WO2005118924A1 - Loaded polymer fibre, method for the production thereof, use of the same, and composition comprising such fibres - Google Patents

Loaded polymer fibre, method for the production thereof, use of the same, and composition comprising such fibres Download PDF

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Publication number
WO2005118924A1
WO2005118924A1 PCT/FR2005/050364 FR2005050364W WO2005118924A1 WO 2005118924 A1 WO2005118924 A1 WO 2005118924A1 FR 2005050364 W FR2005050364 W FR 2005050364W WO 2005118924 A1 WO2005118924 A1 WO 2005118924A1
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WO
WIPO (PCT)
Prior art keywords
fiber
fibers
charged
polymer
fiber according
Prior art date
Application number
PCT/FR2005/050364
Other languages
French (fr)
Inventor
Gaël CADORET
Richard Morlat
Catherine Bianchi
Original Assignee
Saint-Gobain Materiaux De Construction Sas
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Saint-Gobain Materiaux De Construction Sas filed Critical Saint-Gobain Materiaux De Construction Sas
Priority to US11/597,629 priority Critical patent/US20080044654A1/en
Priority to CA002568433A priority patent/CA2568433A1/en
Priority to BRPI0511491-8A priority patent/BRPI0511491A/en
Priority to JP2007514039A priority patent/JP2008500463A/en
Priority to EP05762544A priority patent/EP1769108A1/en
Priority to MXPA06013618A priority patent/MXPA06013618A/en
Publication of WO2005118924A1 publication Critical patent/WO2005118924A1/en
Priority to NO20065922A priority patent/NO20065922L/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B16/00—Use of organic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of organic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B16/04—Macromolecular compounds
    • C04B16/06—Macromolecular compounds fibrous
    • C04B16/0616—Macromolecular compounds fibrous from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B16/0625—Polyalkenes, e.g. polyethylene
    • C04B16/0633—Polypropylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/005—Reinforced macromolecular compounds with nanosized materials, e.g. nanoparticles, nanofibres, nanotubes, nanowires, nanorods or nanolayered materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • 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
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/04—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/46—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04C—STRUCTURAL ELEMENTS; BUILDING MATERIALS
    • E04C5/00—Reinforcing elements, e.g. for concrete; Auxiliary elements therefor
    • E04C5/07—Reinforcing elements of material other than metal, e.g. of glass, of plastics, or not exclusively made of metal
    • E04C5/073—Discrete reinforcing elements, e.g. fibres
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2933—Coated or with bond, impregnation or core
    • Y10T428/2964—Artificial fiber or filament
    • Y10T428/2967—Synthetic resin or polymer

Definitions

  • the present invention relates to the field of fibers, and more particularly relates to a charged polymeric fiber.
  • Polymer fibers find applications in many fields.
  • This charged polypropylene fiber has a titer of 1 dtex, a high tenacity and a Young's modulus greater than that of an unfilled polypropylene fiber.
  • This fiber is proposed as reinforcement of mortars, concretes or cementitious pastes. It is currently difficult to have a high purity of carbon nanotubes. In fact, catalyst residues can form micronic impurities liable to degrade the properties of the final fiber. In addition, it is difficult to manufacture large quantities of carbon nanotubes, which is reflected in the cost of the fiber. Furthermore, this charged polymer fiber was produced under laboratory conditions, without taking industrial constraints into account. especially in terms of reliability and performance. The proposed manufacturing is therefore not realistic for industrial production.
  • the present invention proposes to provide a polymeric fiber, which has good mechanical properties, in particular a high Young's modulus, while being easy to manufacture on an industrial scale.
  • the first object of the invention is a charged polymeric fiber comprising by mass of additives, the charged polymeric fiber having a Young's modulus greater than that of an uncharged polymeric fiber and the additives comprising mineral additives having minus a submicron dimension.
  • the combination of a polymer and mineral additives having at least one submicron dimension according to the invention makes it possible to obtain a fiber having an increased Young's modulus compared to an uncharged fiber based on the same polymer.
  • the mineral additives according to the invention are readily available in nature or are easily synthesizable, and if necessary easily purifiable. These additives also have the advantage of being inexpensive.
  • the manufacture of the fiber according to the invention is compatible with industrial requirements.
  • the submicron dimension according to the invention is understood as the submicron dimension of the mineral additives taken on average.
  • the submicron dimension corresponds for example to a diameter or a thickness.
  • the term fiber is defined broadly. Without any other adjective or precision added, the term fiber designates both an unstretched fiber (in solid phase) and a drawn fiber (in one or more times).
  • the fiber designates both a yarn or a monofilament, as well as a set of filaments (of textile fiber type) identical or different from each other.
  • the fiber can be continuous or cut, short or long.
  • the submicron dimension of the mineral additives can be less than 500 nm, and preferably less than 100 nm.
  • the mineral additives can be of spherical, rod-like or lamellar type structure. Naturally, a combination of additives with different structures is possible.
  • the mineral additives can have a form factor greater than 5, and preferably greater than 50. It is recalled that the form factor is defined as the ratio of the largest of the dimensions to the smallest of the dimensions.
  • the mineral additives can be metal oxides or clays.
  • the metal oxides mention may be made of aluminas, barium oxides, titanium oxides, zirconium oxides, manganese oxides, talc, magnesia and calcium carbonate.
  • the clays can be lamellar, that is to say in sheets, or fibrous.
  • the mineral additives can comprise an exfoliable lamellar clay preferably chosen from synthetic and natural phyllosilicates, smectite clays such as montmorillonite, nontronite, beidellite, hectorite, saponite, sauconite, vermiculite and the like, as well as magadiite, kenyaite, stevensite, halloysite, aluminate oxides, hydrotalcite and the like.
  • the clays can have a negative surface charge of at least 20 milliequivalents, preferably at least 50 milliequivalents, and more preferably between 50 and 150 milliequivalents, per 100 grams of said additives.
  • the clays can thus be modified by organic molecules capable of being absorbed inside the minerals, for example between the sheets of the clays, which allows their exfoliation. Even if the clay can have any cation exchange capacity, it is nevertheless preferable for the clay to exfoliate properly.
  • the mineral additives can be chosen from montmorillonite and boehmite. Boehmite is based on alumina monohydrate AI-O-OH. Boehmite is for example in the form of sticks. Montmorillonite has exfoliable sheets and can be distributed homogeneously in the mass of the polymeric fiber loaded according to the invention. Montmorillonite and boehmite also have a particularly high Young's modulus, greater than 100 GPa.
  • the mineral additives can be surface modified by at least one of the following agents: cationic surfactants, amphoteric agents, derivatives of aliphatic, aromatic or arylaliphatic amines, phosphines and sulfides, and preferably salts of ammonium, phosphonium or sulfonium. These agents serve as a blowing agent for sheet clays. Furthermore, these agents also promote the dispersion of the mineral additives according to the invention.
  • the mineral additives can also be modified by an adhesion promoter which is preferably an organosilane compound and even more preferably a silane, an amino silane, a vinyl silane and their mixtures.
  • the proportion by weight of mineral additives relative to the total weight of the fiber may preferably be less than 10%, even more preferentially less than 5%.
  • the charged polymeric fiber may be based on a polymer, for example chosen from polyolefins, polyamides, polyesters, polyacrylonitrile and polyvinyl alcohols and their copolymers.
  • the charged polymeric fiber can be a charged polyolefin fiber, such as polyethylene or polypropylene and even more preferably filled polypropylene.
  • the fiber may also comprise a mixture of a polyolefin and a polyolefin having polar functions, which is preferably a grafted polyolefin of maleic anhydride, glycidyl methacrylate, vinyl pyrrolidone, styrene-methacrylate, acrylates or acetates, the content by weight polyolefin having polar functions relative to the total weight of the charged polymer fiber preferably being less than 10% and even more preferably less than 5%.
  • the polyolefin having polar functions can be grafted before or after synthesis. The latter promotes the dispersion of a spinning mixture and fiber drawing.
  • the percentage of polyolefin having polar functions can be limited for a greater increase in the Young's modulus.
  • the titer of the charged polymer fiber can be between 0.5 to 10 dtex, more advantageously from 0.5 to 2 dtex.
  • a particularly advantageous reinforcing effect in composites can be obtained with a fiber (monofilament) of relatively small section.
  • the cross section of a charged polymer fiber according to the invention is not necessarily circular and may have an irregular or multilobal shape.
  • the charged polymeric fiber according to the invention may have a tenacity equal to at least 80% of that of the uncharged fiber.
  • the charged polymer fiber has a high tenacity, of at least 4 cN / dtex, preferably of at least 5 cN / dtex, very preferably of at least 7 cN / dtex, and in particular from 8 to 9 cN / dtex.
  • This range of toughness can be achieved by adjusting the spinning and drawing process appropriately.
  • a basic polyolefin material can be specifically chosen with an appropriate molecular weight distribution.
  • the charged polymeric fiber may preferably comprise, on the surface, a size which contains an amino or polyamine, phosphoric or polyphosphoric compound, more preferably an ester of phosphoric acid based on fatty chain.
  • a simple modification of the exposed surface of the fiber by a sizing makes it possible to effectively and durably improve the interaction between the fiber and a cement matrix.
  • the surface properties of the polymeric fiber are modified by one or more sizing agents providing a spinning assistance function.
  • the spinning assistance function consists in facilitating the constitution of the polymeric fiber at at least one spinning stage: it is in particular a question of lubricating the fibers (monofilaments at this stage) to improve the handling by transport members at different stages of manufacturing, to minimize the electrostatic charges carried by the fiber. For example, you can choose a product from the products marketed under the names SILASTOL Cut 5A and Cut 5B from SCHILL & SEILACHER, SYNTHESIN 7292 from Dr.
  • the size may be present on the fiber in an amount of 0.05 to 5% by weight of dry matter relative to the dry weight of fiber.
  • the sizing also provides a wettability function by the composition based on hydraulic binder, of adhesion promoter to the matrix with hydraulic setting and gives the fiber-cement composite even increased mechanical properties.
  • the wettability function of the hydraulic binder composition consists in facilitating the dispersion of the polymer fibers in the matrix, resulting from the good dispersion of the fibrous material in the initial mixture of binder and water from which the product is made.
  • This function mainly uses the surface polarity of the fibrous material to make it hydrophilic.
  • the function of promoting adhesion to the matrix with hydraulic setting consists in reinforcing the interaction between the fibrous reinforcement and the matrix of the hardened product.
  • This latter function also calls for the presence of polar functional groups at the surface of the fibers.
  • These functions can be provided by one or more agents chosen from lubricants, antistatics, surfactants, fatty chain compounds and polymers with polar functions, in which a lubricant can be a fatty chain compound, as well as a surfactant can be a fatty chain compound or an antistatic can be a polymer with polar functions.
  • a drawn fiber can be in the form of a wire cut to a length of the order of 2 to 20 mm, in particular from 5 to 12 mm.
  • the present invention also relates to the use of a charged polymeric fiber as described above as a reinforcing fiber in a fiber-based product.
  • the present invention then relates to a product based on fibers, characterized in that it comprises charged polymeric fibers as defined above.
  • the product is in the form of fabric, veil, long fiber mat, cut fiber mat, unidirectional product, non-woven product, rope, net, ribbon, strap, band, or even in the form of a mixture of said products. fibers with fibers of a distinct nature and preferably in the form of a mixed fiber.
  • a mixed fiber is the fiber marketed under the name Twintex by Saint-Gobain and which contains polypropylene filaments and glass filaments.
  • Multiple areas of application of the charged polymer fiber according to the invention are possible: carpets, hygienic applications, ribbons, ropes and twines, the textile industry (clothing, threads), household textiles (non-woven for decoration, woven for walls, ...), geotextiles, agrotextiles, packaging, medical textiles, bioactive fibers, multicomponent fibers, high-resistance technical yarns or monofilaments (seat belts, protective nets , or fishing, etc.).
  • the charged polymer fiber according to the invention can be full or essentially full, that is to say comprise for example a hollow core along the axis of the fiber.
  • the charged polymer fiber (sized or not) according to the invention can be coated.
  • the fiber can be incorporated in various forms in petroleum products, in bituminous products and for example in the form of masts in asphalt-based products such as roofing elements. Fiber in various forms can also be thermoformed.
  • the product comprises a mineral matrix, preferably a mass with hydraulic setting and the product is preferably chosen from glues, mortars, concretes, grouts and fiber-cement.
  • the mass with hydraulic setting consists of a binder with hydraulic setting, chosen mainly from the various existing cements, possibly additives of inert or active fillers.
  • fillers and additives there may be mentioned rheology additives (dispersants, plasticizers, superplasticizers, flocculants), mineral fillers (silica, fly ash, dairy, pozzolans, carbonates), as well as support or reinforcing fibers for filtration or draining processes (natural fibers, especially cellulose, or synthetic).
  • rheology additives disersants, plasticizers, superplasticizers, flocculants
  • mineral fillers sica, fly ash, dairy, pozzolans, carbonates
  • support or reinforcing fibers for filtration or draining processes natural fibers, especially cellulose, or synthetic.
  • the fibers according to the invention are particularly effective as reinforcing fiber cement in proportions of the order of 0.2 to 5% by weight of the fibers relative to the total dry weight of the initial mixture.
  • the fibers according to the invention are particularly effective as reinforcement of mortars, in proportions of the order of 0.01 to 0.2% by weight of the fibers relative to the total dry weight of the initial mixture for an "anticrack" and from 0.2 to 5% for structural effects.
  • the fibers can be cut strands having a length of between 2 and 20 mm and more particularly between 5 and 12 mm.
  • the product can have various shapes (hollow, tubular) and preferably a flat or corrugated plate shape.
  • Hydraulic binder articles formed into plates can be manufactured by a technique of filtration of an aqueous suspension comprising a binder with hydraulic setting, reinforcing fibers and optionally fillers.
  • a commonly used process based on this technique is known as the Hatschek process: a very dilute aqueous suspension is contained in a tank equipped with means for ensuring a homogeneous distribution of the constituents in the volume of the tank; a filter drum submerges partially in the tank, and its rotation results in the deposition on its surface of a thin film of materials (fibers and hydrated binder); this film is entrained by a felt towards a format cylinder on which it is continuously wound; when the film has reached the desired thickness, it is cut so as to unwind from the cylinder an individual sheet of material with hydraulic setting.
  • the sheet can then be formed into a shaped product and acquires its final characteristics by hardening the binder.
  • a product of greater thickness can be obtained by superimposing an appropriate number of sheets, and pressing them to ensure the cohesion of the whole.
  • Such plates are used as a roofing or facade element.
  • the product can comprise a polymer matrix which is preferably chosen from a polyethylene, polypropylene, polyamide, polyester, epoxy and phenolic matrix.
  • the main fields of application of composites, for example based on polypropylene, are: transport (parts under the hood, rear board, etc.), electrical applications, household and consumer goods, buildings and public works and industrial goods.
  • the invention further relates to a process for manufacturing a charged polymeric fiber as defined above comprising a step of spinning a polymeric composition comprising mineral additives having at least a submicron dimension.
  • the additives according to the invention are easily dispersible and do not significantly modify the rheological properties (viscosity, etc.) of the polymer composition to be spun.
  • the polymeric composition can be obtained by extrusion.
  • the extrusion temperature should be adjusted depending on the polymer and said additives.
  • the spinning temperature can be between 250 ° C and 300 ° C for charged polypropylene.
  • the spinning step may include cooling preferably with air cooled and suitably humidified, for good heat exchange capacity, and radial cooling.
  • the method comprises a step of drawing below the melting temperature, immediately after spinning or in recovery.
  • the method may include a step of passing the fiber through continuous drawing means. This step can be achieved using rollers at different temperatures and different speeds and using ovens.
  • the method comprises a step of preparing said composition comprising at least one filtration operation. In this way, potential impurities and aggregates are removed before spinning, for example using a filter at the extruder outlet.
  • the stage of preparation of said composition can include the production of a premix then put in the form of granules to dilute with the polymer and optionally with the modified polymer.
  • This premix is obtained by dilution in polymer of a master mixture in granules and preferably non-commercial which contains the mineral additives according to the invention.
  • the masterbatch can be filtered.
  • a sizing step can intervene in the spinning step.
  • a sizing step can take place after stretching and be followed by a drying step using air oven (s).
  • the size can be applied pure or from an aqueous solution, dispersion or emulsion or based on another suitable liquid vehicle.
  • the invention also relates to a method of manufacturing a product based on charged fibers as defined above and a mass with hydraulic setting.
  • an initial mixture based on hydraulic binder, water and fibers as defined above is prepared, the fibers are filtered on a fixed or moving support to form an elementary sheet. wet, a plurality of elementary sheets are optionally superimposed to form a wet intermediate product and the wet sheet or intermediate product is dried.
  • the invention also relates to a composition for material with hydraulic setting comprising a hydraulic binder and fibers as described above. These compositions can be cement preparations to be suspended for the draining process or cement preparations for mortars for other shaping processes.
  • the invention finally relates to a composition comprising a polymer matrix and fibers as described above.
  • Such matrices can preferably be thermoplastic matrices, thermosetting matrices, and preferably polyethylene, polypropylene, polyamides, polyesters, epoxy, phenolic matrices.
  • the reference fiber is an uncharged fiber of high tenacity and small diameter (Idtex) obtained without mineral additives according to the invention from polypropylene resin HF445FB from the company Boréalis having a flow index of the melt state called M FI (for melt flow index in English) of 18 g / 10 min measured at 230 ° C and 2.16 kg.
  • M FI melt flow index in English
  • the fiber that is to say all monofilament, will freeze after rapid cooling and with cooling air controlled in temperature and speed.
  • Dr Boehme a size having the reference Synthesin 7292 marketed by the company Dr Boehme is deposited on the polypropylene fiber at the outlet of the die, at a rate of 0.45% by weight of dry extract of polypropylene fiber.
  • the fiber is then wound, then unrolled and drawn continuously in a drawing zone comprising different series of heated rollers and having an increasing speed of rotation. Hot air or steam ovens are interposed between the different series of rollers. At the end of the stretching zone, the fiber is cooled. The fiber is then cut into 30 mm sections to carry out the tests.
  • EXAMPLE 2 A polypropylene fiber filled with the following polymeric composition is made, expressed in% by weight of material relative to the total weight of the fiber: - 5.5% of the product Nanomer C44PA produced by the company Nanocor and containing approximately 45% montmorillonite and polypropylene (PP), - 94.5% PP Boréalis HF445FB.
  • Montmorillonite is a clay whose sheets have an average nanometric thickness and an average length of a few hundred nanometers, giving a form factor greater than 50.
  • the polymeric composition is produced in a single-screw extruder at a temperature of approximately 250 ° C. and is brought to a die having holes of diameter equal to 0.35 mm.
  • the viscosity of the composition is comparable to that of the polymer used.
  • a size having the reference Synthesin 7292 sold by the company Dr Boehme is deposited on the polypropylene fiber loaded at the outlet of the die, at a rate of 0.45% by weight of dry extract of charged polypropylene fiber.
  • a polypropylene fiber charged is made from the following polymeric composition, expressed in% by weight of material relative to the total weight of the fiber: - 40% of a premix concentrated to 5% in montmorillonite and under form of granules, this premix being obtained from 87.5% of PP Boréalis HF445FB and from 12.5% of Nanoblend 1001 sold by the company Polyone which contains approximately 40% of montmorillonite and of PP, - 60% of PP Boréalis HF445FB.
  • the clay sheets have an average nanometric thickness and an average length of a few hundred nanometers, giving a form factor greater than 50.
  • the pre-mixing carried out in a co-rotating twin-screw extruder at a temperature of 220 ° C. passes through a filter having holes of approximately 40 ⁇ m and then is brought to a die having holes of diameter equal to 3 mm in order to manufacture granules.
  • the polymeric composition is produced in a single screw extruder at a temperature of approximately 250 ° C. and is brought to a die having holes of diameter equal to 0.35 mm.
  • the viscosity of the composition is comparable to that of the polymer used.
  • a size having the reference Synthesin 7292 sold by the company Dr Boehme is deposited on the polypropylene fiber loaded at the outlet of the die, at a rate of 0.45% by weight of dry extract of charged polypropylene fiber.
  • a polypropylene fiber charged is made from the following polymeric composition, expressed in% by weight of material relative to the total weight of the fiber: - 40% of a premix concentrated to 5% in montmorillonite and under form of granules, this premix being obtained from 87.5% of PP Borealis HF445FB and 12.5% of Nanoblend 1001, - 58% of PP Borealis HF445FB, - 2% of grafted polypropylene 1% maleic anhydride, says PPgMA, Polybond3200 reference from the Crompton Company.
  • the sheets of clay have an average nanometric thickness and an average length of a few hundred nanometers, giving a form factor greater than 50.
  • the fiber is produced under conditions similar to those of the example
  • a polypropylene fiber filled with the following polymeric composition is made, expressed in% by weight of material relative to the total weight of the fiber: - 60% of a premix concentrated to 5% in montmorillonite and under form of granules, this premix being obtained from 87.5% of PP Borealis HF445FB and 12.5% of Nanoblend 1001, - 37% of PP Borealis HF445FB, - 3% of PPgMA reference Polybond3200 from the Company Crompton.
  • the sheets of clay have an average nanometric thickness and an average length of a few hundred nanometers, giving a form factor greater than 50.
  • the fiber is produced under conditions similar to those of Example 3.
  • a polypropylene fiber charged is made from the following polymeric composition, expressed in% by weight of material relative to the total weight of the fiber: - 60% of a premix concentrated to 5% in montmorillonite and under form of granules, this pre-mixture being obtained from 87.5% of PP Boréalis HF445FB and 12.5% of Nanoblend 1012 sold by the company Polyone containing approximately 40% of montmorillonite and of PP, - 37% of PP Boréalis HF445FB, - 3% of PPgMA reference Polybond3200 from the company Crompton.
  • the sheets of clay have an average nanometric thickness and an average length of a few hundred nanometers, giving a form factor greater than 50.
  • EXAMPLE 7 A polypropylene fiber loaded with the following polymeric composition is made, expressed in% by weight of material relative to the total weight of the fiber: - 20% of a premix concentrated to 5% in montmorillonite and under form of granules, this premix being obtained from 84.5% PP Borealis HF445FB and 15.5% of the product PL19315 marketed by the company Multibase and which contains approximately 32% of montmorillonite and of the PP, - 79.5 % of PP Boréalis HF445FB, - 0.5% of PPgMA of reference Polybond3200 from the company Crompton.
  • the sheets of clay have an average nanometric thickness and an average length of a few hundred nanometers, giving a form factor greater than 50.
  • the fiber is produced under conditions similar to those of the example
  • a polypropylene fiber charged is made from the following polymeric composition, expressed in% by weight of material relative to the total weight of the fiber: - 60% of a premix concentrated to 5% in modified montmorillonite and in the form of granules, this premix being obtained from 90% of PP, 5% of PPgMA and 5% of modified montmorillonite containing approximately 62% of montmorillonite and an alkyl ammonium, - 40% of PP Boréalis HF445FB.
  • the clay sheets have an average nanometric thickness and an average length of a few hundred nanometers, giving a form factor greater than 50.
  • the premix produced in a co-rotating twin-screw extruder at a temperature of 180 ° C passes through a filter having holes of approximately 40 ⁇ m and then is brought to a die having holes of diameter equal to 3 mm in order to manufacture granules.
  • This premix is a mixture diluted from 80% of PP Boréalis HF445FB, with 20% of a non-commercial masterbatch under form of granules and which contains 50% of PP Boréalis HF445FB, 25% of PPgMA reference Polybond 3200 from the company Crompton and 25% of the modified montmorillonite in reference powder Cloisite C20A sold by the company Southern Clay Products.
  • the masterbatch produced in a co-rotating twin-screw extruder at a temperature of 180 ° C. passes through a filter having holes of approximately 40 ⁇ m and then is brought to a die having holes of diameter equal to 3 mm in order to manufacture the granules of masterbatch.
  • the polymeric composition is produced in a single screw extruder at a temperature of approximately 250 ° C. and is brought to a die having holes of diameter equal to 0.35 mm.
  • the viscosity of the composition is comparable to that of the polymer used.
  • a size having the reference Synthesin 7292 sold by the company Dr Boehme is deposited on the polypropylene fiber loaded at the outlet of the die, at a rate of 0.45% by weight of dry extract of charged polypropylene fiber.
  • a polypropylene fiber filled with the following polymeric composition is made, expressed in% by weight of material relative to the total weight of the fiber: 70% of a premix based on modified boehmite concentrated at 3 % and in the form of granules, this pre-mixture being obtained from 94% of PP Boréalis HF445FB, 3% of PPgMA of reference Polybond3200 and 3% of boehmite sold under the name CAM9010 by the company SAINT GOBAIN and modified in surface with 0.5% of ( ⁇ -aminopropyl) triethoxysilane sold under the name A1 100 by the company Aldrich, - 30% of PP Borealis HF445FB.
  • This boehmite is in the form of rods with an average diameter of approximately 20 nm and an average length between 100 and 200 nm, ie a form factor greater than 5.
  • the fiber is manufactured under conditions similar to those of Example 3.
  • TESTS The results of reference fiber # 1 and loaded fibers # 2 to # 8 before drawing (cold and continuous) are reported in Table 1 below.
  • the results for reference fiber # 1 and loaded fibers # 2 to # 8 after drawing (cold and continuous) are shown in Table 2 below.
  • the Young's modulus is defined as being the secant modulus, equal to the ratio of a stress for a conventional deformation respectively 1, 5 or 10%.
  • the Young's moduli are calculated from the toughness-elongation curves obtained on a unitary fiber using a Fafegraph marketed by the company Textechno.
  • the diameters are measured using a Vibromat sold by the company Textechno.
  • the measurement conditions are determined by ISO5079 standard.
  • the distance between the jaws is 10 mm for the fibers before drawing and 20 mm after drawing in the solid state and continuously at a maximum drawing rate while avoiding the breaking of the fibers (continuous yarns at this stage).
  • EXAMPLE 10 A cementitious product was manufactured by filtration, by a laboratory method reproducing fairly faithfully the main characteristics of the products obtained by industrial methods such as the Hatschek technique. Two cement compositions are prepared on the basis of the following cement matrix suspended with a large excess of water:
  • a first cement reference composition is thus prepared with charged polypropylene fibers identical to the reference fiber of Example No. 1. These fibers are also manufactured in a similar manner to that of Example No. 1 but with an additional post-sizing step, carried out after drawing, at a rate of 0.4% by weight of dry extract of charged polypropylene fiber.
  • a second cement composition is thus prepared with charged polypropylene fibers identical to the fiber of Example No. 5. These fibers are also produced in a similar manner to that of Example No. 5 but with an additional post-sizing step, carried out after drawing, at a rate of 0.4% by weight of dry extract of charged polypropylene fiber. The fibers are cut to 10 mm in length.
  • the composition is filtered through a metal grid to form a unitary layer about 1 mm thick.
  • Six unit layers are superimposed and subjected to a pressing cycle to obtain a material containing before setting about 50% water by weight relative to the weight of cement, and a thickness of about 6 mm.
  • This laboratory material undergoes a cure of 6 days at 40 ° C. in a sealed bag, before being cut into a test tube 20 mm wide and longer than 260 mm, which test tubes are placed in cold water for 24 hours to be mechanically stressed in traction.
  • the tensile tests were carried out by installing the test pieces between the jaws of a traction machine with a distance between jaws of 180 mm.
  • the tensile test is carried out at a separation speed of 1.2 mm / min.
  • the test pieces 10a correspond to the reference test pieces (with uncharged fibers).
  • the test pieces 10b correspond to the test pieces according to the invention (with charged fibers).
  • the force - displacement curve is plotted which has a typical appearance of the results observed with products obtained by the Hatschek technique. At the beginning of the displacement, the force increases rapidly, then there is a plateau where the force evolves slowly corresponding to the multifissuring of the test tube until the appearance of a macrocrack, after which the force drops by sliding effect during the opening of the macrocrack.
  • the length of the multi-cracking plate reflects the strengthening effect of the plate by all of the fibers. It is observed in particular that the breaking force, defined as the force divided by the width of the test piece and presented in table 3, is particularly high for each test piece 10b and in addition is greater than the breaking force of the reference test pieces 10a.
  • the level of calcium carbonate is increased to 60% or even 80% and conversely the rate of cement is greatly reduced. It is also possible to produce test pieces containing fibers identical to the fibers of Examples 2 to 4 or 6 to 9 in a similar manner.
  • EXAMPLE 11 This example 11 illustrates the application of the fibers loaded according to the invention to the manufacture of a cementitious product by the Hatschek process. Aqueous suspensions are prepared on the basis of a matrix identical to that with charged fibers of Example 10. Each suspension is introduced into the tank of a Hatschek machine, for the formation of a film and winding on a d format cylinder '' a sheet of hydrated cementitious material about 1 mm thick.
  • the charged polymer fibers according to the invention for example charged polypropylene fibers similar to the fibers of examples n ° 2 to n ° 9 or charged polymer fibers having a higher titer, can be used as technical yarns or high resistance monofilaments, to make seat belts, packaging, safety nets, fishing nets etc.
  • the polypropylene fibers loaded according to the invention can be used to manufacture unidirectional fabrics or of the mat type further heat-compactable according to the methods described in the articles entitled: “The Hot Compaction behavior of woven oriented PP fibers and tapes. I. Mechanical properties ”, by PJ Hine et al.
  • polypropylene fibers loaded according to the invention can also be used to manufacture agrotextiles and geotextiles according to the method described in the article entitled “Geotextiles and geomembranes” by K. Chan in the book “Polypropylene an AZ reference” edited by J. Karger-Kocsis, published by Kluwer Académie Publisher, 1999.
  • Polypropylene fibers loaded according to the invention can also be used to manufacture thermoformed all polypropylene (PP) composites, filament windings of PP yarns, all PP sandwich panels composed of fabric or mat surfaces made of PP fibers and at the heart of PP honeycomb or PP foam.
  • PP polypropylene
  • the polypropylene fibers loaded according to the invention can also be used to manufacture: - bundles of impregnated yarns according to the method described in "Technical impregnation for fiber bundles or tow" by A. Lutz et al.
  • the charged polymer fiber according to the invention can also be a fiber obtained by a continuous drawing process in one step (without recovery).
  • the charged polymeric fiber according to the invention can also be a fiber obtained by spinning a polymeric composition without prior premixing.
  • the polymeric fiber loaded according to the invention can also be a fiber obtained by solvent spinning (spining gel or wet spinning in English) from a polymer dissolved, from polymer precursors.
  • solvent spinning spining gel or wet spinning in English
  • the charged polymeric fiber according to the invention can equally well be a fiber obtained from a charged fibrous ribbon.

Abstract

The invention relates to a loaded polymer fibre comprising a mass of additives and having a Young's modulus which is higher than that of a non-charged polymer fibre, said additives comprising mineral additives having at least one submicronic dimension.

Description

FIBRE POLYMERIQUE CHARGEE, SON PROCEDE DE FABRICATION, SON UTILISATION ET COMPOSITION COMPRENANT DE TELLES FIBRES.FILLED POLYMERIC FIBER, METHOD FOR PRODUCING THE SAME, USE THEREOF AND COMPOSITION COMPRISING SUCH FIBERS.
La présente invention se rapporte au domaine des fibres, et plus particulièrement concerne une fibre polymérique chargée. Les fibres polymériques trouvent des applications dans de nombreux domaines. On peut par exemple se référer à l'article intitulé « textile applications of polypropylène fibers » de M. Jambrich et P. Hodul inséré dans le livre « Polypropylène an A Z référence » édité par J. Karger-Kocsis, publié parThe present invention relates to the field of fibers, and more particularly relates to a charged polymeric fiber. Polymer fibers find applications in many fields. One can for example refer to the article entitled "textile applications of polypropylene fibers" by M. Jambrich and P. Hodul inserted in the book "Polypropylene an A Z reference" edited by J. Karger-Kocsis, published by
Kluwer Académie Publisher, 1999. Les fibres polymériques sont utilisées seules pour leurs caractéristiques propres ou encore en association avec d'autres matériaux, d'autres fibres, incorporées dans des matrices diverses (minérales, polymères etc) notamment pour une fonction de renforcement. En outre, ces fibres servent pour la fabrication des produits de forme variée : voile, tissu, mat, unidirectionnel, etc. Aussi, Il existe une demande pour une fibre polymérique présentant de bonnes propriétés mécaniques. Le document US6331265 divulgue une fibre de polypropylène chargée au moyen de 3% de nanotubes de carbone introduits dans la masse du polypropylène. Ces nanotubes de carbone sont longs d'environ 1 μm et ont un diamètre de 1 à 50 nm. Cette fibre de polypropylène chargée présente un titre de 1 dtex, une haute ténacité et un module d'Young supérieur à celui d'une fibre de polypropylène non chargée. Cette fibre est proposée comme renforcement de mortiers, bétons ou pâtes cimentaires. Il est actuellement difficile d'avoir une pureté élevée des nanotubes de carbone. En effet, des résidus de catalyseur peuvent former des impuretés microniques susceptibles de dégrader les propriétés de la fibre finale. En outre, il est difficile de fabriquer de grande quantité de nanotubes de carbone ce qui se répercute dans le coût de la fibre. Par ailleurs, cette fibre polymérique chargée a été réalisée dans des conditions de laboratoire, sans tenir compte des contraintes industrielles notamment en termes de fiabilité et de rendement. La fabrication proposée n'est donc pas réaliste pour une production industrielle. La présente invention se propose de fournir une fibre polymérique, qui a de bonnes propriétés mécaniques, en particulier un module d'Young élevé, tout en étant facile à fabriquer à l'échelle industrielle. A cet égard, l'invention a pour premier objet une fibre polymérique chargée comprenant en masse des additifs, la fibre polymérique chargée présentant un module d'Young supérieur à celui d'une fibre polymérique non chargée et les additifs comprenant des additifs minéraux ayant au moins une dimension submicronique. L'association d'un polymère et des additifs minéraux ayant au moins une dimension submicronique selon l'invention permet d'obtenir une fibre présentant un module d'Young augmenté par rapport à une fibre non chargée à base du même polymère. Par ailleurs, les additifs minéraux selon l'invention sont facilement disponibles dans la nature ou sont aisément synthétisables, et si nécessaire facilement purifiables. Ces additifs présentent aussi l'avantage d'être peu onéreux. La fabrication de la fibre selon l'invention est compatible avec les exigences industrielles. Dans la présente demande, la dimension submicronique selon l'invention s'entend comme la dimension submicronique des additifs minéraux prise en moyenne. La dimension submicronique correspond par exemple à un diamètre ou une épaisseur. Dans la présente demande, le terme fibre est défini au sens large. Sans autre adjectif ou précision rajouté(s), le terme fibre désigne aussi bien une fibre non étirée (en phase solide) qu'une fibre étirée (en une ou plusieurs fois). Et la fibre désigne aussi bien un fil ou un monofilament, qu'un ensemble de filaments (de type fibre textile) identiques ou différents les uns des autres. La fibre peut être continue ou coupée, courte ou longue. De manière avantageuse, la dimension submicronique des additifs minéraux peut être inférieure à 500 nm, et de préférence inférieure à 100 nm. Les additifs minéraux peuvent être de structure sphérique, en bâtonnets ou de type lamellaire. Naturellement, une combinaison d'additifs avec des structures différentes est envisageable. De préférence, les additifs minéraux peuvent présenter un facteur de forme supérieur à 5, et de préférence supérieur à 50. On rappelle que le facteur de forme se définit comme le rapport de la plus grande des dimensions sur la plus petite des dimensions. Un facteur de forme élevé assure une haute ténacité, en particulier lorsque la grande dimension des additifs selon l'invention est sensiblement parallèle à l'axe de la fibre. Les additifs minéraux peuvent être des oxydes métalliques ou des argiles. Parmi les oxydes métalliques, on peut citer les alumines, les oxydes de baryum, les oxydes de titane, les oxydes de zirconium, les oxydes de manganèse, le talc, la magnésie et le carbonate de calcium. Les argiles peuvent être lamellaires, c'est-à-dire en feuillets, ou fibreuses. Les additifs minéraux peuvent comprendre une argile lamellaire exfoliable de préférence choisie parmi les phyllosilicates synthétiques et naturels, les argiles smectites tels que la montmorillonite, la nontronite, la beidellite, l'hectorite, la saponite, la sauconite, la vermiculite et les équivalents, ainsi que la magadiite, la kenyaite, la stevensite, la halloysite, les oxydes d'aluminates, l'hydrotalcite et les équivalents. De préférence les argiles peuvent avoir une charge négative de surface d'au moins 20 milliéquivalents, préférentiellement d'au moins 50 milliéquivalents, et plus préférentiellement entre 50 et 150 milliéquivalents, pour 100 grammes desdits additifs. Les argiles peuvent être ainsi modifiées par des molécules organiques capables d'être absorbées à l'intérieur des minéraux, par exemples entre les feuillets des argiles, ce qui permet leur exfoliation. Même si l'argile peut avoir n'importe quelle capacité d'échange cationique, il est néanmoins préférable que l'argile s'exfolie correctement. De préférence, les additifs minéraux peuvent être choisis parmi la montmorillonite et la boehmite. La boehmite est à base d'alumine monohydrate AI-O-OH. La boehmite est par exemple sous forme de bâtonnets. La montmorillonite possède des feuillets exfoliables et peut être répartie de façon homogène dans la masse de la fibre polymérique chargée selon l'invention. La montmorillonite et la boehmite possèdent en outre un module d'Young particulièrement élevé, supérieur à 100 GPa. Les additifs minéraux peuvent être modifiés en surface par l'un au moins des agents suivants : des tensioactifs cationiques, des agents amphotères, des dérivés d'aminés aliphatiques, aromatiques ou arylaliphatique, des phosphines et des sulfides, et de préférence des sels d'ammonium, de phosphonium ou de sulfonium. Ces agents servent d'agent gonflant pour les argiles en feuillets. Par ailleurs, ces agents favorisent aussi la dispersion des additifs minéraux selon l'invention. Les additifs minéraux peuvent aussi être modifiés par un promoteur d'adhésion qui est de préférence un composé organosilane et encore plus préférentiellement un silane, un amino silane, un vinyl silane et leurs mélanges. Le taux en poids d'additifs minéraux par rapport au poids total de la fibre peut être de préférence inférieur à 10%, encore plus préférentiellement inférieur à 5%. La fibre polymérique chargée peut être à base d'un polymère par exemple choisi parmi les polyoléfines, les polyamides, les polyesters, le polyacrylonitrile et les alcools polyvinyliques et leurs copolymères. De manière avantageuse, la fibre polymérique chargée peut être une fibre de polyoléfine chargée, tels que le polyéthylène ou le polypropylène et encore plus préférentiellement de polypropylène chargé. La fibre peut comprendre en outre un mélange d'une polyoléfine et d'une polyoléfine ayant des fonctions polaires, qui de préférence est une polyoléfine greffée anhydride maléique, glycidyl méthacrylate, vinyl pyrrolidone, styrène- méthacrylate, acrylates ou acétates, le taux en poids de la polyoléfine ayant des fonctions polaires par rapport au poids total de la fibre polymérique chargée étant de préférence inférieur à 10% et encore plus préférentiellement inférieur à 5%. La polyoléfine ayant des fonctions polaires peut être greffée avant ou après synthèse. Cette dernière favorise la dispersion d'un mélange à filer et l'étirage de la fibre. Le pourcentage de polyoléfine ayant des fonctions polaires peut être limité pour une plus grande augmentation du module d'Young. Le titre de la fibre polymérique chargée peut être compris entre 0,5 à 10 dtex, plus avantageusement de 0,5 à 2 dtex. Un effet de renforcement particulièrement avantageux dans les composites peut être obtenu avec une fibre (monofilament) de relativement faible section. La section d'une fibre polymérique chargée selon l'invention est non nécessairement circulaire et peut affecter une forme irrégulière ou multilobale. La fibre polymérique chargée selon l'invention peut posséder une ténacité égale au moins à 80% de celle de la fibre non chargée. Dans un mode de réalisation particulièrement avantageux, la fibre polymérique chargée a une ténacité élevée, d'au moins 4 cN/dtex, de préférence d'au moins 5 cN/dtex, très préférentiellement d'au moins 7 cN/dtex, et en particulier de 8 à 9 cN/dtex. Cette gamme de ténacité peut être atteinte en réglant le procédé de filage et d'étirage de manière appropriée. A titre d'exemple, une matière polyoléfinique de base peut être spécifiquement choisie avec une distribution des masses moléculaires adaptée. La fibre polymérique chargée peut de préférence comprendre en surface un ensimage qui contient un composé aminé ou polyaminé, phosphorique ou polyphosphorique, plus préférentiellement un ester d'acide phosphorique sur base de chaîne grasse. Une simple modification de la surface exposée de la fibre par un ensimage permet d'améliorer efficacement et durablement l'interaction entre la fibre et une matrice cimentaire. Les propriétés superficielles de la fibre polymérique sont modifiées par un ou plusieurs agents d'ensimage apportant une fonction d'assistance au filage. La fonction d'assistance au filage consiste à faciliter la constitution de la fibre polymérique à au moins un stade du filage : il s'agit notamment de lubrifier les fibres (monofilaments à ce stade) pour améliorer la prise en charge par des organes de transport à différents stades de la fabrication, de minimiser les charges électrostatiques portées par la fibre. Par exemple, on peut choisir un produit parmi les produits commercialisés sous les appellations SILASTOL Cut 5A et Cut 5B de SCHILL & SEILACHER, SYNTHESIN 7292 de Dr. BOEHME, KB 144/2 de COGNIS, STANTEX S6077 de COGNIS et STANTEX S6087/4 de COGNIS. L'ensimage peut être présent sur la fibre à raison de 0,05 à 5 % en poids de matière sèche par rapport au poids sec de fibre. Pour les applications matrices à prise hydraulique, l'ensimage apporte également une fonction de mouillabilité par la composition à base de liant hydraulique, de promoteur d'adhésion à la matrice à prise hydraulique et confère au composite fibre-ciment des propriétés mécaniques encore augmentées. La fonction de mouillabilité par la composition à base de liant hydraulique consiste à faciliter la dispersion des fibres polymériques dans la matrice, découlant de la bonne dispersion du matériau fibreux dans le mélange initial de liant et d'eau à partir duquel est fabriqué le produit. Cette fonction fait principalement appel à la polarité de surface du matériau fibreux pour le rendre hydrophile. La fonction de promotion d'adhésion à la matrice à prise hydraulique consiste à renforcer l'interaction entre le renfort fibreux et la matrice du produit durci. Cette dernière fonction fait également appel à la présence de groupes fonctionnels polaires en surface des fibres. Ces fonctions peuvent être apportées par un ou plusieurs agents choisis parmi des lubrifiants, des antistatiques, des tensioactifs, des composés à chaîne grasse et des polymères à fonctions polaires, dans lesquels un lubrifiant peut être un composé à chaîne grasse, de même qu'un tensioactif peut être un composé à chaîne grasse ou qu'un antistatique peut être un polymère à fonctions polaires. Une fibre étirée peut se présenter sous forme d'un fil coupé à une longueur de l'ordre de 2 à 20 mm, en particulier de 5 à 12 mm. La présente invention a également pour objet l'utilisation d'une fibre polymérique chargée telle que décrite précédemment en tant que fibre de renforcement dans un produit à base de fibres. La présente invention a ensuite pour objet un produit à base de fibres caractérisé en ce qu'il comprend des fibres polymériques chargées telles que définies précédemment. De manière avantageuse, le produit est sous forme de tissu, voile, mat à fibre longue, mat à fibre coupé, produit unidirectionnel, produit non tissé, corde, filet, ruban, sangle, bande, ou encore sous forme d'un mélange desdites fibres avec des fibres de nature distincte et de préférence sous forme d'une fibre co- mêlée. Un exemple de fibre co-mêlée est la fibre commercialisée sous le nom Twintex par Saint-Gobain et qui contient des filaments de polypropylène et des filaments de verre. De multiples domaines d'application de la fibre polymérique chargée selon l'invention sont possibles : les moquettes, les applications hygiéniques, les rubans, cordes et ficelles, l'industrie textile (vêtements, fils), les textiles de la maison (non tissés pour décoration, tissés pour les murs, ...), les géotextiles, les agrotextiles, l'emballage, les textiles médicaux, les fibres bioactives, les fibres multicomposants, les fils techniques ou monofilaments haute résistance (ceinture de sécurité, filets de protection, ou de pêche, etc.). Naturellement, la fibre polymérique chargée selon l'invention peut être pleine ou essentiellement pleine c'est-à-dire comporter par exemple un cœur creux le long de l'axe de la fibre. Naturellement, la fibre polymérique chargée (ensimée ou non) selon l'invention peut être revêtue. La fibre peut être incorporée sous diverses formes dans des produits dérivés du pétrole, dans des produits bitumeux et par exemple sous forme de mâts dans des produits à base d'asphalte tels que des éléments de toiture. La fibre sous diverses formes peut aussi être thermoformée. Dans un premier mode avantageux de réalisation de l'invention, le produit comprend une matrice minérale, de préférence une masse à prise hydraulique et le produit est de préférence choisi parmi les colles, les mortiers, les bétons, les coulis et les fibrociments. La masse à prise hydraulique est constituée à partir d'un liant à prise hydraulique, choisi principalement parmi les différents ciments existants, éventuellement additives de charges inertes ou actives. Parmi des charges et additifs, on peut mentionner des additifs de rhéologie (dispersants, plastifiants, superplastifiants, flocculants), des charges minérales (silice, cendres volantes, laitiers, pouzzolanes, carbonates), ainsi que des fibres de support ou d'armature pour des procédés de filtration ou d'égouttage (fibres naturelles, notamment de cellulose, ou synthétiques). Lors d'essais de flexion, les produits connus de ce type périssent très couramment par atteinte de la résistance en compression au niveau de la zone couramment dite supérieure. La demanderesse a déterminé que cette situation résulte d'une « déformabilité » trop importante des fibres reprenant la traction dans la zone inférieure, la fissure progressant d'autant plus que les fibres s'allongent. Aussi, la réduction de l'allongement des fibres en face tendue est obtenue par le haut module d'Young des fibres chargées selon l'invention. L'accroissement du module d'Young des fibres chargées permet donc de limiter la déformation de la zone inférieure. Ceci limite la remontée de l'axe neutre et donc limite l'accroissement de la contrainte de compression en zone supérieure. Ainsi, ces produits à prise hydraulique présentent une charge de rupture particulièrement élevée. Les fibres selon l'invention sont particulièrement efficaces en tant que renforcement de fibrociments en des proportions de l'ordre de 0,2 à 5 % en poids des fibres par rapport au poids total sec de mélange initial. Les fibres selon l'invention sont particulièrement efficaces en tant que renforcement de mortiers, en des proportions de l'ordre de 0,01 à 0,2 % en poids des fibres par rapport au poids total sec de mélange initial pour un « anticrack » et de 0,2 à 5 % pour des effets structuraux. Dans ce premier mode, les fibres peuvent être des fils coupés ayant une longueur comprise entre 2 et 20 mm et plus particulièrement entre 5 et 12 mm. Le produit peut avoir des formes variées (creuses, tubulaires) et de préférence une forme de plaque plane ou ondulée. Les articles à base de liant hydraulique façonnés en plaques peuvent être fabriqués par une technique de filtration d'une suspension aqueuse comprenant un liant à prise hydraulique, des fibres d'armature et éventuellement de charges. Un procédé couramment utilisé reposant sur cette technique est connu sous le nom de procédé Hatschek : une suspension aqueuse très diluée est contenue dans une cuve équipée de moyens pour assurer une distribution homogène des constituants dans le volume de la cuve ; un tambour filtrant plonge partiellement dans la cuve, et sa rotation entraîne le dépôt à sa surface d'une fine pellicule de matières (fibres et liant hydraté) ; cette pellicule est entraînée par un feutre vers un cylindre format sur lequel elle s'enroule continûment; lorsque la pellicule a atteint l'épaisseur souhaitée, on la coupe de façon à dérouler du cylindre une feuille individuelle de matériau à prise hydraulique. La feuille peut alors être mise sous la forme d'un produit façonné et acquiert ses caractéristiques définitives par durcissement du liant. Un produit d'épaisseur supérieure peut être obtenu en superposant un nombre approprié de feuilles, et en les pressant pour assurer la cohésion de l'ensemble. De telles plaques sont utilisées en tant qu'élément de toiture ou de façade. Dans un deuxième mode de réalisation de l'invention, le produit peut comprendre une matrice polymérique qui est choisie de préférence parmi une matrice polyéthylène, polypropylène, polyamide, polyester, époxy et phénolique. Les principaux domaines d'applications des composites par exemple à base de polypropylène sont : les transports (pièces sous capot, planche arrière etc), les applications électriques, les biens domestiques et de consommation, les bâtiments et travaux publics et les biens industriels. L'invention a par ailleurs pour objet un procédé de fabrication d'une fibre polymérique chargée telle que définie précédemment comprenant une étape de filage d'une composition polymérique comprenant des additifs minéraux ayant au moins une dimension submicronique. Les additifs selon l'invention sont facilement dispersables et ne modifient pas fortement les propriétés rhéologiques (viscosité..) de la composition polymérique à filer. La composition polymérique peut être obtenue par extrusion. La température d'extrusion est à ajuster en fonction du polymère et desdits additifs. Et, à titre d'exemple, la température de filage peut être entre 250°C et 300°C pour du polypropylène chargé. L'étape de filage peut comprendre un refroidissement de préférence à l'air refroidi et humidifié convenablement, pour une bonne capacité d'échange thermique, et un refroidissement radial. Dans un mode de réalisation préféré, le procédé comprend une étape d'étirage en dessous de la température de fusion, immédiatement après le filage ou en reprise. De préférence, le procédé peut comprendre une étape de défilement de la fibre dans des moyens d'étirages en continu. Cette étape peut être obtenue à l'aide de rouleaux à différentes températures et de vitesses distinctes et à l'aide de fours. Dans un mode de réalisation préféré, le procédé comprend une étape de préparation de ladite composition comportant au moins une opération de filtration. De cette façon, on élimine les impuretés et agrégats potentiels avant le filage, par exemple à l'aide d'un filtre en sortie d'extrudeuse. En outre, pour une meilleure maîtrise de mise en oeuvre (en termes de concentration, de dispersion, de compatibilité etc), l'étape de préparation de ladite composition peut inclure la réalisation d'un pré-mélange mis ensuite sous forme de granulés à diluer avec le polymère et optionnellement du polymère modifié. Ce pré-mélange est obtenu par dilution dans du polymère d'un mélange maître en granulés et de préférence non commercial qui contient les additifs minéraux selon l'invention. Pendant sa fabrication, le mélange maître peut être filtré. Une étape d'ensimage peut intervenir dans l'étape de filage. Une étape d'ensimage peut intervenir après l'étirage et être suivie d'une étape de séchage à l'aide de four(s) à air. L'ensimage peut être appliqué pur ou à partir d'une solution, dispersion ou émulsion aqueuse ou à base d'un autre véhicule liquide adapté. L'invention a également pour objet un procédé de fabrication d'un produit à base de fibres chargées telles que définies précédemment et d'une masse à prise hydraulique. Suivant ce procédé, on prépare un mélange initial à base de liant hydraulique, d'eau et de fibres telles que définies précédemment, on filtre les fibres sur un support fixe ou en mouvement pour former une feuille élémentaire humide, on superpose éventuellement une pluralité de feuilles élémentaires pour former un produit intermédiaire humide et on fait sécher la feuille ou le produit intermédiaire humide. L'invention a pour aussi objet une composition pour matériau à prise hydraulique comprenant un liant hydraulique et des fibres telles que décrites précédemment. Ces compositions peuvent être des préparations cimentaires à mettre en suspension pour procédé d'égouttage ou des préparations cimentaires pour mortiers pour autres procédés de mise en forme. L'invention a enfin pour objet une composition comprenant une matrice polymère et des fibres telles que décrites précédemment. De telles matrices peuvent être de préférence des matrices thermoplastiques, des matrices thermodurcissables, et de préférence des matrices polyéthylène, polypropylène, polyamides, polyesters, époxy, phénoliques.Kluwer Académie Publisher, 1999. Polymer fibers are used alone for their own characteristics or in combination with other materials, other fibers, incorporated in various matrices (mineral, polymers, etc.) notably for a reinforcing function. In addition, these fibers are used for the manufacture of products of various shapes: veil, fabric, mat, unidirectional, etc. Also, there is a demand for a polymeric fiber having good mechanical properties. Document US 6331265 discloses a polypropylene fiber loaded with 3% carbon nanotubes introduced into the bulk of the polypropylene. These carbon nanotubes are approximately 1 μm long and have a diameter of 1 to 50 nm. This charged polypropylene fiber has a titer of 1 dtex, a high tenacity and a Young's modulus greater than that of an unfilled polypropylene fiber. This fiber is proposed as reinforcement of mortars, concretes or cementitious pastes. It is currently difficult to have a high purity of carbon nanotubes. In fact, catalyst residues can form micronic impurities liable to degrade the properties of the final fiber. In addition, it is difficult to manufacture large quantities of carbon nanotubes, which is reflected in the cost of the fiber. Furthermore, this charged polymer fiber was produced under laboratory conditions, without taking industrial constraints into account. especially in terms of reliability and performance. The proposed manufacturing is therefore not realistic for industrial production. The present invention proposes to provide a polymeric fiber, which has good mechanical properties, in particular a high Young's modulus, while being easy to manufacture on an industrial scale. In this regard, the first object of the invention is a charged polymeric fiber comprising by mass of additives, the charged polymeric fiber having a Young's modulus greater than that of an uncharged polymeric fiber and the additives comprising mineral additives having minus a submicron dimension. The combination of a polymer and mineral additives having at least one submicron dimension according to the invention makes it possible to obtain a fiber having an increased Young's modulus compared to an uncharged fiber based on the same polymer. Furthermore, the mineral additives according to the invention are readily available in nature or are easily synthesizable, and if necessary easily purifiable. These additives also have the advantage of being inexpensive. The manufacture of the fiber according to the invention is compatible with industrial requirements. In the present application, the submicron dimension according to the invention is understood as the submicron dimension of the mineral additives taken on average. The submicron dimension corresponds for example to a diameter or a thickness. In the present application, the term fiber is defined broadly. Without any other adjective or precision added, the term fiber designates both an unstretched fiber (in solid phase) and a drawn fiber (in one or more times). And the fiber designates both a yarn or a monofilament, as well as a set of filaments (of textile fiber type) identical or different from each other. The fiber can be continuous or cut, short or long. Advantageously, the submicron dimension of the mineral additives can be less than 500 nm, and preferably less than 100 nm. The mineral additives can be of spherical, rod-like or lamellar type structure. Naturally, a combination of additives with different structures is possible. Preferably, the mineral additives can have a form factor greater than 5, and preferably greater than 50. It is recalled that the form factor is defined as the ratio of the largest of the dimensions to the smallest of the dimensions. A high form factor ensures high toughness, in particular when the large dimension of the additives according to the invention is substantially parallel to the axis of the fiber. The mineral additives can be metal oxides or clays. Among the metal oxides, mention may be made of aluminas, barium oxides, titanium oxides, zirconium oxides, manganese oxides, talc, magnesia and calcium carbonate. The clays can be lamellar, that is to say in sheets, or fibrous. The mineral additives can comprise an exfoliable lamellar clay preferably chosen from synthetic and natural phyllosilicates, smectite clays such as montmorillonite, nontronite, beidellite, hectorite, saponite, sauconite, vermiculite and the like, as well as magadiite, kenyaite, stevensite, halloysite, aluminate oxides, hydrotalcite and the like. Preferably, the clays can have a negative surface charge of at least 20 milliequivalents, preferably at least 50 milliequivalents, and more preferably between 50 and 150 milliequivalents, per 100 grams of said additives. The clays can thus be modified by organic molecules capable of being absorbed inside the minerals, for example between the sheets of the clays, which allows their exfoliation. Even if the clay can have any cation exchange capacity, it is nevertheless preferable for the clay to exfoliate properly. Preferably, the mineral additives can be chosen from montmorillonite and boehmite. Boehmite is based on alumina monohydrate AI-O-OH. Boehmite is for example in the form of sticks. Montmorillonite has exfoliable sheets and can be distributed homogeneously in the mass of the polymeric fiber loaded according to the invention. Montmorillonite and boehmite also have a particularly high Young's modulus, greater than 100 GPa. The mineral additives can be surface modified by at least one of the following agents: cationic surfactants, amphoteric agents, derivatives of aliphatic, aromatic or arylaliphatic amines, phosphines and sulfides, and preferably salts of ammonium, phosphonium or sulfonium. These agents serve as a blowing agent for sheet clays. Furthermore, these agents also promote the dispersion of the mineral additives according to the invention. The mineral additives can also be modified by an adhesion promoter which is preferably an organosilane compound and even more preferably a silane, an amino silane, a vinyl silane and their mixtures. The proportion by weight of mineral additives relative to the total weight of the fiber may preferably be less than 10%, even more preferentially less than 5%. The charged polymeric fiber may be based on a polymer, for example chosen from polyolefins, polyamides, polyesters, polyacrylonitrile and polyvinyl alcohols and their copolymers. Advantageously, the charged polymeric fiber can be a charged polyolefin fiber, such as polyethylene or polypropylene and even more preferably filled polypropylene. The fiber may also comprise a mixture of a polyolefin and a polyolefin having polar functions, which is preferably a grafted polyolefin of maleic anhydride, glycidyl methacrylate, vinyl pyrrolidone, styrene-methacrylate, acrylates or acetates, the content by weight polyolefin having polar functions relative to the total weight of the charged polymer fiber preferably being less than 10% and even more preferably less than 5%. The polyolefin having polar functions can be grafted before or after synthesis. The latter promotes the dispersion of a spinning mixture and fiber drawing. The percentage of polyolefin having polar functions can be limited for a greater increase in the Young's modulus. The titer of the charged polymer fiber can be between 0.5 to 10 dtex, more advantageously from 0.5 to 2 dtex. A particularly advantageous reinforcing effect in composites can be obtained with a fiber (monofilament) of relatively small section. The cross section of a charged polymer fiber according to the invention is not necessarily circular and may have an irregular or multilobal shape. The charged polymeric fiber according to the invention may have a tenacity equal to at least 80% of that of the uncharged fiber. In a particularly advantageous embodiment, the charged polymer fiber has a high tenacity, of at least 4 cN / dtex, preferably of at least 5 cN / dtex, very preferably of at least 7 cN / dtex, and in particular from 8 to 9 cN / dtex. This range of toughness can be achieved by adjusting the spinning and drawing process appropriately. By way of example, a basic polyolefin material can be specifically chosen with an appropriate molecular weight distribution. The charged polymeric fiber may preferably comprise, on the surface, a size which contains an amino or polyamine, phosphoric or polyphosphoric compound, more preferably an ester of phosphoric acid based on fatty chain. A simple modification of the exposed surface of the fiber by a sizing makes it possible to effectively and durably improve the interaction between the fiber and a cement matrix. The surface properties of the polymeric fiber are modified by one or more sizing agents providing a spinning assistance function. The spinning assistance function consists in facilitating the constitution of the polymeric fiber at at least one spinning stage: it is in particular a question of lubricating the fibers (monofilaments at this stage) to improve the handling by transport members at different stages of manufacturing, to minimize the electrostatic charges carried by the fiber. For example, you can choose a product from the products marketed under the names SILASTOL Cut 5A and Cut 5B from SCHILL & SEILACHER, SYNTHESIN 7292 from Dr. BOEHME, KB 144/2 from COGNIS, STANTEX S6077 from COGNIS and STANTEX S6087 / 4 from Cognis. The size may be present on the fiber in an amount of 0.05 to 5% by weight of dry matter relative to the dry weight of fiber. For matrix applications with hydraulic setting, the sizing also provides a wettability function by the composition based on hydraulic binder, of adhesion promoter to the matrix with hydraulic setting and gives the fiber-cement composite even increased mechanical properties. The wettability function of the hydraulic binder composition consists in facilitating the dispersion of the polymer fibers in the matrix, resulting from the good dispersion of the fibrous material in the initial mixture of binder and water from which the product is made. This function mainly uses the surface polarity of the fibrous material to make it hydrophilic. The function of promoting adhesion to the matrix with hydraulic setting consists in reinforcing the interaction between the fibrous reinforcement and the matrix of the hardened product. This latter function also calls for the presence of polar functional groups at the surface of the fibers. These functions can be provided by one or more agents chosen from lubricants, antistatics, surfactants, fatty chain compounds and polymers with polar functions, in which a lubricant can be a fatty chain compound, as well as a surfactant can be a fatty chain compound or an antistatic can be a polymer with polar functions. A drawn fiber can be in the form of a wire cut to a length of the order of 2 to 20 mm, in particular from 5 to 12 mm. The present invention also relates to the use of a charged polymeric fiber as described above as a reinforcing fiber in a fiber-based product. The present invention then relates to a product based on fibers, characterized in that it comprises charged polymeric fibers as defined above. Advantageously, the product is in the form of fabric, veil, long fiber mat, cut fiber mat, unidirectional product, non-woven product, rope, net, ribbon, strap, band, or even in the form of a mixture of said products. fibers with fibers of a distinct nature and preferably in the form of a mixed fiber. An example of a mixed fiber is the fiber marketed under the name Twintex by Saint-Gobain and which contains polypropylene filaments and glass filaments. Multiple areas of application of the charged polymer fiber according to the invention are possible: carpets, hygienic applications, ribbons, ropes and twines, the textile industry (clothing, threads), household textiles (non-woven for decoration, woven for walls, ...), geotextiles, agrotextiles, packaging, medical textiles, bioactive fibers, multicomponent fibers, high-resistance technical yarns or monofilaments (seat belts, protective nets , or fishing, etc.). Naturally, the charged polymer fiber according to the invention can be full or essentially full, that is to say comprise for example a hollow core along the axis of the fiber. Naturally, the charged polymer fiber (sized or not) according to the invention can be coated. The fiber can be incorporated in various forms in petroleum products, in bituminous products and for example in the form of masts in asphalt-based products such as roofing elements. Fiber in various forms can also be thermoformed. In a first advantageous embodiment of the invention, the product comprises a mineral matrix, preferably a mass with hydraulic setting and the product is preferably chosen from glues, mortars, concretes, grouts and fiber-cement. The mass with hydraulic setting consists of a binder with hydraulic setting, chosen mainly from the various existing cements, possibly additives of inert or active fillers. Among fillers and additives, there may be mentioned rheology additives (dispersants, plasticizers, superplasticizers, flocculants), mineral fillers (silica, fly ash, dairy, pozzolans, carbonates), as well as support or reinforcing fibers for filtration or draining processes (natural fibers, especially cellulose, or synthetic). During bending tests, known products of this type very commonly perish upon reaching the compressive strength at the level of the commonly called upper zone. The Applicant has determined that this situation results from excessive "deformability" of the fibers taking up the traction in the lower zone, the crack progressing all the more as the fibers become longer. Also, the reduction in the elongation of the fibers on the tensioned face is obtained by the high Young modulus of the fibers loaded according to the invention. The increase in the Young's modulus of the charged fibers therefore makes it possible to limit the deformation of the lower zone. This limits the ascent of the neutral axis and therefore limits the increase in the compression stress in the upper zone. Thus, these hydraulic setting products have a particularly high breaking load. The fibers according to the invention are particularly effective as reinforcing fiber cement in proportions of the order of 0.2 to 5% by weight of the fibers relative to the total dry weight of the initial mixture. The fibers according to the invention are particularly effective as reinforcement of mortars, in proportions of the order of 0.01 to 0.2% by weight of the fibers relative to the total dry weight of the initial mixture for an "anticrack" and from 0.2 to 5% for structural effects. In this first mode, the fibers can be cut strands having a length of between 2 and 20 mm and more particularly between 5 and 12 mm. The product can have various shapes (hollow, tubular) and preferably a flat or corrugated plate shape. Hydraulic binder articles formed into plates can be manufactured by a technique of filtration of an aqueous suspension comprising a binder with hydraulic setting, reinforcing fibers and optionally fillers. A commonly used process based on this technique is known as the Hatschek process: a very dilute aqueous suspension is contained in a tank equipped with means for ensuring a homogeneous distribution of the constituents in the volume of the tank; a filter drum submerges partially in the tank, and its rotation results in the deposition on its surface of a thin film of materials (fibers and hydrated binder); this film is entrained by a felt towards a format cylinder on which it is continuously wound; when the film has reached the desired thickness, it is cut so as to unwind from the cylinder an individual sheet of material with hydraulic setting. The sheet can then be formed into a shaped product and acquires its final characteristics by hardening the binder. A product of greater thickness can be obtained by superimposing an appropriate number of sheets, and pressing them to ensure the cohesion of the whole. Such plates are used as a roofing or facade element. In a second embodiment of the invention, the product can comprise a polymer matrix which is preferably chosen from a polyethylene, polypropylene, polyamide, polyester, epoxy and phenolic matrix. The main fields of application of composites, for example based on polypropylene, are: transport (parts under the hood, rear board, etc.), electrical applications, household and consumer goods, buildings and public works and industrial goods. The invention further relates to a process for manufacturing a charged polymeric fiber as defined above comprising a step of spinning a polymeric composition comprising mineral additives having at least a submicron dimension. The additives according to the invention are easily dispersible and do not significantly modify the rheological properties (viscosity, etc.) of the polymer composition to be spun. The polymeric composition can be obtained by extrusion. The extrusion temperature should be adjusted depending on the polymer and said additives. And, for example, the spinning temperature can be between 250 ° C and 300 ° C for charged polypropylene. The spinning step may include cooling preferably with air cooled and suitably humidified, for good heat exchange capacity, and radial cooling. In a preferred embodiment, the method comprises a step of drawing below the melting temperature, immediately after spinning or in recovery. Preferably, the method may include a step of passing the fiber through continuous drawing means. This step can be achieved using rollers at different temperatures and different speeds and using ovens. In a preferred embodiment, the method comprises a step of preparing said composition comprising at least one filtration operation. In this way, potential impurities and aggregates are removed before spinning, for example using a filter at the extruder outlet. In addition, for better control of implementation (in terms of concentration, dispersion, compatibility, etc.), the stage of preparation of said composition can include the production of a premix then put in the form of granules to dilute with the polymer and optionally with the modified polymer. This premix is obtained by dilution in polymer of a master mixture in granules and preferably non-commercial which contains the mineral additives according to the invention. During its manufacture, the masterbatch can be filtered. A sizing step can intervene in the spinning step. A sizing step can take place after stretching and be followed by a drying step using air oven (s). The size can be applied pure or from an aqueous solution, dispersion or emulsion or based on another suitable liquid vehicle. The invention also relates to a method of manufacturing a product based on charged fibers as defined above and a mass with hydraulic setting. According to this process, an initial mixture based on hydraulic binder, water and fibers as defined above is prepared, the fibers are filtered on a fixed or moving support to form an elementary sheet. wet, a plurality of elementary sheets are optionally superimposed to form a wet intermediate product and the wet sheet or intermediate product is dried. The invention also relates to a composition for material with hydraulic setting comprising a hydraulic binder and fibers as described above. These compositions can be cement preparations to be suspended for the draining process or cement preparations for mortars for other shaping processes. The invention finally relates to a composition comprising a polymer matrix and fibers as described above. Such matrices can preferably be thermoplastic matrices, thermosetting matrices, and preferably polyethylene, polypropylene, polyamides, polyesters, epoxy, phenolic matrices.
L'invention va maintenant être décrite de façon non limitative dans les exemples suivants.The invention will now be described without limitation in the following examples.
EXEMPLE 1 (référence) La fibre de référence est une fibre non chargée de haute ténacité et de faible diamètre (Idtex) obtenue sans additifs minéraux selon l'invention à partir de résine de polypropylène HF445FB de la société Boréalis ayant un indice d'écoulement à l'état fondu dit M FI (pour melt flow index en anglais) de 18 g/10 min mesuré à 230°C et 2,16 kg. En sortie de la filière- qui a des trous de diamètre environ égal à 0,35 mmEXAMPLE 1 (reference) The reference fiber is an uncharged fiber of high tenacity and small diameter (Idtex) obtained without mineral additives according to the invention from polypropylene resin HF445FB from the company Boréalis having a flow index of the melt state called M FI (for melt flow index in English) of 18 g / 10 min measured at 230 ° C and 2.16 kg. At the outlet of the die - which has holes with a diameter of approximately 0.35 mm
- la fibre, c'est-à-dire tout monofilament, va se figer après un refroidissement rapide et avec un air de refroidissement contrôlé en température et en vitesse. Lors du filage, un ensimage ayant la référence Synthesin 7292 commercialisé par la société Dr Boehme est déposé sur la fibre de polypropylène en sortie de filière, à raison de 0,45% en poids d'extrait sec de fibre de polypropylène. La fibre est ensuite bobinée, puis déroulée et étirée en continu dans une zone d'étirage comportant différentes séries de rouleaux chauffés et ayant une vitesse de rotation croissante. Des fours à air chaud ou à vapeur sont intercalés entre les différentes séries de rouleaux. A la fin de la zone d'étirage, la fibre est refroidie. La fibre est ensuite coupée en tronçon de 30 mm pour réaliser les tests. EXEMPLE 2 On fabrique une fibre de polypropylène chargée à partir de la composition polymérique suivante, exprimée en % de poids de matière par rapport au poids total de la fibre: - 5,5% du produit Nanomer C44PA fabriqué par la société Nanocor et contenant environ 45% de montmorillonite et du polypropylène (PP), - 94,5% de PP Boréalis HF445FB.- the fiber, that is to say all monofilament, will freeze after rapid cooling and with cooling air controlled in temperature and speed. During spinning, a size having the reference Synthesin 7292 marketed by the company Dr Boehme is deposited on the polypropylene fiber at the outlet of the die, at a rate of 0.45% by weight of dry extract of polypropylene fiber. The fiber is then wound, then unrolled and drawn continuously in a drawing zone comprising different series of heated rollers and having an increasing speed of rotation. Hot air or steam ovens are interposed between the different series of rollers. At the end of the stretching zone, the fiber is cooled. The fiber is then cut into 30 mm sections to carry out the tests. EXAMPLE 2 A polypropylene fiber filled with the following polymeric composition is made, expressed in% by weight of material relative to the total weight of the fiber: - 5.5% of the product Nanomer C44PA produced by the company Nanocor and containing approximately 45% montmorillonite and polypropylene (PP), - 94.5% PP Boréalis HF445FB.
La montmorillonite est une argile dont les feuillets ont une épaisseur moyenne nanométrique et une longueur moyenne de quelques centaines de nanomètre, donnant un facteur de forme supérieur à 50. La composition polymérique est réalisée dans une extrudeuse monovis à une température d'environ 250°C et est amenée à une filière ayant des trous de diamètre égal à 0,35 mm. La viscosité de la composition est comparable à celle du polymère utilisé. Lors du filage, un ensimage ayant la référence Synthesin 7292 commercialisé par la société Dr Boehme est déposé sur la fibre de polypropylène chargée en sortie de filière, à raison de 0,45% en poids d'extrait sec de fibre de polypropylène chargée. EXEMPLE 3 On fabrique une fibre de polypropylène chargée à partir de la composition polymérique suivante, exprimée en % de poids de matière par rapport au poids total de la fibre: - 40% d'un pré-mélange concentré à 5% en montmorillonite et sous forme de granulés, ce pré-mélange étant obtenu à partir de 87,5% de PP Boréalis HF445FB et de 12,5% de Nanoblend 1001 vendu par la société Polyone qui contient environ 40% de montmorillonite et du PP, - 60% de PP Boréalis HF445FB. Les feuillets de l'argile ont une épaisseur moyenne nanométrique et une longueur moyenne de quelques centaines de nanomètres, donnant un facteur de forme supérieur à 50. Le pré-mélange réalisé dans une extrudeuse bis-vis corotative à une température de 220°C, passe dans un filtre ayant des trous de 40 μm environ et ensuite est amené à une filière ayant des trous de diamètre égal à 3 mm afin de fabriquer des granulés. La composition polymérique est réalisée dans une extrudeuse monovis à une température d'environ 250°C et est amenée à une filière ayant des trous de diamètre égal à 0,35 mm. La viscosité de la composition est comparable à celle du polymère utilisé. Lors du filage, un ensimage ayant la référence Synthesin 7292 commercialisé par la société Dr Boehme est déposé sur la fibre de polypropylène chargée en sortie de filière, à raison de 0,45% en poids d'extrait sec de fibre de polypropylène chargée.Montmorillonite is a clay whose sheets have an average nanometric thickness and an average length of a few hundred nanometers, giving a form factor greater than 50. The polymeric composition is produced in a single-screw extruder at a temperature of approximately 250 ° C. and is brought to a die having holes of diameter equal to 0.35 mm. The viscosity of the composition is comparable to that of the polymer used. During spinning, a size having the reference Synthesin 7292 sold by the company Dr Boehme is deposited on the polypropylene fiber loaded at the outlet of the die, at a rate of 0.45% by weight of dry extract of charged polypropylene fiber. EXAMPLE 3 A polypropylene fiber charged is made from the following polymeric composition, expressed in% by weight of material relative to the total weight of the fiber: - 40% of a premix concentrated to 5% in montmorillonite and under form of granules, this premix being obtained from 87.5% of PP Boréalis HF445FB and from 12.5% of Nanoblend 1001 sold by the company Polyone which contains approximately 40% of montmorillonite and of PP, - 60% of PP Boréalis HF445FB. The clay sheets have an average nanometric thickness and an average length of a few hundred nanometers, giving a form factor greater than 50. The pre-mixing carried out in a co-rotating twin-screw extruder at a temperature of 220 ° C., passes through a filter having holes of approximately 40 μm and then is brought to a die having holes of diameter equal to 3 mm in order to manufacture granules. The polymeric composition is produced in a single screw extruder at a temperature of approximately 250 ° C. and is brought to a die having holes of diameter equal to 0.35 mm. The viscosity of the composition is comparable to that of the polymer used. During spinning, a size having the reference Synthesin 7292 sold by the company Dr Boehme is deposited on the polypropylene fiber loaded at the outlet of the die, at a rate of 0.45% by weight of dry extract of charged polypropylene fiber.
EXEMPLE 4 On fabrique une fibre de polypropylène chargée à partir de la composition polymérique suivante, exprimée en % de poids de matière par rapport au poids total de la fibre: - 40% d'un pré-mélange concentré à 5% en montmorillonite et sous forme de granulés, ce pré-mélange étant obtenu à partir de 87,5% de PP Boréalis HF445FB et de 12,5% de Nanoblend 1001 , - 58% de PP Boréalis HF445FB, - 2% de polypropylène greffé 1 % anhydride maléïque, dit PPgMA, de référence Polybond3200 de la Société Crompton. Les feuillets de l'argile ont une épaisseur moyenne nanométrique et une longueur moyenne de quelques centaines de nanomètres, donnant un facteur de forme supérieur à 50. La fibre est fabriquée dans des conditions similaires à celles de l'exempleEXAMPLE 4 A polypropylene fiber charged is made from the following polymeric composition, expressed in% by weight of material relative to the total weight of the fiber: - 40% of a premix concentrated to 5% in montmorillonite and under form of granules, this premix being obtained from 87.5% of PP Borealis HF445FB and 12.5% of Nanoblend 1001, - 58% of PP Borealis HF445FB, - 2% of grafted polypropylene 1% maleic anhydride, says PPgMA, Polybond3200 reference from the Crompton Company. The sheets of clay have an average nanometric thickness and an average length of a few hundred nanometers, giving a form factor greater than 50. The fiber is produced under conditions similar to those of the example
3. EXEMPLE 5 On fabrique une fibre de polypropylène chargée à partir de la composition polymérique suivante, exprimée en % de poids de matière par rapport au poids total de la fibre: - 60% d'un pré-mélange concentré à 5% en montmorillonite et sous forme de granulés, ce pré-mélange étant obtenu à partir de 87,5% de PP Boréalis HF445FB et de 12,5% de Nanoblend 1001 , - 37% de PP Boréalis HF445FB, - 3% de PPgMA de référence Polybond3200 de la Société Crompton. Les feuillets de l'argile ont une épaisseur moyenne nanométrique et une longueur moyenne de quelques centaines de nanomètres, donnant un facteur de forme supérieur à 50. La fibre est fabriquée dans des conditions similaires à celles de l'exemple 3.3. EXAMPLE 5 A polypropylene fiber filled with the following polymeric composition is made, expressed in% by weight of material relative to the total weight of the fiber: - 60% of a premix concentrated to 5% in montmorillonite and under form of granules, this premix being obtained from 87.5% of PP Borealis HF445FB and 12.5% of Nanoblend 1001, - 37% of PP Borealis HF445FB, - 3% of PPgMA reference Polybond3200 from the Company Crompton. The sheets of clay have an average nanometric thickness and an average length of a few hundred nanometers, giving a form factor greater than 50. The fiber is produced under conditions similar to those of Example 3.
EXEMPLE 6 On fabrique une fibre de polypropylène chargée à partir de la composition polymérique suivante, exprimée en % de poids de matière par rapport au poids total de la fibre: - 60% d'un pré-mélange concentré à 5% en montmorillonite et sous forme de granulés, ce pré-mélange étant obtenu à partir de 87,5% de PP Boréalis HF445FB et de 12,5% de Nanoblend 1012 vendu par la société Polyone contenant environ 40% de montmorillonite et du PP, - 37% de PP Boréalis HF445FB, - 3% de PPgMA de référence Polybond3200 de la Société Crompton. Les feuillets de l'argile ont une épaisseur moyenne nanométrique et une longueur moyenne de quelques centaines de nanomètre, donnant un facteur de forme supérieur à 50. La fibre est fabriquée dans des conditions similaires à celles de l'exemple 3. EXEMPLE 7 On fabrique une fibre de polypropylène chargée à partir de la composition polymérique suivante, exprimée en % de poids de matière par rapport au poids total de la fibre: - 20% d'un pré-mélange concentré à 5% en montmorillonite et sous forme de granulés, ce pré-mélange étant obtenu à partir de 84,5% PP Boréalis HF445FB et de 15,5% du produit PL19315 commercialisé par la société Multibase et qui contient environ 32% de montmorillonite et du PP, - 79,5% de PP Boréalis HF445FB, - 0,5% de PPgMA de référence Polybond3200 de la Société Crompton. Les feuillets de l'argile ont une épaisseur moyenne nanométrique et une longueur moyenne de quelques centaines de nanomètre, donnant un facteur de forme supérieur à 50. La fibre est fabriquée dans des conditions similaires à celles de l'exempleEXAMPLE 6 A polypropylene fiber charged is made from the following polymeric composition, expressed in% by weight of material relative to the total weight of the fiber: - 60% of a premix concentrated to 5% in montmorillonite and under form of granules, this pre-mixture being obtained from 87.5% of PP Boréalis HF445FB and 12.5% of Nanoblend 1012 sold by the company Polyone containing approximately 40% of montmorillonite and of PP, - 37% of PP Boréalis HF445FB, - 3% of PPgMA reference Polybond3200 from the company Crompton. The sheets of clay have an average nanometric thickness and an average length of a few hundred nanometers, giving a form factor greater than 50. The fiber is produced under conditions similar to those of Example 3. EXAMPLE 7 A polypropylene fiber loaded with the following polymeric composition is made, expressed in% by weight of material relative to the total weight of the fiber: - 20% of a premix concentrated to 5% in montmorillonite and under form of granules, this premix being obtained from 84.5% PP Borealis HF445FB and 15.5% of the product PL19315 marketed by the company Multibase and which contains approximately 32% of montmorillonite and of the PP, - 79.5 % of PP Boréalis HF445FB, - 0.5% of PPgMA of reference Polybond3200 from the company Crompton. The sheets of clay have an average nanometric thickness and an average length of a few hundred nanometers, giving a form factor greater than 50. The fiber is produced under conditions similar to those of the example
3.3.
EXEMPLE 8 On fabrique une fibre de polypropylène chargée à partir de la composition polymérique suivante, exprimée en % de poids de matière par rapport au poids total de la fibre: - 60% d'un pré-mélange concentré à 5% en montmorillonite modifiée et sous forme de granulés, ce pré-mélange étant obtenu à partir de 90% de PP, de 5% de PPgMA et des 5% de montmorillonite modifiée contenant environ 62% de montmorillonite et un alkyl ammonium, - 40% de PP Boréalis HF445FB. Les feuillets de l'argile ont une épaisseur moyenne nanométrique et une longueur moyenne de quelques centaines de nanomètres, donnant un facteur de forme supérieur à 50. Le pré-mélange réalisé dans une extrudeuse bis-vis corotative à une température de 180°C, passe dans un filtre ayant des trous de 40 μm environ et ensuite est amené à une filière ayant des trous de diamètre égal à 3 mm afin de fabriquer des granulés. Ce pré-mélange est un mélange dilué à partir de 80% du PP Boréalis HF445FB, avec 20% d'un mélange maître non commercial sous forme de granulés et qui contient 50% du PP Boréalis HF445FB, 25% du PPgMA de référence Polybond 3200 de la société Crompton et 25% de la montmorillonite modifiée en poudre de référence Cloisite C20A vendue par la société Southern Clay Products. Le mélange maître réalisé dans une extrudeuse bis-vis corotative à une température de 180°C, passe dans un filtre ayant des trous de 40 μm environ et ensuite est amené à une filière ayant des trous de diamètre égal à 3 mm afin de fabriquer les granulés de mélange maître. La composition polymérique est réalisée dans une extrudeuse monovis à une température d'environ 250°C et est amenée à une filière ayant des trous de diamètre égal à 0,35 mm. La viscosité de la composition est comparable à celle du polymère utilisé. Lors du filage, un ensimage ayant la référence Synthesin 7292 commercialisé par la société Dr Boehme est déposé sur la fibre de polypropylène chargée en sortie de filière, à raison de 0,45% en poids d'extrait sec de fibre de polypropylène chargée.EXAMPLE 8 A polypropylene fiber charged is made from the following polymeric composition, expressed in% by weight of material relative to the total weight of the fiber: - 60% of a premix concentrated to 5% in modified montmorillonite and in the form of granules, this premix being obtained from 90% of PP, 5% of PPgMA and 5% of modified montmorillonite containing approximately 62% of montmorillonite and an alkyl ammonium, - 40% of PP Boréalis HF445FB. The clay sheets have an average nanometric thickness and an average length of a few hundred nanometers, giving a form factor greater than 50. The premix produced in a co-rotating twin-screw extruder at a temperature of 180 ° C, passes through a filter having holes of approximately 40 μm and then is brought to a die having holes of diameter equal to 3 mm in order to manufacture granules. This premix is a mixture diluted from 80% of PP Boréalis HF445FB, with 20% of a non-commercial masterbatch under form of granules and which contains 50% of PP Boréalis HF445FB, 25% of PPgMA reference Polybond 3200 from the company Crompton and 25% of the modified montmorillonite in reference powder Cloisite C20A sold by the company Southern Clay Products. The masterbatch produced in a co-rotating twin-screw extruder at a temperature of 180 ° C., passes through a filter having holes of approximately 40 μm and then is brought to a die having holes of diameter equal to 3 mm in order to manufacture the granules of masterbatch. The polymeric composition is produced in a single screw extruder at a temperature of approximately 250 ° C. and is brought to a die having holes of diameter equal to 0.35 mm. The viscosity of the composition is comparable to that of the polymer used. During spinning, a size having the reference Synthesin 7292 sold by the company Dr Boehme is deposited on the polypropylene fiber loaded at the outlet of the die, at a rate of 0.45% by weight of dry extract of charged polypropylene fiber.
EXEMPLE 9 On fabrique une fibre de polypropylène chargée à partir de la composition polymérique suivante, exprimée en % de poids de matière par rapport au poids total de la fibre: - 70% d'un pré-mélange à base de boehmite modifiée concentrée à 3% et sous forme de granulés, ce pré-mélange étant obtenu à partir de 94% de PP Boréalis HF445FB, de 3% de PPgMA de référence Polybond3200 et de 3% de boehmite vendue sous le nom CAM9010 par la société SAINT GOBAIN et modifiée en surface avec 0,5% de (γ- aminopropyl) triethoxysilane commercialisé sous l'appellation A1 100 par la société Aldrich, - 30% de PP Boréalis HF445FB.EXAMPLE 9 A polypropylene fiber filled with the following polymeric composition is made, expressed in% by weight of material relative to the total weight of the fiber: 70% of a premix based on modified boehmite concentrated at 3 % and in the form of granules, this pre-mixture being obtained from 94% of PP Boréalis HF445FB, 3% of PPgMA of reference Polybond3200 and 3% of boehmite sold under the name CAM9010 by the company SAINT GOBAIN and modified in surface with 0.5% of (γ-aminopropyl) triethoxysilane sold under the name A1 100 by the company Aldrich, - 30% of PP Borealis HF445FB.
Cette boehmite est sous forme de bâtonnets a un diamètre moyen d'environ 20 nm et une longueur moyenne entre 100 et 200 nm soit un facteur de forme supérieur à 5. La fibre est fabriquée dans des conditions similaires à celles de l'exemple 3. TESTS Les résultats de la fibre de référence n°1 et des fibres chargées n°2 à n°8 avant étirage (à froid et en continu) sont consignés dans le tableau 1 ci-après. Les résultats de la fibre de référence n°1 et des fibres chargées n°2 à n°8 après étirage (à froid et en continu) sont consignés dans le tableau 2 ci-après. Le module d'Young est défini comme étant le module sécant, égal au rapport d'une contrainte pour une déformation conventionnelle respectivement 1 , 5 ou 10%. Les modules d'Young sont calculés à partir des courbes ténacité- élongation obtenu sur une fibre unitaire à l'aide d'un Fafegraph commercialisé par la société Textechno. Les diamètres sont mesurés à l'aide d'un Vibromat commercialisé par la société Textechno. Les conditions de mesure sont déterminées par la norme ISO5079. La distance entre les mors est de 10 mm pour les fibres avant étirage et de 20 mm après étirage à l'état solide et en continu à un taux d'étirage maximum tout en évitant la rupture des fibres (fils continus à ce stade).This boehmite is in the form of rods with an average diameter of approximately 20 nm and an average length between 100 and 200 nm, ie a form factor greater than 5. The fiber is manufactured under conditions similar to those of Example 3. TESTS The results of reference fiber # 1 and loaded fibers # 2 to # 8 before drawing (cold and continuous) are reported in Table 1 below. The results for reference fiber # 1 and loaded fibers # 2 to # 8 after drawing (cold and continuous) are shown in Table 2 below. The Young's modulus is defined as being the secant modulus, equal to the ratio of a stress for a conventional deformation respectively 1, 5 or 10%. The Young's moduli are calculated from the toughness-elongation curves obtained on a unitary fiber using a Fafegraph marketed by the company Textechno. The diameters are measured using a Vibromat sold by the company Textechno. The measurement conditions are determined by ISO5079 standard. The distance between the jaws is 10 mm for the fibers before drawing and 20 mm after drawing in the solid state and continuously at a maximum drawing rate while avoiding the breaking of the fibers (continuous yarns at this stage).
Figure imgf000018_0001
Tableau 1
Figure imgf000019_0001
Tableau 2 Le module d'Young des fibres n°2 à n°9 non étirées ou étirées est nettement supérieur à celui de la fibre de référence n°1 respectivement non étirée et étirée. En outre, les fibres n°2 à n°9 étirées conservent une haute ténacité. Les exemples suivants illustrent l'application de différentes fibres de polypropylène chargées selon l'invention à la fabrication d'un produit cimentaire.
Figure imgf000018_0001
Table 1
Figure imgf000019_0001
Table 2 The Young's modulus of fibers n ° 2 to n ° 9 not drawn or drawn is significantly higher than that of the reference fiber n ° 1 respectively not drawn and drawn. In addition, fibers No. 2 to No. 9 stretched retain a high tenacity. The following examples illustrate the application of different polypropylene fibers loaded according to the invention in the manufacture of a cementitious product.
EXEMPLE 10 Un produit cimentaire a été fabriqué par filtration, par une méthode de laboratoire reproduisant assez fidèlement les caractéristiques principales des produits obtenus par des méthodes industrielles telles que la technique Hatschek. On prépare deux compositions cimentaires sur la base de la matrice cimentaire suivante mise en suspension avec un large excès d'eau : EXAMPLE 10 A cementitious product was manufactured by filtration, by a laboratory method reproducing fairly faithfully the main characteristics of the products obtained by industrial methods such as the Hatschek technique. Two cement compositions are prepared on the basis of the following cement matrix suspended with a large excess of water:
Figure imgf000020_0001
Figure imgf000020_0001
On prépare ainsi une première composition cimentaire de référence avec des fibres de polypropylène chargées identiques à la fibre de référence de l'exemple n°1. Ces fibres sont également fabriquées de manière similaire à celle de l'exemple n°1 mais avec une étape supplémentaire de post ensimage, réalisé après étirage, à raison de 0,4 % en poids d'extrait sec de fibre de polypropylène chargée. On prépare ainsi une deuxième composition cimentaire avec des fibres de polypropylène chargées identiques à la fibre de l'exemple n°5. Ces fibres sont également fabriquées de manière similaire à celle de l'exemple n°5 mais avec une étape supplémentaire de post ensimage, réalisé après étirage, à raison de 0,4 % en poids d'extrait sec de fibre de polypropylène chargée. Les fibres sont coupées à 10 mm de longueur. Pour chaque composition, on filtre la composition à travers une grille métallique pour former une couche unitaire d'environ 1 mm d'épaisseur. Six couches unitaires sont superposées et soumises à un cycle de pressage pour obtenir un matériau contenant avant prise environ 50% d'eau en poids par rapport au poids de ciment, et une épaisseur d'environ 6 mm. Ce matériau de laboratoire subit une cure de 6 jours à 40°C dans un sac étanche, avant d'être découpé en eprouvette de 20 mm de large et de longueur supérieure à 260 mm, lesquelles éprouvettes sont mises dans l'eau froide pendant 24 heures pour être sollicitées mécaniquement en traction. Les tests de traction ont été effectués en installant les éprouvettes entre les mors d'une machine de traction avec une distance entre mors de 180 mm. Le test de traction est réalisé à une vitesse d'écartement de 1 ,2 mm/min. Les éprouvettes 10a correspondent aux éprouvettes de référence (avec fibres non chargées). Les éprouvettes 10b correspondent aux éprouvettes selon l'invention (avec fibres chargées). On trace la courbe force - déplacement qui a une allure typique des résultats observés avec des produits obtenus par la technique de Hatschek. Au début du déplacement la force augmente rapidement, puis on observe un plateau où la force évolue lentement correspondant à la multifissuration de l'éprouvette jusqu'à l'apparition d'une macrofissure, après quoi la force chute par effet de glissement pendant l'ouverture de la macrofissure. La longueur du plateau de multifissuration reflète l'effet de renforcement de la plaque par l'ensemble des fibres. On observe en particulier que la force à rupture, définie comme la force divisée par la largeur de l'éprouvette et présentée dans le tableau 3, est particulièrement élevée pour chaque eprouvette 10b et en outre est supérieure à la force de rupture des éprouvettes de référence 10a.A first cement reference composition is thus prepared with charged polypropylene fibers identical to the reference fiber of Example No. 1. These fibers are also manufactured in a similar manner to that of Example No. 1 but with an additional post-sizing step, carried out after drawing, at a rate of 0.4% by weight of dry extract of charged polypropylene fiber. A second cement composition is thus prepared with charged polypropylene fibers identical to the fiber of Example No. 5. These fibers are also produced in a similar manner to that of Example No. 5 but with an additional post-sizing step, carried out after drawing, at a rate of 0.4% by weight of dry extract of charged polypropylene fiber. The fibers are cut to 10 mm in length. For each composition, the composition is filtered through a metal grid to form a unitary layer about 1 mm thick. Six unit layers are superimposed and subjected to a pressing cycle to obtain a material containing before setting about 50% water by weight relative to the weight of cement, and a thickness of about 6 mm. This laboratory material undergoes a cure of 6 days at 40 ° C. in a sealed bag, before being cut into a test tube 20 mm wide and longer than 260 mm, which test tubes are placed in cold water for 24 hours to be mechanically stressed in traction. The tensile tests were carried out by installing the test pieces between the jaws of a traction machine with a distance between jaws of 180 mm. The tensile test is carried out at a separation speed of 1.2 mm / min. The test pieces 10a correspond to the reference test pieces (with uncharged fibers). The test pieces 10b correspond to the test pieces according to the invention (with charged fibers). The force - displacement curve is plotted which has a typical appearance of the results observed with products obtained by the Hatschek technique. At the beginning of the displacement, the force increases rapidly, then there is a plateau where the force evolves slowly corresponding to the multifissuring of the test tube until the appearance of a macrocrack, after which the force drops by sliding effect during the opening of the macrocrack. The length of the multi-cracking plate reflects the strengthening effect of the plate by all of the fibers. It is observed in particular that the breaking force, defined as the force divided by the width of the test piece and presented in table 3, is particularly high for each test piece 10b and in addition is greater than the breaking force of the reference test pieces 10a.
Figure imgf000021_0001
Figure imgf000021_0001
Tableau 3Table 3
Dans une variante de réalisation, on augmente le taux de carbonate de calcium jusqu'à 60% voire 80% et inversement on réduit fortement le taux de ciment. On peut aussi réaliser de manière similaire des éprouvettes contenant des fibres identiques aux fibres des exemples 2 à 4 ou 6 à 9. EXEMPLE 11 Cet exemple 1 1 illustre l'application des fibres chargées selon l'invention à la fabrication d'un produit cimentaire par le procédé Hatschek. On prépare des suspensions aqueuses sur la base d'une matrice identique à celle avec des fibres chargées de l'exemple 10. Chaque suspension est introduite dans la cuve d'une machine Hatschek, pour formation d'une pellicule et enroulement sur cylindre format d'une feuille de matériau cimentaire hydraté d'environ 1 mm d'épaisseur. Après découpe, des feuilles de matériau hydraté sont superposées sur une forme pour former des plaques planes ou ondulées possédant une épaisseur de 6 mm. Les plaques sont soumises à des essais mécaniques après 28 jours de cure à l'atmosphère ambiante. Des éprouvettes de mêmes dimensions qu'à l'exemple 10 sont soumises aux tests de traction dans les mêmes conditions. Les courbes force - déplacement sont d'allure similaire avec un plateau de multifissuration et une décroissance après déchaussement. On observe que la force à rupture est particulièrement élevée pour chaque eprouvette. On peut aussi réaliser de manière similaire des éprouvettes contenant des fibres identiques aux fibres des exemples 2 à 4 ou 6 à 9.In an alternative embodiment, the level of calcium carbonate is increased to 60% or even 80% and conversely the rate of cement is greatly reduced. It is also possible to produce test pieces containing fibers identical to the fibers of Examples 2 to 4 or 6 to 9 in a similar manner. EXAMPLE 11 This example 11 illustrates the application of the fibers loaded according to the invention to the manufacture of a cementitious product by the Hatschek process. Aqueous suspensions are prepared on the basis of a matrix identical to that with charged fibers of Example 10. Each suspension is introduced into the tank of a Hatschek machine, for the formation of a film and winding on a d format cylinder '' a sheet of hydrated cementitious material about 1 mm thick. After cutting, sheets of hydrated material are superimposed on a form to form flat or corrugated plates having a thickness of 6 mm. The plates are subjected to mechanical tests after 28 days of curing in the ambient atmosphere. Test pieces of the same dimensions as in Example 10 are subjected to the tensile tests under the same conditions. The force - displacement curves are similar in appearance with a multi-cracking plateau and a decrease after loosening. It is observed that the breaking force is particularly high for each specimen. It is also possible to produce test pieces containing fibers identical to the fibers of Examples 2 to 4 or 6 to 9 in a similar manner.
AUTRES UTILISATIONS DE FIBRES POLYMERIQUES CHARGEESOTHER USES OF LOADED POLYMERIC FIBERS
Les fibres polymériques chargées selon l'invention, par exemple des fibres de polypropylène chargées similaires aux fibres des exemples n°2 à n°9 ou des fibres polymériques chargées ayant un plus gros titre, peuvent être utilisées comme fils techniques ou monofilaments haute résistance, pour fabriquer des ceintures de sécurité, des emballages, des filets de protection, des filets de pêche etc. Ainsi, les fibres polypropylène chargées selon l'invention peuvent être utilisées pour fabriquer des tissus unidirectionnels ou de type mats en outre compactables à chaud suivant les procédés décrits dans les articles intitulés : « The Hot Compaction behaviour of woven oriented PP fibres and tapes. I. Mechanical properties », de P.J. Hine et coll. publié dans Polymer 44, 2003, pp 1 1 17-1 131 , et « The hot compaction of high modulus melt-spun polyéthylène fibres » de P.J. Hine et coll. publié dans Journal of Materials Science, 28, 1993, pp 316-324. Les fibres polypropylène chargées selon l'invention peuvent être aussi utilisées pour fabriquer des agrotextiles et des géotextiles selon le procédé décrit dans l'article intitulé "Geotextiles and geomembranes " de K. Chan dans le livre « Polypropylène an A Z référence » édité par J. Karger-Kocsis, publié par Kluwer Académie Publisher, 1999. Des fibres polypropylène chargées selon l'invention peuvent être aussi utilisées pour fabriquer des composites tout polypropylène (PP) thermoformés, des enroulements filamentaires de fils de PP, des panneaux sandwich tout PP composés en surfaces de tissus ou de mats en fibres de PP et au cœur de nid d'abeilles en PP ou de mousse de PP. On peut se référer à l'article intitulé "Composites for recyelability", de T. Pejis publié dans MaterialsToday, 2003, pp 30-35. Un tel composite présente l'avantagne d'être entièrement recyclable. Les fibres polypropylène chargées selon l'invention peuvent être aussi utilisées pour fabriquer : - des faisceaux de fils imprégnés suivant la méthode décrite dans "Imprégnation techniques for fiber bundles or tow " de A. Lutz et coll. dans le livre « Polypropylène an A Z référence » édité par J. Karger- Kocsis, publié par Kluwer Académie Publisher, 1999, des plaques composites avec un tissu, des unidirectionnels ou un mat en fibres de PP, imprégnés de résine thermodurcissable : suivant la méthode décrite dans « Melting behavior of gelspun/drawn polyolefins" de C.W.M. Bastiaansen et coll., publié dans Makromol. Chem., Macromol. Sym 28, 1989, pp 73-84, un mélange de fibres de PP avec des fibres de verre, par exemple suivant le procédé Twintex de Saint -Gobain. Par ailleurs, la fibre polymérique chargée selon l'invention peut aussi bien être une fibre obtenue par un procédé d'étirage en continu en une étape (sans reprise). La fibre polymérique chargée selon l'invention peut aussi bien être une fibre obtenue par filage d'une composition polymérique sans prémélange préalable. La fibre polymérique chargée selon l'invention peut aussi bien être une fibre obtenue par filage en voie solvant (gel spining ou encore wet spinning en anglais) à partir d'un polymère mis en solution, à partir de précurseurs de polymère. On peut se référer à l'article intitulé « Study on gel spinning process of ultra-high molecular weight polyéthylène », Y. Zhang, C. Xiao.J. Guangxia, A. Shulin, Journal of applied polymer science, 1999, vol4, n°3, pp670-675. La fibre polymérique chargée selon l'invention peut aussi bien être une fibre obtenue à partir d'un ruban fibrille chargé. The charged polymer fibers according to the invention, for example charged polypropylene fibers similar to the fibers of examples n ° 2 to n ° 9 or charged polymer fibers having a higher titer, can be used as technical yarns or high resistance monofilaments, to make seat belts, packaging, safety nets, fishing nets etc. Thus, the polypropylene fibers loaded according to the invention can be used to manufacture unidirectional fabrics or of the mat type further heat-compactable according to the methods described in the articles entitled: “The Hot Compaction behavior of woven oriented PP fibers and tapes. I. Mechanical properties ”, by PJ Hine et al. published in Polymer 44, 2003, pp 1 1 17-1 131, and "The hot compaction of high modulus melt-spun polyethylene fibers" by PJ Hine et al. published in Journal of Materials Science, 28, 1993, pp 316-324. The polypropylene fibers loaded according to the invention can also be used to manufacture agrotextiles and geotextiles according to the method described in the article entitled "Geotextiles and geomembranes" by K. Chan in the book "Polypropylene an AZ reference" edited by J. Karger-Kocsis, published by Kluwer Académie Publisher, 1999. Polypropylene fibers loaded according to the invention can also be used to manufacture thermoformed all polypropylene (PP) composites, filament windings of PP yarns, all PP sandwich panels composed of fabric or mat surfaces made of PP fibers and at the heart of PP honeycomb or PP foam. We can refer to the article entitled "Composites for recyelability", by T. Pejis published in MaterialsToday, 2003, pp 30-35. Such a composite has the advantage of being fully recyclable. The polypropylene fibers loaded according to the invention can also be used to manufacture: - bundles of impregnated yarns according to the method described in "Technical impregnation for fiber bundles or tow" by A. Lutz et al. in the book "Polypropylene an AZ reference" edited by J. Karger- Kocsis, published by Kluwer Académie Publisher, 1999, composite plates with a fabric, unidirectional or mat in PP fibers, impregnated with thermosetting resin: according to the method described in "Melting behavior of gelspun / drawn polyolefins" by CWM Bastiaansen et al., published in Makromol. Chem., Macromol. Sym 28, 1989, pp 73-84, a mixture of PP fibers with glass fibers, by example according to Saint -Gobain's Twintex process In addition, the charged polymer fiber according to the invention can also be a fiber obtained by a continuous drawing process in one step (without recovery). The charged polymeric fiber according to the invention can also be a fiber obtained by spinning a polymeric composition without prior premixing. The polymeric fiber loaded according to the invention can also be a fiber obtained by solvent spinning (spining gel or wet spinning in English) from a polymer dissolved, from polymer precursors. We can refer to the article entitled “Study on gel spinning process of ultra-high molecular weight polyethylene”, Y. Zhang, C. Xiao.J. Guangxia, A. Shulin, Journal of applied polymer science, 1999, vol4, n ° 3, pp670-675. The charged polymeric fiber according to the invention can equally well be a fiber obtained from a charged fibrous ribbon.

Claims

REVENDICATIONS
1. Fibre polymérique chargée comprenant en masse des additifs, la fibre polymérique chargée présentant un module d'Young supérieur à celui d'une fibre polymérique non chargée caractérisée en ce que les additifs comprennent des additifs minéraux ayant au moins une dimension submicronique.1. A charged polymeric fiber comprising additives by mass, the charged polymeric fiber having a Young's modulus greater than that of an uncharged polymeric fiber, characterized in that the additives include mineral additives having at least one submicron dimension.
2. Fibre polymérique chargée selon la revendication 1 caractérisée en ce que la dimension submicronique des additifs minéraux est inférieure à 500 nm, et de préférence inférieure à 100 nm.2. Filled polymeric fiber according to claim 1 characterized in that the submicron dimension of the mineral additives is less than 500 nm, and preferably less than 100 nm.
3. Fibre polymérique chargée selon l'une des revendications précédentes caractérisée en ce que les additifs minéraux sont de structure sphérique, en bâtonnets, ou de type lamellaire.3. Filled polymeric fiber according to one of the preceding claims, characterized in that the mineral additives are of spherical structure, in rods, or of lamellar type.
4. Fibre polymérique chargée selon l'une des revendications précédentes caractérisée en ce que les additifs minéraux présentent un facteur de forme supérieur à 5, et de préférence supérieur à 50.4. Filled polymeric fiber according to one of the preceding claims, characterized in that the mineral additives have a form factor greater than 5, and preferably greater than 50.
5. Fibre polymérique chargée selon l'une des revendications précédentes caractérisée en ce que les additifs minéraux sont choisis parmi des oxydes métalliques, des argiles et leurs mélanges. 5. Filled polymer fiber according to one of the preceding claims, characterized in that the mineral additives are chosen from metal oxides, clays and their mixtures.
6. Fibre polymérique chargée selon l'une des revendications précédentes caractérisée en ce que les additifs minéraux comprennent une argile lamellaire exfoliable de préférence choisie parmi les phyllosilicates synthétiques et naturels, les argiles smectites, la magadiite, la kenyaite, la stevensite, la halloysite, les oxydes d'aluminates, l'hydrotalcite et les équivalents.6. Filled polymeric fiber according to one of the preceding claims, characterized in that the mineral additives comprise an exfoliable lamellar clay preferably chosen from synthetic and natural phyllosilicates, smectite clays, magadiite, kenyaite, stevensite, halloysite, aluminate oxides, hydrotalcite and the like.
7. Fibre polymérique chargée selon l'une des revendications précédentes caractérisée en ce que les additifs minéraux sont choisis parmi la montmorillonite et la boehmite.7. Filled polymer fiber according to one of the preceding claims, characterized in that the mineral additives are chosen from montmorillonite and boehmite.
8. Fibre polymérique chargée selon l'une des revendications précédentes caractérisée en ce que les additifs minéraux sont modifiés en surface par l'un au moins des agents suivants : des tensioactifs cationiques, des agents amphotères, des dérivés d'aminés aliphatiques, aromatiques ou arylaliphatique, des phosphines, des sulfides et de préférence par des sels d'ammonium, de sulfonium ou de phosphonium.8. Filled polymer fiber according to one of the preceding claims, characterized in that the mineral additives are surface-modified by at least one of the following agents: cationic surfactants, amphoteric agents, derivatives of aliphatic or aromatic amines or arylaliphatic, phosphines, sulfides and preferably with ammonium, sulfonium or phosphonium salts.
9. Fibre polymérique chargée selon l'une des revendications précédentes, caractérisée en ce que les additifs minéraux peuvent être modifiés par un promoteur d'adhésion qui est de préférence un composé organosilane.9. Filled polymer fiber according to one of the preceding claims, characterized in that the mineral additives can be modified by an adhesion promoter which is preferably an organosilane compound.
10. Fibre polymérique chargée selon l'une des revendications précédentes, caractérisée en ce que le taux en poids d'additifs minéraux par rapport au poids total de la fibre est inférieur à 10%, de préférence inférieur à 5%.10. Filled polymeric fiber according to one of the preceding claims, characterized in that the rate by weight of mineral additives relative to the total weight of the fiber is less than 10%, preferably less than 5%.
11. Fibre polymérique chargée selon l'une des revendications précédentes caractérisée en ce qu'elle est une fibre de polyoléfine chargée et de préférence de polypropylène chargé.11. Filled polymeric fiber according to one of the preceding claims, characterized in that it is a charged polyolefin fiber and preferably polypropylene charged.
12. Fibre polymérique chargée selon la revendication précédente, caractérisée en ce que, la fibre comprend un mélange d'une polyoléfine et d'une polyoléfine ayant des fonctions polaires et qui est de préférence une polyoléfine greffée anhydride maléique, glycidyl méthacrylate, vinyl pyrrolidone, styrène-méthacrylate, acrylates ou acétates, le taux en poids de la polyoléfine ayant des fonctions polaires par rapport au poids total de la fibre polymérique chargée étant de préférence inférieur à 10%.12. Filled polymeric fiber according to the preceding claim, characterized in that the fiber comprises a mixture of a polyolefin and of a polyolefin having polar functions and which is preferably a grafted polyolefin of maleic anhydride, glycidyl methacrylate, vinyl pyrrolidone, styrene-methacrylate, acrylates or acetates, the proportion by weight of the polyolefin having polar functions relative to the total weight of the charged polymer fiber is preferably less than 10%.
13. Fibre polymérique chargée selon l'une des revendications précédentes, caractérisée en ce que le titre de la fibre polymérique est compris entre 0,5 et 10 dtex, de préférence entre 0,5 dtex à 2 dtex.13. Filled polymer fiber according to one of the preceding claims, characterized in that the titer of the polymer fiber is between 0.5 and 10 dtex, preferably between 0.5 dtex to 2 dtex.
14. Fibre polymérique chargée selon l'une des revendications précédentes, caractérisée en ce qu'elle a une ténacité d'au moins 4 cN/dtex, de préférence d'au moins 7 cN/dtex. 14. Filled polymer fiber according to one of the preceding claims, characterized in that it has a tenacity of at least 4 cN / dtex, preferably at least 7 cN / dtex.
15. Fibre polymérique chargée selon l'une des revendications précédentes, caractérisée en ce qu'elle comprend en surface un ensimage qui contient un composé aminé ou polyaminé, phosphorique ou polyphosphorique, de préférence un ester d'acide phosphorique sur base de chaîne grasse.15. Filled polymeric fiber according to one of the preceding claims, characterized in that it comprises on the surface a size which contains an amino or polyamine, phosphoric or polyphosphoric compound, preferably an ester of phosphoric acid based on fatty chain.
16. Utilisation d'une fibre polymérique chargée selon l'une des revendications précédentes en tant que fibre de renforcement dans un produit.16. Use of a charged polymer fiber according to one of the preceding claims as a reinforcing fiber in a product.
17. Produit à base de fibres caractérisé en ce qu'il comprend des fibres polymériques chargées selon l'une des revendications 1 à 15. 17. Product based on fibers, characterized in that it comprises charged polymer fibers according to one of claims 1 to 15.
18. Produit à base de fibres selon la revendication précédente caractérisé en ce qu'il est sous forme de tissu, voile, mat à fibre coupé, mat à fibre longue, produit non tissé, produit unidirectionnel, corde, filet, ruban, sangle, bande ou encore sous forme d'un mélange desdites fibres avec des fibres de nature distincte et de préférence sous forme d'une fibre co-mêlée.18. Product based on fibers according to the preceding claim, characterized in that it is in the form of fabric, veil, mat with cut fiber, mat with long fiber, non-woven product, unidirectional product, rope, net, ribbon, strap, strip or also in the form of a mixture of said fibers with fibers of a distinct nature and preferably in the form of a co-mixed fiber.
19. Produit à base de fibres selon l'une des revendications 17 ou 18 caractérisé en ce qu'il comprend une matrice minérale, de préférence une masse à prise hydraulique, et plus préférentiellement le produit est choisi parmi les colles, les mortiers, les bétons, les coulis et les fibrociments. 19. Product based on fibers according to one of claims 17 or 18 characterized in that it comprises a mineral matrix, preferably a mass with hydraulic setting, and more preferentially the product is chosen from glues, mortars, concrete, grout and fiber cement.
20. Produit à base de fibres selon la revendication 19, caractérisé en ce que le produit est un fibrociment et comprend de 0,2 à 5% en poids desdites fibres par rapport au poids total sec d'un mélange initial. 20. Product based on fibers according to claim 19, characterized in that the product is a fiber cement and comprises from 0.2 to 5% by weight of said fibers relative to the total dry weight of an initial mixture.
21. Produit à base de fibres selon l'une des revendications 19 ou 20, caractérisé en ce qu'il a la forme d'une plaque plane ou ondulée. 21. Product based on fibers according to one of claims 19 or 20, characterized in that it has the shape of a flat or corrugated plate.
22. Produit à base de fibres selon l'une des revendications 17 ou 18 caractérisé en ce qu'il comprend une matrice polymérique et qui est choisie de préférence parmi une matrice polyéthylène, polypropylène, polyamides, polyesters, époxy et phénolique.22. Product based on fibers according to one of claims 17 or 18 characterized in that it comprises a polymer matrix and which is preferably chosen from a polyethylene, polypropylene, polyamides, polyesters, epoxy and phenolic matrix.
23. Procédé de fabrication d'une fibre polymérique chargée selon l'une des revendications 1 à 15 comprenant une étape de filage d'une composition polymérique comprenant des additifs minéraux ayant au moins une dimension submicronique.23. A method of manufacturing a charged polymer fiber according to one of claims 1 to 15 comprising a step of spinning a polymer composition comprising mineral additives having at least a submicron dimension.
24. Procédé de fabrication d'une fibre polymérique selon la revendication 23 caractérisé en ce qu'il comprend une étape d'étirage en dessous de la température de fusion.24. A method of manufacturing a polymeric fiber according to claim 23 characterized in that it comprises a step of drawing below the melting temperature.
25. Procédé de fabrication d'une fibre polymérique selon l'une des revendications 23 ou 24 caractérisé en ce qu'il comprend une étape de préparation de ladite composition comportant au moins une opération de filtration. 25. A method of manufacturing a polymeric fiber according to one of claims 23 or 24 characterized in that it comprises a step of preparing said composition comprising at least one filtration operation.
26. Procédé de fabrication d'un produit à base de fibres et d'une masse à prise hydraulique caractérisé en ce que : - l'on prépare un mélange initial à base de liant hydraulique, d'eau et de fibres polymériques chargées définies selon l'une des revendications 1 à 15, - l'on filtre les fibres sur un support fixe ou en mouvement pour former une feuille élémentaire humide, - et l'on superpose une pluralité de feuilles élémentaires pour former un produit intermédiaire humide et en ce que l'on fait sécher le produit intermédiaire humide.26. A method of manufacturing a product based on fibers and a mass with hydraulic setting, characterized in that: - an initial mixture is prepared based on hydraulic binder, water and charged polymer fibers defined according to one of claims 1 to 15, - the fibers are filtered on a fixed or moving support to form a wet elementary sheet, and a plurality of elementary sheets are superimposed to form a wet intermediate product and in that the wet intermediate product is dried.
27. Composition pour matériau à prise hydraulique comprenant un liant hydraulique et des fibres polymériques chargées selon l'une des revendications 1 à 15.27. Composition for material with hydraulic setting comprising a hydraulic binder and charged polymer fibers according to one of claims 1 to 15.
28. Composition comprenant une matrice polymère et des fibres polymériques chargées selon l'une des revendications 1 à 15.28. Composition comprising a polymer matrix and charged polymer fibers according to one of claims 1 to 15.
29. Composition selon la revendication précédente caractérisée en ce que, la matrice est une matrice polyéthylène, polypropylène, polyamide, polyester, époxy ou phénolique. 29. Composition according to the preceding claim, characterized in that the matrix is a polyethylene, polypropylene, polyamide, polyester, epoxy or phenolic matrix.
PCT/FR2005/050364 2004-05-25 2005-05-25 Loaded polymer fibre, method for the production thereof, use of the same, and composition comprising such fibres WO2005118924A1 (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
US11/597,629 US20080044654A1 (en) 2004-05-25 2005-05-25 Loaded Polymer Fibre, Method for the Production Thereof, Use of the Same, and Composition Comprising Such Fibres
CA002568433A CA2568433A1 (en) 2004-05-25 2005-05-25 Loaded polymer fibre, method for the production thereof, use of the same, and composition comprising such fibres
BRPI0511491-8A BRPI0511491A (en) 2004-05-25 2005-05-25 charged polymeric fiber, use thereof, fiber-based product, process for making a charged polymeric fiber, and a fiber-based product and hydraulic handle mass, and composition
JP2007514039A JP2008500463A (en) 2004-05-25 2005-05-25 Filled polymer fiber, process for its production, use thereof and composition comprising such fiber
EP05762544A EP1769108A1 (en) 2004-05-25 2005-05-25 Loaded polymer fibre, method for the production thereof, use of the same, and composition comprising such fibres
MXPA06013618A MXPA06013618A (en) 2004-05-25 2005-05-25 Loaded polymer fibre, method for the production thereof, use of the same, and composition comprising such fibres.
NO20065922A NO20065922L (en) 2004-05-25 2006-12-20 Coated polymer fibers, process for their preparation, use thereof, and composition comprising such fibers

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FR0451027 2004-05-25
FR0451027A FR2870850B1 (en) 2004-05-25 2004-05-25 CHARGED POLYMERIC FIBER, PROCESS FOR PRODUCING THE SAME, USE THEREOF, AND COMPOSITION COMPRISING SUCH FIBERS

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NO20065922L (en) 2007-02-23
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CN101014731A (en) 2007-08-08
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