WO2009127170A2 - Method for production of nanofibres from fluorated copolymers and terpolymers through electrostatic spinning, nanofibres and fabrics - Google Patents

Method for production of nanofibres from fluorated copolymers and terpolymers through electrostatic spinning, nanofibres and fabrics Download PDF

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Publication number
WO2009127170A2
WO2009127170A2 PCT/CZ2009/000048 CZ2009000048W WO2009127170A2 WO 2009127170 A2 WO2009127170 A2 WO 2009127170A2 CZ 2009000048 W CZ2009000048 W CZ 2009000048W WO 2009127170 A2 WO2009127170 A2 WO 2009127170A2
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Prior art keywords
spinning
solution
fluorated
terpolymer
copolymer
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PCT/CZ2009/000048
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French (fr)
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WO2009127170A3 (en
Inventor
Martin Kovac
Original Assignee
Elmarco S.R.O.
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Publication of WO2009127170A2 publication Critical patent/WO2009127170A2/en
Publication of WO2009127170A3 publication Critical patent/WO2009127170A3/en

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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
    • D01D5/0007—Electro-spinning
    • D01D5/0015—Electro-spinning characterised by the initial state of the material
    • D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
    • D01D5/0038—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion the fibre formed by solvent evaporation, i.e. dry electro-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
    • 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
    • D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
    • 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
    • D01F6/32—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising halogenated hydrocarbons as the major constituent

Definitions

  • the invention relates to a method for production of nanofibres from fluorated copolymers and terpolymers through electrostatic spinning. Next to this, the invention relates to nanofibres and a fabric comprising a layer of nanofibres.
  • Fluorated copolymers and terpolymers feature certain properties, which would be suitable for utilisation in nanofibrous layers. Fibrous planar formations from this polymer promise similar or better properties than the current semipermeable fabrics, serving to create semipermeable membranes, e.g. in clothes and footwear.
  • Fluorated copolymers and terpolymers are soluble in a not large spectrum of solvents, out of which usual are aliphatic ketones, or aromatic hydrocarbons. Nevertheless it is not possible to produce the nanofibres through electrostatic spinning from solutions in these solvents with good result because the created fibres are not of a submicrone character, the layers of these fibres comprise numbers of structure defects, and the spinning process does not run continually.
  • US 4.878.908 discloses the production of fibres through electrostatic spinning of aqueous dispersion with PTFE particles having dimensions of 0,22 microns in a mixture with aqueous solution of polyethylene oxide (PEO), while after a thermal sintering there are produced the fibres having diameter of 1 ,0 to 5,0 micrometers, thus the microfibres.
  • the fabrics made of these fibres do not show such advantageous properties like fabrics of nanofibres, especially they do not have such a large specific surface at a very low basis weight.
  • US 2007/0274862 further discloses a testing element to detect presence of certain substances in liquids, which in one of possible embodiments comprises fluorated or partially fluorated polymers.
  • a testing element to detect presence of certain substances in liquids, which in one of possible embodiments comprises fluorated or partially fluorated polymers.
  • the goal of the invention is to propose a method for production of nanofibres from fluorated copolymers and terpolymers through electrostatic spinning, which would remedy disadvantages of background art.
  • the goal of the invention has been achieved through the method for production of nanofibres from solution of fluorated copolymer or terpolymer according to the invention, whose principle consists in that the fluorated copolymer or terpolymer is before spinning dissolved in a solvent system based on a mixture of a liquid amide (e. g.
  • the produced solution is capable of electrostatic spinning with results corresponding to electrostatic spinning of to date common spinnable polymer solutions. It is also possible to subject to a spinning a mixed solution of various fluorated copolymers or terpolymers or mixture of these polymers with solid component.
  • the fluorated copolymer or terpolymer is before spinning dissolved in a solvent system on basis of a mixture of liquid tertiary amide, and/or dimethyl sulfoxide and aliphatic ketone with maximum of seven atoms of carbon in molecule and/or liquid ester of aliphatic carboxylic acids, and this solution is brought into electrostatic field between a spinning electrode and a collecting electrode.
  • the fluorated copolymer or terpolymer is before spinning dissolved in a solvent system on basis of a mixture of liquid tertiary amide and/or dimethyl sulfoxide and aliphatic ketone with maximum of seven atoms of carbon in molecule and/or liquid ester of aliphatic carboxylic acids with maximum of six atoms of carbon, and this solution is brought into electrostatic field between the spinning electrode and the collecting electrode.
  • Stable and repeatable spinning results could be achieved by a solvent system, at which the aliphatic ketone is 4-methyl-pentan-2-on or heptan-2-on or their mixture.
  • liquid amide is dimethylformamide, dimethylacetamide, N-methyl-pyrrolidone, or hexamethylphosphoramide or their mixture. Nevertheless it is possible to use any from the above mentioned solvent systems depending on content of a particular copolymer or terpolymer.
  • viscosity of the solution subject to spinning is within the range from 50 to 5000 mPa.S, advantageously in the range between 150 and 2000 mPa.S, and the best between 300 and 1000 mPa.s, while it is possible to perform spinning of solutions with higher viscosity in dependence on their content.
  • the solutions with lower viscosity as a rule show ..spraying" (i.e. they create nanoparticles and not nanofibres), but in dependence on content of the solution, it is possible in some cases to produce very thin nanofibres.
  • Advantageous volume ratio of liquid amide and aliphatic ketone in solution for spinning is within interval from 4 : 1 to 1 : 4, while the best results in spinning are achieved if the ratio of liquid amide and aliphatic ketone in solution for spinning is from 3:1 to 1 :3.
  • Such solutions of fluorated copolymers and terpolymers are able of continuous electrostatic spinning upon production of nanofibres, while good spinning results are achieved when the solution of copolymer or terpolymer is in electrostatic field for spinning to be found on surface of active zone of spinning means of the spinning electrode.
  • the spinning electrode is with advantage formed of rotating spinning electrode of an oblong shape, which extends by a section of its perimeter into the solution of fluorated copolymer, or terpolymer in a reservoir.
  • such spinning electrode comprises a couple of faces made of electrically non-conducting material, in between which there are positioned spinning members formed of a wire, which are divided equally along the perimeter, parallel with axis of rotation and mutually electrically connected in conductive manner. It may also be advantageous, if the solution of fluorated copolymer, or terpolymer is in electrostatic field for spinning to be found on a surface of an active spinning zone of a wire of the spinning means.
  • Active spinning zone of the wire is within the course of spinning in a stable position towards the collecting electrode and the solution of fluorated copolymer or terpolymer is delivered to the active spinning zone of the wire through deposition or by movement of the wire in direction of its length.
  • the principle of the invention lies in nanofibres, which are produced from fluorated copolymer or terpolymer through electrostatic spinning.
  • the principle of the invention also lies in the fabric comprising a layer of nanofibres, which are produced from fluorated copolymer or terpolymer through electrostatic spinning.
  • Such device is represented for example by the device known from the CZ patent 294274, which comprises rotatably mounted spinning electrode extending by a section of its perimeter into the polymer solution stored in a reservoir.
  • the spinning electrode carries out upon its rotation the polymer solution on its surface into the electrostatic spinning field of a high intensity, while a portion of its surface which is to be found against the collecting electrode represents an active spinning zone of the spinning electrode.
  • Structure of the rotating spinning electrode may vary in dependence on technology and particular requirements, while it can correspond to the spinning electrode described for example in CZ PV 2005-360 or CZ PV 2006-545.
  • rotating spinning electrode is not a condition, because spinning of solution of fluorated copolymers or terpolymers runs successfully also at application of the wire spinning electrodes known from CZ PV 2007-485.
  • the active spinning zone is during the spinning process in a stable position towards the collecting electrode, while the solution for spinning is delivered to the active spinning zone either by deposition or by motion of the wire in direction of its length.
  • non-ionising cylindric collecting electrode known from CZ PV 2006-477 is used preferably, while at some applications it may be advantageous to use another collecting electrode.
  • the solution being found on the active spinning zone of the spinning electrode is due to action of force of electrostatic spinning field in a known procedure transformed into nanofibres, which further deposit on a suitable substrate, that may be the planar or linear formation formed in principle of any material with various electric properties.
  • a suitable substrate that may be the planar or linear formation formed in principle of any material with various electric properties.
  • Exemplary conditions under which the below mentioned solutions of fluorated copolymers and terpolymers were subject to spinning, are as follows: a high voltage of direct current of 7OkV was continuously supplied to the spinning electrode, while the collecting electrode was grounded; rotation speed of the spinning electrode 6 rot/min; shift of the substrate 20 cm/min; relative humidity of environment 20% at the temperature of 23°C. Nevertheless these values are illustrative only for laboratory conditions, under which the verification tests were performed. The principle of the invention is applicable even under substantially different conditions.
  • the solution for spinning was prepared so that 75 g of dimethylformamide of technical purity was added to 75 g of 30% by weight of ETFE-terpolymer solution in 4-methyl-pentan-2-on upon constant mixing by mechanic stirrer in an enclosed vessel at the temperature of 20°C within 5 minutes. At the same temperature the solution was subject to mixing for another 60 min.
  • the produced solution had a concentration of ETFE terpolymer 15% by weight and the weight ratio of solvents was approximately 2:3 (4-methyl-pentan- 2-on : dimethylformamide). In contrary way, i.e.
  • Example 3 Solution of ETFE-terpolymer dissolved in a mixture of 4-methyl-pentan- 2-on and 1-methyl-2-pyrrolidone at the weight ratio of 2:3 of 15% by weight concentration and viscosity of 1150 mPa.s.
  • Layers of nanofibres produced through electrostatic spinning of fluorated copolymer or terpolymer have advantageous properties, as such nanofibrous layer is permeable for water vapour, but at the same time it is hydrophobic, thus non-permeable for water. Thanks to this the layer of nanofibres in combination with carrying layer, on which the layer of nanofibres is deposited, and protective layer, which protects the layer of nanofibres from other side before mechanical damage, may be used in the same way as the known semipermeable membranes, especially in outdoor and sportswear and footwear.
  • the carrying layer is vapour-permeable as well as water-permeable and creates with advantage the inner layer of clothes or footwear or it is combined with this layer.
  • the protective layer is with advantage formed of outer layer of the clothes and it is vapour-permeable as well as water-permeable and its main task is to protect the nanofibrous layer against damage.
  • the basis weight of nanofibrous layer varies from 2 g/m 2 to 20 g/m 2 , with advantage from 3 g/m 2 to 10 g/m 2 .
  • the nanofibrous layer may be perforated with the goal to increase the vapour-permeability while the water repellency is preserved.
  • the nanofibrous layers of fluorated copolymer or terpolymer according to the invention are further usable for example at production of vapour-permeable membranes or filters for various applications.
  • the composition of the solution being subject to spinning may be changed, while e.g. by increasing its electric conductivity, the diameter of nanofibres is reduced.
  • One of possibilities how to increase the electric conductivity of solution is e.g. adding of a suitable quantity of a quarternary ammonium salt.

Abstract

The invention relates to the method for production of nanofibres from fluorated copolymers and terpolymers through electrostatic spinning. The fluorated copolymer or terpolymer is before spinning dissolved in solvent system on basis of a mixture of liquid amide (e. g. DMF, DMAc, HMPA, N- methylpyrollidone) or DMSO and aliphatic ketone with maximum of ten atoms of carbon in molecule and this solution is brought into the electrostatic field between a spinning electrode and a collecting electrode.

Description

Method for production of nanofibres from fluorated copolymers and terpolymers through electrostatic spinning, nanofibres and fabrics
Technical field
The invention relates to a method for production of nanofibres from fluorated copolymers and terpolymers through electrostatic spinning. Next to this, the invention relates to nanofibres and a fabric comprising a layer of nanofibres.
Background art
Fluorated copolymers and terpolymers feature certain properties, which would be suitable for utilisation in nanofibrous layers. Fibrous planar formations from this polymer promise similar or better properties than the current semipermeable fabrics, serving to create semipermeable membranes, e.g. in clothes and footwear.
Fluorated copolymers and terpolymers are soluble in a not large spectrum of solvents, out of which usual are aliphatic ketones, or aromatic hydrocarbons. Nevertheless it is not possible to produce the nanofibres through electrostatic spinning from solutions in these solvents with good result because the created fibres are not of a submicrone character, the layers of these fibres comprise numbers of structure defects, and the spinning process does not run continually.
Beside others, US 4.878.908 discloses the production of fibres through electrostatic spinning of aqueous dispersion with PTFE particles having dimensions of 0,22 microns in a mixture with aqueous solution of polyethylene oxide (PEO), while after a thermal sintering there are produced the fibres having diameter of 1 ,0 to 5,0 micrometers, thus the microfibres. The fabrics made of these fibres do not show such advantageous properties like fabrics of nanofibres, especially they do not have such a large specific surface at a very low basis weight.
US 2007/0274862 further discloses a testing element to detect presence of certain substances in liquids, which in one of possible embodiments comprises fluorated or partially fluorated polymers. Production course of these nanofibres through electrostatic spinning and its conditions are not described in any manner in this document, and due to the above mentioned fact it could be reasonably supposed, if ever these are nanofibres, they show numbers of surface defects and are not suitable for practical application either for industrial production.
The goal of the invention is to propose a method for production of nanofibres from fluorated copolymers and terpolymers through electrostatic spinning, which would remedy disadvantages of background art.
Principle of the invention
The goal of the invention has been achieved through the method for production of nanofibres from solution of fluorated copolymer or terpolymer according to the invention, whose principle consists in that the fluorated copolymer or terpolymer is before spinning dissolved in a solvent system based on a mixture of a liquid amide (e. g. dimethylformamide, dimethylacetamide, or other amide) and/or dimethyl sulfoxide and at least one solvent from the group of aliphatic ketone with maximum of ten atoms of carbon in molecule and/or liquid ester of aliphatic carboxylic acids and/or tetrahydrofuran in a suitable mutual ratio, and this solution is brought into the electrostatic field between a spinning electrode and a collecting electrode.
Due to dissolution in the given solvent system the produced solution is capable of electrostatic spinning with results corresponding to electrostatic spinning of to date common spinnable polymer solutions. It is also possible to subject to a spinning a mixed solution of various fluorated copolymers or terpolymers or mixture of these polymers with solid component.
According to the claim 2 it is advantageous, if the fluorated copolymer or terpolymer is before spinning dissolved in a solvent system on basis of a mixture of liquid tertiary amide, and/or dimethyl sulfoxide and aliphatic ketone with maximum of seven atoms of carbon in molecule and/or liquid ester of aliphatic carboxylic acids, and this solution is brought into electrostatic field between a spinning electrode and a collecting electrode.
It is further advantageous if the fluorated copolymer or terpolymer is before spinning dissolved in a solvent system on basis of a mixture of liquid tertiary amide and/or dimethyl sulfoxide and aliphatic ketone with maximum of seven atoms of carbon in molecule and/or liquid ester of aliphatic carboxylic acids with maximum of six atoms of carbon, and this solution is brought into electrostatic field between the spinning electrode and the collecting electrode.
Stable and repeatable spinning results could be achieved by a solvent system, at which the aliphatic ketone is 4-methyl-pentan-2-on or heptan-2-on or their mixture.
At the same time it is advantageous, if the liquid amide is dimethylformamide, dimethylacetamide, N-methyl-pyrrolidone, or hexamethylphosphoramide or their mixture. Nevertheless it is possible to use any from the above mentioned solvent systems depending on content of a particular copolymer or terpolymer.
For the method according to the invention is it further advantageous, if viscosity of the solution subject to spinning is within the range from 50 to 5000 mPa.S, advantageously in the range between 150 and 2000 mPa.S, and the best between 300 and 1000 mPa.s, while it is possible to perform spinning of solutions with higher viscosity in dependence on their content. The solutions with lower viscosity as a rule show ..spraying" (i.e. they create nanoparticles and not nanofibres), but in dependence on content of the solution, it is possible in some cases to produce very thin nanofibres.
Advantageous volume ratio of liquid amide and aliphatic ketone in solution for spinning is within interval from 4 : 1 to 1 : 4, while the best results in spinning are achieved if the ratio of liquid amide and aliphatic ketone in solution for spinning is from 3:1 to 1 :3.
To reduce the resultant diameter of nanofibres it is advantageous if the electric conductivity of solution for spinning is increased still before spinning. This increase may be performed, for example, by addition of quartemary ammonium salt.
Such solutions of fluorated copolymers and terpolymers are able of continuous electrostatic spinning upon production of nanofibres, while good spinning results are achieved when the solution of copolymer or terpolymer is in electrostatic field for spinning to be found on surface of active zone of spinning means of the spinning electrode.
At the same time it is advantageous, if the solution of fluorated copolymers and terpolymers is delivered into electrostatic field for spinning by a surface of the spinning electrode.
According to the claim 15, the spinning electrode is with advantage formed of rotating spinning electrode of an oblong shape, which extends by a section of its perimeter into the solution of fluorated copolymer, or terpolymer in a reservoir.
In advantageous embodiment according to the claim 16 such spinning electrode comprises a couple of faces made of electrically non-conducting material, in between which there are positioned spinning members formed of a wire, which are divided equally along the perimeter, parallel with axis of rotation and mutually electrically connected in conductive manner. It may also be advantageous, if the solution of fluorated copolymer, or terpolymer is in electrostatic field for spinning to be found on a surface of an active spinning zone of a wire of the spinning means.
Active spinning zone of the wire is within the course of spinning in a stable position towards the collecting electrode and the solution of fluorated copolymer or terpolymer is delivered to the active spinning zone of the wire through deposition or by movement of the wire in direction of its length.
Next to this, the principle of the invention lies in nanofibres, which are produced from fluorated copolymer or terpolymer through electrostatic spinning.
At the same time it is advantageous if the nanofibres are produced in a method according to any of the claims 1 to 18.
The principle of the invention also lies in the fabric comprising a layer of nanofibres, which are produced from fluorated copolymer or terpolymer through electrostatic spinning.
At the same time it is advantageous if the nanofibres are produced in a method according to any of the claims 1 to 18.
At higher basis weights of fabric, it is advantageous if it is perforated.
Examples of embodiment
For spinning of below mentioned exemplary solutions of fluorated copolymers and terpolymers, there was used a device for electrostatic spinning of polymer solutions in electrostatic spinning field created between a spinning electrode and a collecting electrode by bringing a high voltage of direct current to one of the electrodes and a high voltage of direct current of opposite polarity to the second electrode, possibly by grounding of one of them. Such device is represented for example by the device known from the CZ patent 294274, which comprises rotatably mounted spinning electrode extending by a section of its perimeter into the polymer solution stored in a reservoir. The spinning electrode carries out upon its rotation the polymer solution on its surface into the electrostatic spinning field of a high intensity, while a portion of its surface which is to be found against the collecting electrode represents an active spinning zone of the spinning electrode. Structure of the rotating spinning electrode may vary in dependence on technology and particular requirements, while it can correspond to the spinning electrode described for example in CZ PV 2005-360 or CZ PV 2006-545.
Application of the rotating spinning electrode is not a condition, because spinning of solution of fluorated copolymers or terpolymers runs successfully also at application of the wire spinning electrodes known from CZ PV 2007-485. At these electrodes the active spinning zone is during the spinning process in a stable position towards the collecting electrode, while the solution for spinning is delivered to the active spinning zone either by deposition or by motion of the wire in direction of its length.
In all cases the non-ionising cylindric collecting electrode known from CZ PV 2006-477 is used preferably, while at some applications it may be advantageous to use another collecting electrode.
The solution being found on the active spinning zone of the spinning electrode is due to action of force of electrostatic spinning field in a known procedure transformed into nanofibres, which further deposit on a suitable substrate, that may be the planar or linear formation formed in principle of any material with various electric properties. In the below described examples of embodiment is as a substrate used the polypropylene spunbond of a basis weight of 19 g/m2 with antistatic surface finish.
Exemplary conditions, under which the below mentioned solutions of fluorated copolymers and terpolymers were subject to spinning, are as follows: a high voltage of direct current of 7OkV was continuously supplied to the spinning electrode, while the collecting electrode was grounded; rotation speed of the spinning electrode 6 rot/min; shift of the substrate 20 cm/min; relative humidity of environment 20% at the temperature of 23°C. Nevertheless these values are illustrative only for laboratory conditions, under which the verification tests were performed. The principle of the invention is applicable even under substantially different conditions.
Example 1
The solution for spinning was prepared so that 75 g of dimethylformamide of technical purity was added to 75 g of 30% by weight of ETFE-terpolymer solution in 4-methyl-pentan-2-on upon constant mixing by mechanic stirrer in an enclosed vessel at the temperature of 20°C within 5 minutes. At the same temperature the solution was subject to mixing for another 60 min. The produced solution had a concentration of ETFE terpolymer 15% by weight and the weight ratio of solvents was approximately 2:3 (4-methyl-pentan- 2-on : dimethylformamide). In contrary way, i.e. by dissolution of ETFE- terpolymer first in dimethylformamide and only after then in 4-methyl-pentan-2- on, the solution only up to the weight ratio of 4-methyl-pentan-2-on : dimethylformamide 3:7 may be produced due to lower solubility of polymer in dimethylformamide. Through a combined addition of solvents nearly any ratio between the components of solvents may be achieved.
The distance between the collecting electrode and spinning electrode 180 mm.
Example 2
Solution of ETFE-terpolymer dissolved in a mixture of 4-methyl-pentan-2- on and dimethylacetamide at the weight ratio of 7:2 at concentration of 25% by weight and viscosity about 500OmPa. s.
The distance between the collecting electrode and spinning electrode 210 mm.
Example 3 Solution of ETFE-terpolymer dissolved in a mixture of 4-methyl-pentan- 2-on and 1-methyl-2-pyrrolidone at the weight ratio of 2:3 of 15% by weight concentration and viscosity of 1150 mPa.s.
The distance between the collecting electrode and spinning electrode 210 mm.
Example 4
Solution of ETFE-terpolymer dissolved in a mixture of 4-methyl-pentan-2- on and dimethylacetamide at the weight ratio of 1 :2 of 12% by weight concentration and viscosity of 210 mPa.s.
The distance between the collecting electrode and spinning electrode 210 mm.
Example 5
Solution of ETFE-terpolymer dissolved in a mixture of 4-methyl-pentan-2- on and dimethylacetamide at the weight ratio of 2:3 of 15% by weight concentration and viscosity of 780 mPa.S.
The distance between the collecting electrode and spinning electrode 210 mm.
Example 6
Solution of ETFE-terpolymer dissolved in a mixture of 4-methyl-pentan-2- on and hexamethyl phosphoramide at the weight ratio of 2:3 and of 15% concentration. The distance between the collecting electrode and spinning electrode 210 mm.
Example 7
Solution of ETFE-terpolymer dissolved in a mixture of heptan-2-on and dimethylformamide at the volume ratio of 1 :2 of 15% by weight concentration.
The distance between the collecting electrode and spinning electrode 210 mm.
In all cases a long-term continual spinning process has been achieved and at the same time the diameter of nanofibres did not exceed 1000nm, and the diameter of majority of the nanofibres varied within interval from 200 to 700 nm.
Layers of nanofibres produced through electrostatic spinning of fluorated copolymer or terpolymer have advantageous properties, as such nanofibrous layer is permeable for water vapour, but at the same time it is hydrophobic, thus non-permeable for water. Thanks to this the layer of nanofibres in combination with carrying layer, on which the layer of nanofibres is deposited, and protective layer, which protects the layer of nanofibres from other side before mechanical damage, may be used in the same way as the known semipermeable membranes, especially in outdoor and sportswear and footwear. The carrying layer is vapour-permeable as well as water-permeable and creates with advantage the inner layer of clothes or footwear or it is combined with this layer. The protective layer is with advantage formed of outer layer of the clothes and it is vapour-permeable as well as water-permeable and its main task is to protect the nanofibrous layer against damage. Air permeability and water repellency expressively exceeds the properties of to date known membranes from expanded PTFE, etc. At the same time the basis weight of nanofibrous layer varies from 2 g/m2 to 20 g/m2, with advantage from 3 g/m2 to 10 g/m2. At higher values of basis weight the nanofibrous layer may be perforated with the goal to increase the vapour-permeability while the water repellency is preserved. The nanofibrous layers of fluorated copolymer or terpolymer according to the invention are further usable for example at production of vapour-permeable membranes or filters for various applications.
By modifying the composition of the solution being subject to spinning the resultant diameter of produced nanofibres may be changed, while e.g. by increasing its electric conductivity, the diameter of nanofibres is reduced. One of possibilities how to increase the electric conductivity of solution is e.g. adding of a suitable quantity of a quarternary ammonium salt.

Claims

1. The method for production of nanofibres from fluorated copolymer or terpolymer through electrostatic spinning, characterised in that the fluorated copolymer or terpolymer is before spinning dissolved in a solvent system on basis of liquid amide and/or dimethyl sulfoxide and at least one solvent from the group of aliphatic ketone with maximum of ten atoms of carbon in molecule, a liquid ester of aliphatic carboxylic acids, tetrahydrofuran in a suitable mutual ratio, and this solution is brought into the electrostatic field between a spinning electrode and a collecting electrode.
2. The method according to the claim 1 , characterised in that the fluorated copolymer or terpolymer is before spinning dissolved in the solvent system on basis of a mixture of liquid tertiary amide, and/or dimethyl sulfoxide and aliphatic ketone with maximum of seven atoms of carbon in molecule and/or liquid ester of aliphatic carboxylic acids and this solution is brought into electrostatic field between the spinning electrode and the collecting electrode.
3. The method according to the claim 1 or 2, characterised in that the fluorated copolymer or terpolymer is before spinning dissolved in the solvent system on basis of a mixture of liquid tertiary amide and/or dimethyl sulfoxide and aliphatic ketone with maximum of seven atoms of carbon in molecule and/or liquid ester of aliphatic carboxylic acids with maximum of six atoms of carbon, and this solution is brought into electrostatic field between the spinning electrode and the collecting electrode.
4. The method according to any of the claims 1 to 3, characterised in that the aliphatic ketone is the 4-methyl-pentan-2-on or heptan-2-on or their mixture.
5. The method according to any of the claims 1 to 3, characterised in that the liquid amide is dimethylformamide, dimethylacetamide, N-methyl- pyrrolidone, or hexamethylphosphoramide or their mixture.
6. The method according to any of the claims 1 to 5, characterised in that the viscosity of solution of fluorated copolymer or terpolymer is within the range of 50 - 5000 mPa.s.
7. The method according to the claim 1 to 5, characterised in that the viscosity of solution of fluorated copolymer or terpolymer in solution is within the range of 150-2000 mPa.s.
8. The method according to the claim 1 to 5, characterised in that the viscosity of solution of fluorated copolymer or terpolymer in solution is within the range of 300-1000 mPa.s.
9. The method according to any of the claims 1 to 8, characterised in that the volume ratio of liquid amide and aliphatic ketone in solution is within the range from 4 : 1 to 1 : 4.
10. The method according to any of the claims 1 to 8, characterised in that the volume ratio of liquid amide and aliphatic ketone in solution is within the range from 3 : 1 do 1 : 3.
11. The method according to any of the claims 1 to 10, characterised in that the electric conductivity of solution is increased before spinning.
12. The method according to the claim 11 , characterised in that the electric conductivity of solution is increased by addition of a quartemary ammonium salt.
13. The method according to any of the previous claims, characterised in that the solution of fluorated copolymer or terpolymer in electrostatic field for spinning is to be found on surface of an active zone of spinning means of the spinning electrode.
14. The method according to the claim 13, characterised in that the solution of fluorated copolymer and terpolymer is delivered into electrostatic field for spinning by surface of the spinning electrode.
15. The method according to the claim 14, characterised in that the spinning electrode is formed of rotating spinning electrode of an oblong shape, which extends by a section of its perimeter into the solution of fluorated copolymer, or terpolymer in a reservoir.
16. The method according to the claim 15, characterised in that the rotating spinning electrode comprises a couple of faces made of electrically non-conducting material, in between which there are positioned spinning members formed of a wire divided equally along the perimeter, parallel with axis of rotation and mutually electrically connected in a conductive manner.
17. The method according to the claim 13, characterised in that the solution of fluorated copolymer, or terpolymer is in electrostatic field for spinning to be found on surface of active spinning zone of wire of the spinning means.
18. The method according to the claim 17, characterised in that the active spinning zone of the wire is within the course of spinning in a stable position towards the collecting electrode and the solution of fluorated copolymer or terpolymer is delivered to the active spinning zone of the wire through deposition or by movement of the wire in direction of its length.
19. The nanofibres characterised in that they are produced from fluorated copolymer or terpolymer through electrostatic spinning.
20. The nanofibres according to the claim 19, characterised in that they are produced according to any of the claims 1 to 18.
21. The fabric comprising a layer of nanofibres, characterised in that the nanofibres are produced from fluorated copolymer or terpolymer through electrostatic spinning.
22. The fabric comprising a layer of nanofibres, characterised in that the nanofibres are produced by a method according to any of the claims 1 to 18.
23. The fabric according to the claim 22, characterised in that it is perforated.
PCT/CZ2009/000048 2008-04-15 2009-04-03 Method for production of nanofibres from fluorated copolymers and terpolymers through electrostatic spinning, nanofibres and fabrics WO2009127170A2 (en)

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Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2683857A2 (en) * 2011-03-09 2014-01-15 Board of Regents, The University of Texas System Apparatuses and methods for the production of fibers
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US9034031B2 (en) 2009-08-07 2015-05-19 Zeus Industrial Products, Inc. Prosthetic device including electrostatically spun fibrous layer and method for making the same
US9198999B2 (en) 2012-09-21 2015-12-01 Merit Medical Systems, Inc. Drug-eluting rotational spun coatings and methods of use
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US9655710B2 (en) 2011-01-28 2017-05-23 Merit Medical Systems, Inc. Process of making a stent
US9796830B2 (en) 2012-10-12 2017-10-24 Gabae Technologies Inc. High dielectric compositions for particle formation and methods of forming particles using same
US9827703B2 (en) 2013-03-13 2017-11-28 Merit Medical Systems, Inc. Methods, systems, and apparatuses for manufacturing rotational spun appliances
US9856588B2 (en) 2009-01-16 2018-01-02 Zeus Industrial Products, Inc. Electrospinning of PTFE
US9987833B2 (en) 2012-01-16 2018-06-05 Merit Medical Systems, Inc. Rotational spun material covered medical appliances and methods of manufacture
US10010395B2 (en) 2012-04-05 2018-07-03 Zeus Industrial Products, Inc. Composite prosthetic devices
US10028852B2 (en) 2015-02-26 2018-07-24 Merit Medical Systems, Inc. Layered medical appliances and methods
US10507268B2 (en) 2012-09-19 2019-12-17 Merit Medical Systems, Inc. Electrospun material covered medical appliances and methods of manufacture
US10799617B2 (en) 2013-03-13 2020-10-13 Merit Medical Systems, Inc. Serially deposited fiber materials and associated devices and methods
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1431697A (en) * 1972-04-22 1976-04-14 Teijin Ltd Decorative film laminates slit fibres thereof and method for their preparation
US20020100725A1 (en) * 2001-01-26 2002-08-01 Lee Wha Seop Method for preparing thin fiber-structured polymer web
WO2006089531A2 (en) * 2005-02-24 2006-08-31 Philipps-Universität Marburg Hydrophobic fluorinated polymer surfaces
WO2006131081A1 (en) * 2005-06-07 2006-12-14 Elmarco, S.R.O. A method and device for production of nanofibres from the polymeric solution through electrostatic spinning
WO2007013858A1 (en) * 2005-07-25 2007-02-01 National University Of Singapore Method & apparatus for producing fiber yarn
WO2008028428A1 (en) * 2006-09-04 2008-03-13 Elmarco S.R.O. Rotary spinning electrode

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101069821A (en) * 2007-03-06 2007-11-14 天津大学 Cross-linked modified PVOF-HFP superfine fiber film and preparing method

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1431697A (en) * 1972-04-22 1976-04-14 Teijin Ltd Decorative film laminates slit fibres thereof and method for their preparation
US20020100725A1 (en) * 2001-01-26 2002-08-01 Lee Wha Seop Method for preparing thin fiber-structured polymer web
WO2006089531A2 (en) * 2005-02-24 2006-08-31 Philipps-Universität Marburg Hydrophobic fluorinated polymer surfaces
WO2006131081A1 (en) * 2005-06-07 2006-12-14 Elmarco, S.R.O. A method and device for production of nanofibres from the polymeric solution through electrostatic spinning
WO2007013858A1 (en) * 2005-07-25 2007-02-01 National University Of Singapore Method & apparatus for producing fiber yarn
WO2008028428A1 (en) * 2006-09-04 2008-03-13 Elmarco S.R.O. Rotary spinning electrode

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 200833 Thomson Scientific, London, GB; AN 2008-E72586 XP002547886 & CN 101 069 821 A (UNIV TIANJIN) 14 November 2007 (2007-11-14) *
WANG M; VAIL S A; KEIRSTEAD A E; MARQUEZ M; GUST D; GARCIA A A: "Preparation of photochromic poly(vinylidene fluoride-co-hexafluoropropylene) fibers by electrospinning" POLYMER, ELSEVIER SCIENCE PUBLISHERS B.V, GB, vol. 50, no. 16, 31 July 2009 (2009-07-31) , pages 3974-3980, XP026351544 ISSN: 0032-3861 [retrieved on 2009-06-26] *
YEE; KOTAKI W A; LIU M; LU Y; X: "Morphology, polymorphism behavior and molecular orientation of electrospun poly(vinylidene fluoride) fibers" POLYMER, ELSEVIER SCIENCE PUBLISHERS B.V, GB, vol. 48, no. 2, 18 January 2007 (2007-01-18), pages 512-521, XP005824207 ISSN: 0032-3861 *

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