WO2018224583A1 - Fluorinated polymer multilayer fibre - Google Patents

Fluorinated polymer multilayer fibre Download PDF

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Publication number
WO2018224583A1
WO2018224583A1 PCT/EP2018/064985 EP2018064985W WO2018224583A1 WO 2018224583 A1 WO2018224583 A1 WO 2018224583A1 EP 2018064985 W EP2018064985 W EP 2018064985W WO 2018224583 A1 WO2018224583 A1 WO 2018224583A1
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WIPO (PCT)
Prior art keywords
layer
fiber
ene
dicarboxylic
functionalized
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PCT/EP2018/064985
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French (fr)
Inventor
Simon JESTIN
Samuel Devisme
Stéphane Bizet
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Arkema France
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Publication of WO2018224583A1 publication Critical patent/WO2018224583A1/en

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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
    • D01F8/06—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyolefin as 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
    • 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
    • D01F8/10—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained by reactions only involving carbon-to-carbon unsaturated bonds as 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
    • 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
    • D01F8/12—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyamide as 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
    • 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

Definitions

  • the present invention relates to the field of composite piezoelectric fibers. More particularly, the invention relates to multi-component piezoelectric effect fibers consisting solely of polymeric materials. The invention also relates to the process for manufacturing these fibers, as well as their applications in various sectors of technical textiles, filtration, and electronics.
  • ferroelectric and ferroelectric relaxer materials that generate mechanical actuation induced by an external electric field have attracted a lot of attention and have been recognized for applications in various transducers, actuators and sensors.
  • ceramics are the most commonly used because of their good actuation properties and their very wide bandwidth. However, they have a fragility that prevents them from being applied to curved or complex surfaces.
  • VDF vinylidene fluoride
  • TrFE trifluoroethylene
  • Such fibers have been manufactured in the laboratory as a single-component or multi-component.
  • the article by B. Glauss et al. in Materials 2013, 6, 2642-61 discloses two-component hot-spun fibers consisting of a conductive polypropylene core (supplemented with multi-walled carbon nanotubes and sodium stearate), and a PVDF homopolymer sheath. .
  • These fibers have been characterized by various analytical methods (wide-angle X-ray diffraction, transmission electron microscopy, differential calorimetry, rheometry) but their mechanical and electrical properties have not been reported.
  • the invention relates to a piezoelectric polymer fiber consisting of three layers: a layer B consisting of at least one fluorinated polymer, a layer A comprising at least one polyolefin and a polyamide layer C, said layer B being contact over its entire surface on one hand, with said layer C, and, secondly, with said layer A, said layer C being located inside the fiber.
  • At least one of the layers A and C is charged with conductive particles such as carbon nanotubes, carbon blacks, graphene, graphite, nano carbon fibers, nanowires or metal nanoparticles (silver nanowires for example). This promotes the polarization and the piezoelectric behavior of the fiber.
  • the invention relates to a method of manufacturing the tricomponent fiber described above by coextrusion of the polymers constituting the layers A, B and C in the molten state, followed by a drawing step.
  • the drawing step is carried out at a temperature between the glass transition temperature, Tg, and the melting temperature, Tf of the polymers constituting the layers A, B and C, that is, that is to say at a temperature between the highest Tg and the lowest Tf of the various constituents, which amounts to a range between 40 ° C and 130 ° C.
  • the invention also relates to a piezoelectric device manufactured from the tricomponent fiber described.
  • the invention also relates to textile materials which comprise the tri-component fibers described.
  • the present invention makes it possible to overcome the disadvantages of the prior art.
  • the invention makes it possible to obtain entirely polymeric piezoelectric fibers having increased flexibility over ceramic-based fibers, enabling them to be used in "smart" materials, especially textile materials.
  • the fibers according to the invention have improved adhesion properties between the different layers, which guarantees their drawability. Indeed, such a fiber to obtain its mechanical characteristics must be stretched in the spinning process, without impact on the cohesion of its various constituents. Moreover, especially for use in textile clothing, this fiber will be strongly mechanized and to maintain its integrity, strong adhesion in the different layers is preferred.
  • the stretching of the fiber makes it possible to generate the beta crystalline phase necessary for the piezoelectric effect.
  • Another advantage of the fibers according to the invention, having a good adhesion between the layers of filaments, lies in the fact that the stretching temperatures of the multicomponent fiber remain in conventional ranges of drawing temperatures, ie below the melting point of the component having the lowest melting point, typically below 150 ° C.
  • Figure 1 shows a bi-component fiber A / B (the filament of Example 1) unstretched, seen in cross-section under a scanning electron microscope.
  • Material A is a mixture of 70% by weight of HDPE high density polyethylene and 30% by weight of a PEf functionalized polyethylene.
  • Material B is a compound made of PVDF at 80% by weight and a PVDFf at 20% by weight.
  • Figure 2 shows the image of a fracture facies, obtained by scanning electron microscopy, of the two-component fiber of Example 1 strongly stretched (at the end of the stress-strain curve).
  • Figure 3 shows a bi-component fiber B / C seen under a scanning electron microscope.
  • Material B is an m-PVDF compound made of 80% by weight PVDF and a 20% by weight PVDFf.
  • Material C is a conductive polymer compound of polyamide 12 (PA12) loaded with 5% by weight of carbon nanotubes (CNTs).
  • Figures 4 to 6 are diagrams showing the tensile test results corresponding respectively to Comparative Examples 1 and 1, Comparative 2 and 2, and Comparative 3 and 3.
  • a first object of the invention is to propose a tri-component piezoelectric polymer fiber, that is to say composed of three layers of different polymers: a layer B consisting of at least one fluorinated polymer, a layer A comprising at least one least one polyolefin and one polyamide layer C, said layer B being in contact over its entire surface on the one hand, with said layer C, and, on the other hand, with said layer A.
  • the layer C is located at inside the fiber.
  • Such a structure gives rise to different geometries, such as coaxial geometry or islands-in-sea structure.
  • the polymers present in each of the layers A, B and C have crystallization temperatures Te respecting the condition: Te A ⁇ Te B ⁇ Te C in order to ensure the best possible cohesion within the fiber sorting -component.
  • the fiber is made by simultaneous coextrusion of the three materials.
  • solidification of the core is ensured first followed by that of the fluorinated material and finally the outer layer. This procedure makes it possible to avoid the phenomena of decohesion at the interfaces due to shrinkage on crystallization, and leads to the production of a denser and more tenacious fiber.
  • the measurement of the crystallization temperature is carried out by differential thermal analysis according to the ISO 11357-3 standard "Plastics - Differential Scanning Calorimetry (DSC) Part 3: Determination of temperature and enthalpy of melting and crystallization".
  • the fluoropolymer of the layer B is a functionalized fluoropolymer or a mixture of a fluoropolymer with a functionalized fluoropolymer
  • said layer A comprises a mixture of a polyolefin with a functionalized polyolefin carrying a function reactive with respect to the function carried by said functionalized fluoropolymer.
  • This particular structure ensures a cohesive interface between the layer B and the layer A of the bi- or tri-component fiber, and does not cause delamination during a mechanical stress.
  • the fluoropolymer of layer B is any polymer having in its chain at least one monomer chosen from compounds containing a vinyl group capable of opening to polymerize and which contains, directly attached to this vinyl group, at least one atom of fluorine, a fluoroalkyl group or a fluoroalkoxy group.
  • vinyl fluoride vinylidene fluoride
  • VDF vinylidene fluoride
  • VF3 trifluoroethylene
  • CTFE chlorotrifluoroethylene
  • TFE 1,2-difluoroethylene
  • TFE tetrafluoroethylene
  • HFP hexafluoropropylene
  • the fluoropolymer may be a homopolymer or a copolymer, it may also include non-fluorinated monomers such as ethylene.
  • said fluoropolymer is a polyvinylidene polyfluoride (PVDF) homopolymer or a copolymer of VDF containing, by weight, at least 50% of VDF, more preferably at least 75% and better still at least 85%, with at least one comonomer selected from trifluoroethylene (TrFE), chlorotrifluoroethylene (CTFE), CFE or 1,1-chlorofluoroethylene, CDFE or 2-chloro-1,1, -trifluoroethylene, hexafluoropropene (HFP), Tetrafluoroethylene (TFE).
  • PVDF polyvinylidene polyfluoride
  • said fluoropolymer is a terpolymer such as P (VDF-TrFE-CFE) or P (VDF-TrFE-CTFE).
  • the layer B entering a tri-composite fiber according to the invention is a functionalized fluoropolymer or a mixture of a fluoropolymer described above with a functionalized fluoropolymer.
  • the functionalized fluoropolymer carries an implanted monomer grafted, as described in doucment EP 1484346.
  • the unsaturated grafted monomer is selected from unsaturated carboxylic acids and their derivatives.
  • unsaturated carboxylic acids are those having 2 to 20 carbon atoms such as acrylic, methacrylic, maleic, fumaric and itaconic acids.
  • the functional derivatives of these acids include, for example, anhydrides, ester derivatives, amide derivatives, imide derivatives and metal salts (such as alkali metal salts) of unsaturated carboxylic acids.
  • grafting monomers include, for example, maleic, fumaric, itaconic, citraconic, allylsuccinic, cyclohex-4-ene-1,2-dicarboxylic, 4-methylcyclohex-4-ene-1,2-dicarboxylic, bicyclo (2 , 2, 1) hept-5-ene-2,3-dicarboxylic acid, x-methylbicyclo (2,2,1-hept-5-ene-2,3-dicarboxylic acid), maleic, itaconic, citraconic, allylsuccinic, cyclohex anhydrides 4-ene-1,2-dicarboxylic, 4-methylenecyclohex-4-ene-1,2-dicarboxylic, bicyclo (2,2,1) hept-5-ene-2,3-dicarboxylic acid, and x-methylbicyclo ( 2,2, l) hept-5-ene-2,2-dicarboxylic acid.
  • the polyolefin (PO) that can be used in the layer A of the fiber according to the invention is a polymer comprising, as monomer, an alpha-olefin, that is to say homopolymers of a fine particle or copolymers of at least an alpha-olefin and at least one other copolymerizable monomer, the alpha-olefin preferably having from 2 to 30 carbon atoms.
  • alpha-olefin By way of example of an alpha-olefin, mention may be made of ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3 1-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene, 1-dococene, 1-tetracocene, 1-hexacocene, 1-octacocene , and 1-triacontene. These alpha-olefins may be used alone or as a mixture of two or more.
  • ethylene in particular low density polyethylene (LDPE), high density polyethylene (HDPE), linear low density polyethylene (LLDPE), very low polyethylene density (VLDPE), polyethylene obtained by metallocene catalysis, homopolymers and copolymers of propylene, polyalphaoyl fines mainly amorphous or attactiques (APAO), ethylene / alpha-olefin copolymers such as ethylene / propylene, EPR (ethylene-propylene-rubber) elastomers, and EPDM (ethylene-propylene-diene), and polyethylene blends with EPR or EPDM, block copolymers styrene / ethylene-butene / styrene (SEBS), styrene / butadiene / styrene (SBS), styrene / isoprene / styrene
  • SEBS styrene / ethylene-butene /
  • the functionalized polyolefin may be a polymer of alpha olefins having reactive units (functionalities); such reactive units are acid, anhydride or epoxy functions.
  • reactive units are acid, anhydride or epoxy functions.
  • a functionalized polyolefin is, for example, a PE / EPR mixture, the weight ratio of which can vary widely, for example between 40/60 and 90/10, said mixture being co-grafted with an anhydride, in particular maleic anhydride, according to a grafting rate of, for example, 0.01 to 5% by weight.
  • the functionalized polyolefin may be chosen from the (co) polymers mentioned above, grafted with maleic anhydride or glycidyl methacrylate, in which the degree of grafting is, for example, from 0.01 to 5% by weight.
  • the functionalized polyolefin may also be a copolymer or copolymer of at least the following units: (1) ethylene, (2) alkyl (meth) acrylate or saturated carboxylic acid vinyl ester and (3) anhydride such as maleic anhydride or (meth) acrylic acid or epoxy such as glycidyl (meth) acrylate.
  • anhydride such as maleic anhydride or (meth) acrylic acid or epoxy such as glycidyl (meth) acrylate.
  • the ethylene preferably represents at least 60% by weight and the ter monomer (the function) represents, for example, from 0.1 to 10% by weight of the copolymer:
  • ethylene / vinyl acetate or (meth) acrylate / (meth) acrylic acid copolymers or examples of such polymers that may be mentioned are the ter polymers of ethylene, of alkyl acrylate and of maleic anhydride or of glycidyl methacrylate such as the Lotader® of the Applicant or polyolefins grafted with maleic anhydride such as the Orevac® of the Applicant and ter polymers of ethylene, alkyl acrylate and of (meth) acrylic acid, maleic anhydride or glycidyl methacrylate.
  • the layer C is polyamide.
  • the polyamide is chosen so that its crystallization temperature is higher than that of layers A and B.
  • the polyamide of layer C is polyamide 12 (PA 12), which is an aliphatic polyamide manufactured by opening of the lauryllactam cycle (thus a polylauroamide). Its inherent viscosity can be between 1 and 2 and advantageously between 1.2 and 1.8. The inherent viscosity is measured at 20 ° C for a concentration of 0.5% in meta-cresol.
  • Polyamides 11, 6, 6.10, 6.12, 10.10, 10.12 and 6.6 are also suitable for layer C.
  • the polyamide of layer C may contain from 0 to 30% by weight of at least one product chosen from plasticizers and shock modifiers for respectively 100 to 70% of polyamide.
  • plasticizer By way of example of plasticizer, mention may be made of benzene sulphonamide derivatives, such as n-butyl benzene sulphonamide (BBSA), ethyl toluene sulphonamide or N-cyclohexyl toluene sulphonamide; esters of hydroxy-benzoic acids, such as 2-ethylhexyl parahydroxybenzoate and 2-decyl hexyl parahydroxybenzoate; esters or ethers of tetrahydrofurfuryl alcohol, such as oligoethyleneoxytetrahydrocrofuryl alcohol; esters of citric acid or of hydroxy-malonic acid, such as oligoethyleneoxy malonate.
  • BBSA n-butyl benzene sulphonamide
  • esters of hydroxy-benzoic acids such as 2-ethylhexyl parahydroxybenzoate and 2-decyl hexyl parahydroxybenzoate
  • BBSA n-butyl benzene sulfonamide
  • impact modifier include polyolefins, crosslinked polyolefins, elastomers EPR, EPDM, SBS and SEBS these elastomers can be grafted to facilitate their compatibilization with polyamide, copolymers with polyamide blocks and polyether blocks. These polyamide block copolymers and polyether blocks are known in themselves, they are also known by the name PEBA (polyether block amide). Acrylic elastomers can also be mentioned, for example those of the NBR, HNBR or X-NBR type.
  • This polyamide may contain additives such as anti-UV, stabilizers, antioxidants, or flame retardants.
  • the polyamide inner layer When the polyamide inner layer is loaded with conductive particles, it brings the conductivity and mechanical properties to the fiber according to the invention.
  • at least one of the layers A and C is charged with conductive particles such as carbon nanotubes, carbon blacks, graphene, graphite, carbon nanofibers, metal nanowires or nanoparticles ( silver nanowires for example).
  • the polymers thus charged become electrical conductors and are able to act as electrodes.
  • the optimal charge ratio is thus between 2 and 30% by weight relative to the weight of each layer A and C, depending on the conductive charge considered to obtain sufficient electrical conductivity to the use of the polymer as an electrode.
  • the layers adhere to one another without a coextrusion binder.
  • the adhesion of the various polymers within a multi-component fiber core-bark-bark or islands-in-sea tri-component is a determining criterion for obtaining the desired properties:
  • Another object of the invention is to provide a process for preparing the three-component fiber described above by coextrusion of the polymers constituting the layers A, B and C in the molten state, followed by a hot stretching step.
  • the method for manufacturing the tricomponent fiber comprises the following steps: providing the polymers making up each of the layers A, B and C in the molten state; coextruding said polymers in the molten state in the form of filaments.
  • the processing temperatures of polymers A, B and C must be as close as possible and define that of the tri-component (or bi-component) die.
  • this die temperature is ideally between 210 ° C and 240 ° C; stretch the fiber thus extruded.
  • the melt stretch has no influence on the adhesion of the layers A, B C and has little impact on the final beta phase level in the fluorinated phase.
  • the post-stretching step once the filament has cooled and solidified, which will give the wire its high mechanical properties as well as obtaining the PVDF in its majority beta form.
  • This post-stretching step is carried out in the solid state and preferably at a temperature between 80 and 120 ° C.
  • the stretching factor R designating the speed ratio between the stretching rollers is preferably between 3 and 6, this ratio leading to the mentioned mechanical and beta phase properties.
  • the production of a piezoelectric polymer fiber is preferably carried out when the electrodes are directly manufactured during the spinning step.
  • One simple way is to use multi-component spinning (or coextrusion) in which the piezo-active material (PVDF, VDF copolymers or terpolymers) is surrounded by electrically conductive polymers that act as electrodes.
  • the polymer material used is an electrostrictive and electroactive material, for example a polymer (P (VDF-TrFE-CFE) or P (VDF-TrFE-CTFE).
  • the application of a field electrical connection across the material causes a reduction in its size in the direction of application of the field and its elongation in the direction perpendicular to the applied field.
  • a fiber according to the invention composed of such a polymer, and having a conductive core, constituting a first electrode, and a conductive outer coating constituting a second electrode can thus constitute an actuator, the application of an electric field between these electrodes makes it possible to modify the mechanical characteristics of the fiber, if this fiber is integrated into a textile structure. the application of this electric field makes it possible to modify the mechanical characteristics of this textile structure.
  • the spinning of multi-component fibers makes it possible to obtain new properties by the combination of different materials within the same filament.
  • These multi-component fibers can find applications in various sectors of technical textiles, filtration, but also in electronics.
  • the invention also relates to a piezoelectric device manufactured from the tricomponent fiber described.
  • the invention also relates to textile materials which comprise tri-component fibers described.
  • High density polyethylene polyethylene characterized by a melt index of 23 g / 10 '(190 ° C. under 2.16 kg), a melting temperature of 128 ° C. and a crystallization temperature of 117 ° C. measured by thermal analysis.
  • Functionalized polyethylene (denoted by PEf): terpolymer of ethylene, of butyl acrylate and of glycidyl methacrylate, characterized by a melt index of 12 g / 10 '(190 ° C. under 2.16 kg), a melting temperature of 74 ° C and a crystallization temperature of 54 ° C.
  • Polyvinylidene fluoride (denoted PVDF): homopolymer of vinylidene fluoride characterized by a melt index of 33 g / 10 '(230 ° C. under 2.16 kg), a melting point of 172 ° C. and a crystallization temperature of 138 ° C measured by thermal analysis.
  • Functionalized vinylidene fluoride (denoted PVDFf): homopolymer of vinylidene fluoride grafted with 0.5% by weight of maleic anhydride characterized by a melt index of 16 g / 10 '(230 ° C. under 3.8 kg), a temperature of melting at 172 ° C and a crystallization temperature of 137 ° C measured by thermal analysis.
  • Polyamide 12 (denoted PA12): homopolymer of lauryllactam characterized by a melt index of 50 g / 10 '(235 ° C. under 2.16 kg) and a melting temperature of 180 ° C. and a crystallization temperature of 153 ° C., measured by thermal analysis.
  • Carbon black (denoted CB):
  • NTC Nanotubes of carbon
  • Functionalized compounds are HDPE mixtures with functionalized HDPE or PVDF mixtures with functionalized PVDF.
  • Conductive compounds are the HDPE mixtures (functionalized or not) with the conductive fillers or PA12 with the conductive fillers.
  • the functionalized compounds are made by molten route according to an extrusion process.
  • a bi-screw extruder is preferably used and allows the mixing of non-functional polymers with functionalised polymers at controlled rates.
  • the granules of each material are mixed in selected proportions in the solid state and then conveyed in the extrusion machine according to an increasing temperature profile whose values are generally between Tf + 20 and Tf + 70 ° C. At the end of the extrusion, a rod is obtained and then granulated.
  • the first step of producing a conductive compound consists in the manufacture of a masterbatch concentrated in conductive fillers, a mixture also called master batch.
  • This masterbatch is produced by extrusion in a molten state using a high shear mixing tool such as a twin-screw co-extruder or shear profile extruder.
  • This step is essential to optimally disperse the conductive filler in the polymer.
  • a high level of filler is used in the masterbatch, typically between 15 and 50% by weight, and makes it possible to obtain a high viscosity that promotes shearing and therefore dispersion of the fillers.
  • the material is melt convected in the extrusion machine according to an increasing temperature profile whose values are generally between Tf + 20 and Tf + 70 ° C.
  • the conductive fillers are provided by a lateral doser to the molten material in a desired quantity.
  • a rod is obtained at the extruder outlet, cooled and granulated.
  • Bicomponent and tri-component filament spinning From the functionalized and conductive compounds, two-component and three-component structures were produced under the following conditions.
  • Example 1 Two-component fiber A / B
  • Material A is a mixture of 70% by weight of HDPE high density polyethylene and 30% by weight of a PEf functionalized polyethylene.
  • Material B is a compound made of PVDF at 80% by weight and a PVDFf at 20% by weight. These compounds A and B are melted and conveyed in two single-screw extruders, which optionally fill two booster pumps for setting the output rate. At the end of the extrusion or pumping step, the two compounds A and B are conveyed in a pipe and then injected into a two-component spin pack for bringing the compounds A and B respectively to the periphery (sheath ) and in the center (heart) of each extruded filament.
  • the spin pack is produced according to the knowledge of those skilled in the art to provide the two-component spinning core-bark geometry and can be constituted among other parts of an injection cone, flow distribution plates, filters, a support plate and a die.
  • this temperature T is preferably between 205 and 220 ° C and a two-component monofilament die is used.
  • the extrusion flow rates are chosen so as to obtain an A / B core volume ratio of 30/70.
  • the extruded filament is cooled in ambient air, driven by an omega roller drawing bench to fix the diameter and the stretch in the molten state. This filament is then collected and wound without stretching in the additional solid state.
  • FIG. 1 illustrates the non-stretched bi-component fiber A / B of Example 1.
  • Material B is an m-PVDF compound made of 80% by weight PVDF and a 20% by weight PVDFf.
  • Material C is a conductive polymer compound of polyamide 12 (PA12) loaded with 5% by weight of carbon nanotubes (CNTs).
  • PA12 polyamide 12
  • CNTs carbon nanotubes
  • the polymers B and C are extruded through a two-component monofilament die and respectively placed in sheath and core of the two-component geometry.
  • the temperature of implementation preferably chosen is between 210 and 230 ° C.
  • the filaments are collected without undergoing stretching in the solid state.
  • Adhesion between the A / B and B / C layers was evaluated by a two-component filament tensile test.
  • a universal test machine is used in traction test mode. It is equipped with a fixed crossbar and an instrumented moving beam, a force sensor and jaws and jaws suitable for filament testing.
  • a device allows the recording of the force measured by the sensor as a function of the displacement of the movable cross member.
  • the filaments are placed between the two jaws and the tensile test is carried out until the filaments are completely broken, using a test speed of 50 or 100% / min according to ISO 5079 or ISO 2062, according to that we test mono or multi-filaments.
  • FIG. 2 shows the fiber of example 1, stretched at 800%. It shows that the two materials remain adhered even after a large stretch, and break simultaneously.
  • the filament example 1 has a curve stress - smooth elongation and characteristic of a single-component filament.
  • the comparative Example 1 filament which does not consist of functionalized polymers, exhibits a different behavior. A significant drop in stress is observed as soon as the elastic regime changes to the plastic deformation regime. This drop is characteristic of a rupture of one of the two components, in this case that of the HDPE sheath. This sheath is loosened / delaminated progressively from the PVDF core of the filament as shown by the noisy behavior of the curve.
  • Example 1 HDPE PVDF 230 ⁇ A / B: Comparative 33/66

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  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
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Abstract

The invention concerns composite piezoelectric fibres. More particularly, the invention relates to multi-component piezoelectric-effect fibres consisting solely of polymer materials. The invention also relates to the method for producing these fibres, as well as to the applications thereof in various sectors of technical textiles, filtration, and electronics.

Description

FIBRE MULTICOUCHE DE POLYMERES FLUORES  MULTILAYER FIBER OF FLUORINATED POLYMERS
DOMAINE TECHNIQUE TECHNICAL AREA
La présente invention concerne le domaine des fibres piézoélectriques composites. Plus particulièrement, l'invention se rapporte à des fibres à effet piézo-électrique multi-composant constituées uniquement de matériaux polymères. L'invention a trait également au procédé de fabrication de ces fibres, ainsi qu'à leurs applications dans des secteurs variés du textile technique, de la fïltration, et dans l'électronique. The present invention relates to the field of composite piezoelectric fibers. More particularly, the invention relates to multi-component piezoelectric effect fibers consisting solely of polymeric materials. The invention also relates to the process for manufacturing these fibers, as well as their applications in various sectors of technical textiles, filtration, and electronics.
ARRIÈRE-PLAN TECHNIQUE TECHNICAL BACKGROUND
Les matériaux ferroélectriques et ferroélectriques relaxeurs qui génèrent un actionnement mécanique induit par un champ électrique externe ont attiré beaucoup d'attention et ont été reconnus pour des applications dans divers transducteurs, actionneurs et capteurs. The ferroelectric and ferroelectric relaxer materials that generate mechanical actuation induced by an external electric field have attracted a lot of attention and have been recognized for applications in various transducers, actuators and sensors.
Parmi les matériaux piézoélectriques, les céramiques sont les plus couramment utilisées du fait de leurs bonnes propriétés d' actionnement et de leur bande passante très large. Elles présentent cependant une fragilité qui empêche de les appliquer sur des surfaces courbes ou complexes. Among the piezoelectric materials, ceramics are the most commonly used because of their good actuation properties and their very wide bandwidth. However, they have a fragility that prevents them from being applied to curved or complex surfaces.
D'autres dispositifs électro-conducteurs utilisent des films polymères en sandwich entre deux électrodes. Parmi les polymères utilisables, les polymères fluorés à base notamment de fluorure de vinylidène (VDF) représentent une classe de composés ayant des propriétés remarquables pour un grand nombre d'applications. Le polyfluorure de vinylidène (PVDF) et les copolymères comprenant du VDF et du trifluoroéthylène (TrFE) sont particulièrement intéressants en raison de leurs propriétés piézoélectriques. Other electrically conductive devices use polymer films sandwiched between two electrodes. Among the polymers that can be used, fluorinated polymers based in particular on vinylidene fluoride (VDF) represent a class of compounds having remarkable properties for a large number of applications. Polyvinylidene fluoride (PVDF) and copolymers comprising VDF and trifluoroethylene (TrFE) are particularly interesting because of their piezoelectric properties.
Ces structures flexibles piézoélectriques sont uniquement disponibles commercialement sous forme de films. Certaines applications exigent cependant de disposer de fibres piézoélectriques polymères, qui peuvent être implantées directement au sein de certains matériaux, pour former des matériaux « intelligents » (« smart materials »). These flexible piezoelectric structures are only commercially available in the form of films. However, some applications require polymeric piezoelectric fibers, which can be implanted directly within certain materials, to form "smart" materials.
De telles fibres ont été fabriquées au laboratoire sous forme de mono-composant ou multi- composant. L'article de B. Glauss et al. dans Materials 2013, 6, 2642-61 décrit des fibres bi-composant obtenues par filage à chaud, consistant en un cœur en polypropylène conducteur (additionné de nanotubes de carbone multi-parois et de stéarate de sodium), et une gaine en PVDF homopolymère. Ces fibres ont été caractérisées par diverses méthodes analytiques (diffraction des rayons X à grand angle, microscopie électronique à transmission, calorimétrie différentielle, rhéométrie) mais leurs propriétés mécaniques et électriques n'ont pas été rapportées. Such fibers have been manufactured in the laboratory as a single-component or multi-component. The article by B. Glauss et al. in Materials 2013, 6, 2642-61 discloses two-component hot-spun fibers consisting of a conductive polypropylene core (supplemented with multi-walled carbon nanotubes and sodium stearate), and a PVDF homopolymer sheath. . These fibers have been characterized by various analytical methods (wide-angle X-ray diffraction, transmission electron microscopy, differential calorimetry, rheometry) but their mechanical and electrical properties have not been reported.
Les travaux de R. Martins et al. dans J. Text. Eng. 2014, 60(2), 27-34 concernent la fabrication de filaments bi-composant piézo-électriques de constitution similaire (une couche interne de polypropylène conductrice et une couche de PVDF homopolymère). Ces fibres ont été soumises à des essais en traction, qui montrent que les deux couches cassent séparément à des taux d'étirement de 30% (voir Fig. 10). Ceci témoigne d'une faible adhésion entre les couches. The work of R. Martins et al. in J. Text. Eng. 2014, 60 (2), 27-34 relate to the manufacture of two-component piezoelectric filaments of similar constitution (an inner layer of conductive polypropylene and a layer of PVDF homopolymer). These fibers were subjected to tensile tests, which show that the two layers break separately at stretching rates of 30% (see Fig. 10). This shows a weak adhesion between the layers.
Le même inconvénient est observé pour des fibres tri-composant décrites dans la publication de R. Martins et al. dans J. Appl. Polym. Sci. 2014, DOI : 10.1002/APP.40710. Ces fibres ont un cœur et une gaine en polypropylène conductrice, et une couche centrale en PVDF homopolymère. Les images de microscopie d'une section transversale de ces fibres montrent des interfaces décohésives entre les couches (voir Fig. 7). La figure 9 de ce document démontre également une adhésion interfaciale faible entre les couches de polyfluorure de vinylidène et de polypropylène. En effet, les courbes de traction révèlent la présence systématique d'une chute brutale de contrainte au cours de l'essai de traction avant la rupture complète de la fibre. Cette chute brutale de contrainte provient de la rupture de la couche externe de polypropylène et de la décohésion à l'interface polypropylène/polyfluorure de vinylidène. Cette décohésion interfaciale fait qu'après la rupture de la couche de polypropylène, celle-ci glisse sur la couche de polyfluorure de vinylidène pendant la traction, et que la contrainte est uniquement supportée par cette dernière. Un autre inconvénient concerne les conditions d'étirement de la fibre lors du procédé de filage. Dans ce même document, l'étirement a été réalisé à 210°C (voir table 1), ce qui se situe au-delà de la température de fusion du PVDF et du polypropylène. The same disadvantage is observed for tri-component fibers described in the publication by R. Martins et al. in J. Appl. Polym. Sci. 2014, DOI: 10.1002 / APP.40710. These fibers have a conductive polypropylene core and sheath, and a homopolymer PVDF core layer. The microscopic images of a cross-section of these fibers show decohesive interfaces between the layers (see Fig. 7). Figure 9 of this document also demonstrates poor interfacial adhesion between the polyvinylidene fluoride and polypropylene layers. Indeed, the tensile curves reveal the systematic presence of a sudden drop in stress during the tensile test before complete failure of the fiber. This sudden drop in stress results from the rupture of the polypropylene outer layer and the decohesion at the polypropylene / polyvinylidene fluoride interface. This interfacial decohesion makes that after the rupture of the polypropylene layer, it slides on the polyvinylidene fluoride layer during traction, and that the stress is only supported by the latter. Another disadvantage relates to the conditions of stretching of the fiber during the spinning process. In this same document, the stretching was carried out at 210 ° C. (see Table 1), which is beyond the melting temperature of PVDF and polypropylene.
Il existe donc un besoin de mettre au point des fibres multi-composant qui présentent à la fois de bonnes propriétés mécaniques, notamment une adhésion accrue entre la couche de polymère électroactif et celle(s) de polymère(s) faisant office d'électrode(s), lui permettant de maintenir son intégrité lors des sollicitations mécaniques comme l'étirage, et simultanément des propriétés de matériaux relaxeurs avec des effets électrostrictifs importants. RESUME DE L'INVENTION There is therefore a need to develop multi-component fibers that have both good mechanical properties, including increased adhesion between the electroactive polymer layer and (s) polymer (s) as an electrode ( s), allowing it to maintain its integrity during mechanical stresses such as stretching, and simultaneously properties of relaxing materials with significant electrostrictive effects. SUMMARY OF THE INVENTION
Selon un premier aspect, l'invention concerne une fibre polymère piézoélectrique constituée de trois couches : une couche B constituée d'au moins un polymère fluoré, une couche A comprenant au moins une polyoléfme et une couche C en polyamide, ladite couche B étant en contact sur toute sa surface d'une part, avec ladite couche C, et, d'autre part, avec ladite couche A, ladite couche C étant située à l'intérieur de la fibre. According to a first aspect, the invention relates to a piezoelectric polymer fiber consisting of three layers: a layer B consisting of at least one fluorinated polymer, a layer A comprising at least one polyolefin and a polyamide layer C, said layer B being contact over its entire surface on one hand, with said layer C, and, secondly, with said layer A, said layer C being located inside the fiber.
Selon un mode de réalisation, dans la fibre polymère selon l'invention, au moins l'une des couches A et C est chargée de particules conductrices telles que les nanotubes de carbone, les noirs de carbone, le graphène, le graphite, les nano fibres de carbone, nanofils ou nanoparticules métalliques (nanofils d'argent par exemple). Ceci favorise la polarisation et le comportement piézo-électrique de la fibre. According to one embodiment, in the polymer fiber according to the invention, at least one of the layers A and C is charged with conductive particles such as carbon nanotubes, carbon blacks, graphene, graphite, nano carbon fibers, nanowires or metal nanoparticles (silver nanowires for example). This promotes the polarization and the piezoelectric behavior of the fiber.
Selon un autre aspect, l'invention concerne un procédé de fabrication de la fibre tricomposant décrite plus haut par coextrusion des polymères constituant les couches A, B et C à l'état fondu, suivie d'une étape d'étirage. Selon un mode de réalisation, l'étape d'étirage s'effectue à une température située entre la température de transition vitreuse, Tg, et la température de fusion, Tf des polymères constituant les couches A, B et C, c'est-à-dire à une température comprise entre la Tg la plus haute et la Tf la plus basse des différents constituants, ce qui revient à une plage située entre entre 40°C et 130°C. According to another aspect, the invention relates to a method of manufacturing the tricomponent fiber described above by coextrusion of the polymers constituting the layers A, B and C in the molten state, followed by a drawing step. According to one embodiment, the drawing step is carried out at a temperature between the glass transition temperature, Tg, and the melting temperature, Tf of the polymers constituting the layers A, B and C, that is, that is to say at a temperature between the highest Tg and the lowest Tf of the various constituents, which amounts to a range between 40 ° C and 130 ° C.
Plus particulièrement pour une couche B en PVDF, cet étirage se fait entre 80 et 120°C. L'invention a également pour objet un dispositif piézoélectrique fabriqué à partir de la fibre tricomposant décrite. More particularly for a PVDF layer B, this stretching is between 80 and 120 ° C. The invention also relates to a piezoelectric device manufactured from the tricomponent fiber described.
L'invention vise également les matériaux textiles qui comprennent les fibres tri-composant décrites. The invention also relates to textile materials which comprise the tri-component fibers described.
La présente invention rend possible de surmonter les inconvénients de l'art antérieur. En particulier, l'invention permet d'obtenir des fibres piézoélectriques entièrement polymères, présentant une flexibilité accrue par rapport aux fibres à base de céramique, leur permettant une utilisation dans les matériaux « intelligents », notamment les matériaux textiles. De plus, les fibres selon l'invention ont des propriétés améliorées d'adhésion entre les différentes couches, ce qui garantit leur capacités d'étirage. En effet, une telle fibre pour obtenir ses caractéristiques mécaniques doit être étirée dans le procédé de filage, sans impact sur la cohésion de ses différents constituants. De plus, en particulier pour l'usage en textile habillement, cette fibre sera fortement sollicitée mécaniquement et pour maintenir son intégrité, une adhésion forte en les différentes couches est à privilégier. Enfin, dans le cas de l'utilisation de PVDF dans la couche B, l'étirage de la fibre permet de générer la phase cristalline béta nécessaire à l'effet piézoélectrique. Un autre avantage des fibres selon l'invention, présentant une bonne adhésion entre les couches de filaments, réside dans le fait que les températures d'étirage de la fibre multi composant restent dans des gammes classiques de températures d'étirage, à savoir en-dessous de la température de fusion du composant ayant le plus bas point de fusion, typiquement inférieure à 150°C. The present invention makes it possible to overcome the disadvantages of the prior art. In particular, the invention makes it possible to obtain entirely polymeric piezoelectric fibers having increased flexibility over ceramic-based fibers, enabling them to be used in "smart" materials, especially textile materials. In addition, the fibers according to the invention have improved adhesion properties between the different layers, which guarantees their drawability. Indeed, such a fiber to obtain its mechanical characteristics must be stretched in the spinning process, without impact on the cohesion of its various constituents. Moreover, especially for use in textile clothing, this fiber will be strongly mechanized and to maintain its integrity, strong adhesion in the different layers is preferred. Finally, in the case of the use of PVDF in layer B, the stretching of the fiber makes it possible to generate the beta crystalline phase necessary for the piezoelectric effect. Another advantage of the fibers according to the invention, having a good adhesion between the layers of filaments, lies in the fact that the stretching temperatures of the multicomponent fiber remain in conventional ranges of drawing temperatures, ie below the melting point of the component having the lowest melting point, typically below 150 ° C.
BREVE DESCRIPTION DES FIGURES BRIEF DESCRIPTION OF THE FIGURES
La Figure 1 représente une fibre bi-composant A/B (le filament de l'exemple 1) non-étirée, vue en section transversale au microscope électronique à balayage. Le matériau A est un mélange à 70% en poids d'un Polyéthylène haute densité PEHD et 30% en poids d'un Polyéthylène fonctionnalisé PEf. Le matériau B est un compound fait de PVDF à 80% en poids et d'un PVDFf à 20% en poids. Figure 1 shows a bi-component fiber A / B (the filament of Example 1) unstretched, seen in cross-section under a scanning electron microscope. Material A is a mixture of 70% by weight of HDPE high density polyethylene and 30% by weight of a PEf functionalized polyethylene. Material B is a compound made of PVDF at 80% by weight and a PVDFf at 20% by weight.
La Figure 2 représente l'image d'un faciès de rupture, obtenue par microscopie électronique à balayage, de la fibre bi-composant de l'exemple 1 fortement étirée (à la fin de la courbe contrainte allongement). La Figure 3 représente une fibre bi-composant B/C vue au microscope électronique à balayage. Le matériau B est un compound m-PVDF fait de PVDF à 80% en poids et d'un PVDFf à 20% en poids. Le matériau C est un compound polymère conducteur de polyamide 12 (PA12) chargé à 5% en poids de nanotubes de carbone (NTC). La fibre m-PVDF/PA12 % NTC a un ratio B/C = 33/66 à gauche et 90/10 à droite. Les Figures 4 à 6 sont des diagrammes représentant les résultats de tests de traction correspondant respectivement aux exemples 1 et 1 comparatif, 2 et 2 comparatif, et 3 et 3 comparatif. Figure 2 shows the image of a fracture facies, obtained by scanning electron microscopy, of the two-component fiber of Example 1 strongly stretched (at the end of the stress-strain curve). Figure 3 shows a bi-component fiber B / C seen under a scanning electron microscope. Material B is an m-PVDF compound made of 80% by weight PVDF and a 20% by weight PVDFf. Material C is a conductive polymer compound of polyamide 12 (PA12) loaded with 5% by weight of carbon nanotubes (CNTs). The m-PVDF / PA12% NTC fiber has a B / C ratio = 33/66 on the left and 90/10 on the right. Figures 4 to 6 are diagrams showing the tensile test results corresponding respectively to Comparative Examples 1 and 1, Comparative 2 and 2, and Comparative 3 and 3.
DESCRIPTION DE MODES DE REALISATION DESCRIPTION OF EMBODIMENTS
L'invention sera maintenant décrite plus en détail sans limitation dans la description suivante. Un premier objectif de l'invention est de proposer une fibre polymère piézoélectrique tri- composant, c'est-à-dire constituée de trois couches de polymères différents: une couche B constituée d'au moins un polymère fluoré, une couche A comprenant au moins une polyoléfme et une couche C en polyamide, ladite couche B étant en contact sur toute sa surface d'une part, avec ladite couche C, et, d'autre part, avec ladite couche A. La couche C est située à l'intérieur de la fibre. Une telle structure donne lieu à différentes géométries, comme la géométrie coaxiale ou la structure îles-en-mer. The invention will now be described in more detail without limitation in the following description. A first object of the invention is to propose a tri-component piezoelectric polymer fiber, that is to say composed of three layers of different polymers: a layer B consisting of at least one fluorinated polymer, a layer A comprising at least one least one polyolefin and one polyamide layer C, said layer B being in contact over its entire surface on the one hand, with said layer C, and, on the other hand, with said layer A. The layer C is located at inside the fiber. Such a structure gives rise to different geometries, such as coaxial geometry or islands-in-sea structure.
Selon un mode de réalisation, les polymères présents dans chacune des couches A, B et C présentent des températures de cristallisation Te respectant la condition : Te A< Te B < Te C afin d'assurer la meilleure cohésion possible au sein de la fibre tri-composant. En effet, la fibre est réalisée par coextrusion simultanée des trois matériaux. En respectant cet ordre de température on garantit la solidification du cœur en premier suivie de celle du matériau fluoré et enfin de la couche externe. Cette procédure permet d'éviter les phénomènes de décohésion aux interfaces dus au retrait à la cristallisation, et conduit à l'obtention d'une fibre plus dense et plus tenace. La mesure de la température de cristallisation est réalisée par analyse thermique différentielle selon la norme ISO 11357-3 « Plastics - Differential Scanning Calorimetry (DSC) Part 3 : Détermination of temeprature and enthalpy of melting and crystallization ». According to one embodiment, the polymers present in each of the layers A, B and C have crystallization temperatures Te respecting the condition: Te A <Te B <Te C in order to ensure the best possible cohesion within the fiber sorting -component. Indeed, the fiber is made by simultaneous coextrusion of the three materials. By respecting this temperature order, solidification of the core is ensured first followed by that of the fluorinated material and finally the outer layer. This procedure makes it possible to avoid the phenomena of decohesion at the interfaces due to shrinkage on crystallization, and leads to the production of a denser and more tenacious fiber. The measurement of the crystallization temperature is carried out by differential thermal analysis according to the ISO 11357-3 standard "Plastics - Differential Scanning Calorimetry (DSC) Part 3: Determination of temperature and enthalpy of melting and crystallization".
Selon un mode de réalisation de la fibre tri-composant, le polymère fluoré de la couche B est un polymère fluoré fonctionnalisé ou un mélange d'un polymère fluoré avec un polymère fluoré fonctionnalisé, et ladite couche A comprend un mélange d'une polyoléfme avec une polyoléfme fonctionnalisée porteuse d'une fonction réactive vis-à-vis de la fonction portée par ledit polymère fluoré fonctionnalisé. According to one embodiment of the tri-component fiber, the fluoropolymer of the layer B is a functionalized fluoropolymer or a mixture of a fluoropolymer with a functionalized fluoropolymer, and said layer A comprises a mixture of a polyolefin with a functionalized polyolefin carrying a function reactive with respect to the function carried by said functionalized fluoropolymer.
Cette structure particulière garantit une interface cohésive entre la couche B et la couche A de la fibre bi- ou tri-composant, et n'entraîne pas de délamination lors d'une sollicitation mécanique. This particular structure ensures a cohesive interface between the layer B and the layer A of the bi- or tri-component fiber, and does not cause delamination during a mechanical stress.
Couche B B layer
Le polymère fluoré de la couche B est tout polymère ayant dans sa chaîne au moins un monomère choisi parmi les composés contenant un groupe vinyle capable de s'ouvrir pour se polymériser et qui contient, directement attaché à ce groupe vinyle, au moins un atome de fluor, un groupe fluoroalkyle ou un groupe fluoroalkoxy. A titre d'exemple de monomère on peut citer le fluorure de vinyle; le fluorure de vinylidène (VDF); le trifluoroethylene (VF3); le chlorotrifluoroethylene (CTFE); le 1 ,2-difluoroethylene; le tetrafluoroethylene (TFE); l'hexafluoropropylene (HFP); les perfluoro(alkyl vinyl) ethers tels que le perfluoro(methyl vinyl)ether (PMVE), le perfluoro(ethyl vinyl) ether (PEVE) et le perfluoro(propyl vinyl) ether (PPVE); le perfluoro( 1,3 -dioxole); le perfluoro(2,2-dimethyl- 1,3 -dioxole) (PDD); le produit de formule CF2=CFOCF2CF(CF3)OCF2CF2X dans laquelle X est S02F, C02H, CH20H, CH20CN ou CH20PO3H; le produit de formule CF2=CFOCF2CF2S02F; le produit de formule F(CF2)nCH20CF=CF2 dans laquelle n est 1, 2, 3, 4 or 5; le produit de formule R1CH20CF=CF2 dans laquelle RI est l'hydrogène ou F(CF2)z et z vaut 1 , 2, 3 ou 4; le produit de formule R30CF=CH2 dans laquelle R3 est F(CF2)z- et z est 1, 2, 3 or 4; le perfluorobutyl ethylene (PFBE); le3,3,3-trifluoropropene et le 2- trifluoromethyl-3 ,3 ,3 -trifluoro- 1 -propene. The fluoropolymer of layer B is any polymer having in its chain at least one monomer chosen from compounds containing a vinyl group capable of opening to polymerize and which contains, directly attached to this vinyl group, at least one atom of fluorine, a fluoroalkyl group or a fluoroalkoxy group. By way of example of monomer, mention may be made of vinyl fluoride; vinylidene fluoride (VDF); trifluoroethylene (VF3); chlorotrifluoroethylene (CTFE); 1,2-difluoroethylene; tetrafluoroethylene (TFE); hexafluoropropylene (HFP); perfluoro (alkyl vinyl) ethers such as perfluoro (methyl vinyl) ether (PMVE), perfluoro (ethyl vinyl) ether (PEVE) and perfluoro (propyl vinyl) ether (PPVE); perfluoro (1,3-dioxole); perfluoro (2,2-dimethyl-1,3-dioxole) (PDD); the product of formula CF2 = CFOCF2CF (CF3) OCF2CF2X wherein X is SO2F, CO2H, CH20H, CH20CN or CH20PO3H; the product of formula CF2 = CFOCF2CF2S02F; the product of formula F (CF 2) nCH 2 OCOF = CF 2 wherein n is 1, 2, 3, 4 or 5; the product of formula R1CH20CF = CF2 wherein R1 is hydrogen or F (CF2) z and z is 1, 2, 3 or 4; the product of formula R30CF = CH2 wherein R3 is F (CF2) z- and z is 1, 2, 3 or 4; perfluorobutyl ethylene (PFBE); 3,3,3-trifluoropropene and 2-trifluoromethyl-3,3,3-trifluoro-1-propene.
Le polymère fluoré peut être un homopolymère ou un copolymère, il peut aussi comprendre des monomères non fluorés tels que l'éthylène. Selon un mode de réalisation, ledit polymère fluoré est un polyfluorure de vinylidène (PVDF) homopolymère ou un copolymère de VDF, contenant, en poids, au moins 50% de VDF, plus préférentiellement au moins 75% et mieux encore au moins 85%, avec au moins un comonomère choisi parmi le trifluoroéthylène (TrFE), le chlorotrifluoroéthylène (CTFE), le CFE ou 1,1-chlorofluoroéthylène, le CDFE ou 2-chloro- 1,1, -trifluoroéthylène, l'hexafluoropropène (HFP), le tétrafluoroéthylène (TFE). The fluoropolymer may be a homopolymer or a copolymer, it may also include non-fluorinated monomers such as ethylene. According to one embodiment, said fluoropolymer is a polyvinylidene polyfluoride (PVDF) homopolymer or a copolymer of VDF containing, by weight, at least 50% of VDF, more preferably at least 75% and better still at least 85%, with at least one comonomer selected from trifluoroethylene (TrFE), chlorotrifluoroethylene (CTFE), CFE or 1,1-chlorofluoroethylene, CDFE or 2-chloro-1,1, -trifluoroethylene, hexafluoropropene (HFP), Tetrafluoroethylene (TFE).
Selon un mode de réalisation, ledit polymère fluoré est un terpolymère tel que le P(VDF-TrFE- CFE) ou le P(VDF-TrFE-CTFE). According to one embodiment, said fluoropolymer is a terpolymer such as P (VDF-TrFE-CFE) or P (VDF-TrFE-CTFE).
Selon un mode de réalisation, la couche B entrant dans une fibre tri-composite selon l'invention est un polymère fluoré fonctionnalisé ou un mélange d'un polymère fluoré décrit plus haut avec un polymère fluoré fonctionnalisé. According to one embodiment, the layer B entering a tri-composite fiber according to the invention is a functionalized fluoropolymer or a mixture of a fluoropolymer described above with a functionalized fluoropolymer.
Selon un mode de réalisation, le polymère fluoré fonctionnalisé est porteur d'un monomère instauré greffé, comme décrit dans le doucment EP 1484346. Le monomère insaturé greffé est chois parmi les acides carboxyliques insaturés et leurs dérivés. According to one embodiment, the functionalized fluoropolymer carries an implanted monomer grafted, as described in doucment EP 1484346. The unsaturated grafted monomer is selected from unsaturated carboxylic acids and their derivatives.
Des exemples d'acides carboxyliques insaturés sont ceux ayant 2 à 20 atomes de carbone tels que les acides acrylique, méthacrylique, maléique, fumarique et itaconique. Les dérivés fonctionnels de ces acides comprennent par exemple les anhydrides, les dérivés esters, les dérivés amides, les dérivés imides et les sels métalliques (tels que les sels de métaux alcalins) des acides carboxyliques insaturés. On peut encore citer l'acide undécylènique. Examples of unsaturated carboxylic acids are those having 2 to 20 carbon atoms such as acrylic, methacrylic, maleic, fumaric and itaconic acids. The functional derivatives of these acids include, for example, anhydrides, ester derivatives, amide derivatives, imide derivatives and metal salts (such as alkali metal salts) of unsaturated carboxylic acids. We can also mention undecylenic acid.
Des acides dicarboxyliques insaturés ayant 4 à 10 atomes de carbone et leurs dérivés fonctionnels, particulièrement leurs anhydrides, sont des monomères de greffage particulièrement préférés. Unsaturated dicarboxylic acids having 4 to 10 carbon atoms and their functional derivatives, particularly their anhydrides, are particularly preferred grafting monomers.
Ces monomères de greffage comprennent par exemple les acides maléique, fumarique, itaconique, citraconique, allylsuccinique, cyclohex-4-ène-l,2-dicarboxylique, 4— méthyl- cyclohex-4-ène-l,2-dicarboxylique, bicyclo(2,2,l)hept-5-ène-2,3-dicarboxylique, x— méthylbicyclo(2,2,l-hept-5-ène-2,3-dicarboxylique, les anhydrides maléique, itaconique, citraconique, allylsuccinique, cyclohex-4-ène-l,2-dicarboxylique, 4— méthylènecyclohex-4- ène-l,2-dicarboxylique, bicyclo(2,2,l)hept-5-ène-2,3-dicarboxylique, et x— méthylbicyclo(2,2,l)hept-5-ène-2,2-dicarboxylique. These grafting monomers include, for example, maleic, fumaric, itaconic, citraconic, allylsuccinic, cyclohex-4-ene-1,2-dicarboxylic, 4-methylcyclohex-4-ene-1,2-dicarboxylic, bicyclo (2 , 2, 1) hept-5-ene-2,3-dicarboxylic acid, x-methylbicyclo (2,2,1-hept-5-ene-2,3-dicarboxylic acid), maleic, itaconic, citraconic, allylsuccinic, cyclohex anhydrides 4-ene-1,2-dicarboxylic, 4-methylenecyclohex-4-ene-1,2-dicarboxylic, bicyclo (2,2,1) hept-5-ene-2,3-dicarboxylic acid, and x-methylbicyclo ( 2,2, l) hept-5-ene-2,2-dicarboxylic acid.
Couche A Layer A
La polyoléfïne (PO) utilisable dans la couche A de la fibre selon l'invention est un polymère comprenant comme monomère une alpha-oléfine, c'est-à-dire les homopolymères d'une o lé fine ou les copolymères d'au moins une alpha-oléfine et d'au moins un autre monomère copolymérisable, l'alpha-oléfîne ayant avantageusement de 2 à 30 atomes de carbone. The polyolefin (PO) that can be used in the layer A of the fiber according to the invention is a polymer comprising, as monomer, an alpha-olefin, that is to say homopolymers of a fine particle or copolymers of at least an alpha-olefin and at least one other copolymerizable monomer, the alpha-olefin preferably having from 2 to 30 carbon atoms.
A titre d'exemple d'alpha-oléfme, on peut citer l'éthylène, le propylène, 1 -butène, 1-pentène, 3-méthyl-l -butène, 1-hexène, 4-méthyl- 1-pentène, 3 -méthyl- 1-pentène, 1-octène, 1 -décène, 1- dodécène, 1-tétradécène, 1-hexadécène, 1-octadécène, 1-eicocène, 1-dococène, 1-tétracocène, 1-hexacocène, 1-octacocène, et 1-triacontène. Ces alpha-oléfmes peuvent être utilisées seules ou en mélange de deux ou plus de deux. By way of example of an alpha-olefin, mention may be made of ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3 1-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene, 1-dococene, 1-tetracocene, 1-hexacocene, 1-octacocene , and 1-triacontene. These alpha-olefins may be used alone or as a mixture of two or more.
A titre d'exemples, on peut citer : les homopolymères et copolymères de l'éthylène, en particulier le polyéthylène basse densité (LDPE), le polyéthylène haute densité (HDPE), le polyéthylène linéaire basse densité (LLDPE), le polyéthylène très basse densité (VLDPE), le polyéthylène obtenu par catalyse métallocène, les homopolymères et copolymères du propylène, les polyalphao lé fines essentiellement amorphes ou attactiques (APAO), les copolymères éthylène/alpha-oléfïne tels qu'éthylène/propylène, les élastomères EPR (éthylène-propylène-rubber), et EPDM (éthylène- propylène-diène), et les mélanges de polyéthylène avec un EPR ou un EPDM, les copolymères blocs styrène/éthylène-butène/styrène (SEBS), styrène/ butadiène/styrène (SBS), styrène/isoprène/styrène (SIS), et styrène/éthylène-propylène/styrène (SEPS), les copolymères de l'éthylène avec au moins un produit choisi parmi les sels ou les esters d'acides carboxyliques insaturés tels que par exemple les (méth)acrylates d'alkyle, l'alkyle pouvant avoir jusqu'à 24 atomes de carbone, les esters vinyliques d'acides carboxyliques saturés tels que par exemple l'acétate ou le propionate de vinyle, et les diènes tels que par exemple le 1 ,4-hexadiène ou le polybutadiène. By way of examples, mention may be made of: homopolymers and copolymers of ethylene, in particular low density polyethylene (LDPE), high density polyethylene (HDPE), linear low density polyethylene (LLDPE), very low polyethylene density (VLDPE), polyethylene obtained by metallocene catalysis, homopolymers and copolymers of propylene, polyalphaoyl fines mainly amorphous or attactiques (APAO), ethylene / alpha-olefin copolymers such as ethylene / propylene, EPR (ethylene-propylene-rubber) elastomers, and EPDM (ethylene-propylene-diene), and polyethylene blends with EPR or EPDM, block copolymers styrene / ethylene-butene / styrene (SEBS), styrene / butadiene / styrene (SBS), styrene / isoprene / styrene (SIS), and styrene / ethylene-propylene / styrene (SEPS), copolymers of ethylene with at least a product chosen from unsaturated carboxylic acid salts or esters such as, for example, alkyl (meth) acrylates, alkyl having up to 24 carbon atoms, vinyl esters of saturated carboxylic acids such as for example acetate or vinyl propionate, and dienes such as for example 1,4-hexadiene or polybutadiene.
La polyoléfïne fonctionnalisée peut être un polymère d'alpha oléfmes ayant des motifs réactifs (les fonctionnalités) ; de tels motifs réactifs sont les fonctions acides, anhydrides, ou époxy. À titre d'exemple, on peut citer les polyoléfmes précédentes greffées ou co- ou ter polymérisées par des époxydes insaturés tels que le (méth)acrylate de glycidyle, ou par des acides carboxyliques ou les sels ou esters correspondants tels que l'acide (méth)acrylique (celui-ci pouvant être neutralisé totalement ou partiellement par des métaux tels que Zn, etc.) ou encore par des anhydrides d'acides carboxyliques tels que l'anhydride maléique. Une polyoléfïne fonctionnalisée est par exemple un mélange PE/EPR, dont le ratio en poids peut varier dans de larges mesures, par exemple entre 40/60 et 90/10, ledit mélange étant co-greffé avec un anhydride, notamment anhydride maléique, selon un taux de greffage par exemple de 0,01 à 5% en poids. The functionalized polyolefin may be a polymer of alpha olefins having reactive units (functionalities); such reactive units are acid, anhydride or epoxy functions. By way of example, mention may be made of the preceding polyolefms grafted or copolymerized with unsaturated epoxides such as glycidyl (meth) acrylate, or with carboxylic acids or the corresponding salts or esters such as acid ( meth) acrylic (which can be totally or partially neutralized by metals such as Zn, etc.) or by anhydrides of carboxylic acids such as maleic anhydride. A functionalized polyolefin is, for example, a PE / EPR mixture, the weight ratio of which can vary widely, for example between 40/60 and 90/10, said mixture being co-grafted with an anhydride, in particular maleic anhydride, according to a grafting rate of, for example, 0.01 to 5% by weight.
La polyoléfïne fonctionnalisée peut être choisie parmi les (co)polymères cités plus haut, greffés avec anhydride maléique ou méthacrylate de glycidyle, dans lesquels le taux de greffage est par exemple de 0,01 à 5% en poids. The functionalized polyolefin may be chosen from the (co) polymers mentioned above, grafted with maleic anhydride or glycidyl methacrylate, in which the degree of grafting is, for example, from 0.01 to 5% by weight.
La polyoléfïne fonctionnalisée peut aussi être un co- ou ter polymère d'au moins les motifs suivants : (1) éthylène, (2) (méth)acrylate d'alkyle ou ester vinylique d'acide carboxylique saturé et (3) anhydride tel que anhydride maléique ou acide (méth)acrylique ou époxy tel que (méth)acrylate de glycidyle. A titre d'exemple de polyoléfïnes fonctionnalisées de ce dernier type, on peut citer les copolymères suivants, où l'éthylène représente de préférence au moins 60% en poids et où le ter monomère (la fonction) représente par exemple de 0,1 à 10% en poids du copolymère : The functionalized polyolefin may also be a copolymer or copolymer of at least the following units: (1) ethylene, (2) alkyl (meth) acrylate or saturated carboxylic acid vinyl ester and (3) anhydride such as maleic anhydride or (meth) acrylic acid or epoxy such as glycidyl (meth) acrylate. By way of example of functionalized polyolefins of the latter type, mention may be made of the following copolymers, in which the ethylene preferably represents at least 60% by weight and the ter monomer (the function) represents, for example, from 0.1 to 10% by weight of the copolymer:
- les copolymères éthylène/(méth)acrylate d'alkyle / acide (méth)acrylique ou anhydride maléique ou méthacrylate de glycidyle; ethylene / alkyl (meth) acrylate / (meth) acrylic acid or maleic anhydride or glycidyl methacrylate copolymers;
- les copolymères éthylène/acétate de vinyle/anhydride maléique ou méthacrylate de glycidyle; ethylene / vinyl acetate / maleic anhydride or glycidyl methacrylate copolymers;
- les copolymères éthylène/acétate de vinyle ou (méth)acrylate d'alkyle / acide (méth)acrylique ou A titre d'exemples de tels polymères, on peut citer les ter polymères de l'éthylène, d'acrylate d'alkyle et d'anhydride maléique ou de méthacrylate de glycidyle comme les Lotader®de la Demanderesse ou des polyoléfïnes greffées par de l'anhydride maléique comme les Orevac®de la Demanderesse ainsi que des ter polymères de l'éthylène, d'acrylate d'alkyle et d'acide (meth) acrylique, anhydride maléique ou méthacrylate de glycidyle. ethylene / vinyl acetate or (meth) acrylate / (meth) acrylic acid copolymers or examples of such polymers that may be mentioned are the ter polymers of ethylene, of alkyl acrylate and of maleic anhydride or of glycidyl methacrylate such as the Lotader® of the Applicant or polyolefins grafted with maleic anhydride such as the Orevac® of the Applicant and ter polymers of ethylene, alkyl acrylate and of (meth) acrylic acid, maleic anhydride or glycidyl methacrylate.
Couche C La nomenclature utilisée pour définir les polyamides est décrite dans la norme ISO 1874- 1 :2011 "Plastiques - Matériaux polyamides (PA) pour moulage et extrusion - Partie 1 : Désignation", notamment en page 3 (tableaux 1 et 2) et est bien connue de l'homme du métier. Layer C The nomenclature used to define polyamides is described in ISO 1874-1: 2011 "Plastics - Polyamides (PA) for molding and extrusion - Part 1: Designation", in particular on page 3 (Tables 1 and 2) and is well known to those skilled in the art.
La couche C est en polyamide. Le polyamide est choisi de telle sorte que sa température de cristallisation est supérieure à celle des couches A et B. Selon un mode de réalisation, le polyamide de la couche C est le polyamide 12 (PA 12), qui est un polyamide aliphatique fabriqué par ouverture du cycle lauryllactame (donc un polylauroamide). Sa viscosité inhérente peut être comprise entre 1 et 2 et avantageusement entre 1,2 et 1,8. La viscosité inhérente est mesurée à 20°C pour une concentration de 0,5%> dans le méta-cresol. The layer C is polyamide. The polyamide is chosen so that its crystallization temperature is higher than that of layers A and B. According to one embodiment, the polyamide of layer C is polyamide 12 (PA 12), which is an aliphatic polyamide manufactured by opening of the lauryllactam cycle (thus a polylauroamide). Its inherent viscosity can be between 1 and 2 and advantageously between 1.2 and 1.8. The inherent viscosity is measured at 20 ° C for a concentration of 0.5% in meta-cresol.
Les polyamides 11, 6, 6.10, 6.12, 10.10, 10.12 et 6.6 conviennent également pour la couche C. Le polyamide de la couche C peut contenir de 0 à 30%> en poids d'au moins un produit choisi parmi les plastifiants et les modifiants choc pour respectivement 100 à 70% de polyamide. Polyamides 11, 6, 6.10, 6.12, 10.10, 10.12 and 6.6 are also suitable for layer C. The polyamide of layer C may contain from 0 to 30% by weight of at least one product chosen from plasticizers and shock modifiers for respectively 100 to 70% of polyamide.
A titre d'exemple de plastifiant on peut citer les dérivés de benzène sulfonamide, tels que le n- butyl benzène sulfonamide (BBSA), l'éthyl toluène sulfonamide ou le N-cyclohexyl toluène sulfonamide; les esters d'acides hydroxy-benzoïques, tels que le parahydroxybenzoate d'éthyl- 2 hexyle et le parahydroxybenzoate de décyl-2 hexyle ; les esters ou éthers du tétrahydrofurfuryl alcool, comme l'oligoéthylèneoxytétrahydromrfurylalcool ; les esters de l'acide citrique ou de l'acide hydroxy-malonique, tels que l'oligoéthylèneoxy malonate. On peut citer aussi le decyl héxyl parahydroxybenzoate et l'éthyl héxyl parahydroxybenzoate. Un plastifiant particulièrement préféré est le n-butyl benzène sulfonamide (BBSA). A titre d'exemple de modifiant choc on peut citer les polyoléfïnes, les polyoléfïnes réticulées, les élastomères EPR, EPDM, SBS et SEBS ces élastomères pouvant être greffés pour faciliter leur compatibilisation avec le polyamide, les copolymères à blocs polyamides et blocs polyethers. Ces copolymères à blocs polyamides et blocs polyethers sont connus en eux mêmes, ils sont aussi désignés par l'appellation PEBA (polyéther bloc amide). On peut encore citer les élastomères acryliques par exemple ceux du type NBR, HNBR, X-NBR. By way of example of plasticizer, mention may be made of benzene sulphonamide derivatives, such as n-butyl benzene sulphonamide (BBSA), ethyl toluene sulphonamide or N-cyclohexyl toluene sulphonamide; esters of hydroxy-benzoic acids, such as 2-ethylhexyl parahydroxybenzoate and 2-decyl hexyl parahydroxybenzoate; esters or ethers of tetrahydrofurfuryl alcohol, such as oligoethyleneoxytetrahydrocrofuryl alcohol; esters of citric acid or of hydroxy-malonic acid, such as oligoethyleneoxy malonate. Mention may also be made of decyl hexyl parahydroxybenzoate and ethyl hexyl parahydroxybenzoate. A particularly preferred plasticizer is n-butyl benzene sulfonamide (BBSA). As an example of impact modifier include polyolefins, crosslinked polyolefins, elastomers EPR, EPDM, SBS and SEBS these elastomers can be grafted to facilitate their compatibilization with polyamide, copolymers with polyamide blocks and polyether blocks. These polyamide block copolymers and polyether blocks are known in themselves, they are also known by the name PEBA (polyether block amide). Acrylic elastomers can also be mentioned, for example those of the NBR, HNBR or X-NBR type.
Ce polyamide peut contenir des additifs tels que anti UV, stabilisants, antioxydants, ou ignifugeants. This polyamide may contain additives such as anti-UV, stabilizers, antioxidants, or flame retardants.
Lorsque la couche intérieure en polyamide est chargée de particules conductrices, elle apporte la conductivité et des propriétés mécaniques à la fibre selon l'invention. Selon un mode de réalisation, au moins l'une des couches A et C est chargée de particules conductrices telles que les nanotubes de carbone, les noirs de carbone, le graphène, le graphite, les nanofibres de carbone, les nanofils ou nanoparticules métalliques (nanofils d'argent par exemple). Les polymères ainsi chargés deviennent des conducteurs électriques et sont aptes à jouer le rôle d'électrodes. Le taux de charges optimal est ainsi compris entre 2 et 30% massique par rapport au poids de chaque couche A et C, selon la charge conductrice considérée pour obtenir une conductivité électrique suffisante à l'utilisation du polymère comme électrode. When the polyamide inner layer is loaded with conductive particles, it brings the conductivity and mechanical properties to the fiber according to the invention. According to one embodiment, at least one of the layers A and C is charged with conductive particles such as carbon nanotubes, carbon blacks, graphene, graphite, carbon nanofibers, metal nanowires or nanoparticles ( silver nanowires for example). The polymers thus charged become electrical conductors and are able to act as electrodes. The optimal charge ratio is thus between 2 and 30% by weight relative to the weight of each layer A and C, depending on the conductive charge considered to obtain sufficient electrical conductivity to the use of the polymer as an electrode.
Les couches adhèrent les unes sur les autres sans liant de coextrusion. The layers adhere to one another without a coextrusion binder.
L'adhésion des différents polymères au sein d'une fibre multi composant de type cœur-écorce- écorce ou iles-en-mer tri composant est un critère déterminant pour l'obtention des propriétés recherchées : The adhesion of the various polymers within a multi-component fiber core-bark-bark or islands-in-sea tri-component is a determining criterion for obtaining the desired properties:
- possibilité d'étirement de la fibre multi composant sans délaminage des couches et obtention du polymère fluoré sous phase beta majoritaire ; - possibility of stretching the multi-component fiber without delamination of the layers and obtaining the fluoropolymer under major beta phase;
- tenue mécanique de la fibre après étirement en vue d'application textiles ; - interface cohésive entre les différents constituants de la fibre permet une polarisation du polymère fluoré en évitant les problèmes de claquage électrique sous haute tension à l'interface (présence d'air évitée) ; - mechanical strength of the fiber after stretching for textile application; - Cohesive interface between the various constituents of the fiber allows polarization of the fluoropolymer avoiding the problems of electrical breakdown under high voltage at the interface (presence of air avoided);
- meilleure récupération des charges piézo-électriques générée par déformation du polymère fluoré piézo-électrique. - Better recovery of piezoelectric charges generated by deformation of the piezoelectric fluoropolymer.
Un autre objectif de l'invention est de fournir un procédé de préparation de la fibre tricomposant décrite plus haut par coextrusion des polymères constituant les couches A, B et C à l'état fondu, suivie d'une étape d'étirage à chaud. Another object of the invention is to provide a process for preparing the three-component fiber described above by coextrusion of the polymers constituting the layers A, B and C in the molten state, followed by a hot stretching step.
Plus précisément, le procédé de fabrication de la fibre tricomposant comprend les étapes suivantes : fournir les polymères composant chacune des couches A, B et C à l'état fondu ; coextruder lesdits polymères à l'état fondu sous forme de filaments. Les températures de mise en œuvre des polymères A, B et C doivent être les plus proches possible et définissent celle de la filière tri-composant (ou bi composant). Dans le cas d'une fibre constituée de PA12, PVDF, HDPE cette température de filière est idéalement comprise entre 210°C et 240 °C ; étirer la fibre ainsi extrudée. L'étirement à l'état fondu n'a pas d'influence sur l'adhésion des couches A, B C et n'a que peu d'impact sur le taux de phase beta final dans la phase fluorée. Conformément aux pratiques de l'homme du métier, c'est l'étape de post étirement, une fois le filament refroidi et solidifié, qui va conférer au fil ses prorpriétés mécaniques élevées ainsi que l'obtention du PVDF sous sa forme béta majoritaire. Cette étape de post étirement est effectuée à l'état solide et préférentiellement à une température comprise entre 80 et 120°C. Le facteur d'étirement R désignant le ratio de vitesse entre les rouleaux d'étirement est préférentiellement compris entre 3 et 6, ce ratio conduissant aux propriétés mécaniques et de phase béta mentionnées. - enrouler ensemble lesdits filaments extrudés pour former une fibre. More specifically, the method for manufacturing the tricomponent fiber comprises the following steps: providing the polymers making up each of the layers A, B and C in the molten state; coextruding said polymers in the molten state in the form of filaments. The processing temperatures of polymers A, B and C must be as close as possible and define that of the tri-component (or bi-component) die. In the case of a fiber consisting of PA12, PVDF, HDPE this die temperature is ideally between 210 ° C and 240 ° C; stretch the fiber thus extruded. The melt stretch has no influence on the adhesion of the layers A, B C and has little impact on the final beta phase level in the fluorinated phase. In accordance with the practices of the person skilled in the art, it is the post-stretching step, once the filament has cooled and solidified, which will give the wire its high mechanical properties as well as obtaining the PVDF in its majority beta form. This post-stretching step is carried out in the solid state and preferably at a temperature between 80 and 120 ° C. The stretching factor R designating the speed ratio between the stretching rollers is preferably between 3 and 6, this ratio leading to the mentioned mechanical and beta phase properties. - Winding together said extruded filaments to form a fiber.
La réalisation d'une fibre piézo-électrique polymère est préférentiellement réalisée lorsque les électrodes sont directement fabriquées pendant l'étape de filage. Une façon simple est d'utiliser le filage multi-composant, (ou coextrusion) dans laquelle le matériau piézo-actif (PVDF, copolymères ou terpolymères de VDF) est entouré de polymères conducteurs électriques qui jouent le rôle d'électrodes. II est également possible que le matériau polymère utilisé soit un matériau électrostrictif et électroactif, par exemple un polymère (P(VDF-TrFE-CFE) ou P(VDF-TrFE-CTFE). Dans ces matériaux, l'application d'un champ électrique aux bornes du matériau provoque une réduction de sa taille dans le sens d'application du champ ainsi que son allongement dans le sens perpendiculaire au champ appliqué. Une fibre selon l'invention composée d'un tel polymère, et ayant une âme conductrice, constituant une première électrode, et un revêtement extérieur conducteur constituant une seconde électrode peut ainsi constituer un actionneur. L'application d'un champ électrique entre ces électrodes permet de modifier les caractéristiques mécaniques de la fibre. Si cette fibre est intégrée dans une structure textile, l'application de ce champ électrique permet de modifier les caractéristiques mécaniques de cette structure textile. The production of a piezoelectric polymer fiber is preferably carried out when the electrodes are directly manufactured during the spinning step. One simple way is to use multi-component spinning (or coextrusion) in which the piezo-active material (PVDF, VDF copolymers or terpolymers) is surrounded by electrically conductive polymers that act as electrodes. It is also possible that the polymer material used is an electrostrictive and electroactive material, for example a polymer (P (VDF-TrFE-CFE) or P (VDF-TrFE-CTFE). In these materials, the application of a field electrical connection across the material causes a reduction in its size in the direction of application of the field and its elongation in the direction perpendicular to the applied field.A fiber according to the invention composed of such a polymer, and having a conductive core, constituting a first electrode, and a conductive outer coating constituting a second electrode can thus constitute an actuator, the application of an electric field between these electrodes makes it possible to modify the mechanical characteristics of the fiber, if this fiber is integrated into a textile structure. the application of this electric field makes it possible to modify the mechanical characteristics of this textile structure.
Le filage de fibres multi-composant permet d'obtenir de nouvelles propriétés par la combinaison de différents matériaux au sein d'un même filament. Ces fibres multi-composant peuvent trouver des applications dans des secteurs variés du textile technique, de la fîltration, mais également dans l'électronique. L'invention a également pour objet un dispositif piézoélectrique fabriqué à partir de la fibre tricomposant décrite. The spinning of multi-component fibers makes it possible to obtain new properties by the combination of different materials within the same filament. These multi-component fibers can find applications in various sectors of technical textiles, filtration, but also in electronics. The invention also relates to a piezoelectric device manufactured from the tricomponent fiber described.
L'invention vise également les matériaux textiles qui comprennent des fibres tri-composant décrites. The invention also relates to textile materials which comprise tri-component fibers described.
EXEMPLES EXAMPLES
Les exemples suivants illustrent l'invention sans la limiter. The following examples illustrate the invention without limiting it.
Afin de mieux étudier les propriétés des fibres multi-composant et les interactions (notamment l'adhésion) entre la couche A et la couche B, d'une part, et entre la couche B et la couche C, d'autre part, des fibres bi-composant A/B et B/C ont été fabriquées et étudiées (voir les exemples 1-3), en parallèle des fibres tri-composant selon l'invention (exemple 4). In order to better study the properties of the multi-component fibers and the interactions (in particular the adhesion) between the layer A and the layer B, on the one hand, and between the layer B and the layer C, on the other hand, Two-component fibers A / B and B / C were manufactured and studied (see Examples 1-3), in parallel with the tri-component fibers according to the invention (Example 4).
Produits products
Matériaux polymères de la couche A Polyéthylène haute densité (noté HDPE) : polyéthylène caractérisé par un indice de fluidité de 23 g/10' (190°C sous 2,16 kg), une température de fusion de 128°C et une température de cristallisation de 117°C mesurées par analyse thermique. Polymeric materials of layer A High density polyethylene (denoted HDPE): polyethylene characterized by a melt index of 23 g / 10 '(190 ° C. under 2.16 kg), a melting temperature of 128 ° C. and a crystallization temperature of 117 ° C. measured by thermal analysis.
Polyéthylène fonctionnalisé (noté PEf) : terpolymère d'éthylène, d'acrylate de butyle et de méthacrylate de glycidyle caractérisé par un indice de fluidité de 12 g/10' (190°C sous 2,16kg), une température de fusion de 74°C et une température de cristallisation de 54°C.  Functionalized polyethylene (denoted by PEf): terpolymer of ethylene, of butyl acrylate and of glycidyl methacrylate, characterized by a melt index of 12 g / 10 '(190 ° C. under 2.16 kg), a melting temperature of 74 ° C and a crystallization temperature of 54 ° C.
Matériaux polymères de la couche B Polymeric materials of layer B
Polyfluorure de vinylidène (noté PVDF) : homopolymère de fluorure de vinylidène caractérisé par un indice de fluidité de 33 g/10' (230°C sous 2,16 kg), une température de fusion de 172°C et une température de cristallisation de 138°C mesurées par analyse thermique. Polyvinylidene fluoride (denoted PVDF): homopolymer of vinylidene fluoride characterized by a melt index of 33 g / 10 '(230 ° C. under 2.16 kg), a melting point of 172 ° C. and a crystallization temperature of 138 ° C measured by thermal analysis.
Polyfluorure de vinylidène fonctionnalisé (noté PVDFf) : homopolymère de fluorure de vinylidène greffé avec 0.5% en poids d'anhydride maléique caractérisé par un indice de fluidité de 16 g/10' (230°C sous 3,8 kg), une température de fusion de 172°C et une température de cristallisation de 137°C mesurées par analyse thermique.  Functionalized vinylidene fluoride (denoted PVDFf): homopolymer of vinylidene fluoride grafted with 0.5% by weight of maleic anhydride characterized by a melt index of 16 g / 10 '(230 ° C. under 3.8 kg), a temperature of melting at 172 ° C and a crystallization temperature of 137 ° C measured by thermal analysis.
Matériaux polymères de la couche C Polymeric materials of layer C
Polyamide 12 (noté PA12): homopolymère de lauryllactame caractérisé par un indice de fluidité de 50 g/10' (235°C sous 2.16 kg) et une température de fusion de 180°C et une température de cristallisation de 153°C mesurées par analyse thermique. Polyamide 12 (denoted PA12): homopolymer of lauryllactam characterized by a melt index of 50 g / 10 '(235 ° C. under 2.16 kg) and a melting temperature of 180 ° C. and a crystallization temperature of 153 ° C., measured by thermal analysis.
Matériaux conducteurs Conductive materials
Noir de carbone (noté CB) : Carbon black (denoted CB):
- Nanotubes de carbone (noté NTC).  - Nanotubes of carbon (noted NTC).
Préparation des compounds fonctionnalisés et conducteurs Preparation of functionalized and conductive compounds
On appelle compounds fonctionnalisés les mélanges HDPE avec HDPE fonctionnalisé ou les mélanges PVDF avec PVDF fonctionnalisé. On appelle compounds conducteurs les mélanges HDPE (fonctionnalisés ou non) avec les charges conductrices ou PA12 avec les charges conductrices. Les compounds fonctionnalisés sont réalisés par voie fondue selon un procédé d'extrusion. Pour cela une extrudeuse de type bi-vis est utilisée préférentiellement et permet le mélange de polymères non fonctionnels à des polymères fonctionnalisés en taux contrôlés. Les granulés de chaque matière sont mélangés en proportions choisies à l'état solide puis convoyés dans la machine d'extrusion selon un profil croissant de température dont les valeurs sont généralement comprises entre Tf+20 et Tf+70 °C. A l'issue de l'extrusion, un jonc est obtenu puis granulé. Functionalized compounds are HDPE mixtures with functionalized HDPE or PVDF mixtures with functionalized PVDF. Conductive compounds are the HDPE mixtures (functionalized or not) with the conductive fillers or PA12 with the conductive fillers. The functionalized compounds are made by molten route according to an extrusion process. For this purpose a bi-screw extruder is preferably used and allows the mixing of non-functional polymers with functionalised polymers at controlled rates. The granules of each material are mixed in selected proportions in the solid state and then conveyed in the extrusion machine according to an increasing temperature profile whose values are generally between Tf + 20 and Tf + 70 ° C. At the end of the extrusion, a rod is obtained and then granulated.
La première étape de réalisation d'un compound conducteur consiste en la fabrication d'un mélange-maître concentré en charges conductrices, mélange aussi appelé master-batch. Ce mélange-maître est réalisé par extrusion en voie fondue grâce à un outil mélange à fort taux de cisaillement tel qu'un comalaxeur ou une extrudeuse de type bi-vis à profil cisaillant. Cette étape est indispensable pour disperser de façon optimale la charge conductrice dans le polymère. De façon avantageuse, un fort taux de charges est utilisé dans le mélange-maître, typiquement compris entre 15 et 50 % en poids, et permet d'obtenir une forte viscosité favorisant le cisaillement et donc la dispersion des charges. La matière est convoyée en voie fondue dans la machine d'extrusion selon un profil de température croissant dont les valeurs sont généralement comprises entre Tf+20 et Tf+70 °C. Les charges conductrices sont apportées par un doseur latéral à la matière en fusion en quantité souhaitée. Un jonc est obtenu en sortie d'extrudeuse, refroidi puis granulé. The first step of producing a conductive compound consists in the manufacture of a masterbatch concentrated in conductive fillers, a mixture also called master batch. This masterbatch is produced by extrusion in a molten state using a high shear mixing tool such as a twin-screw co-extruder or shear profile extruder. This step is essential to optimally disperse the conductive filler in the polymer. Advantageously, a high level of filler is used in the masterbatch, typically between 15 and 50% by weight, and makes it possible to obtain a high viscosity that promotes shearing and therefore dispersion of the fillers. The material is melt convected in the extrusion machine according to an increasing temperature profile whose values are generally between Tf + 20 and Tf + 70 ° C. The conductive fillers are provided by a lateral doser to the molten material in a desired quantity. A rod is obtained at the extruder outlet, cooled and granulated.
Ces granulés de mélange-maître sont dilués dans la matrice considérée par procédé d'extrusion en voie fondue, sur une machine de type bi-vis. De la même façon, un profil croissant de température est appliqué à la matière en fusion pour permettre la dilution optimale du mélange- maître, dont les valeurs sont comprises entre Tf+20 et Tf+70 °C. These masterbatch granules are diluted in the matrix considered by melt extrusion process, on a bi-screw type machine. In the same way, an increasing temperature profile is applied to the melt to allow optimum dilution of the masterbatch, whose values are between Tf + 20 and Tf + 70 ° C.
Filage des filaments bi-composants et tri-composants A partir des compounds fonctionnalisés et conducteurs, des structures bi-composants et tri- composants ont été réalisées dans les conditions suivantes. Bicomponent and tri-component filament spinning From the functionalized and conductive compounds, two-component and three-component structures were produced under the following conditions.
Exemple 1 : Fibre bi-composant A/B Example 1: Two-component fiber A / B
Le matériau A est un mélange à 70% en poids d'un Polyéthylène haute densité PEHD et 30% en poids d'un Polyéthylène fonctionnalisé PEf. Le matériau B est un compound fait de PVDF à 80% en poids et d'un PVDFf à 20% en poids. Ces compounds A et B sont fondus et convoyés dans deux extrudeuses monovis, qui de façon optionnelle remplissent deux pompes de gavage servant à fixer le débit de sortie. A l'issue de l'étape d'extrusion ou de pompage, les deux compounds A et B sont acheminés dans une conduite puis injectés dans un pack de filage bi-composant permettant d'amener les compounds A et B respectivement en périphérie (gaine) et au centre (cœur) de chaque filament extrudé. Le pack de filage est réalisé selon les connaissances de l'homme du métier pour assurer le filage bi-composant de géométrie cœur-écorce et peut être constitué entre autres parties d'un cône d'injection, de plaques de répartition de flux, de filtres, d'une plaque de support ainsi que d'une filière. Material A is a mixture of 70% by weight of HDPE high density polyethylene and 30% by weight of a PEf functionalized polyethylene. Material B is a compound made of PVDF at 80% by weight and a PVDFf at 20% by weight. These compounds A and B are melted and conveyed in two single-screw extruders, which optionally fill two booster pumps for setting the output rate. At the end of the extrusion or pumping step, the two compounds A and B are conveyed in a pipe and then injected into a two-component spin pack for bringing the compounds A and B respectively to the periphery (sheath ) and in the center (heart) of each extruded filament. The spin pack is produced according to the knowledge of those skilled in the art to provide the two-component spinning core-bark geometry and can be constituted among other parts of an injection cone, flow distribution plates, filters, a support plate and a die.
Les éléments spécifiques à chaque compound : extrudeuse, pompe, conduite sont portés à des températures permettant la fusion dudit compound ΎΆ et TÎB , le pack de filage est quant à lui porté à une température à T>TÎB dans le cas ou TfB>Tfc. Cette température T ne doit pas conduire à la dégradation de l'un ou l'autre des compounds A ou B. The elements specific to each compound: extruder, pump, pipe are brought to temperatures permitting the melting of said compound ΎΆ and TIB, the spin pack is brought to a temperature at T> TÎB in the case where TfB> Tfc. This temperature T must not lead to the degradation of one or the other compounds A or B.
Pour les compounds A et B cités en exemple 1 , cette température T se situe préférentiellement entre 205 et 220°C et une filière mono filament bi-composant est utilisée. Les débits d'extrusion sont choisis de manière à obtenir un ratio volumique gaine A / cœur B de 30/70. For compounds A and B cited in Example 1, this temperature T is preferably between 205 and 220 ° C and a two-component monofilament die is used. The extrusion flow rates are chosen so as to obtain an A / B core volume ratio of 30/70.
Le filament extrudé est refroidi à l'air ambiant, entraîné par banc de tirage à rouleaux oméga permettant de fixer le diamètre et l'étirement à l'état fondu. Ce filament est ensuite collecté et bobiné sans étirement à l'état solide supplémentaire. The extruded filament is cooled in ambient air, driven by an omega roller drawing bench to fix the diameter and the stretch in the molten state. This filament is then collected and wound without stretching in the additional solid state.
La Figure 1 annexée illustre la fibre bi-composant A/B de l'exemple 1 , non-étirée. The appended FIG. 1 illustrates the non-stretched bi-component fiber A / B of Example 1.
Exemple 2 : Fibre bi-composant B/C Example 2: Bi-component fiber B / C
Le matériau B est un compound m-PVDF fait de PVDF à 80% en poids et d'un PVDFf à 20% en poids. Le matériau C est un compound polymère conducteur de polyamide 12 (PA12) chargé à 5% en poids de Nanotubes de carbone (NTC). De la même façon que pour l'exemple 1 , les polymères B et C sont extrudés à travers une filière bi composant mono filament et placés respectivement en gaine et en cœur de la géométrie bi-composant. La température de mise en œuvre préférentiellement choisie se situe entre 210 et 230°C. Les filaments sont collectés sans subir d' étirement à l'état solide. La Figure 3 annexée illustre les fibres obtenues selon l'exemple 2 : les fibres m-PVDF/PA12 % NTC en ratios B/C = 33/66 à gauche ou 90/10 à droite. Caractérisation de l'adhésion par test de traction sur fibre Material B is an m-PVDF compound made of 80% by weight PVDF and a 20% by weight PVDFf. Material C is a conductive polymer compound of polyamide 12 (PA12) loaded with 5% by weight of carbon nanotubes (CNTs). In the same way as for example 1, the polymers B and C are extruded through a two-component monofilament die and respectively placed in sheath and core of the two-component geometry. The temperature of implementation preferably chosen is between 210 and 230 ° C. The filaments are collected without undergoing stretching in the solid state. The attached FIG. 3 illustrates the fibers obtained according to Example 2: the m-PVDF / PA12% NTC fibers in ratios B / C = 33/66 on the left or 90/10 on the right. Characterization of adhesion by tensile test on fiber
L'adhésion entre les couches A/B et B/C a été évaluée par un test de traction sur filament bi- composant. Pour ce faire, une machine d'essais universelle est utilisée en mode essai de traction. Elle est munie d'une traverse fixe et d'une traverse mobile instrumentée, d'un capteur de force et de mâchoires et mors adaptés aux essais sur filaments. Un dispositif permet l'enregistrement de la force mesurée par le capteur en fonction du déplacement de la traverse mobile. Les filaments sont placés entre les deux mâchoires et l'essai de traction est réalisé jusqu'à rupture totale des filaments, en utilisant une vitesse d'essai de 50 ou de 100%/min conformément à l'ISO 5079 ou ISO 2062, selon que l'on teste des mono ou multi- filaments. Adhesion between the A / B and B / C layers was evaluated by a two-component filament tensile test. To do this, a universal test machine is used in traction test mode. It is equipped with a fixed crossbar and an instrumented moving beam, a force sensor and jaws and jaws suitable for filament testing. A device allows the recording of the force measured by the sensor as a function of the displacement of the movable cross member. The filaments are placed between the two jaws and the tensile test is carried out until the filaments are completely broken, using a test speed of 50 or 100% / min according to ISO 5079 or ISO 2062, according to that we test mono or multi-filaments.
La Figure 2 annexée montre la fibre de l'exemple 1, étirée à 800%. Elle montre que les deux matériaux restent adhérés même après un étirement important, et rompent simultanément. The appended FIG. 2 shows the fiber of example 1, stretched at 800%. It shows that the two materials remain adhered even after a large stretch, and break simultaneously.
Les structures réalisées sont montrées dans le Tableau I ci-dessous. Les courbes correspondant aux tests de traction des exemples 1 et 1 comparatif, 2 et 2 comparatif, et 3 et 3 comparatif sont représentées dans les figures 4, 5 et 6 respectivement. The structures produced are shown in Table I below. The curves corresponding to the tensile tests of Comparative Examples 1 and 1, Comparative 2 and 2, and Comparative 3 and 3 are shown in Figures 4, 5 and 6 respectively.
Figure 4 : Le filament exemple 1 présente une courbe contrainte - allongement lisse et caractéristique d'un filament mono-composant. Le filament exemple 1 comparatif, qui n'est pas constitué de polymères fonctionnalisés, présente un comportement différent. Une chute importante de contrainte est observée dès le passage du régime élastique au régime de déformation plastique. Cette chute est caractéristique d'une rupture d'un des deux composants, dans ce cas celle de la gaine HDPE. Cette gaine est déchaussée/délaminée progressivement du cœur PVDF du filament comme le montre le comportement bruité de la courbe. Figure 4: The filament example 1 has a curve stress - smooth elongation and characteristic of a single-component filament. The comparative Example 1 filament, which does not consist of functionalized polymers, exhibits a different behavior. A significant drop in stress is observed as soon as the elastic regime changes to the plastic deformation regime. This drop is characteristic of a rupture of one of the two components, in this case that of the HDPE sheath. This sheath is loosened / delaminated progressively from the PVDF core of the filament as shown by the noisy behavior of the curve.
Figure 5 : De la même façon que pour l'exemple 1, la courbe exemple 2 utilisant des polymères A et B, respectivement fonctionnalisé et chargé, présente un comportement classique de traction pour un mono filament mono composant. A l'inverse lorsque la gaine est PVDF non fonctionnalisé, exemple 2 comparatif, on remarque des délaminations / micro ruptures tout au long de l'étirage du filament ainsi qu'une défaillance plus importante vers 350% signe d'une délamination importante. L'amélioration de l'adhésion du PVDF au PA12 est bien due à la fonctionnalisation du PVDF et non à la présence de NTC dans le PA12. En effet, ce même comportement amélioré est observé avec des PA12 non chargés comme le montre la Figure 6. Couche A Couche B Couche C Diamètre Ratio du entre les filament couchesFigure 5: In the same way as for Example 1, the curve Example 2 using polymers A and B, respectively functionalized and loaded, has a conventional traction behavior for a single-component monofilament. Conversely, when the sheath is unfunctionalized PVDF, Comparative Example 2, delamination / micro breaks are observed throughout the stretching of the filament as well as a greater failure towards 350% sign of a significant delamination. The improvement of PVDF adhesion to PA12 is due to the functionalization of PVDF and not to the presence of CNTs in PA12. Indeed, this same improved behavior is observed with unloaded PA12 as shown in Figure 6. Layer A Layer B Layer C Diameter Ratio of between layer filament
Exemple 1 Mélange Mélange 360 A/B : Example 1 Blend 360 A / B:
HDPE/HDPEf PVDF/PVDFf 30/70 70/30 en poids 80/20 en poids  HDPE / HDPEf PVDF / PVDFf 30/70 70/30 by weight 80/20 by weight
Exemple 1 HDPE PVDF 230 μιη A/B : comparatif 33/66 Example 1 HDPE PVDF 230 μιη A / B: Comparative 33/66
Exemple 2 Mélange Mélange 365 μιη B/C : Example 2 Blend Mixing 365 μιη B / C:
PVDF/PVDFf conducteur 90/10 80/20 en poids PA12/NTC/CB  PVDF / PVDFf conductor 90/10 80/20 by weight PA12 / NTC / CB
Exemple 2 PVDF Mélange 240 μιη B/C : comparatif conducteur 90/10  Example 2 PVDF Mixing 240 μιη B / C: 90/10 Comparative Conductor
PA12/NTC/CB  PA12 / CNT / CB
Exemple 3 Mélange PA12 330 μιη B/C :  Example 3 Mixture PA12 330 μιη B / C:
PVDF/PVDFf 85/15 80/20 en poids  PVDF / PVDFf 85/15 80/20 by weight
Exemple 3 PVDF PA12 240 μιη B/C : comparatif 75/25 Example 3 PVDF PA12 240 μιη B / C: Comparative 75/25
Exemple 4 Mélange Mélange Mélange Example 4 Mixture Mixture Mixture
selon conducteur PVDF/PVDFf conducteur  according to driver PVDF / PVDFf driver
l'invention HDPE/HDPEf/NT 80/20 en poids PA12/NTC/C the invention HDPE / HDPEf / NT 80/20 by weight PA12 / NTC / C
C/CB B  C / CB B
Exemple 4 Mélange PVDF Mélange  Example 4 Mixture PVDF Mixture
comparatif conducteur conducteur comparative driver driver
HDPE/NTC/CB PA12/NTC/C  HDPE / NTC / CB PA12 / NTC / C
B  B
Tableau I Table I

Claims

REVENDICATIONS
1. Fibre polymère piézoélectrique constituée de trois couches : une couche B constituée d'au moins un polymère fluoré, une couche A comprenant au moins une polyoléfme et une couche C en polyamide, ladite couche B étant en contact sur toute sa surface d'une part, avec ladite couche C, et, d'autre part, avec ladite couche A, ladite couche C étant située à l'intérieur de la fibre. 1. Piezoelectric polymer fiber consisting of three layers: a layer B consisting of at least one fluorinated polymer, a layer A comprising at least one polyolefin and a polyamide layer C, said layer B being in contact over its entire surface with a on the one hand, with said layer C, and on the other hand with said layer A, said layer C being located inside the fiber.
2. Fibre selon la revendication 1 dans laquelle ladite couche B est constituée d'au moins un polymère fluoré fonctionnalisé ou un mélange d'un polymère fluoré avec un polymère fluoré fonctionnalisé. 2. Fiber according to claim 1 wherein said layer B consists of at least one functionalized fluoropolymer or a mixture of a fluoropolymer with a functionalized fluoropolymer.
3. Fibre selon la revendication 2, dans laquelle ladite couche A comprend un mélange d'une polyoléfme avec une polyoléfme fonctionnalisée porteuse d'une fonction réactive vis-à-vis de la fonction portée par ledit polymère fluoré fonctionnalisé. 3. The fiber of claim 2, wherein said layer A comprises a mixture of a polyolefin with a functionalized polyolefin carrying a function reactive with the function carried by said functionalized fluoropolymer.
4. Fibre selon l'une des revendications 1 à 3 dans laquelle les polymères présents dans chacune des couches A, B et C présentent des températures de cristallisation Te respectant la condition : Te A< Te B < Te C, les températures de cristallisation étant mesurées par analyse thermique différentielle. 4. Fiber according to one of claims 1 to 3 wherein the polymers present in each of the layers A, B and C have crystallization temperatures Te respecting the condition: Te A <Te B <Te C, the crystallization temperatures being measured by differential thermal analysis.
5. Fibre selon l'une des revendications 1 à 4 présentant une structure coaxiale. 5. Fiber according to one of claims 1 to 4 having a coaxial structure.
6. Fibre selon l'une des revendications 1 à 4 présentant une structure îles-en-mer. 6. Fiber according to one of claims 1 to 4 having an islands-in-sea structure.
7. Fibre selon l'une des revendications 1 à 6 dans laquelle ladite couche C est en polyamide 12. 7. Fiber according to one of claims 1 to 6 wherein said layer C is polyamide 12.
8. Fibre selon l'une des revendications précédentes dans laquelle au moins une des couches A et C est chargée de particules conductrices telles que les nanotubes de carbone, les noirs de carbone, le graphène, le graphite, les nanofibres de carbone, nanofîls ou nanoparticules métalliques. 8. Fiber according to one of the preceding claims wherein at least one of the layers A and C is charged with conductive particles such as carbon nanotubes, carbon blacks, graphene, graphite, nanofibers of carbon, nanofil or metallic nanoparticles.
9. Fibre selon l'une des revendications 2 à 8, dans laquelle ledit polymère fluoré fonctionnalisé est porteur d'un monomère instauré greffé choisi parmi les acides carboxyliques insaturés et leurs dérivés. 9. Fiber according to one of claims 2 to 8, wherein said functionalized fluoropolymer carries a grafted initiated monomer selected from unsaturated carboxylic acids and their derivatives.
10. Fibre selon la revendication 9, dans laquelle ledit monomère de greffage est choisi parmi les acides maléique, fumarique, itaconique, citraconique, allylsuccinique, cyclohex-4- ène- 1 ,2-dicarboxylique, 4— méthyl-cyclohex-4-ène- 1 ,2-dicarboxylique, bicyclo(2,2,l)hept-5-ène-2,3-dicarboxylique, x— méthylbicyclo(2,2,l-hept-5-ène-2,3- dicarboxylique, les anhydrides maléique, itaconique, citraconique, allylsuccinique, cyclohex-4-ène- 1 ,2-dicarboxylique, 4— méthylènecyclohex-4-ène- 1 ,2-dicarboxylique, bicyclo(2,2,l)hept-5-ène-2,3-dicarboxylique, et x— méthylbicyclo(2,2,l)hept-5-ène- 2,2-dicarboxylique. 10. Fiber according to claim 9, wherein said grafting monomer is selected from maleic, fumaric, itaconic, citraconic, allylsuccinic, cyclohex-4-ene-1,2-dicarboxylic, 4-methyl-cyclohex-4-ene acids. 1,2-dicarboxylic, bicyclo (2,2,1) hept-5-ene-2,3-dicarboxylic acid, x-methylbicyclo [2,2,1-hept-5-ene-2,3-dicarboxylic acid, maleic, itaconic, citraconic, allylsuccinic, cyclohex-4-ene-1,2-dicarboxylic, 4-methylenecyclohex-4-ene-1,2-dicarboxylic, bicyclo (2,2,1) hept-5-ene-2 anhydrides , 3-dicarboxylic, and x-methylbicyclo (2,2,1) hept-5-ene-2,2-dicarboxylic acid.
11. Fibre selon la revendication 3 dans laquelle ladite polyoléfïne fonctionnalisée porte des groupements époxy. 11. The fiber of claim 3 wherein said functionalized polyolefin carries epoxy groups.
12. Procédé de fabrication d'une fibre polymère piézoélectrique selon l'une des revendications 1 à 11 comprenant les étapes suivantes : 12. A method of manufacturing a piezoelectric polymer fiber according to one of claims 1 to 11 comprising the following steps:
fournir les polymères composant chacune des couches A, B et C à l'état fondu, coextruder lesdits polymères à l'état fondu sous forme de filaments,  supplying the polymers comprising each of the layers A, B and C in the molten state, coextruding said polymers in the molten state in the form of filaments,
enrouler ensemble lesdits filaments extrudés pour former une fibre,  winding said extruded filaments together to form a fiber,
étirer à chaud la fibre ainsi extrudée  hot stretch the fiber thus extruded
13. Dispositif piézoélectrique fabriqué à partir de fibres selon l'une des revendications 1 à 11. 13. Piezoelectric device made from fibers according to one of claims 1 to 11.
14. Matériau textile comprenant des fibres selon l'une des revendications 1 à 11. 14. Textile material comprising fibers according to one of claims 1 to 11.
PCT/EP2018/064985 2017-06-09 2018-06-07 Fluorinated polymer multilayer fibre WO2018224583A1 (en)

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