WO2023209037A1 - Filage humide à base microfluidique de fibres polymères solides individuelles - Google Patents

Filage humide à base microfluidique de fibres polymères solides individuelles Download PDF

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Publication number
WO2023209037A1
WO2023209037A1 PCT/EP2023/061015 EP2023061015W WO2023209037A1 WO 2023209037 A1 WO2023209037 A1 WO 2023209037A1 EP 2023061015 W EP2023061015 W EP 2023061015W WO 2023209037 A1 WO2023209037 A1 WO 2023209037A1
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Prior art keywords
liquid
capillary tube
shell
core
fiber
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PCT/EP2023/061015
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English (en)
Inventor
Kongchang Wei
Luciano BOESEL
René Rossi
Wuchao WANG
Khushdeep SHARMA
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Empa Eidgenössische Materialprüfungs- Und Forschungsanstalt
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Publication of WO2023209037A1 publication Critical patent/WO2023209037A1/fr

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    • 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
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • 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
    • D01D5/06—Wet spinning methods
    • 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
    • D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
    • D01D5/30—Conjugate filaments; Spinnerette packs therefor
    • D01D5/34—Core-skin structure; Spinnerette packs therefor
    • 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
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/18—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from other substances

Definitions

  • the invention relates to a method for producing individual solid polymer fibers from a precursor liquid comprising polymerizable and/or cross-linkable polymer precursors by microfluidicbased wet spinning. Furthermore, the invention is directed to a microfluidic-based wet spinning device for producing an individual solid polymer fiber.
  • Synthetic fibers are used in the manufacture of materials in many fields of technology ranging e.g. from optics over textiles to mechanical engineering.
  • synthetic fibers are produced by spinning.
  • continuous filaments or fiber mats are produced by different spinning techniques.
  • melt spinning allows to produce synthetic fibers from molten thermoplastic materials.
  • solution spinning uses spinning solutions comprising precursor materials in a solvent whereby the precursor materials of the spinning solutions are solidified to form the target fibers. Solution spinning can be carried out quite differently.
  • Well-known methods are inter alia dry spinning, wet spinning, dry-jet wet spinning, and electrospinning.
  • fibers which comprise (a) a polymeric core that comprises a core-forming polymer and (b) a polymeric sheath that comprises a sheath-forming polymer that is different than the core-forming polymer.
  • core-forming polymers include, for instance, crosslinked polysiloxanes and thermoplastic polymers, among others.
  • sheath-forming polymers include, for instance, solventsoluble polymers, degradable polymers and hydrogel-forming polymers, among others.
  • KR 10169598 B 1 (Dong-A Univ. Res. Found for Industry-Academy Coop.) relates to a method for manufacturing a polymer fiber using a microfluidic device and, particularly, to a method for manufacturing a polymer fiber manufactured by injecting a precursor solution and a support crosslinking solution to a microfluidic device.
  • the method comprises the steps of: (1) preparing (i) a precursor solution containing a monomer, a crosslinking agent, an alginate, and a photoinitiator, and (ii) an alignate crosslinking solution containing a metal cation; (2) injecting the precursor solution and the alginate crosslinking solution into the microfluidic device to manufacture a metal-alginate support structure; (3) photopolymerizing the monomer by irradiation with a light source in the microfluidic device, in order to manufacture a cross-linked polymer/alginate support composite fiber; and (4) reacting the manufactured cross-linked polymer/alginate support composite fiber with a chelating agent to remove the alginate support from polymer/alginate support composite fiber so as to obtain a cross-linked polymer fiber without support.
  • fibers produced in this manner comprise a considerable amount of imperfections, making them for example unsuitable for optical applications.
  • this method is practical only for producing hydrophilic fibers, of which the precursors are miscible with the alginate aqueous solution. It is however not possible to produce hydrophobic fibers from other precursors that are not miscible with alginate aqueous solutions, such as e.g. polydimethylsiloxane (PDMS) fibers.
  • PDMS polydimethylsiloxane
  • the object of the present invention to provide new and improved solutions for producing polymer fibers.
  • the method should allow to produce individual polymer fibers consisting of different materials and having various thicknesses and lengths in a targeted manner.
  • the solution should make it possible to produce polymer fibers as uniform as possible and in particular having a quality suitable for optical applications.
  • the invention is concerned with a method for producing an individual solid polymer fiber from a precursor liquid comprising aggregatable, polymerizable and/or cross-linkable polymer precursors, especially from a precursor liquid comprising polymerizable and/or cross-linkable polymer precursors, by microfluidic-based wet spinning, the method comprising the steps of: a) Introducing the precursor liquid through a first inlet into a first capillary tube, whereby at least a downstream end of the first capillary tube coaxially protrudes into a second capillary tube, and injecting the precursor liquid into the second capillary tube, to obtain a core flow of the precursor liquid in the second capillary tube; b) Producing a liquid fiber with core-shell structure in the second capillary tube by simultaneously introducing a shell liquid into the second capillary tube through a second inlet such that the second liquid forms a tubular and coaxial shell flow around the core flow of the precursor liquid; c) Optionally, injecting the precursor liquid through a first inlet
  • the inventive method makes use of a removable shell as tubular mold for shaping and trapping the curable polymer precursor in a core channel. This without need of mixing the curable polymer precursor and the shell liquid beforehand. This allows for producing a wider range of individual polymer fibers and by adjusting the dimensions of the capillary tubes, polymer fibers with various thicknesses up to several millimetres and lengths of more than one meter can be produced in a highly targeted manner. Furthermore, the polymer fibers obtainable with the inventive method are highly uniform and, depending on the materials used, even suitable for optical applications.
  • a fiber having a liquid core embedded in a cured shell is produced. This allows for decoupling the curing of the liquid curable polymer precursor from the wet spinning process.
  • steps g) and/or h) take place outside the stationary liquid phase and/or in time after steps a) to e).
  • the inventive method allows to produce high quality continuous polymer optical fibers (POF) even with sensitive functional molecules, e.g. perovskite nanocrystals.
  • polymer opticalfibers having a low modulus of elasticity of ⁇ 3 MPa or even ⁇ 1 MPa are available.
  • Such POF feature an increased sensitivity for small pressures and cannot be produced by common moulding techniques because the fibers would break during demoulding due to the too low modulus of elasticity.
  • polymerizable and/or cross-linkable polymer precursors are selected from polymerizable and/or crosslinkable monomers, oligomers and/or polymers.
  • the precursor liquid comprises: polyols as well as diisocyanates, triisocyanates and/or polyurethane prepolymers, capable of forming polyurethane polymers epoxy resins, optionally with hardeners crosslinkable siloxane polymers, especially polydimethylsiloxane polymers ethylenically unsaturated monomers, especially alkenes, vinyl monomers, alkenyl monomers and/or (meth)acrylates, monomers having amine, carboxyl and/or acyl groups, e.g. amino acids, capable of forming polyamides, and/or monomers and/or oligomers containing active groups for click-chemistry and capable of forming polymers, e.g.
  • monomers and/or oligomers containing groups that react in azidealkyne cycloaddition reactions, thiol-ene reactions, and/or amino-yne reactions monomers selected from a-hydroxy acids, especially lactic acid or its cyclic di-ester lactide, glycolic acid, mandelic acid, and/or citric acid; aggregatable polymers, especially polylactic acid (PLA) and/or polycaprolacton (PCL).
  • PVA polylactic acid
  • PCL polycaprolacton
  • the precursor liquid comprises (meth)acrylates and/or crosslinkable polydimethylsiloxane polymers.
  • aggregatable polymers are polylactic acid (PLA) and/or polycaprolacton (PCL).
  • PLA polylactic acid
  • PCL polycaprolacton
  • Such polymers can be solidified via solvent-exchanged polymer aggregation.
  • aggregatable polymers are dissolved in one or more solvent(s) as the precursor liquid.
  • polymerizable precursors are lactic acid or its cyclic di-ester lactide.
  • polystyrene resin examples include polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyrene resin, polystyren
  • polymerizable precursors are mixtures of crosslinkable siloxane polymers or alkene polymers and/or macromers, e.g. dodecyldimethacrylateand, and (metha)acrylate precursors, especially capable of forming amphiphilic polymer co-networks.
  • the precursor liquid furthermore comprises for example a solvent, a crosslinking agent, a thermal polymerization initiator, a photopolymerization initiator, a chain transfer agent, a functional molecule and/or a molecular weight regulator.
  • these substances are chosen depending on the specific polymerizable and/or cross-linkable polymer precursors and are in particular added in order to enable and control the solidifying of the liquid core in step g).
  • Functional molecules can e.g. be selected from fluorophores, chromophores and/or nanoparticles. Such molecules can for example be incorporated in the fibers to adapt the fibers to specific applications. Especially, functional molecules may comprise nanocrystals, e.g. perovskite nanocrystals.
  • the shell liquid in particular is a solution of a solvent, especially water, and a solvent-soluble non-crosslinked polymer.
  • the shell liquid is a solution of water and a homopolymer and/or a copolymer formed for example from one or more of the following monomers: ethylene oxide, vinyl pyrrolidone, vinyl alcohol, vinyl acetate, vinyl pyridine, methyl vinyl ether, acrylic acid and salts thereof, methacrylic acid and salts thereof, hydroxyethyl methacrylate, acrylamide, N,N- dimethyl acrylamide, N-hydroxymethyl acrylamide, alkyl oxazolines, saccharide monomers, polysaccharides, dextran, alginate, amino acids, hydrophilic polypeptides, proteins and/or gelatin.
  • monomers ethylene oxide, vinyl pyrrolidone, vinyl alcohol, vinyl acetate, vinyl pyridine, methyl vinyl ether, acrylic acid and salts thereof, methacrylic acid and salts thereof, hydroxyethyl methacrylate, acrylamide, N,N- dimethyl acrylamide, N-hydroxymethyl acrylamide, alkyl
  • the shell liquid is an aqueous hydrogel precursor solution, in particular an aqueous polysaccharide solution.
  • the shell liquid is an aqueous alginate solution, in particular an aqueous alkaline metal alginate solution, e.g. a sodium alginate solution.
  • a concentration of the homopolymer and/or a copolymer, especially the hydrogel precursor, in particular an alginate is from 0.05 - 10 wt%, especially 0.1 - 5 wt%, in particular 1 - 3 wt%.
  • the precursor liquid is essentially immiscible with the shell liquid.
  • step b) a well-defined phase interface between the core and the shell in the liquid fiber can be obtained. Additionally, diffusion of precursor liquid into the cured shell is reduced.
  • step d) the liquid fiber with core-shell structure, optionally having a sheath, as produced in step b) or in step c) preferably is introduced into the stationary liquid phase below the liquid surface of the stationary liquid phase. This reduces turbulences and improves the overall quality of the fibers obtainable.
  • the second capillary tube or the third capillary tube if the latter is present, is submerged in the stationary liquid phase.
  • the third liquid in step c) and/or the stationary liquid phase in step d) comprises or consists of a polar solvent, especially methanol, ethanol and/or water, in particular water.
  • the stationary liquid phase can have a temperature between 0 - 95°C, in particular between 15 - 90°C, especially between room temperature and 80°C.
  • the temperature of the stationary liquid phase is between 15 - 30°C, especially room temperature.
  • the temperature of the stationary liquid phase is an elevated temperature, especially above room temperature, in particular above 30°C. This allows performing a pre-curing step and/or a partial curing of the liquid core in stationary liquid phase.
  • the temperature of the stationary liquid phase is between 45 - 85°C, especially between 55 - 75°C, particularly between 60 - 70°C, e.g. 65°C. These temperatures are especially beneficial when using crosslinkable siloxane polymers, especially polydimethylsiloxane polymers, as precursor liquid and/or when producing PDMS fibers.
  • the third liquid in step c) and/or the stationary liquid phase in step d) is a curing agent for the shell liquid and is selected from an aqueous solution of a salt of a divalent metal cation, especially selected from of Ca 2+ , Mg 2+ , Zn 2+ , Fe 2+ , Cu 2+ , and/or Ba 2+ .
  • an aqueous solution Ca 2+ salt e.g. an aqueous solution of CaCI 2 .
  • a concentration of the salt of the divalent metal cation, especially CaCI 2 , in the aqueous solution is from 0.05 - 10 wt%, especially 0.1 - 5 wt%, in particular 0.5 - 2 wt%.
  • step c) is performed and in step c) a curing agent for the shell liquid selected from an aqueous solution of a salt of divalent metal cation is used as the third liquid.
  • the shell of the liquid fiber with core-shell structure is directly cured through the concentric sheath flow of the third liquid within the third capillary tube.
  • the third liquid forms another tubular mold for shaping and trapping the liquid fiber with core-shell structure. This may further improve uniformity of the liquid fiber.
  • the stationary liquid phase in step d) allows the fibers to be spun-out of the device in a smooth and stable manner.
  • the stationary liquid phase in step d) is an aqueous solution, e.g. water.
  • step c) is not performed and in step d) a curing agent for the shell liquid selected from an aqueous solution of a salt of divalent metal cation is used as the stationary liquid phase.
  • a curing agent for the shell liquid selected from an aqueous solution of a salt of divalent metal cation is used as the stationary liquid phase.
  • the shell of the liquid fiber with coreshell structure is cured within the stationary liquid phase, which in addition allows the fibers to be spun-out of the device in a smooth and stable manner.
  • the shell liquid in the liquid fiber with core-shell structure produced in the second capillary tube, is in direct contact with the precursor liquid at least in a downstream section of the second capillary tube.
  • the downstream end of the first capillary tube is located within the second capillary tube, whereby the downstream end of the first capillary tube, in flow direction of the liquid fiber, in particular is located inside the first half, especially within the first quarter, of the second capillary tube.
  • the downstream end of the second capillary tube in particular is located inside the third capillary tube.
  • at least an outer diameter, especially an inner and the outer diameter, of the second capillary tube tapers, especially step-like, towards the downstream end, in particular to form a second capillary nozzle at least an outer diameter, especially an inner and the outer diameter, of the second capillary tube tapers, especially step-like, towards the downstream end, in particular to form a second capillary nozzle.
  • a length of the tapered section of the first capillary tube is 25 - 75%, especially 40 - 60%, of the whole length of the first capillary tube; and, especially, a length of the tapered section of the second capillary tube is 25 - 75%, especially 40 - 60%, of the whole length of the second capillary tube.
  • the shell liquid and the precursor liquid in the liquid fiber with core-shell structure are separated by the first capillary tube when flowing through the second capillary tube.
  • the shell liquid and the precursor liquid are not in direct contact in the second capillary tube.
  • the first capillary tube extends completely through the second capillary tube, and, preferably, the downstream end of the first capillary tube, in flow direction of the liquid fiber, is located further downstream the downstream end of the second capillary tube.
  • the downstream ends of the first and the second capillary tubes are located inside the third capillary tube, especially within the first half, in particular within the first quarter, of the third capillary tube.
  • the sheath fluid first is contacted with the shell fluid in the third capillary tube in order to pre-cure the shell fluid before the precursor fluid is introduced through the first capillary tube further downstream into the hollow central section of the pre-cured shell fluid.
  • the pre-cured shell fluid thereby still is fluid but forms a more stable interface with the precursor fluid what further reduces mixing of the fluids at the interface.
  • the expression "whereby at least a downstream end of the first capillary tube coaxially protrudes into a second capillary tube” in particular is to be interpreted as to include the first capillary tube extending completely through the second capillary tube, and, preferably, the downstream end of the first capillary tube, in flow direction of the liquid fiber, beeing located further downstream the downstream end of the second capillary tube.
  • the first and the second capillary tubes, and optionally the third capillary tube in particular each have a constant inner and/or outer diameter.
  • the embodiment where the shell liquid and the precursor liquid are not in direct contact in the second capillary tube and the embodiment with the first capillary tube extending completely through the second capillary tube allows the pre-curing of the shell liquid before it gets in contact with the precursor liquid. This is due to the extended first capillary tube or core channel, respectively. This improves the stability of the liquid fiber with core-shell structure by having an at least partly gelled shell at the onset when forming the core-shell interface. Fluctuations of the core-shell interface are thus reduced due to the less fluid or non-liquid nature of the shell liquid (hydrogel flow).
  • these embodiments in particular provide polymer fibers with better structural consistency and/or allow fiber spinning at lower spinning rate (hence easier post-spinning online treatment such as UV irradiation and automatic collection).
  • an inner diameter of the first capillary tube at the downstream end equals 40 - 60%, especially 45 - 55%, of the inner diameter of the second capillary tube at the upstream end; and, especially, an inner diameter of the second capillary tube at the downstream end equals 40 - 60% especially 45 - 55%, of the inner diameter of the third capillary tube at the upstream end.
  • an inner diameter of the second capillary tube at the upstream end equals 1 10 - 150%, especially 120 - 140%, of the outer diameter of the first capillary tube at the downstream end; and, especially, an inner diameter of the third capillary tube at the upstream end equals 1 10 - 150%, especially 120 - 140%, of the outer diameter of the second capillary tube at the downstream end.
  • an inner diameter of the first capillary tube at the downstream end is 0.3 - 5.0 mm and/or an inner diameter of the second capillary tube at the upstream end is from 0.7 - 6.0 mm; and, especially, an inner diameter of the second capillary tube at the downstream end is 0.3 - 5.0 mm, and/or an inner diameter of the third capillary tube at the upstream end is from 0.7 - 6.0 mm.
  • inner and outer diameters preferably are choses depending on desired thicknesses of the fibers to be produced.
  • the shell liquid is introduced into the second capillary tube at the upstream end face of the second capillary tube, especially through an annular opening formed by the first capillary tube and/or the downstream end of the first capillary tube coaxially protruding into or extending through the second capillary tube; and, especially, the third liquid is introduced into the third capillary tube at the upstream end face of the third capillary tube, especially through an annular opening formed by the downstream end of the second capillary tube coaxially protruding into the third capillary tube.
  • the shell liquid is guided along the outer surface of the first capillary tube, especially the tapered section, before introducing it into the second capillary tube or the third capillary tube; and, especially, the third liquid is guided along the outer surface of the second capillary tube, especially along the tapered section, before introducing it into the third capillary tube.
  • a ratio of the flow rates of core flow : shell flow is from 1 : 0.1 - 10, particularly 1 : 0.5 - 1 .5, in particular 1 : 0.8 - 1.2; and, especially, a ratio of the flow rates of core flow : shell flow: sheat flow is from 1 : (0.1 - 10) : (1 - 50), particularly 1 : 0.5 - 1.5 : 2 - 15, in particular 1 : 0.5 - 0. 9 : 5 - 12.
  • the flow rate is meant to be the volumetric flow rate or the volume of liquid that passes per unit time.
  • the flow of the precursor liquid in the second capillary tube, the liquid fiber with core-shell structure in the second capillary tube, the core-shell flow in the third capillary tube and/or the liquid fiberwith core-shell-sheath structure are controlled to flow laminarly. This can be achieved by appropriate dimensions of the capillaries and flow rates of the liquids.
  • the diameter of the first, the second and optionally the third capillary tube and/or the flow rates of the core flow, the shell flow and optionally the sheath flow are selected such that the solid polymer fiber obtainable in step h) has a diameter of 1 - 5'000 gm, especially 10 - 2'500
  • the capillary tubes are embedded within a solid material, especially such that the capillary tubes pass though the solid material along a straight line.
  • an annular cavity is formed for guiding a liquid between the outer surface of the tapered section and/or outer surface of the respective capillary tube and the solid material, and whereby each cavity is accessible from the outside through a free passage in the solid material forming the second inlet, and optionally the third inlet.
  • the solid material for example is an inorganic material and/or a plastic material.
  • An inorganic material is for example glass.
  • a plastic material is for example a photopolymerized resin, polydimethylsiloxane and/or poly(methyl methacrylate) (PMMA).
  • the capillaries are made from glass. Since glass is highly inert to various chemicals, the inventive method can be implemented with essentially any kind of substances. However, capillaries made from plastic and/or metallic materials might be suitable as well.
  • solidifying the core of the core-shell fiber in step g) is effected by irradiation with electromagnetic radiation and/or heating. This allows for curing and/or polymerizing the precursor liquid in the core of the fibers.
  • electromagnetic radiation and/or heating are known to the skilled person.
  • step g) solidifying the core of the core-shell fiber in step g) is effected by electromagnetic radiation having a wavelength of 280 - 380 nm. Heating can be effected at temperatures in the range of for example 40 - 200°C, e.g.
  • Aggregation in step g) can for example be effected by solvent-exchanged polymer aggregation.
  • the fiber with a solid core comprises aggregated polymers. This is meant to be non- covalently bonded polmyers. E.g. bonding between the polymers in the fibers is for example effected by weak intermolecular forces, such as van der Waal forces.
  • Removing the cured shell from the solid core is in particular affected by dissolving the cured shell in a solvent, e.g. an aqueous solution.
  • a solvent e.g. an aqueous solution.
  • the solvent is present as an aqueous alkaline metal salt solution, e.g. an NaCI solution, and/or as an aqueous solution comprising a chelating agent, e.g. ethylenediaminetetraacetic acid, capable of binding divalent metal cations, especially Ca 2+ , Mg 2+ , Zn 2+ , Fe 2+ , Cu 2+ , and/or Ba 2+ .
  • a chelating agent e.g. ethylenediaminetetraacetic acid
  • the fiber having a core embedded in a cured shell is taken up on a storage unit, especially on a winder and/or a reel. Thereby, in particular, the fiber having a core embedded in a cured shell is guided with one or more godet unit(s).
  • the individual solid polymer fiber is produced without application of electrical fields and/or the inventive method does not comprise a step of applying an electrical field to produce the fibers.
  • Another aspect of the present invention is directed to a liquid fiber having a liquid core embedded in a liquid shell, whereby the liquid core is made of a precursor liquid comprising polymerizable and/or cross-linkable polymer precursors and the liquid shell is an aqueous hydrogel precursor solution.
  • Another aspect of the present invention is directed to a fiber having a liquid core embedded in a cured shell, whereby the liquid core is made of a precursor liquid comprising polymerizable and/or cross-linkable polymer precursors and the cured shell is a hydrogel.
  • the present invention is directed to a solid fiber having a cured core embedded in a cured shell, whereby the core is made of a cured precursor liquid comprising polymerizable and/or cross-linkable polymer precursors and the cured shell is a hydrogel.
  • the present invention is directed to a solid fiber obtained or obtainable by a method as described above.
  • the liquid core, the cured core, the shell liquid and the cured shell are composed, configured and/or obtainable as described above in connection with the inventive method.
  • the diameter of the liquid core or the cured core is from 1 - 5'000
  • a length of the fibers preferably is at least 10 cm, especially at least 25 cm, in particular at least 50 cm or at least 100 cm.
  • the length of the fibers is at least 10 m, especially at least 100 m, in particular at least 1’000 m.
  • a further aspect is directed to a microfluidic-based wet spinning device for producing an individual solid polymer fiber from a precursor liquid comprising polymerizable and/or crosslinkable polymer precursors, whereby the device comprises: a) a first inlet for introducing a precursor liquid into a first capillary tube, whereby at least a downstream end of the first capillary tube coaxially protrudes into a second capillary tube, for injecting the precursor liquid into the second capillary tube, to obtain a core flow of the precursor liquid in the second capillary tube; b) a second inlet configured for introducing a shell liquid into the second capillary tube such that the second liquid forms a tubular and coaxial shell flow around the core flow of the precursor liquid whereby a liquid fiber with core-shell structure is producible in the second capillary tube; c) optionally, a third capillary tube, whereby at least a downstream end of the second capillary tube coaxially protrudes into the third capillary tube, such that the
  • the capillaries and the inlets are configured and arranged as described above in connection with the inventive method.
  • the device preferably comprises at least two, especially at least three, independently controllable pump devices for introducing the precursor liquid into the first capillary tube, the shell liquid into the second capillary tube, and optionally the third liquid into the third capillary tube.
  • the invention is directed to the use of a device as described above for producing an individual solid polymer fiber from a precursor liquid comprising polymerizable and/or cross-linkable polymer precursors.
  • Fig. 1 A schematic cross-section of a first microfluidic wet spinning device for producing an individual solid polymer fiber from a precursor liquid comprising polymerizable and/or cross-linkable polymer precursors;
  • Fig. 2 A cross-section of a liquid fiber with core-shell-sheath structure flowing through the last capillary tube at section S of Fig. 1 .
  • FIG. 3 A schematic illustration of the transformation from a fiber with a liquid core embedded within a cured shell (A) to a fiber with a cured core embedded within the cured shell (B) to the solid target fiber after removal of the shell (C);
  • Fig. 4 Thin polydimethylsiloxane (PDMS) fibers (A) and thick PDMS fibers (B) produced with the inventive method; A digital micrograph (C) shows light guiding behavior of the thick PDMS fiber;
  • PDMS polydimethylsiloxane
  • Fig. 5 Polyacrylate fibers produced with the inventive method: (A) thick polyacrylate fibers; (B) thin polyacylate fibers and (C) a digital micrograph showing light guiding behavior of the polyacrylate fibers;
  • Fig. 6 A schematic cross-section of a second microfluidic wet spinning device for producing an individual solid polymer fiber from a precursor liquid comprising polymerizable and/or cross-linkable polymer precursors;
  • Fig. 8 Amphiphilic polymer optical fibers (polysiloxane/polyacrylate amphiphilic polymer co-network) produced with the inventive method;
  • Fig. 10 A diagram showing the mechanical behavior of soft POF produced with the inventive method under tensile load
  • Fig. 1 1 A diagram showing the decrease in light intensity in polymer optical fibers (POF) as a function of applied pressure.
  • Fig. 1 shows a schematic cross-section of a first inventive microfluidic wet spinning device 10 for producing an individual solid polymer fiber with the inventive method.
  • the device 10 comprises a first capillary tube 1 1 protruding coaxially into an upper end 12a of a second capillary tube 12.
  • the lower ends 1 1 b, 12b of both, the first and the second capillary tubes 1 1 , 12 taper, such that glass nozzles are formed.
  • the tapered lower end 12b of the second capillary tube 12 protrudes coaxially into a third capillary tube 13 in the form a straight glass capillary.
  • the three capillary tubes 1 1 , 12, 13 are embedded within a solid block 14 of a synthetic material, i.e.
  • the two upper capillary tubes 1 1, 12 at their upper ends 1 1 1 a, 12a have for example an outer diameter of 1 mm and an inner diameter of 0.772 mm.
  • the two upper capillary tubes 1 1 , 12 At their lower ends 1 1 b, 12b, have for example an outer diameter of 0.6 mm and an inner diameter of 0.4 mm.
  • the lowest capillary tube 13 for example has an outer diameter of 1 mm and an inner diameter of 0.772 mm over its entire length.
  • the upper end 1 1a, i.e. the upstream end, of the topmost capillary tube 1 1 is open and forms a first inlet 11 for introducing a first liquid L1, e.g. a precursor liquid.
  • a first liquid L1 e.g. a precursor liquid.
  • annular openings are formed, which allow to introduce a second liquid L2, e.g. a shell liquid, and a third liquid L3, e.g. a sheath liquid, into the respective capillary tubes 12, 13.
  • the annular openings communicate with annular cavities 14a, 14b formed around each tapered section of the two upper capillary tubes 1 1, 12.
  • the annular cavities 14a, 14b are configured for guiding the liquids L2, L3 between the outer surface of the tapered section of the respective capillary tube 1 1 , 12 and the solid material 14.
  • Each annular cavity 14a, 14b is accessible from the outside through a free passage in the solid material forming a second inlet I2 for the second liquid L2 and a third inlet I3 for the third liquid L3.
  • the lower end 13b of the third capillary tube 13 protrudes into a receptacle 15 comprising a stationary liquid phase SP. Additionally, there are three godets 16 arranged to direct a fiber produced from the receptacle 15 towards a storage unit 17 in the form of a winder for taking up the fiber.
  • the device can for example be operated as follows:
  • the first liquid L1 e.g. a precursor liquid comprising polymerizable and/or cross-linkable polymer precursors, is introduced at the first inlet 11 into the topmost capillary tube 1 1 .
  • the first liquid L1 then is injected into the second capillary tube 12, to obtain a core flow of the first liquid in the second capillary tube 12.
  • a liquid fiber with core-shell structure is produced by simultaneously introducing the second liquid L2, e.g. a hydrogel precursor, into the second capillary tube 12 through the second inlet I2 and the annular cavity 14a, such that the second liquid L2 forms a tubular and coaxial shell flow around the core flow of the first liquid L1 .
  • the second liquid L2 e.g. a hydrogel precursor
  • the liquid fiber with core-shell structure produced in the second capillary tube 12 then is injected into the third capillary tube 13 to obtain a core-shell flow in the third capillary tube 13.
  • a third liquid L3 or a sheath liquid e.g. a curing agent for the second liquid, is introduced into the third capillary tube 13 through the third inlet I3 and the annular cavity 1 b, such that the third liquid L3 forms a tubular and concentric sheath flow around the core-shell flow in the third capillary tube 13, whereby a liquid fiber with core-shell-sheat structure is produced.
  • the so produced liquid fiber with core-shell-sheat structure then is guided through the stationary liquid phase SP, and taken up on the storage unit 17, i.e. the winder.
  • Fig. 2 shows a cross section of the liquid fiber with core-shell-sheat structure at section S of Fig. 1.
  • the liquid precursor liquid L1 forms a core of the liquid fiber, whereby the core is encapsulated in the sheet liquid L2.
  • the sheet liquid L2 forms a tubular coaxial shell flow around the core flow of the precursor liquid L1.
  • sheath liquid L3 forms a tubular coaxial shell flow around the shell flow L2.
  • the shell liquid L2 e.g. a hydrogel precursor, is cured, whereby a fiber with liquid core 22 of the precursor liquid L1 embedded within the cured shell 21 as shown in Fig. 3-A is produced.
  • the first liquid i.e. the precursor liquid comprising polymerizable and/or cross-linkable polymer precursors
  • the second liquid e.g. a hydrogel precursor
  • the stationary liquid phase SP comprises the curing agent for the second liquid. So to say, in this alternative, the second inlet I2 acts as the first inlet and the third inlet I3 acts as the second inlet.
  • the fiber after taking the fiber from the stationary liquid phase SP, the fiber is treated as illustrated in Fig. 3. Specifically, the fiber with the liquid core 22 within the cured shell 21 is subjected to a solidification treatment ST. e.g. by irradiating the fiber with UV light and/or by providing thermal energy, in order to cure the precursor liquid in the liquid fiber core 22. This results in a fiber as shown in Fig. 3-B having a solid core 22' within the cured shell 21.
  • a solidification treatment ST e.g. by irradiating the fiber with UV light and/or by providing thermal energy
  • the cured shell 21 is removed from the fiber in a removal step RS, e.g. by immersing the fiber in a solvent, to obtain the solid target fiber without shell as shown in Fig. 3- C.
  • PDMS optical fibers were fabricated with the above described device 10 according to the above described alternative implementation without using inlet 11.
  • inlet I2 inlet I2
  • aqueous alginate solution 2 wt% in H 2 O
  • I3 flow rate: 50 ,L/min
  • An aqueous solution of CaCI 2 0.7 wt% in H 2 O was used as the stationary liquid phase SP in the receptacle 15.
  • Fig. 4 shows photographs of a two types of fibers obtained in this manner: The left side (A) shows a fiber having a diameter of 700 pm and the right side (B) a fiber with a diameter of 1 '304 pm. As evident from the digital micrograph (C), the fibers are suitable for guiding visible light.
  • polyacrylate polymer optical fibers were produced with the above described device 10.
  • acrylate monomer precursors Norland Optical Adhesive 83H, i.e. NOA83H
  • NOA83H Norland Optical Adhesive 83H
  • An aqueous alginate solution (2 wt% in H 2 O) was used as the shell liquid and introduced into inlet I2 whereas an aqueous solution of CaCI 2 (0.7 wt% in H 2 O) was used as the third liquid or sheath flow, respectively, and introduced into inlet I3.
  • Polyacrylate fibers with different diameters were achieved by controlling the core and shell flow rates.
  • Thick fibers were produced with the following flow rates: 500 pL/min for the precursor liquid, 300 pL/min for the sheet liquid and 5000 pL/min for the sheath liquid.
  • Thin fibers were produced with the following flow rates: 50 pL/min for the precursor liquid, 40 pL/min for the sheet liquid and 300 pL/min for the sheath liquid.
  • the liquid core of NOA83H monomer precursors was cured by UV irradiation (for 20 min at 10 mW/cm 2 at a wavelength of 365 nm).
  • Fig. 5 shows photographs of the thicker (A) and the thinner fibers (B) having diameters of 372 pm or 325 pm, respectively. As evident from the digital micrograph (C), the fibers are suitable for guiding visible light.
  • Fig. 6 shows a schematic cross-section of a second inventive microfluidic wet spinning device 10’ for producing an individual solid polymer fiber with the inventive method.
  • the second device 10’ at the upper end comprises a first capillary tube 1 1’ extending coaxially through a second capillary tube 12’ and ending in an upper end 13a’ of the third capillary tube 13’.
  • the lower end 12b’ of the second capillary tube 13’ coaxially protrudes into the upper end 13a’ of the third capillary tube 13’ too.
  • the lower end 1 1 b’ of the first capillary tube 1 1’ protrudes out of the lower end 12b’ of the second capillary tube 12’.
  • all of the capillary tubes 1 1’, 12’, 13’ have constant inner and outer diameters.
  • the upper end 1 1a’, i.e. the upstream end, of the topmost capillary tube 1 1’ is open and forms a first inlet 11’ for introducing a first liquid L1 , e.g. a precursor liquid.
  • a first liquid L1 e.g. a precursor liquid.
  • annular openings are formed, which allow to introduce a second liquid L2, e.g. a shell liquid, and a third liquid L3, e.g. a sheath liquid, through inlets 12’, 13’ into the respective capillary tubes 12’, 13’.
  • the lower end 13b’ of the third capillary tube 13’ protrudes into a receptacle 15’ comprising a stationary liquid phase, e.g. water. Additionally, there are godets and storage units (not shown in Fig. 6) similar to the ones shown in Fig. 1 .
  • the device 10’ can for example be operated as follows:
  • the first liquid L1 e.g. a precursor liquid comprising polymerizable and/or cross-linkable polymer precursors, is introduced at the first inlet 11’ into the topmost capillary tube 1 1’.
  • the first liquid L1 then is guided into the second capillary tube 12’, to obtain a core flow of the first liquid in the second capillary tube 12’.
  • the core flow is confined within the first capillary tube 1 1’ extending through the second capillary tube 12’.
  • a liquid fiber with core-shell structure is produced by simultaneously introducing the second liquid L2, e.g. a hydrogel precursor, into the second capillary tube 12’ through the second inlet I2’ such that the second liquid L2 forms a tubular and coaxial shell flow around the first capillary tube 1 1’ and the core flow of the first liquid L1 flowing therein.
  • the second liquid L2 e.g. a hydrogel precursor
  • liquids L1 and L2 are separated by the first capillary tube 1 1’. Nevertheless, they form a liquid fiber with core-shell structure.
  • the liquid fiber with core-shell structure produced in the second capillary tube 12’ then is injected into the third capillary tube 13’ whereby the third liquid L3 or a sheath liquid, e.g. a curing agent for the second liquid, is introduced into the third capillary tube 13’ through the third inlet I3’, such that the third liquid L3 forms a tubular and concentric sheath flow around the core-shell flow in the third capillary tube 13’.
  • the third liquid L3 is first brought in contact with the second liquid L2 in the pre-curing zone PZ whereby the sheet liquid L2 is precured by the sheath liquid L3.
  • the precursor fluid L1 is introduced through the first capillary tube 1 1’ further downstream into the hollow central section within the pre-cured shell fluid L2, whereby a liquid fiber with core-shell-sheat structure is produced.
  • the pre-cured shell fluid L2 forms a more stable interface with the precursor fluid L1 what further reduces mixing of the fluids.
  • device 10 with only two capillary tubes if production of the fibers always is effected in line with the alternative implementation.
  • capillary tubes 1 1 , 12, 13 with other dimensions can be foreseen.
  • Fig. 7 shows a photograph of polylactic acid (PLA) fibers produced with the inventive method.
  • a non-toxic solvent i.e. Cyrene® (Dihydroglucosenon; polar solvent)
  • toxic solvents e.g. dichloromethane
  • Fig. 8 shows a photograph of amphiphilic polymer optical fibers composed of polysiloxane/polyacrylate amphiphilic polymer co-network produced with the inventive method.
  • the fibers have a low modulus of elasticity of E ⁇ 2 MPa.
  • Such fibers can be produced from precursors with very low viscosities what so far was not possible with any other method.
  • Fig. 9 shows polyurethane fibers produced with the inventive method from polyol and isocyanate precursors.
  • Fig. 10 shows a strain (e) versus stress (a) diagram obtained by tensile testing of a soft polymer optic fiber (POF) produced according to the inventive method.
  • the data shows a modulus of elasticity (E) of only around 0.35 MPa.
  • Fig. 1 1 shows the decrease in light intensity in polymer optical fibers (POF) produced according to the inventive method with low modulus of elasticity (E ⁇ 0.35 MPa and 1 MPa) as a function of applied pressure, in comparison with an ordinary fiber (E ⁇ 5 MPa).

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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)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)

Abstract

Un procédé de production d'une fibre polymère solide individuelle à partir d'un liquide précurseur (L1) comprenant des précurseurs polymères agrégeables, polymérisables et/ou réticulables, en particulier à partir d'un liquide précurseur comprenant des précurseurs polymères polymérisables et/ou réticulables, par filage humide à base microfluidique comprend les étapes consistant : a) à introduire le liquide précurseur (L1) dans un premier tube capillaire (11) faisant saillie de manière coaxiale dans un deuxième tube capillaire (12) ; b) à produire une fibre liquide à structure âme-gaine dans le deuxième tube capillaire (12) ; c) éventuellement, à injecter la fibre liquide à structure âme-gaine produite à l'étape b) dans un troisième tube capillaire (13) pour produire une fibre à structure âme-gaine-enveloppe ; d) à guider la fibre liquide à structure âme-gaine, présentant éventuellement une enveloppe, telle que produite à l'étape b) ou à l'étape c) à travers une phase liquide stationnaire (SP) ; e) à durcir la feuille liquide de la fibre à structure âme-gaine de l'étape c) et/ou de l'étape d) pour obtenir une fibre présentant une âme liquide (22) intégrée dans une gaine durcie (21) ; f) à collecter la fibre ; g) après l'étape f), à solidifier l'âme liquide (22) de la fibre ; h) à retirer la gaine durcie (21) de l'âme solide (22') pour obtenir la fibre polymère solide.
PCT/EP2023/061015 2022-04-26 2023-04-26 Filage humide à base microfluidique de fibres polymères solides individuelles WO2023209037A1 (fr)

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Citations (3)

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US20120301963A1 (en) * 2009-10-14 2012-11-29 The University Of Tokyo Covered micro gel fiber
US20130071948A1 (en) * 2010-01-20 2013-03-21 Japan Science And Technology Agency Process for producing supramolecular fiber
WO2014143866A1 (fr) 2013-03-15 2014-09-18 Arsenal Medical, Inc. Fibres de type âme-gaine et leurs procédés de fabrication et d'utilisation

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KR20150124910A (ko) 2014-04-28 2015-11-06 가톨릭대학교 산학협력단 세포 이동 촉진용 조성물

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US20120301963A1 (en) * 2009-10-14 2012-11-29 The University Of Tokyo Covered micro gel fiber
US20130071948A1 (en) * 2010-01-20 2013-03-21 Japan Science And Technology Agency Process for producing supramolecular fiber
WO2014143866A1 (fr) 2013-03-15 2014-09-18 Arsenal Medical, Inc. Fibres de type âme-gaine et leurs procédés de fabrication et d'utilisation

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