WO2017167941A1 - Procédé de préparation de précurseur de fibre de carbone ou de précurseur de bandelettes découpées en carbone - Google Patents

Procédé de préparation de précurseur de fibre de carbone ou de précurseur de bandelettes découpées en carbone Download PDF

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Publication number
WO2017167941A1
WO2017167941A1 PCT/EP2017/057641 EP2017057641W WO2017167941A1 WO 2017167941 A1 WO2017167941 A1 WO 2017167941A1 EP 2017057641 W EP2017057641 W EP 2017057641W WO 2017167941 A1 WO2017167941 A1 WO 2017167941A1
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Prior art keywords
carbon
acid
additive
precursor
slit
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PCT/EP2017/057641
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English (en)
Inventor
Olivier Lhost
Pascal Navez
Marc Dupire
Guy Debras
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Total Research & Technology Feluy
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Publication of WO2017167941A1 publication Critical patent/WO2017167941A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • 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
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/041—Carbon nanotubes
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • 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
    • D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
    • D01F11/04—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers
    • D01F11/06—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/04—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/20—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of cyclic compounds with one carbon-to-carbon double bond in the side chain
    • D01F6/22—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of cyclic compounds with one carbon-to-carbon double bond in the side chain from polystyrene
    • 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
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • 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
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
    • D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/04—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/42—Formation of filaments, threads, or the like by cutting films into narrow ribbons or filaments or by fibrillation of films or filaments

Definitions

  • the present invention relates to a process for preparing carbon fiber precursor or carbon slit tape precursor based.
  • the invention also relates to the carbon fiber precursor or carbon slit tape precursor obtained with said process.
  • the present invention also relates to a process for preparing carbon fibers or slit tapes by thermal graphitization treatment of said carbon fiber precursor or slit tape precursor.
  • Carbon fibers are well appreciated for their mechanical properties: the carbon fibers modulus can range from 228 GPa to more than 690 GPa depending on the heat temperature imposed during the calcination.
  • PAN Polyacrylonitrile
  • Polyethylene fibers have also been considered as starting materials for carbon fiber production. Whatever the starting materials are, a high temperature-graphitization step is necessary to transform the precursor into carbon fibers.
  • a high temperature-graphitization step is necessary to transform the precursor into carbon fibers.
  • the fibers need to be "stabilized” for example, by grafting with HS0 3 " groups.
  • fiber parts with a too low grafting level will be destroyed rather than grafitized during the subsequent thermal treatment.
  • the resulting carbon fibers are not adequate because they either present inter- fiber bonding; or have less than desirable physical and chemical properties.
  • the inventors have now discovered that these objects can be met either individually or in any combination by the present processes.
  • the inventors have surprisingly found that the present process allows preparing carbon fiber precursors or slit tape precursors from polyolefin or polystyrene that can afford carbon fibers or slit tapes with improved properties such as high stiffness, high tensile strength, low weight, high chemical resistance, high temperature tolerance and low thermal expansion.
  • the present process allows producing low-cost carbon fiber precursors or slit tape precursors from polyolefins and polystyrene.
  • the present process allows increased level of grafting.
  • the inventors have discovered that the present process proceeds via show short time reactions.
  • the invention provides a process for preparing a carbon fiber precursor or a carbon slit tape precursor, comprising the steps of:
  • At least one additive (a1 ) selected from the group comprising carbon nanotubes, carbon fibers, carbon black, graphene, nanographene, graphite, expanded graphite, nanographite, fullerenes, and mixture thereof; and/or
  • At least one additive (a2) selected from the group comprising calcium carbonate, sodium carbonate, lithium carbonate, sodium bicarbonate, potassium bicarbonate, magnesium carbonate, alumina, hydrated alumina, magnesia, silicon aluminum oxynitride, borosilicate, silicon carbide, silica, boron carbide, titanium carbide, boron nitride, boron nitride nanotubes, boron nitride nanosheets, silicon nitride, aluminum nitride, titanium nitride, titanium diboride, aluminum dodecaboride, diatomite, feldspar, gypsum, hormite, kaolin, mica, nepheline syenite, perlite, phyrophyllite, smectite, talc, vermiculite, zeolite, calcite, wollastonite, calcium metasilicate, calcium sulfate, aluminum silicate, silicon dioxide,
  • step b) forming the mixture obtained in step a) into a fiber or slit tape having at least one dimension ranging from 500 nm to 200 ⁇ ;
  • step b) subjecting the fiber or slit tape obtained in step b) to a thermal treatment in the presence of at least one inorganic acid;
  • the invention provides a process for preparing a carbon fiber precursor or a carbon slit tape precursor, comprising the steps of:
  • At least one additive (a1 ) selected from the group comprising carbon nanotubes, carbon fibers, carbon black, graphene, nanographene, graphite, expanded graphite, nanographite, fullerenes, and mixture thereof; and/or
  • At least one additive (a2) selected from the group comprising calcium carbonate, sodium carbonate, lithium carbonate, sodium bicarbonate, potassium bicarbonate, magnesium carbonate, alumina, hydrated alumina, magnesia, silicon aluminum oxynitride, borosilicate, silicon carbide, boron carbide, titanium carbide, boron nitride, boron nitride nanotubes, boron nitride nanosheets, silicon nitride, aluminum nitride, titanium nitride, titanium diboride, aluminum dodecaboride, diatomite, feldspar, gypsum, hormite, kaolin, mica, nepheline syenite, perlite, phyrophyllite, smectite, talc, vermiculite, zeolite, calcite, wollastonite, calcium metasilicate, calcium sulfate, aluminum silicate, silicon dioxide, titanium dioxide, clay
  • step b) subjecting the fiber or slit tape obtained in step b) to a thermal treatment in the presence of at least one inorganic acid;
  • the invention provides a carbon fiber precursor or a carbon slit tape precursor obtained by a process according the first aspect of the invention.
  • the invention encompasses a process for preparing carbon fibers or slit tapes comprising the step of: subjecting carbon fibers precursor or carbon slit tapes precursor according to the second aspect or prepared according to the first aspect to a thermal graphitization treatment; thereby obtaining carbon fibers or slit tape.
  • a resin means one resin or more than one resin.
  • a process for the preparation of a carbon fiber or a slit tape precursor comprising the steps of:
  • At least one additive (a1 ) selected from the group comprising carbon nanotubes, carbon fibers, carbon black, graphene, nanographene, graphite, expanded graphite, nanographite, fullerenes, and mixture thereof; and/or
  • At least one additive selected from the group comprising calcium carbonate, sodium carbonate, lithium carbonate, sodium bicarbonate, potassium bicarbonate, magnesium carbonate, alumina, hydrated alumina, magnesia, silicon aluminum oxynitride, borosilicate, silicon carbide, silica, boron carbide, titanium carbide, boron nitride, boron nitride nanotubes, boron nitride nanosheets, silicon nitride, aluminum nitride, titanium nitride, titanium diboride, aluminum dodecaboride, diatomite, feldspar, gypsum, hormite, kaolin, mica, nepheline syenite, perlite, phyrophyllite, smectite, talc, vermiculite, zeolite, calcite, wollastonite, calcium metasilicate, calcium sulfate, aluminum silicate, silicon dioxide, titanium, titanium
  • step (b) forming the mixture obtained in step (a) into a fiber or slit tape having at least one dimension ranging from 500 nm to 200 ⁇ ;
  • step (b) subjecting the fiber or slit tape obtained in step (b) to a thermal treatment in the presence of at least one inorganic acid;
  • a process for the preparation of a carbon fiber or a slit tape precursor comprising the steps of:
  • At least one additive (a1 ) selected from the group comprising carbon nanotubes, carbon fibers, carbon black, graphene, nanographene, graphite, expanded graphite, nanographite, fullerenes, and mixture thereof; and/or
  • At least one additive selected from the group comprising calcium carbonate, sodium carbonate, lithium carbonate, sodium bicarbonate, potassium bicarbonate, magnesium carbonate, alumina, hydrated alumina, magnesia, silicon aluminum oxynitride, borosilicate, silicon carbide, boron carbide, titanium carbide, boron nitride, boron nitride nanotubes, boron nitride nanosheets, silicon nitride, aluminum nitride, titanium nitride, titanium diboride, aluminum dodecaboride, diatomite, feldspar, gypsum, hormite, kaolin, mica, nepheline syenite, perlite, phyrophyllite, smectite, talc, vermiculite, zeolite, calcite, wollastonite, calcium metasilicate, calcium sulfate, aluminum silicate, silicon dioxide, titanium dioxide, clay (a2)
  • step b) forming the mixture obtained in step a) into a fiber or slit tape having at least one dimension ranging from 500 nm to 200 ⁇ ; and c) subjecting the fiber or slit tape obtained in step b) to a thermal treatment in the presence of at least one inorganic acid;
  • polyolefin is selected from the group comprising polyethylene and polypropylene; preferably polyethylene.
  • the polyethylene has a melt flow index MI2 of at least 0.1 g/10 min, for example at a MI2 from at least 0.1 g/10 min to at most 34 g/10 min, for example from at least 0.1 g/10 min to at most 30 g/10 min, preferably from at least 0.1 g/10 min to at most 20 g/10 min, preferably from at least 0.1 g/10 min to at most 6 g/10 min.
  • MI2 melt flow index
  • the polyethylene has a density in the range of at least 0.910 g/cm 3 , preferably at least 0.920 g/cm 3 , preferably at least 0.930 g/cm 3 , preferably at least 0.935 g/cm 3 as measured according to ISO 1 183-1 :2012.
  • the polyethylene has a density of at most 0.970 g/cm 3 .
  • the polypropylene has a melt flow index of at most 100 g/10 min as measured according to ISO 1 133 procedure B condition M, at 230 °C and under a load of 2.16 kg, for example at most 80 g/10 min, preferably at most 70 g/10 min, preferably at most 60 g/10 min, preferably at most 50 g/10 min, preferably at most 40 g/10 min.
  • the polypropylene has a melt flow index of at least 0.1 g/10 min, for example at least 0.5 g/10 min, for example at least 1.0 g/10 min, for example at least 1.5 g/10 min, preferably at least 2.0 g/10 min, preferably from at least 2.0 g/10 min to at most 40 g/10 min.
  • step (a) comprises from 0.001 % to 10.0 % by weight of said at least one additive (a1 ) and/or (a2), preferably from 0.01 % to 5.0 % by weight, preferably from 0.1 % to 3.0 % by weight based on the total weight of said mixture.
  • step a) the polymer is mixed with at least one additive (a1 ) and at least one additive (a2).
  • the additive (a1 ) is a nanoparticle selected from the group comprising carbon nanotubes, carbon nanofibers, carbon black, nanographene, nanographite, and blends thereof, preferably the at least one additive (a1 ) is carbon nanotubes, more preferably multi- walled carbon nanotubes.
  • the additive (a2) is selected from the group comprising calcium carbonate, sodium carbonate, potassium carbonate, lithium carbonate, sodium bicarbonate and potassium bicarbonate; preferably calcium carbonate.
  • step (a) comprises from 0.001 % to 5.0 % by weight of additive (a1 ) and from 0.001 % to 5.0 % by weight of additive (a2).
  • step (c) is selected from the group comprising sulfuric acid, chlorosulfonic acid, fluorosulfonic acid, trifluoromethylsulfonic acid, methylsulfonic acid, perfluoroalkanesulfonic acid, trifluoromethanesulfonic acid, chlorosulfuric acid, fluorosulfuric acid, perchloric acid, camphorsulfonic acid, hydrochloric acid, nitric acid, aqua regia, phosphoric acid, hydrofluoric acid, hydrobromic acid, boric acid, and fluoroboric acid.
  • the inorganic acid used in step (c) is selected from the group comprising sulfuric acid, chlorosulfonic acid, fluorosulfonic acid, trifluoromethylsulfonic acid, methylsulfonic acid, perfluoroalkanesulfonic acid, trifluoromethanesulfonic acid, chlorosulfuric acid, fluorosulfuric acid, perchloric acid
  • thermo treatment is selected from the group comprising irradiation and direct heating; preferably irradiation.
  • step (a) comprises at least one additive (a1 ) and the thermal treatment of step (c) is infrared radiation.
  • step (a) comprises at least one additive (a1 ) and the thermal treatment of step (c) is infrared radiation having a wavelength of at least 700 nm.
  • the IR radiation has a wavelength of at most 1 mm.
  • step (a2) is used in step (a) and the thermal treatment of step (c) is direct heating.
  • Carbon fiber or slit tape precursor obtained by a process according to any one of statements 1 to 22.
  • a process for preparing carbon fibers or slit tapes comprising the step of:
  • the present invention provides a carbon fiber precursor or a carbon slit tape precursor, and a carbon fiber or a slit tape made therefrom.
  • carbon fiber precursor or carbon slit tape precursor and “carbon fiber or slit tape precursor” are synonymous and used interchangeably and refer to the raw material used to make carbon fibers or slit tapes.
  • carbon fiber or slit tape refers to fibers of slit tapes comprising mostly carbon atoms.
  • the process for preparing a carbon fiber precursor or a carbon slit tape precursor comprises the steps of:
  • At least one additive (a1 ) selected from the group comprising carbon nanotubes, carbon fibers, carbon black, graphene, nanographene, graphite, expanded graphite, nanographite, fullerenes, and mixture thereof; and/or
  • At least one additive selected from the group comprising calcium carbonate, sodium carbonate, lithium carbonate, sodium bicarbonate, potassium bicarbonate, magnesium carbonate, alumina, hydrated alumina, magnesia, silicon aluminum oxynitride, borosilicate, silicon carbide, silica, boron carbide, titanium carbide, boron nitride, boron nitride nanotubes, boron nitride nanosheets, silicon nitride, aluminum nitride, titanium nitride, titanium diboride, aluminum dodecaboride, diatomite, feldspar, gypsum, hormite, kaolin, mica, nepheline syenite, perlite, phyrophyllite, smectite, talc, vermiculite, zeolite, calcite, wollastonite, calcium metasilicate, calcium sulfate, aluminum silicate, silicon dioxide, titanium, titanium
  • step (b) forming the mixture obtained in step (a) into a fiber or slit tape having at least one dimension ranging from 500 nm to 200 ⁇ ;
  • step (b) subjecting the fiber or slit tape obtained in step (b) to a thermal treatment in the presence of at least one inorganic acid;
  • the process for preparing a carbon fiber precursor or a carbon slit tape precursor comprises the steps of:
  • At least one additive (a1 ) selected from the group comprising carbon nanotubes, carbon fibers, carbon black, graphene, nanographene, graphite, expanded graphite, nanographite, fullerenes, and mixture thereof; and/or
  • At least one additive selected from the group comprising calcium carbonate, sodium carbonate, lithium carbonate, sodium bicarbonate, potassium bicarbonate, magnesium carbonate, alumina, hydrated alumina, magnesia, silicon aluminum oxynitride, borosilicate, silicon carbide, boron carbide, titanium carbide, boron nitride, boron nitride nanotubes, boron nitride nanosheets, silicon nitride, aluminum nitride, titanium nitride, titanium diboride, aluminum dodecaboride, diatomite, feldspar, gypsum, hormite, kaolin, mica, nepheline syenite, perlite, phyrophyllite, smectite, talc, vermiculite, zeolite, calcite, wollastonite, calcium metasilicate, calcium sulfate, aluminum silicate, silicon dioxide, titanium dioxide, clay (a2)
  • step (b) forming the mixture obtained in step (a) into a fiber or slit tape having at least one dimension ranging from 500 nm to 200 ⁇ ;
  • step (b) subjecting the fiber or slit tape obtained in step (b) to a thermal treatment in the presence of at least one inorganic acid;
  • Step (a) of the present process comprises mixing a polyolefin or a polystyrene with at least one additive (a1 ) and/or (a2).
  • the polyolefins that can be used in the present invention may be any alpha-olefin homopolymer or any copolymer of an olefin and one or more comonomers.
  • the olefin can for example be ethylene, propylene, 1 -butene, 1 -pentene, 1 -hexene, 4-methyl-1 -pentene or 1 -octene, but also cycloolefins such as for example cyclopentene, cyclohexene, cyclooctene or norbornene.
  • the comonomer is different from the olefin and chosen such that it is suited for copolymerization with the olefin.
  • polyolefins for use in the present invention are olefin homopolymers and copolymers of an olefin and one or more comonomers, wherein said olefin and said one or more comonomer is different, and wherein said olefin is ethylene or propylene.
  • the term "comonomer” refers to olefin comonomers which are suitable for being polymerized with olefin monomers, preferably ethylene or propylene monomers. Comonomers may comprise but are not limited to aliphatic C 2 -C 2 o alpha-olefins.
  • Suitable aliphatic C 2 -C 2 o alpha-olefins include ethylene, propylene, 1 -butene, 4-methyl-1 -pentene, 1 -hexene, 1 -octene, 1 -decene, 1 - dodecene, 1 -tetradecene, 1 -hexadecene, 1 -octadecene and 1 -eicosene.
  • the comonomer is 1 -hexene.
  • Preferred polyolefins for use in the present invention are propylene and ethylene polymers.
  • the polyolefin is selected from polyethylene and polypropylene homo- and copolymers.
  • the polyolefin is polyethylene or polypropylene, or a copolymer thereof.
  • the polyolefin is polyethylene.
  • the polyethylene suitable for use in the present invention may be any ethylene homopolymer or any copolymer of ethylene and one or more comonomers.
  • polyethylene polymers and copolymers for use in the present invention can have a melt flow index MI2 of at most 34 g/10 min as measured according to ISO 1 133 Procedure B, condition D at a temperature of 190 °C and a load of 2.16 kg, for example at most 30 g/10 min, preferably at most 20 g/10 min, preferably at most 6 g/10 min.
  • polyethylene polymers and copolymers for use in the present invention can have a melt flow index MI2 of at least 0.1 g/10 min, for example at a MI2 from at least 0.1 g/10 min to at most 34 g/10 min, for example from at least 0.1 g/10 min to at most 30 g/10 min, preferably from at least 0.1 g/10 min to at most 20 g/10 min, preferably from at least 0.1 g/10 min to at most 6 g/10 min.
  • MI2 melt flow index
  • Polyethylene polymers and copolymers for use in the invention can be produced by polymerizing ethylene and optionally one or more co-monomers, such as ethylene, in the presence of a catalyst system and optionally in the presence of hydrogen.
  • a catalyst system and optionally in the presence of hydrogen.
  • the term "catalyst" refers to a substance that causes a change in the rate of a polymerization reaction. In the present invention, it is especially applicable to catalysts suitable for the polymerization of propylene to polypropylene.
  • the catalyst can be a chromium, a Ziegler-Natta or a metallocene catalyst system.
  • the polyolefin can be a polypropylene homopolymer or copolymer. They may be atactic, syndiotactic or isotactic.
  • the one or more comonomers are preferably selected from the group comprising ethylene and C4-C10 alpha-olefins, such as for example 1 -butene, 1 - pentene, 1 -hexene, 1 -octene, or 4-methyl-1 -pentene. Ethylene and 1 -butene are the preferred comonomers.
  • the polypropylene is a propylene homopolymer (or polypropylene with a low comonomer content).
  • the polypropylene polymers and copolymers can have a melt flow index of at most 100 g/10 min as measured according to ISO 1 133 procedure B condition M, at 230 °C and under a load of 2.16 kg, for example at most 80 g/10 min, preferably at most 70 g/10 min, preferably at most 60 g/10 min, preferably at most 50 g/10 min, preferably at most 40 g/10 min.
  • the polypropylene polymers and copolymers can have a melt flow index of at least 0.1 g/10 min, for example at least 0.5 g/10 min, for example at least 1.0 g/10 min, for example at least 1 .5 g/10 min, preferably at least 2.0 g/10 min.
  • the polypropylene polymers and copolymers for use in the present invention can be produced by polymerizing propylene and optionally one or more co-monomers, such as ethylene, in the presence of a catalyst system and optionally in the presence of hydrogen.
  • the catalyst can be a Ziegler-Natta or a metallocene catalyst system.
  • the polystyrenes used in the present invention may be any styrene homopolymer or copolymer.
  • suitable styrene homopolymers are styrene, poly(o methylstyrene). They may be atactic, syndiotactic or isotactic.
  • Styrene copolymers comprise one or more suitable comonomers, i.e. polymerizable compounds different from styrene.
  • suitable comonomers are butadiene, acrylonitrile, acrylic acid or methacrylic acid.
  • styrene copolymers that may be used in the present invention are butadiene-styrene copolymers, which are also referred to as high-impact polystyrene (HIPS).
  • HIPS high-impact polystyrene
  • the mixture can comprise from 0.001 % to 10.0 % by weight of said additive (a1 ) and/or (a2), for example from 0.01 % to 8.0 % by weight; for example from 0.01 % to 6.0 % by weight; for example from 0.01 % to 5.0 % by weight; preferably from 0.01 % to 4 % by weight; preferably from 0.1 % to 3 % by weight based on the total weight of the mixture.
  • Additive (a1 ) is preferably selected from the group comprising carbon nanotubes, carbon fibers, carbon black, graphene, nanographene, graphite, expanded graphite, nanographite, fullerenes, and mixture thereof.
  • said additive (a1 ) is carbon nanotubes.
  • Suitable carbon nanotubes also referred to as "nanotubes" herein, can be cylindrical in shape and structurally related to fullerenes, an example of which is Buckminster fullerene (C60). Suitable carbon nanotubes may be open or capped at their ends. The end cap may for example be a Buckminster-type fullerene hemisphere. Suitable carbon nanotubes used in the present invention can comprise more than 90 %, more preferably more than 95 %, even more preferably more than 99 % and most preferably more than 99.9 % of their total weight in carbon. However, minor amounts of other atoms may also be present.
  • Suitable carbon nanotubes to be used in the present invention can be prepared by any method known in the art. They can be prepared by the catalyst decomposition of hydrocarbons, a technique that is called Catalytic Carbon Vapor Deposition (CCVD). Other methods for preparing carbon nanotubes include the arc-discharge method, the plasma decomposition of hydrocarbons or the pyrolysis of selected polyolefin under selected oxidative conditions.
  • the starting hydrocarbons can be acetylene, ethylene, butane, propane, ethane, methane or any other gaseous or volatile carbon-containing compound.
  • the catalyst if present, is used in either pure or in supported form. Certain carbon nanotubes may contain metal residues from the catalyst used; these residues do not need to be removed by purification.
  • Nanotubes can exist as single-walled nanotubes (SWNT) and multi-walled nanotubes (MWNT), i.e. nanotubes having one single wall and nanotubes having more than one wall, respectively.
  • SWNT single-walled nanotubes
  • MWNT multi-walled nanotubes
  • a one atom thick sheet of atoms for example a one atom thick sheet of nanographite (also called graphene)
  • Multi-walled nanotubes consist of a number of such cylinders arranged concentrically.
  • the arrangement in a multi-walled nanotube can be described by the so- called Russian doll model, wherein a larger doll opens to reveal a smaller doll.
  • Nanotubes may be characterized by their outer diameter or by their length or by both.
  • Suitable carbon nanotubes used in the present invention can generally be characterized by having a size from 0.5 nm to 5000 nm, this definition of size can be limited to diameter and length.
  • Single-walled nanotubes are preferably characterized by an outer diameter of at least 0.5 nm, more preferably of at least 1 .0 nm, and most preferably of at least 2.0 nm.
  • their outer diameter is at most 100 nm, more preferably at most 30 nm and most preferably at most 10 nm.
  • their outer diameter is at least 0.5 nm and at most 50 nm, for example at least 1 .0 nm and most 30 nm, for example at least 2.0 nm and at most 10 nm.
  • the length of single-walled nanotubes is at least 0.1 ⁇ , more preferably at least 0.5 ⁇ .
  • their length is at most 50 ⁇ , more preferably at most 25 ⁇ . In some embodiments their length is at least 0.1 ⁇ and at most 50 ⁇ , for example at least 0.5 ⁇ and at most 25 ⁇ .
  • Multi-walled nanotubes are preferably characterized by an outer diameter of at least 1 .0 nm, more preferably of at least 2.0 nm, 4.0 nm, 6.0 nm or 8.0 nm.
  • the preferred outer diameter is at most 100 nm, more preferably at most 80 nm, 60 nm or 40 nm, and most preferably at most 20 nm.
  • the outer diameter is in the range from 1 .0 nm to 100 nm, for example from 2.0 nm to 80 nm, for example from 4.0 nm to 60 nm, for example from 6.0 to 60 nm, for example from 8.0 to 40 nm.
  • the preferred length of the multi-walled nanotubes is at least 50 nm, more preferably at least 75 nm, and most preferably at least 100 nm. Their preferred length is at most 20 mm, more preferably at most 10 mm, 500 ⁇ , 250 ⁇ , 100 ⁇ , 75 ⁇ , 50 ⁇ , 40 ⁇ , 30 ⁇ or 20 ⁇ , and most preferably at most 10 ⁇ . The most preferred length is in the range from 100 nm to 10 ⁇ .
  • the multi-walled carbon nanotubes have an average outer diameter in the range from 8 nm to 20 nm or an average length in the range from 100 nm to 10 ⁇ or both.
  • the additive (a1 ) comprises multi-walled carbon nanotubes, more preferably multi-walled carbon nanotubes having on average from 5 to 15 walls.
  • the average number of walls of carbon nanotubes is determined by High Resolution Transmission Electronic Microscopy.
  • Non-limiting examples of suitable commercially available multi-walled carbon nanotubes are NanocylTM NC 7000, available from Nanocyl and GraphistrengthTM 100, available from Arkema, FloTubeTM 9000 available from CNano Technology.
  • the additive (a1 ) is carbon nanofibers.
  • Suitable nanofibers for use in the present invention preferably have a diameter of at least 1 nm, more preferably of at least 2 nm and most preferably of at least 5 nm.
  • their diameter is at most 500 nm, more preferably at most 300 nm, and most preferably at most 100 nm.
  • their diameter is at least 1 nm and at most 500 nm, for example at least 2 nm and at most 300 nm, for example at least 5 nm and at most 100 nm.
  • Their length may vary from 10 ⁇ to several centimeters.
  • the additive (a1 ) is carbon black particles.
  • Carbon black is preferably made of microcrystalline, finely dispersed carbon particles, which are obtained through incomplete combustion or thermal decomposition of liquid or gaseous hydrocarbons.
  • Carbon black particles can have a diameter in the range of from 5 nm to 500 nm, though they have a great tendency to form agglomerates.
  • Carbon black comprises from 96 % to 99 % by weight of carbon, relative to its total weight, with the remainder being hydrogen, nitrogen, oxygen, sulfur or any combination of these.
  • additive (a1 ) is graphene, preferably nanographene.
  • Graphene in general, and including nanographene may be a single sheet or a stack of several sheets having both micro- and nano-scale dimensions, such as in some embodiments an average particle size of 1 to 20 ⁇ , specifically 1 to 15 ⁇ , and an average thickness (smallest) dimension in nano-scale dimensions of less than or equal to 50 nm, specifically less than or equal to 25 nm, and more specifically less than or equal to 10 nm.
  • An exemplary nanographene may have an average particle size of 1 to 5 ⁇ , and specifically 2 to 4 ⁇ .
  • Graphene including nanographene, may be prepared by exfoliation of nanographite or by a synthetic procedure by "unzipping" a nanotube to form a nanographene ribbon. Exfoliation to form graphene or nanographene may be carried out by exfoliation of a graphite source such as graphite, intercalated graphite, and nanographite. Exemplary exfoliation methods include, but are not limited to, those practiced in the art such as fluorination, acid intercalation, acid intercalation followed by thermal shock treatment, and the like, or a combination comprising at least one of the foregoing. Exfoliation of the nanographite provides a nanographene having fewer layers than non-exfoliated nanographite.
  • exfoliation of nanographite may provide the nanographene as a single sheet only one molecule thick, or as a layered stack of relatively few sheets.
  • exfoliated nanographene has fewer than 50 single sheet layers, specifically fewer than 20 single sheet layers, specifically fewer than 10 single sheet layers, and more specifically fewer than 5 single sheet layers.
  • the nanographene has an aspect ratio in the range of greater than or equal to about 100:1 , for example, greater than equal to about 1000:1.
  • the nanographene has a surface area greater than or equal to about 40 m 2 /gram nitrogen surface adsorption area.
  • the surface area is greater than or equal to about 100 m 2 /gram nitrogen surface adsorption area.
  • the nanographene is expanded.
  • additive (a1 ) is graphite, preferably nanographite.
  • the nanographite can be multilayered by furnace high temperature expansion from acid- treated natural graphite or microwave heating expansion from moisture saturated natural graphite.
  • the nanographite is a multi-layered nanographite which has at least one dimension with a thickness less than 100 nm.
  • the graphite may be mechanically treated such as by air jet milling to pulverize the nanographite particles. The pulverization of the particles ensures that the nanographite flake and other dimensions of the particles are less than 20 microns, most likely less than 5 microns.
  • Additive (a2) is preferably selected from the group comprising calcium carbonate, sodium carbonate, lithium carbonate, sodium bicarbonate, potassium bicarbonate, magnesium carbonate, alumina, hydrated alumina, magnesia, silicon aluminum oxynitride, borosilicate, silicon carbide, silica, boron carbide, titanium carbide, boron nitride, boron nitride nanotubes, boron nitride nanosheets, silicon nitride, aluminum nitride, titanium nitride, titanium diboride, aluminum dodecaboride, diatomite, feldspar, gypsum, hormite, kaolin, mica, nepheline syenite, perlite, phyrophyllite, smectite, talc, vermiculite, zeolite, calcite, wollastonite, calcium metasilicate, calcium sulfate, aluminum silicate, silicon
  • additive (a2) is preferably selected from the group comprising calcium carbonate, sodium carbonate, lithium carbonate, sodium bicarbonate, potassium bicarbonate, magnesium carbonate, alumina, hydrated alumina, magnesia, silicon aluminum oxynitride, borosilicate, silicon carbide, boron carbide, titanium carbide, boron nitride, boron nitride nanotubes, boron nitride nanosheets, silicon nitride, aluminum nitride, titanium nitride, titanium diboride, aluminum dodecaboride, diatomite, feldspar, gypsum, hormite, kaolin, mica, nepheline syenite, perlite, phyrophyllite, smectite, talc, vermiculite, zeolite, calcite, wollastonite, calcium metasilicate, calcium sulfate, aluminum silicate, silicon dioxide, titanium
  • the additive (a2) is selected from the group comprising calcium carbonate, sodium carbonate, potassium carbonate, lithium carbonate, sodium bicarbonate and potassium bicarbonate; preferably calcium carbonate.
  • Suitable additives (a2) can have a particle size D50 of at most 5 ⁇ , more preferably at most 3 ⁇ and most preferably at most 1 ⁇ .
  • incorporation of the additive such as carbon nanotubes into the polyolefin or polystyrene can be performed via a masterbatch.
  • masterbatch refers to concentrates of additive (such as the carbon nanotubes) in a polymer, which are intended to be subsequently incorporated into the polyolefin or the polystyrene for use in the invention (compatible or non-compatible with the polymer already contained in these masterbatches).
  • masterbatches makes processes more easily adaptable to industrial scale, compared to direct incorporation of the additive powder.
  • the masterbatch can comprise at least 5 % by weight of the additive such as carbon nanotubes based on the total weight of the masterbatch.
  • the masterbatch comprises at least 8 % by weight of carbon nanotubes based on the total weight of the masterbatch.
  • the masterbatch comprises at least 10 % by weight of the additive such as carbon nanotubes based on the total weight of the masterbatch.
  • the mixing step (a) comprises the melt blending product of polyolefin or polystyrene and said additive, either provided as such or as a masterbatch.
  • melt blending encompasses the use of shear force, extensional force, compressive force, ultrasonic energy, electromagnetic energy, thermal energy or combinations comprising at least one of the foregoing forces or forms of energy and is conducted in processing equipment wherein the aforementioned forces are exerted by a single screw, multiple screws, intermeshing co-rotating or counter rotating screws, non- intermeshing co-rotating or counter rotating screws, reciprocating screws, screws with pins, barrels with pins, rolls, rams, helical rotors, or combinations comprising at least one of the foregoing.
  • Melt blending may be conducted in machines such as, single or multiple screw extruders, Buss kneader, Eirich mixers, Henschel, helicones, Ross mixer, Banbury, roll mills, paddle or blades mixer, molding machines such as injection molding machines, vacuum forming machines, blow molding machines, or the like, or combinations comprising at least one of the foregoing machines.
  • melt blending is performed in a twin screw extruder, such as a Brabender co-rotating twin screw extruder and/or a Leistritz extruder.
  • step (a) can comprise the steps of (i) preparing a masterbatch comprising a polyolefin or a polystyrene and the additive; and (ii) blending said masterbach with the at least polyolefin or polystyrene.
  • Step (b) comprises forming the mixture obtained in step (a) into a fiber or slit tape having at least one dimension ranging from 500 nm to 200 ⁇ ; preferably a dimension ranging from 700 nm to 175 ⁇ ; preferably ranging from 900 nm to 150 ⁇ ; preferably ranging from 1 ⁇ to 125 ⁇ ; preferably ranging from 2 ⁇ to 100 ⁇ ; preferably ranging from 3 ⁇ to 80 ⁇ ; more preferably ranging from 4 ⁇ to 60 ⁇ ; most preferably ranging from 5 ⁇ to 40 ⁇ .
  • the dimension is the thickness of said fiber or slit tape.
  • Forming the slit tape or fiber of step (b) can be performed by any of the methods known in the art, such as melt-spinning (single-component, bi-component, or multi- component), solution-spinning, electro-spinning, centrifugal fiber spinning, film-casting and slitting, spun-bond, flash- spinning, and gel-spinning; preferably melt spinning.
  • melt-spinning single-component, bi-component, or multi- component
  • solution-spinning electro-spinning
  • centrifugal fiber spinning film-casting and slitting
  • spun-bond spun-bond
  • flash- spinning flash- spinning
  • gel-spinning preferably melt spinning.
  • the fibers are formed by extruding a molten polyolefin or polystyrene material through a plurality of fine, usually circular, die capillaries as molten threads or filaments which are then subsequently quenched with water or air. Thereafter, the filaments are bundled together to form a "tow" which is then pulled over heated rolls which stretch or draw the towed fibers to a final diameter and are finally collected.
  • the so- obtained fibers may be subjected to a further drawing step. The fibers can then be for example collected on a winder or other suitable collecting means.
  • the slit tapes are formed by extruding a molten polyolefin or polystyrene material through a plurality of slits, usually rectilinear in shape, as a continuous film which is then subsequently quenched in a water bath. Thereafter, the film is cut by a row of industrial razor knives forming a width of individual tapes and these slit tapes are continuously pulled through a either a heated oven, over a heated plate, or over steam heated, hot oil heated or electrically heated "draw” rolls before the oriented slit tapes are traversed onto a package by the winder.
  • the fiber obtained in step (b) can be of any cross-sectional shape, such as circular, star- shaped, hollow fibers, triangular, ribbon (i.e. slit tape), etc.
  • Step (c) of the present process comprises subjecting the fiber or slit tape obtained in step (b) to a thermal treatment in the presence of at least one inorganic acid;
  • the polymer forming the fiber or slit tape is functionalized (grafted).
  • the functionalities introduced to the polymer are HS0 3 " groups, the process is referred to as "sulfonation”.
  • Grafting step (c) is performed in the presence of an inorganic acid.
  • Suitable inorganic acids can be selected from the group comprising sulfuric acid, chlorosulfonic acid, fluorosulfonic acid, trifluoromethylsulfonic acid, methylsulfonic acid, perfluoroalkanesulfonic acid, trifluoromethanesulfonic acid, chlorosulfuric acid, fluorosulfuric acid, perchloric acid, camphorsulfonic acid, drochloric acid, nitric acid, aqua regia, phosphoric acid, hydrofluoric acid, hydrobromic acid, boric acid, and fluoroboric acid.
  • the inorganic acid used in step (c) is selected from chlorosulfonic acid and sulfuric acid; preferably chlorosulfonic acid.
  • the sulfuric acid is provided as at a concentration of at least 90 % by weight, preferably of at least 9 5% by weight, preferably of at least 98 % by weight.
  • the fiber or slit tape is subjected to a thermal treatment. The duration and intensity of the thermal treatment should avoid the melting of the fiber or slit tape. Suitable thermal treatments include direct heating and irradiation.
  • the thermal treatment comprises direct heating, with for example, a hot plate.
  • Suitable direct heating temperatures may range from 40 °C to 180 °C; preferably from 42 °C to 150 °C; more preferably from 45 °C to 120 °C; most preferably from 48 °C to 100 °C.
  • sulfuric acid when sulfuric acid is used, preferred temperature includes progressive heating up to 120 °C - 180 °C. Lower temperatures (60 °C - 90 °C) are preferred when chlorosulfonic acid is used.
  • the thermal treatment is selected from the group comprising infrared radiation, microwaves, visible light, direct heating, ultraviolet radiation, electron beam, a laser beam, UV light, and plasma.
  • the irradiation is infrared radiation (IR).
  • IR radiation has a wavelength of at least 700 nm. In a preferred embodiment the IR radiation has a wavelength of at most 1 mm.
  • step (c) lasts for at most 300 minutes, preferably for at most 280 minutes, preferably for at most 250 minutes, preferably at most 120 minutes, preferably at most 60 minutes, preferably at most 30 minutes, preferably at most 15 minutes. In an embodiment, step (c) lasts for at least 5 minutes, preferably for at least 8 minutes, preferably for at least 10 minutes.
  • step (c) is performed at atmospheric pressure.
  • the pressure is at most the maximum pressure of the vessel wherein the process is carried out.
  • step (c) is practiced without applying a stress (tension) along the length of the fiber.
  • step (c) is practiced by applying a stress along the fiber length.
  • the stress can be applied to, for example, avoid fiber shrinkage.
  • a high degree of axial stress e.g., 10 MPa or higher
  • 0, 0.1 , 0.3, 0.5, 1 , 2, 5, 10, or 20 MPa of stress is applied.
  • step (c) which means 1 % - 100 % of the polymer was grafted
  • the fibers or slit tapes may be optionally washed with one or more solvents.
  • the washing encompasses rinsing, spraying or otherwise contacting the polymer with a solvent or combination of solvents, wherein the solvent or combination of solvents is at a temperature of from -100 °C up to 200 °C.
  • solvents include water, Ci-C 4 alcohols, acetone, dilute acid (such as sulfuric acid), halogenated solvents and combinations thereof.
  • the fibers or slit tapes are washed with water.
  • the fibers or slit tapes may be blotted dry, air dried, heated using a heat source such as a conventional oven, a microwave oven, or by blowing heated gas or gases onto the fibers or slit tapes, or combinations thereof.
  • a heat source such as a conventional oven, a microwave oven, or by blowing heated gas or gases onto the fibers or slit tapes, or combinations thereof.
  • Grafting of a fiber or slit tapes to produce the carbon fiber precursor or slit tape precursor of the present invention induces a weight increase in the precursor, as groups such as HSOy replace hydrogen atoms. Fiber weight increase is therefore an easy way to characterize the grafting efficiency.
  • the present inventors have observed that the process according to the invention yields significant relative weight increase during the grafting of polymer fibers or slit tapes. Carbon fibers and slit tapes with improved properties such as high stiffness, high tensile strength, low weight, high chemical resistance, high temperature tolerance and low thermal expansion may be obtained using the present process.
  • the present invention also encompasses a carbon fiber precursor or slit tape precursor obtained by the present process.
  • the present invention also encompasses a process for preparing carbon fibers or slit tapes comprising the step of subjecting carbon fibers precursors or slit tapes precursors prepared as described herein to a thermal graphitization treatment; thereby obtaining carbon fibers or slit tapes.
  • the present invention therefore also encompasses a process for preparing carbon fibers or slit tapes comprising the steps of
  • At least one additive (a1 ) selected from the group comprising carbon nanotubes, carbon fibers, carbon black, graphene, nanographene, graphite, expanded graphite, nanographite, fullerenes, and mixture thereof; and/or
  • At least one additive selected from the group comprising calcium carbonate, sodium carbonate, lithium carbonate, sodium bicarbonate, potassium bicarbonate, magnesium carbonate, alumina, hydrated alumina, magnesia, silicon aluminum oxynitride, borosilicate, silicon carbide, silica, boron carbide, titanium carbide, boron nitride, boron nitride nanotubes, boron nitride nanosheets, silicon nitride, aluminum nitride, titanium nitride, titanium diboride, aluminum dodecaboride, diatomite, feldspar, gypsum, hormite, kaolin, mica, nepheline syenite, perlite, phyrophyllite, smectite, talc, vermiculite, zeolite, calcite, wollastonite, calcium metasilicate, calcium sulfate, aluminum silicate, silicon dioxide, titanium, titanium
  • step (b) forming the mixture obtained in step (a) into a fiber or slit tape having at least one dimension ranging from 500 nm to 200 ⁇ ;
  • step (b) subjecting the fiber or slit tape obtained in step (b) to a thermal treatment in the presence of at least one inorganic acid; thereby obtaining a carbon fiber precursor or slit tape precursor;
  • step (c) subjecting the carbon fibers precursor or slit tapes precursor obtained in step (c) to a thermal graphitization treatment; thereby obtaining carbon fibers or slit tapes.
  • the present invention also encompasses a process for preparing carbon fibers or slit tapes comprising the steps of
  • At least one additive (a1 ) selected from the group comprising carbon nanotubes, carbon fibers, carbon black, graphene, nanographene, graphite, expanded graphite, nanographite, fullerenes, and mixture thereof; and/or
  • At least one additive selected from the group comprising calcium carbonate, sodium carbonate, lithium carbonate, sodium bicarbonate, potassium bicarbonate, magnesium carbonate, alumina, hydrated alumina, magnesia, silicon aluminum oxynitride, borosilicate, silicon carbide, boron carbide, titanium carbide, boron nitride, boron nitride nanotubes, boron nitride nanosheets, silicon nitride, aluminum nitride, titanium nitride, titanium diboride, aluminum dodecaboride, diatomite, feldspar, gypsum, hormite, kaolin, mica, nepheline syenite, perlite, phyrophyllite, smectite, talc, vermiculite, zeolite, calcite, wollastonite, calcium metasilicate, calcium sulfate, aluminum silicate, silicon dioxide, titanium dioxide, clay (a2)
  • step (b) forming the mixture obtained in step (a) into a fiber or slit tape having at least one dimension ranging from 500 nm to 200 ⁇ ;
  • step (c) subjecting the fiber or slit tape obtained in step (b) to a thermal treatment in the presence of at least one inorganic acid; thereby obtaining a carbon fiber precursor or slit tape precursor; subjecting the carbon fibers precursor or slit tapes precursor obtained in step (c) to a thermal graphitization treatment; thereby obtaining carbon fibers or slit tapes.
  • graphitization refers to the process wherein graphite (free carbon) is formed.
  • thermal graphitization or “carbonization” are used synonymously and refers to the process of formation of graphite through pyrolysis.
  • the thermal carbonization and graphitization treatments of step (d) can be performed using any of the conditions, as known in the art, which cause carbonization of the carbon fiber or slit tape precursor.
  • the carbonization and graphitization steps can be performed at a temperature from 300 °C to 3400 C; for example from 600 C to 2500 °C; more preferably from 700 C to 1700 °C; most preferably from 800 C to 1600 °C; for example from 850 C to 1500 C.
  • the limit for the highest temperature to be imposed can be "final fiber properties" dependent. For example, when highest modulus is targeted, maximum temperature as high as from 2000 C to 3400 °C can be imposed.
  • the carbonization and graphitization steps can be performed by passing the fibers precursor or slit tapes precursor through a furnace or a tube oven at temperatures of from 500 °C to 3000 C. More preferably, the carbonization temperature is at least 600 °C.
  • the carbonization step may be performed in furnace or a tube oven in an atmosphere of inert gas or in a vacuum.
  • activated carbon fibers may be prepared using the methods disclosed herein.
  • the process comprises:
  • At least one additive (a1 ) selected from the group comprising carbon nanotubes, carbon fibers, carbon black, graphene, nanographene, graphite, expanded graphite, nanographite, fullerenes, and mixture thereof; and/or
  • At least one additive selected from the group comprising calcium carbonate, sodium carbonate, lithium carbonate, sodium bicarbonate, potassium bicarbonate, magnesium carbonate, alumina, hydrated alumina, magnesia, silicon aluminum oxynitride, borosilicate, silicon carbide, silica, boron carbide, titanium carbide, boron nitride, boron nitride nanotubes, boron nitride nanosheets, silicon nitride, aluminum nitride, titanium nitride, titanium diboride, aluminum dodecaboride, diatomite, feldspar, gypsum, hormite, kaolin, mica, nepheline syenite, perlite, phyrophyllite, smectite, talc, vermiculite, zeolite, calcite, wollastonite, calcium metasilicate, calcium sulfate, aluminum silicate, silicon dioxide, titanium, titanium
  • step (b) forming the mixture obtained in step (a) into a fiber or slit tape having at least one dimension ranging from 500 nm to 200 ⁇ ;
  • step (b) subjecting the fiber or slit tape obtained in step (b) to a thermal treatment in the presence of at least one inorganic acid; thereby obtaining a carbon fiber precursor or slit tape precursor;
  • step (c) carbonizing the carbon fibers precursor or slit tapes precursor obtained in step (c) by heating it to a temperature from 500 °C to 3000 °C; thereby obtaining carbon fibers or slit tapes.
  • the process comprises:
  • At least one additive (a1 ) selected from the group comprising carbon nanotubes, carbon fibers, carbon black, graphene, nanographene, graphite, expanded graphite, nanographite, fullerenes, and mixture thereof; and/or
  • At least one additive selected from the group comprising calcium carbonate, sodium carbonate, lithium carbonate, sodium bicarbonate, potassium bicarbonate, magnesium carbonate, alumina, hydrated alumina, magnesia, silicon aluminum oxynitride, borosilicate, silicon carbide, boron carbide, titanium carbide, boron nitride, boron nitride nanotubes, boron nitride nanosheets, silicon nitride, aluminum nitride, titanium nitride, titanium diboride, aluminum dodecaboride, diatomite, feldspar, gypsum, hormite, kaolin, mica, nepheline syenite, perlite, phyrophyllite, smectite, talc, vermiculite, zeolite, calcite, wollastonite, calcium metasilicate, calcium sulfate, aluminum silicate, silicon dioxide, titanium dioxide, clay (a2)
  • step (b) forming the mixture obtained in step (a) into a fiber or slit tape having at least one dimension ranging from 500 nm to 200 ⁇ ;
  • step (b) subjecting the fiber or slit tape obtained in step (b) to a thermal treatment in the presence of at least one inorganic acid; thereby obtaining a carbon fiber precursor or slit tape precursor;
  • step (c) carbonizing the carbon fibers precursor or slit tapes precursor obtained in step (c) by heating it to a temperature from 500 °C to 3000 °C; thereby obtaining carbon fibers or slit tapes.
  • the amount of time that the carbon fiber precursor or slit tape precursor is subjected to the carbonization temperature is highly dependent on the carbonization temperature employed. Generally, the higher the carbonization temperature employed, the shorter the amount of time required.
  • the carbonization time is at least 0.02 hour; preferably at least 0.05 hour; preferably at least 0.1 hour; preferably at least 0.25 hour, preferably at least 0.5 hour, preferably at least 1 hour, preferably at least 2 hours, preferably at least 3 hours, preferably at least 4 hours, preferably at least 5 hours, preferably at least 6 hours, preferably at least 7 hours, preferably at least 8 hours, preferably at least 9 hours, preferably at least 10 hours, preferably at least 1 1 hours, preferably at least 12 hours.
  • the carbonization step is conducted in an atmosphere substantially devoid of a reactive gas such as oxygen or hydrogen, and typically under an inert atmosphere.
  • a reactive gas such as oxygen or hydrogen
  • inert atmospheres include nitrogen (N 2 ) and the noble gases such as helium or argon.
  • One or more reactive functionalizing species may be included in the carbonization step or in a post-treatment step (for example at the exit of the furnace as a post-carbonization step) to suitably functionalize the carbon fiber or slit tape, e.g., by inclusion of a fluorocarbon compound to induce fluorination, or inclusion of an oxygen- containing species to induce oxygenation (to include, e.g., hydroxy or ether groups), or inclusion of amino-, thio-, or phosphino-species to aminate, thiolate, or phosphinate the carbon fiber.
  • At least one reactive gas such as oxygen, hydrogen, ammonia, an organoamine, carbon dioxide, methane, a fluoroalkane, a phosphine, or a mercaptan.
  • the one or more reactive gases may, for example, desirably change or adjust the compositional, structural, or physical characteristics of the carbon fiber.
  • the functionalized groups on the carbon fiber can have a variety of functions, e.g., to bind to metal species that are catalytically active, or to modify or adjust the surface miscibility, absorptive, or wettability characteristics, particularly for gas absorption and filtration applications.
  • the pressure employed in the carbonization step can be around 1 atm. However, in some embodiments it may be preferred to use a higher pressure for example above 1 atm, such as at least 1 .5 atm, for example at least 2 atm, 5 atm, for example at least 10 atm, for example at least 20 atm, for example at least 50 atm, or for example at least 100 atm, to, for example, maintain a positive pressure inside the furnace and keep the sample free of oxygen at high temperature to avoid combustion or partial combustion. In other embodiments, it may be preferred to use a lower pressure for example below 1 atm, such as 0.5 atm, 0.1 atm, 0.05 atm, or 0.01 atm.
  • the present invention can be further illustrated by the following examples, although it will be understood that these examples are included merely for purposes of illustration and are not intended to limit the scope of the invention unless otherwise specifically indicated.
  • PE polyethylene
  • CNT carbon nanotubes
  • PE/calcium carbonate PE/ CNT/ calcium carbonate
  • the slit tapes were produced on a LabLine device from Plasticisers Engineering LTD.
  • HDPE high density polyethylene
  • MDPE medium density polyethylene
  • Total HD6207 is a homopolyethylene grade having a density of 0.962 g/cm 3 and a Melt Flow Rate of 0.7 g/10 min as measured according to ISO 1 133 procedure B condition D (190 °C/2.16 kg).
  • M3581 is a metallocene-catalyzed polyethylene with hexene as comonomer.
  • M3581 has a density of 0.935 g/cm 3 as measured according to ISO 1 183-1 :2012, and a Melt Flow Rate of 6.0 g/10 min as measured according to ISO 1 133 procedure B condition D (190 °C/2.16 kg).
  • the carbon nanotubes used are multi-walled carbon nanotubes NanocylTM NC 7000, commercially available from Nanocyl. These nanotubes have a surface area of 250-300 m 2 /g (measured by BET method), a carbon purity of about 90 % by weight (measured by thermal gravimetric analysis), an average diameter of 9.5 nm and an average length of 1.5 ⁇ (as measured by transmission electron microscopy).
  • the amount of calcium carbonate was added on to the polymer powder and shaken until obtaining a homogenous blend.
  • the slit tape was made on the LabLine device equipped with a slit die (60 mm length, 0.6 mm height).
  • the melt temperature was 240 °C for the HD6207 grade and 225 °C for the M3581 .
  • the tape was cooled thanks to an air knife and went on the first chilled roll, after the first roll, the tape went to two heated rolls, respectively 60 °C and 90 °C. These three rolls composed the slow train that turned at 20 rpm. After that, the tape went to the fast rolls passing on to the blades, to cut the tape in slit tapes, the fast rolls turned at 50 rpm.
  • the slit tapes were collected on a paperboard core thanks to a winder.
  • the weight increase was calculated as (m2 - m1 )/m1 * 100.
  • Example 1 with the slit tape made from the pure HDPE (HD6207) (Comparative Example)
  • a slit tape sample (20 ⁇ thickness) was placed in a glass flask of 150 ml, 50 ml of concentrated sulfuric acid were added. No tension was applied.
  • the acid and sample were heated around 80 °C for 4 hours. After washing and drying of the sample, a weight increase of 4.06 % was measured.
  • the tape was flushed with a large amount of demineralized water. The tape was placed in a flask with 100 ml of demineralized water and the pH was measured using a universal paper indicator from Merck. The pH was around 6. The tape was firstly dried on an absorbent paper and thereafter placed in a vacuum oven for 4 hours at 100 °C.
  • Example 2 with the slit tape made from the HDPE at 2 %wt of NC7000 (HD6207/NC7000 2 % wt)
  • a slit tape sample (20 ⁇ thickness) was placed in a glass flask of 150 ml, 50 ml of concentrated sulfuric acid were added. No tension was applied.
  • the acid and sample were illuminated during 2 hours with an infrared lamp (OSRAM 150 Watts) placed at 20 cm of the sample. A temperature elevation of 30 °C was observed. After washing and drying of the sample, a weight increase of 5.15 % was measured.
  • OSRAM 150 Watts infrared lamp
  • the tape was flushed with a large amount of demineralized water.
  • the tape was placed in a flask with 100 ml of demineralized water and the pH was measured using a universal paper indicator from Merck. The pH was around 6.
  • the tape was firstly dried on an absorbent paper and thereafter placed in a vacuum oven for 4 hours at 100 °C thereby obtaining a carbon slip tape precursor.
  • Example 3 with the slit tape made from the pure HDPE (HD6207) (Comparative Example)
  • a slit tape (20 ⁇ thickness) sample was placed in a glass flask of 150 ml, 50 ml of chlorosulfonic acid were added. No tension was applied.
  • the sample was stirred every 15 minutes during 4 hours. After washing and drying of the sample, a weight increase of 7.5 % was measured.
  • the tape was flushed with a large amount of demineralized water.
  • the tape was placed in a flask with 100 ml of demineralized water and the pH was measured using a universal paper indicator from Merck. The pH was around 6.
  • the tape was firstly dried on an absorbent paper and thereafter placed in a vacuum oven for 4 hours at 100 °C.
  • Weight increase was higher than in examples 1 and 2, attributed to the replacement of concentrated sulphuric acid by chlorosulfonic acid.
  • Example 4 with the slit tape made from the pure HDPE (HD6207) (Comparative Example)
  • a slit tape sample (20 ⁇ thickness) was placed in a glass flask of 150 ml, 50 ml of chlorosulfonic acid were added. No tension was applied.
  • the acid and sample were heated around 50 °C for 2 hours. After washing and drying of the sample, a weight increase of 14 % was measured.
  • the tape was flush with a large amount of demineralized water.
  • the tape was placed in a flask with 100 ml of demineralized water and the pH was measured using a universal paper indicator from Merck. The pH was around 6.
  • the tape was firstly dried on an absorbent paper and thereafter placed in a vacuum oven for 4 hours at 100 °C.
  • the sulfonated slit tape sample was placed on a metallic frame in order to have a low tension on the tape.
  • the frame was placed in an oven and the temperature was increased to reach 500 °C.
  • the sample was kept 4 hours at 500 °C and then, cooled at room temperature. After this treatment, the sample could still be handled, proof of a sufficient grafting.
  • Example 5 with the slit tape made from the MDPE at 1 %wt of calcium carbonate (M3581 /calcium carbonate 1 % wt) A slit tape sample (40 ⁇ thickness) was placed in a glass flask of 150 ml, 50 ml of chlorosulfonic acid were added. No tension was applied.
  • the acid and sample were heated around 50 °C for 15 minutes. After washing and drying of the sample, a weight increase of 22 % was measured.
  • the tape was flushed with a large amount of demineralized water.
  • the tape was placed in a flask with 100 ml of demineralized water and the pH was measured using a universal paper indicator from Merck. The pH was around 6.
  • the tape was firstly dried on an absorbent paper and thereafter placed in a vacuum oven for 4 hours at 100 °C thereby obtaining a carbon slip tape precursor.
  • the sulfonated slit tape sample was placed on a metallic frame in order to have a low tension on the tape.
  • the frame was placed in an oven and the temperature was increased to reach 500 °C.
  • the sample was kept 4 hours at 500 °C, it was cooled at room temperature. After this treatment, the sample could still be handled, proof of a sufficient grafting.
  • Example 6 with the slit tape made from the MDPE at 1 %wt of calcium carbonate and 2 % of CNT's (M3581 /calcium carbonate 1 % wt,NC7000 2 % wt)
  • a slit tape sample (40 ⁇ thickness) was placed in a glass flask of 150 ml, 50 ml of chlorosulfonic acid were added. No tension was applied.
  • the acid and sample were illuminated during 2 hours with an infrared lamp (OSRAM 150 Watts) placed at 20 cm of the sample. A temperature elevation of 40 °C was observed. After washing and drying of the sample, a weight increase of 32.5 % was measured.
  • OSRAM 150 Watts infrared lamp
  • the tape was flush with a large amount of demineralized water.
  • the tape was placed in a flask with 100 ml of demineralized water and the pH was measured using a universal paper indicator from Merck. The pH was around 6.
  • the tape was firstly dried on an absorbent paper and thereafter placed in a vacuum oven for 4 hours at 100 °C thereby obtaining a carbon slip tape precursor.
  • the sulfonated slit tape sample was placed on a metallic frame in order to have a low tension on the tape.
  • the frame was placed in an oven and the temperature was increased to reach 500 °C.
  • the sample was kept 4 hours at 500 °C, it was cooled at room temperature. After this treatment, the sample could still be handled, proof of a sufficient grafting.

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Abstract

La présente invention concerne un procédé de préparation d'un précurseur de fibre de carbone ou d'un précurseur de bandelette découpée de fibre de carbone, comprenant les étapes consistant à : a) mélanger au moins une polyoléfine ou au moins un polystyrène, avec au moins un additif (a1) choisi dans le groupe comprenant les nanotubes de carbone, les fibres de carbone, le noir de carbone, le graphène, le nanographène, le graphite, le graphite expansé, le nanographite, les fullerènes, et un mélange de ceux-ci ; et/ou au moins un additif (a2) choisi dans le groupe comprenant le carbonate de calcium, le carbonate de sodium, le carbonate de lithium, le bicarbonate de sodium, le bicarbonate de potassium, le carbonate de magnésium, l'alumine, l'alumine hydratée, la magnésie, l'oxynitrure de silicium aluminium, le borosilicate, le carbure de silicium, le carbure de titane, le nitrure de bore, les nanotubes de nitrure de bore, les nanofeuilles de nitrure de bore, le nitrure de silicium, le nitrure d'aluminium, le nitrure de titane, le diborure de titane, le dodécaborure d'aluminium, la diatomite, le feldspath, le gypse, l'hormite, le kaolin, le mica, la syénite néphélinique, la perlite, la phyrophylllite, la smectite, le talc, la vermiculite, la zéolite, la calcite, la wollastonite, le métasilicate de calcium, le sulfate de calcium, le silicate d'aluminium, le dioxyde de silicium, le dioxyde de titane, l'argile (telle que l'argile kaolinitique, l'argile kaolinitique calcinée, l'argile exfoliée), la dolomite et des mélanges de deux ou plus de deux de ceux-ci ; b) former le mélange obtenu à l'étape (a) en une fibre ou une bandelette découpée ayant au moins une dimension allant de 500 nm à 200 µm ; et c) soumettre la fibre ou bandelette découpée obtenue à l'étape (b) à un traitement thermique en présence d'au moins un acide inorganique ; ce qui permet d'obtenir un précurseur de fibre de carbone ou un précurseur de bandelette découpée de carbone. La présente invention concerne également le précurseur de fibre de carbone ou le précurseur de bandelette découpée en carbone obtenu avec ledit procédé. La présente invention concerne également un procédé de préparation de fibres de carbone ou de bandelettes découpées, par traitement de graphitisation thermique dudit précurseur de fibre de carbone ou dudit précurseur de bandelette découpée.
PCT/EP2017/057641 2016-03-31 2017-03-31 Procédé de préparation de précurseur de fibre de carbone ou de précurseur de bandelettes découpées en carbone WO2017167941A1 (fr)

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WO2018057154A1 (fr) * 2016-09-20 2018-03-29 Dow Global Technologies Llc Procédé de fabrication d'un article à partir de polyoléfine et composition associée
CN108117069A (zh) * 2018-01-23 2018-06-05 杭州高烯科技有限公司 一种大片氧化石墨烯溶液的浓缩方法及装置
CN109988360A (zh) * 2019-04-09 2019-07-09 上海超碳石墨烯产业技术有限公司 一种石墨烯导热高分子材料及其制备方法
CN111945242A (zh) * 2020-08-14 2020-11-17 上海申湘混凝土纤维有限公司 一种晶须碳纳米管改性聚丙烯粗纤维及其制备方法
CN112760784A (zh) * 2020-12-28 2021-05-07 绍兴天普纺织有限公司 一种具有冰凉感的锦涤混纺面料的制备工艺
WO2021148978A1 (fr) 2020-01-22 2021-07-29 Mersen Scotland Holytown Limited Matériaux d'isolation thermique appropriés pour être utilisés à hautes températures et procédé de fabrication desdits matériaux
CN114855453A (zh) * 2022-06-17 2022-08-05 西安理工大学 自组装仿纤维独石结构的高导热复合材料的制备方法
CN115011019A (zh) * 2022-06-23 2022-09-06 青岛优派普环保科技股份有限公司 一种高强度pe燃气管及其制备方法

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018057154A1 (fr) * 2016-09-20 2018-03-29 Dow Global Technologies Llc Procédé de fabrication d'un article à partir de polyoléfine et composition associée
CN108117069A (zh) * 2018-01-23 2018-06-05 杭州高烯科技有限公司 一种大片氧化石墨烯溶液的浓缩方法及装置
CN108117069B (zh) * 2018-01-23 2020-10-23 杭州高烯科技有限公司 一种大片氧化石墨烯溶液的浓缩方法及装置
CN109988360A (zh) * 2019-04-09 2019-07-09 上海超碳石墨烯产业技术有限公司 一种石墨烯导热高分子材料及其制备方法
CN109988360B (zh) * 2019-04-09 2021-09-28 上海超碳石墨烯产业技术有限公司 一种石墨烯导热高分子材料及其制备方法
WO2021148978A1 (fr) 2020-01-22 2021-07-29 Mersen Scotland Holytown Limited Matériaux d'isolation thermique appropriés pour être utilisés à hautes températures et procédé de fabrication desdits matériaux
CN111945242A (zh) * 2020-08-14 2020-11-17 上海申湘混凝土纤维有限公司 一种晶须碳纳米管改性聚丙烯粗纤维及其制备方法
CN112760784A (zh) * 2020-12-28 2021-05-07 绍兴天普纺织有限公司 一种具有冰凉感的锦涤混纺面料的制备工艺
CN114855453A (zh) * 2022-06-17 2022-08-05 西安理工大学 自组装仿纤维独石结构的高导热复合材料的制备方法
CN114855453B (zh) * 2022-06-17 2024-03-08 西安理工大学 自组装仿纤维独石结构的高导热复合材料的制备方法
CN115011019A (zh) * 2022-06-23 2022-09-06 青岛优派普环保科技股份有限公司 一种高强度pe燃气管及其制备方法
CN115011019B (zh) * 2022-06-23 2022-12-16 青岛优派普环保科技股份有限公司 一种高强度pe燃气管及其制备方法

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