application either in combination with the substrate 7, at the same time it may be, if required, in some of the known methods additionally attached to it, or adhesion of the nanofibre layer to the substrate 7 may be increased, e.g. using the method according to CZ 2009-148 or CZ 2009-149, or it is detached from it and is used independently, possibly in combination with other layers of material.
  • the method for production of nanofibres through electrostatic spinning of polymer melt 4 according to the invention is nevertheless not bound only to the construction of the device represented in Fig. 1.
  • the same or very similar results may be achieved also at usage of not represented modified variants of this device, which utilise any other types of collecting electrodes 2 and/or spinning electrodes 3, including the spinning electrodes 3 formed of full cylinder or any other elongated body rotating around its longitudinal axis, a needle or system of needles, a capillary or system of capillaries, etc., possibly variants which in the spinning chamber 1 comprise other number of spinning electrodes 3 and/or collecting electrodes 2.
  • these devices may be of different mutual space arrangement of the spinning electrode 3 (spinning electrodes) and the collecting electrode 2 (collecting electrodes), while e.g. the spinning electrode 3 according to CZ PV 2010-21 1 may be positioned in the space above the collecting electrode 2 (collecting electrodes), so that spinning is performed in direction downwards or askew downwards, eventually other types of spinning electrode 3 may be positioned beside the collecting electrode 2 (collecting electrodes), so that spinning is performed to the side or askew to the side.
  • the substrate 7 is guided outside the space between the spinning electrode 3 and the collecting electrode 2, while the nanofibres being produced are brought to its impact side 71 by means of stream of air or any other gas, or by other suitable manner.
  • Polymer melt 4 for electrostatic spinning according to the invention is prepared by melting the respective polymer, to which before melting and/or during and/or after melting suitable quantity of conducting agent is added.
  • This conducting agent increases electrical conductivity of the polymer melt 4, and due to this increases output of electrostatic spinning as it facilitates transfer of electric charge between the spinning electrode 3 and the collecting electrode 2, and simultaneously facilitates separating of polymeric chains, by which it reduces diameter of fibres being produced and enables creating of nanofibres instead of to date common microfibres.
  • prepared melt 4 is subsequently mixed, preferably in double screw extruder, through which homogeneity is achieved in its whole volume, and after that it is positioned into the reservoir 5, from which it is through the above mentioned method carried out into the electric field and transformed into nanofibres. If sufficient mixing of polymer and conducting agent is secured already during preparation of the melt 4, there is no need to mix the melt 4 additionally.
  • melts 4 of polyethylene, copolymer of polyethylene-acrylic acid with 5% content of acrylic acid, polycaprolactone and polypropylene are as well as conditions under which their electrostatic spinning was performed and achieved results shown in the following examples.
  • the principle of the invention is nevertheless, next to the mentioned polymers and conducting agents, usable also for number of other polymers and conducting agents with similar character.
  • the most suitable conducting agent for electrostatic spinning of melt 4 of polyethylene are tetraalkylammonium halogenides with four identical alkyls (e.g.
  • tetrabutylammonium iodide or tetrabutylammonioum bromide or with three identical and one different alkyl (e.g. triethylhexylammonium bromide), with temperature of melting up to 250°C.
  • alkyl e.g. triethylhexylammonium bromide
  • temperature of melting up to 250°C.
  • Only one of the above mentioned tetraalkylammonium halogenides, or mixture of several of them may be used, while total part of conducting agent in the melt 4 varies in the range from 3 to 25% by weight, preferably from 10 to 15% by weight.
  • the melt 4 was prepared by melting of 28,5 g of polyethylene with Mn ( number average molar mass) 1800 and 1 ,5 g of tetrabutylammonium iodide - i.e. 5% by weight, at temperature of 180°C. After homogenisation in double screw extruder, which was running for period of 10 minutes, the melt 4 was positioned into reservoir 5 of the device for electrostatic spinning in variant represented in Fig. 1 and subjected to spinning at temperature of 180°C. The difference of electric voltage brought to spinning elements 32 of the spinning electrode 3 and to the collecting electrode 2 was 120 kV, distance between the nearest spinning element 32 of the spinning electrode 3 and the collecting electrode 2 was 30 cm. The spinning electrode 3 was rotating around its longitudinal axis 30 at speed of 20 rpm.
  • Fig. 1b represents distribution of diameters of polyethylene fibres in this layer, from which it is obvious that diameter of 95% of produced fibres varied in the range from 200 to 1000 nanometers, so that these were nanofibres, and at only 5% of fibres it exceeded value of 1000 nanometers.
  • Example 2 The melt 4 was prepared by melting of 27 g of polyethylene with Mn 1800 and 3 g of tetrabutylammonium iodide - i.e. 10% by weight, at temperature of 180°C. After homogenisation in double screw extruder, which was running for period of 10 minutes, the melt 4 was positioned into reservoir 5 of the device for electrostatic spinning in variant represented in Fig. 1 and subjected to spinning at temperature of 180°C. The difference of electric voltage brought to spinning elements 32 of the spinning electrode 3 and to the collecting electrode 2 was 120 kV, distance between the nearest spinning element 32 of the spinning electrode 3 and the collecting electrode 2 was 30 cm. The spinning electrode 3 was rotating around its longitudinal axis 30 at speed of 15 rpm.
  • Fig. 2a Through electrostatic spinning a layer of fibres that is represented in the SEM picture in Fig. 2a was produced.
  • Fig. 2b represents distribution of diameters of polyethylene fibres in this layer, from which it is obvious that diameter of 95% of produced fibres varied in the range from 100 to 800 nanometers, so that these were nanofibres, and only at 5% of fibres it exceeded value of 1000 nanometers. The greatest recorded diameter was then 1500 nanometers.
  • melt 4 of polyethylene contained 15% by weight or 20% by weight of tetrabutylammonium iodide.
  • the fibre layer prepared by its electrostatic spinning under the same conditions as in examples 1 and 2 then contained 91 to 97% of fibres having diameter up to 1000 nanometers, thus nanofibres, and 3% to 9% of fibres having diameter above 1000 nanometers, thus microfibres.
  • tetraalkylammonium halogenides with four identical alkyls (e.g. tetrabutylammonioum bromide), or with three identical and one different alkyl (e.g. triethylhexylammonium bromide), and with temperature of melting up to 250°C, or of their mixtures.
  • four identical alkyls e.g. tetrabutylammonioum bromide
  • three identical and one different alkyl e.g. triethylhexylammonium bromide
  • the same tetraalkylammonium halogenides with four identical alkyls or tetraalkylammonium halogenide with three identical and one different alkyl and temperature of melting up to 250°C, possibly their mixtures, may be used as conducting agent also at electrostatic spinning of the melt 4 of copolymer of ethylen-acrylic acid with 5% content of acrylic acid.
  • the total part of conducting agent in the melt 4 thus varies from 5 to 20% by weight, preferably from 8 to 12% by weight.
  • the melt 4 was prepared by melting of 27 g of copolymer of ethylene- acrylic acid with 5% content of acrylic acid with Mn 1800 and 3 g of tetrabutylammonium iodide - i.e. 10% by weight at temperature of 180°C. After homogenisation in double screw extruder, which was running for period of 10 minutes, the melt 4 was positioned into reservoir 5 of the device for electrostatic spinning in variant represented in Fig. 1 and subjected to spinning at temperature of 180°C. The difference of electric voltage brought to spinning elements 32 of the spinning electrode 3 and to the collecting electrode 2 was 120 kV, distance between the nearest spinning element 32 of the spinning electrode 3 and the collecting electrode 2 was 30 cm. The spinning electrode 3 was rotating around its longitudinal axis 30 at speed of 15 rpm.
  • Fig. 3a represents distribution of diameters of fibres of copolymer of ethylene-acrylic acid in this layer, from which it is obvious that diameter of more than 95% of produced fibres varied in the range from 100 to 700 nanometers, so these were nanofibres, only at 5% of fibres their diameter exceeded value of 1000 nanometers. The greatest recorded diameter was 1300 nanometers.
  • the melt 4 of copolymer of ethylene-acrylic acid with 5% content of acrylic acid gradually contained 5% by weight, 15% by weight and 20% by weight of tetrabutylammonium iodide.
  • the layer of fibres produced through its electrostatic spinning under the same conditions as in example 3 then contained 90 to 97% of fibres of diameter up to 1000 nanometers, thus nanofibres, and 3 to 10% fibres having diameter above 1000 nanometers, thus microfibres. Thanks to the same or similar physical properties the same or similar results may be achieved even at usage of other tetraalkylammonium halogenides with four identical alkyls (e.g. tetrabutylammonioum bromide), or with three identical and one different alkyl (e.g. triethylhexylammonium bromide), and with temperature of melting up to 250°C, or of their mixtures.
  • four identical alkyls e.g. tetrabutylammonioum
  • the same tetraalkylammonium halogenides with four identical alkyls or tetraalkylammonium halogenide with three identical and one different alkyl and temperature of melting up to 250°C, possibly their mixtures, may be used as conducting agent also at electrostatic spinning of the melt 4 of polycaprolactone.
  • the total part of conducting agent in the melt 4 thus varies from 1 to 10% by weight, preferably from 3 to 6% by weight.
  • the melt 4 was prepared by melting of 28,5 g of polycaprolactone with Mn 10000, Mw (weight average molar mass) 14000 and 1 ,5 g of tetrabutylammonium iodide - i.e. 5% by weight, at temperature of 180°C. After homogenisation in double screw extruder, which was running for period of 10 minutes, the melt 4 was positioned into reservoir 5 of the device for electrostatic spinning in variant represented in Fig. 1 and subjected to spinning at temperature of 180°C. The difference of electric voltage brought to spinning elements 32 of the spinning electrode 3 and to the collecting electrode 2 was 120 kV, distance between the nearest spinning element 32 of the spinning electrode 3 and the collecting electrode 2 was 30 cm. The spinning electrode 3 was rotating around its longitudinal axis 30 at speed of 12,5 rpm.
  • Fig. 4b represents distribution of diameters of polycaprolactone fibres in this layer, from which it is obvious that diameter of all produced fibres varied in the range from 100 to 300 nanometers, so that these were exclusively nanofibres. The smallest recorded diameter was 64 nanometers, the greatest was 300 nanometers.
  • the melt 4 of polycaprolactone contained 1% by weight, or 10% by weight of tetrabutylammonium iodide.
  • the layer of fibres prepared through its electrostatic spinning under the same conditions as in example 4 then contained exclusively nanofibres having diameter up to 1000 nanometers.
  • tetraalkylammonium halogenides with four identical alkyls (e.g. tetrabutylammonium bromide), or with three identical and one different alkyl (e.g. triethylhexylammonium bromide), and with temperature of melting up to 250°C, or of their mixtures.
  • four identical alkyls e.g. tetrabutylammonium bromide
  • three identical and one different alkyl e.g. triethylhexylammonium bromide
  • the same tetraalkylammonium halogenides with four identical alkyls or tetraalkylammonium halogenides with three identical and one different alkyl and temperature of melting up to 250°C, possible their mixtures are also usable.
  • the part of such conducting agent in the melt 4 thus varies from 3 to 15% by weight, preferably from 5 to 10% by weight.
  • the melt 4 was prepared by melting of 27,9 g of polypropylene with Mn 5000, Mw 14000 and 2,1 g of tetrabutylammonium iodide - i.e. 7% by weight, at temperature of 180°C. After homogenisation in double screw extruder, which was running for period of 10 minutes, the melt 4 was positioned into reservoir 5 of the device for electrostatic spinning in variant represented in Fig. 1 and subjected to spinning at temperature of 210°C. The difference of electric voltage brought to spinning elements 32 of the spinning electrode 3 and to the collecting electrode 2 was 120 kV, distance between the nearest spinning element 32 of the spinning electrode 3 and the collecting electrode 2 was 30 cm. The spinning electrode 3 was rotating around its longitudinal axis 30 at speed of 15 rpm.
  • Fig. 5a represents distribution of diameters of polypropylene fibres in this layer, from which it is obvious that diameter of 97% of produced fibres varied in the range from 200 to 900 nanometers, so that these were nanofibres, and only at less than 3% of fibres their diameter exceeded 1000 nanometers.
  • the melt 4 was prepared by melting of 27g of polypropylene with Mn 5000, Mw 14000 and 3 g of tetrabutylammonium iodide - i.e. 10% by weight, at temperature of 180°C. After homogenisation in double screw extruder, which was running for period of 10 minutes, the melt 4 was positioned into reservoir 5 of the device for electrostatic spinning in variant represented in Fig. 1 and subjected to spinning at temperature of 210°C. The difference of electric voltage brought to spinning elements 32 of the spinning electrode 3 and to the collecting electrode 2 was 120 kV, distance between the nearest spinning element 32 of the spinning electrode 3 and the collecting electrode 2 was 30 cm. The spinning electrode 3 was rotating around its longitudinal axis 30 at speed of 15 rpm.
  • Fig. 6a represents distribution of diameters of polypropylene fibres in this layer, from which it is obvious that diameter of 97% of produced fibres varied in the range from 100 to 900 nanometers, so that these were nanofibres, and only at less than 3% of fibres their diameter exceeded value of 1000 nanometers.
  • melt 4 of polyethylene contained 5% by weight or 15% by weight of tetrabutylammonium iodide.
  • the fibre layer prepared by its electrostatic spinning under the same conditions as in example 6 then contained 94 to 98% of fibres having diameter up to 1000 nanometers, thus nanofibres, and 2% to 6% of fibres having diameter above 1000 nanometers, thus microfibres.
  • tetraalkylphosphonium salt with four identical alkyls (e.g. tetraoctylphosphonium bromide or tetraoctylphosphonium iodide, etc.), tetraalkylphosphonium salts with three identical and one different alkyl (e.g.
  • tributylhexadecylphosphonium bromide tributylhexadecylphosphonium chloride, trihexyltetradecylphosphonium chloride, tributylhexadecylphosphonium tosylate, triisobutyl(methyl)phosphonium tosylate, etc.
  • anion is halogenide, tosylate or bistriflamide, or mixture of such tetraalkylphosphonium salts are usable, regardless their temperature of melting.
  • the part of this conducting agent in the melt 4 of polypropylene varies in the interval from 1 to 5% by weight, preferably from 3 to 4% by weight.
  • the melt 4 was prepared by melting of 29, 1g of polypropylene with Mn 5000, Mw 12000 and 0,9g of tributylhexadecylphosphonium bromide - i.e. 3% by weight, at temperature of 180°C. After homogenisation in double screw extruder, which was running for period of 10 minutes, the melt 4 was positioned into reservoir 5 of the device for electrostatic spanning in variant represented in Fig. 1 and subjected to spinning at temperature of 180°C. The difference of electric voltage brought to spinning elements 32 of the spinning electrode 3 and to the collecting electrode 2 was 120 kV, distance between the nearest spinning element 32 of the spinning electrode 3 and the collecting electrode 2 was 30 cm. The spinning electrode 3 was rotating around its longitudinal axis 30 at speed of 15 rpm.
  • Fig. 7a Through electrostatic spinning a layer of fibres that is represented in the SEM picture in Fig. 7a was produced.
  • Fig. 7b represents distribution of diameters of polypropylene fibres in this layer, from which it is obvious that diameter of all produced fibres varied in the range from 100 to 900 nanometers, so that these were exclusively nanofibres. The smallest recorded diameter was 60 nanometers.
  • melt 4 of polypropylene contained 1% by weight, or 5 % by weight of tributylhexadecylphosphonium bromide.
  • the layer of fibres prepared through its electrostatic spinning under the same conditions as in example 7 then contained exclusively nanofibres having diameter in the range from 100 to 900 nanometers.
  • the melt 4 was prepared by melting of 29, 1g of polypropylene with Mn
  • melt 4 was positioned into reservoir 5 of the device for electrostatic spinning in variant represented in Fig. 1 and subjected to spinning at temperature of 180°C.
  • the difference of electric voltage brought to spinning elements 32 of the spinning electrode 3 and to the collecting electrode 2 was 120 kV, distance between the nearest spinning element 32 of the spinning electrode 3 and the collecting electrode 2 was 30 cm.
  • the spinning electrode 3 was rotating around its longitudinal axis 30 at speed of 15 rpm.
  • Fig. 8a Through electrostatic spinning a layer of fibres that is represented in the SEM picture in Fig. 8a was produced.
  • Fig. 8b represents distribution of diameters of polypropylene fibres in this layer, from which it is obvious that diameter of all produced fibres varied in the range from 100 to 550 nanometers, so that these were exclusively nanofibres. The smallest recorded diameter was 80 nanometers.
  • melt 4 of polypropylene contained 1% by weight, or 5 % by weight of trihexyltetradecylphosphonium chloride.
  • the layer of fibres prepared through its electrostatic spinning under the same conditions as in example 8 then contained exclusively nanofibres having diameter in the range from 80 to 800 nanometers.
  • the melt 4 was prepared by melting of 29, g of polypropylene with Mn 5000, Mw 12000 and 0,9g of triisobutyl(methyl)phosphonium tosylate - i.e. 3% by weight at temperature of 180°C. After homogenisation in double screw extruder, which was running for period of 10 minutes, the melt 4 was positioned into reservoir 5 of the device for electrostatic spinning in variant represented in Fig. 1 and subjected to spinning at temperature of 180°C. The difference of electric voltage brought to spinning elements 32 of the spinning electrode 3 and to the collecting electrode 2 was 120 kV, distance between the nearest spinning element 32 of the spinning electrode 3 and the collecting electrode 2 was 30 cm. The spinning electrode 3 was rotating around its longitudinal axis 30 at speed of 15 rpm.
  • Fig. 9a Through electrostatic spinning a layer of fibres that is represented in the SEM picture in Fig. 9a was produced.
  • Fig. 9b represents distribution of diameters of polypropylene fibres in this layer, from which it is obvious that diameter of all produced fibres varied in the range from 250 to 900 nanometers, so that these were exclusively nanofibres. The smallest recorded diameter was 200 nanometers.
  • melt 4 of polypropylene contained 1% by weight, or 5 % by weight of triisobutyl(methyl)phosphonium tosylate.
  • the layer of fibres prepared through its electrostatic spinning under the same conditions as in example 9 then contained exclusively nanofibres having diameter in the range from 200 to 1000 nanometers.
  • tetraalkylphosphonium salts with four identical alkyls where anion is halogenide, tosylate or bistriflamide e.g. tetraoctylphosphonium bromide, tetraoctylphosphonium iodide, etc.
  • anion is halogenide, tosylate or bistriflamide
  • other tetraalkyphosophonium salts with three identical and one different alkyl, where the anion is halogenide, tosylate or bistriflamide, or their mixtures (e.g.
  • tributylhexadecylphosphonium chloride tributylhexadecylphosphonium tosylate, etc.
  • sodium salts of higher fatty acids like e.g. sodium stearate or sodium octanoate, etc., or their mixtures may be used, while the part of this conducting agent in the melt 4 varies in the interval from 5 to 15% by weight, preferably from 8 to 12% by weight.
  • the melt 4 was prepared by melting of 27g of polypropylene with Mn 5000, Mw 12000 and 3g of sodium stearate - i.e. 10% by weight, at temperature of 260°C. After homogenisation in double screw extruder, which was running for period of 10 minutes, the melt 4 was positioned into reservoir 5 of the device for electrostatic spinning in variant represented in Fig. 1 and subjected to spinning at temperature of 240°C.
  • the difference of electric voltage brought to spinning elements 32 of the spinning electrode 3 and to the collecting electrode 2 was 120 kV, distance between the nearest spinning element 32 of the spinning electrode 3 and the collecting electrode 2 was 30 cm.
  • the spinning electrode 3 was rotating around its longitudinal axis 30 at speed of 15 rpm.
  • Fig. 10a represents distribution of diameters of polypropylene fibres in this layer, from which it is obvious that diameter of all produced fibres varied in the range from 100 to 700 nanometers, so that these were exclusively nanofibres.
  • melt 4 of polypropylene contained 5% by weight, or 15% by weight of sodium stearate.
  • the layer of fibres prepared through its electrostatic spinning under the same conditions as in example 10 then contained exclusively nanofibres having diameter in the range from 100 to 900 nanometers.
  • the melt 4 was prepared by melting of 28, 5g of polypropylene with Mn
  • melt 4 was positioned into reservoir 5 of the device for electrostatic spinning in variant represented in Fig. 1 , and subjected to spinning at temperature of 240°C.
  • the difference of electric voltage brought to spinning elements 32 of the spinning electrode 3 and to the collecting electrode 2 was 120 kV, distance between the nearest spinning element 32 of the spinning electrode 3 and the collecting electrode 2 was 30 cm.
  • the spinning electrode 3 was rotating around its longitudinal axis 30 at speed of 15 rpm.
  • Fig. 1 1b represents distribution of diameters of polypropylene fibres in this layer, from which it is obvious that diameter of all produced fibres varied in the range from 100 to 700 nanometers, so that these were exclusively nanofibres.
  • melt 4 of polypropylene contained 10% by weight, or 15% by weight of sodium octanoate.
  • the layer of fibres prepared through its electrostatic spinning under the same conditions as in example 11 then contained exclusively nanofibres having diameter in the range from 100 to 1000 nanometers.
  • the specified temperatures are optimum for the given combination of polymer and conducting agent, because at higher temperatures thermal decomposition of the conducting agent occurs relatively quickly, so that it does not fulfil the required task, and at lower temperatures viscosity of resultant melt 4 is too high and the melt 4 is not capable of electrostatic spinning.

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

Abstract

Cette invention concerne un procédé de filage électrostatique d'un polymère fondu (4). Dans ledit procédé, un polymère fondu (4) est introduit dans un champ électrique induit entre une électrode tournante (3) et une électrode de collecte (2) ; la conductivité électrique du polymère fondu (4) est accrue par adjonction audit polymère, avant et/ou pendant et/ou après sa préparation, d'une quantité de 1 % à 25 % en poids d'un agent conducteur.
PCT/CZ2011/000070 2010-07-29 2011-07-18 Procédé de filage électrostatique d'un polymère fondu WO2012013167A2 (fr)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9353229B2 (en) 2012-08-14 2016-05-31 Gabae Technologies Llc Compositions incorporating dielectric additives for particle formation, and methods of particle formation using same
US9449736B2 (en) 2013-05-21 2016-09-20 Gabae Technologies Llc High dielectric compositions for particle formation and methods of forming particles using same
JP2017190533A (ja) * 2016-04-11 2017-10-19 花王株式会社 溶融電界紡糸用組成物及びそれを用いた繊維の製造方法
US9796830B2 (en) 2012-10-12 2017-10-24 Gabae Technologies Inc. High dielectric compositions for particle formation and methods of forming particles using same
WO2018173619A1 (fr) 2017-03-22 2018-09-27 東レ株式会社 Procédé de production d'un préimprégné, et procédé de production d'un matériau composite renforcé par des fibres

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1673493A1 (fr) 2003-09-08 2006-06-28 Technicka Univerzita v Liberci Procede de production de nanofibres par filage electrostatique a partir d'une solution polymere et dispositif associe
WO2008011840A2 (fr) 2006-07-24 2008-01-31 Elmarco S.R.O. Électrode de recueil d'un dispositif de production de nanofibres par filage électrostatique de solutions de polymeres
WO2008098526A2 (fr) 2007-02-12 2008-08-21 Elmarco S.R.O. Procédé et dispositif de production de couche de nanoparticules ou de couche de nanofibres à partir de solutions ou de fusions de polymères
EP2059630A1 (fr) 2006-09-04 2009-05-20 Elmarco, S.R.O. Électrode de filage tournante
CZ2009148A3 (cs) 2009-03-09 2010-09-22 Elmarco S.R.O. Zpusob elektrostatického zvláknování polymerní matrice v elektrickém poli o vysoké intenzite
CZ2009149A3 (cs) 2009-03-09 2010-09-22 Elmarco S.R.O. Zpusob ukládání funkcní vrstvy polymerních nanovláken na povrch podkladu
CZ2009525A3 (cs) 2009-08-06 2011-02-16 Elmarco S.R.O. Rotacní zvláknovací elektroda

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070112115A1 (en) * 2005-11-15 2007-05-17 Shalaby Shalaby W Inorganic-organic hybrid micro-/nanofibers
KR20100100814A (ko) * 2007-11-20 2010-09-15 다우 코닝 코포레이션 섬유를 포함하는 물품과 상기 물품을 형성하는 방법
WO2010019649A2 (fr) * 2008-08-13 2010-02-18 Dow Global Technologies Inc. Compositions de polymères activées
WO2010065350A1 (fr) * 2008-11-25 2010-06-10 Dow Global Technologies Inc. Extrusion de polymères organiques à auto-assemblage moléculaire

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1673493A1 (fr) 2003-09-08 2006-06-28 Technicka Univerzita v Liberci Procede de production de nanofibres par filage electrostatique a partir d'une solution polymere et dispositif associe
WO2008011840A2 (fr) 2006-07-24 2008-01-31 Elmarco S.R.O. Électrode de recueil d'un dispositif de production de nanofibres par filage électrostatique de solutions de polymeres
EP2059630A1 (fr) 2006-09-04 2009-05-20 Elmarco, S.R.O. Électrode de filage tournante
WO2008098526A2 (fr) 2007-02-12 2008-08-21 Elmarco S.R.O. Procédé et dispositif de production de couche de nanoparticules ou de couche de nanofibres à partir de solutions ou de fusions de polymères
CZ2009148A3 (cs) 2009-03-09 2010-09-22 Elmarco S.R.O. Zpusob elektrostatického zvláknování polymerní matrice v elektrickém poli o vysoké intenzite
CZ2009149A3 (cs) 2009-03-09 2010-09-22 Elmarco S.R.O. Zpusob ukládání funkcní vrstvy polymerních nanovláken na povrch podkladu
CZ2009525A3 (cs) 2009-08-06 2011-02-16 Elmarco S.R.O. Rotacní zvláknovací elektroda

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PAUL D. DALTON, DIRK GRAFAHREND, KRISTINA KLINKHAMMER, DORIS KLEE, MARTIN MÖLLER: "Electrospinning of Polymer Melts: Phenomenological Observations", POLYMER, vol. 48, 2007, pages 6823 - 6833, XP022313442, DOI: doi:10.1016/j.polymer.2007.09.037

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9353229B2 (en) 2012-08-14 2016-05-31 Gabae Technologies Llc Compositions incorporating dielectric additives for particle formation, and methods of particle formation using same
US9574052B2 (en) 2012-08-14 2017-02-21 Gabae Technologies, Llc Compositions incorporating dielectric additives for particle formation, and methods of particle formation using same
US9796830B2 (en) 2012-10-12 2017-10-24 Gabae Technologies Inc. High dielectric compositions for particle formation and methods of forming particles using same
US9449736B2 (en) 2013-05-21 2016-09-20 Gabae Technologies Llc High dielectric compositions for particle formation and methods of forming particles using same
JP2017190533A (ja) * 2016-04-11 2017-10-19 花王株式会社 溶融電界紡糸用組成物及びそれを用いた繊維の製造方法
WO2018173619A1 (fr) 2017-03-22 2018-09-27 東レ株式会社 Procédé de production d'un préimprégné, et procédé de production d'un matériau composite renforcé par des fibres
US11208535B2 (en) 2017-03-22 2021-12-28 Toray Industries, Inc. Production method for prepreg, and production method for fiber-reinforced composite material

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