EP2889400A1 - Mit anorganischen Partikeln verstärkte Zellulosefasern oder Filamente und Verfahren zu ihrer Herstellung - Google Patents

Mit anorganischen Partikeln verstärkte Zellulosefasern oder Filamente und Verfahren zu ihrer Herstellung Download PDF

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EP2889400A1
EP2889400A1 EP13199519.3A EP13199519A EP2889400A1 EP 2889400 A1 EP2889400 A1 EP 2889400A1 EP 13199519 A EP13199519 A EP 13199519A EP 2889400 A1 EP2889400 A1 EP 2889400A1
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Prior art keywords
particles
reinforcing particles
base material
cellulosic
methylimidazolium
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French (fr)
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Sappi Netherlands Services BV
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; 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
    • 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

Definitions

  • the present invention relates to the field of cellulosic fibres or filaments, and more particularly to those reinforced with inorganic reinforcement particles, as well as their methods of production.
  • cellulose is a straight-chain polymer of anhydroglucose with ⁇ 1-4 glycosidic bonds.
  • cellulose can be used in a great deal of technical applications, and one of the major applications is the use of cellulose in the manufacture of man-made cellulosic fibres or filaments.
  • the manufacturing process of man-made cellulosic fibres or filaments generally involves the dissolution of a cellulosic base material in a suitable solvent to form a spinning solution (or "spinning dope"), followed by the subsequent extrusion of the spinning solution into a regeneration bath where the spinning solution forms into filament.
  • a spinning solution or "spinning dope”
  • cellulose fibres are for example rayon (or viscose) fibre and higher strength dry jet - wet spun fibres such as lyocell (marketed under the name TENCEL).
  • Others include modal/high wet modulus fibre, polynosic fibre, cellulose acetate (diacetate and triacetate), FORTISAN fibre, cuprammonium hydroxide rayon & tyre cord.
  • cellulose as a base material for the manufacture of fibres
  • advantages of using cellulose as a base material for the manufacture of fibres include its low cost, wide availability, biodegradability, biocompatibility, low toxicity, dimensional stability, high tensile strength, high hydrophilicity and amenability to surface derivatization.
  • cellulose exists as a complex aggregation of amorphous and crystalline regions, i.e. it exists as a semi-crystalline polymer in which the more crystalline regions are monoclinic with parallel packing of the polysaccharide chains (Cellulose I).
  • the strength of the currently available, regenerated cellulose fibres is directly influenced by the level of molecular orientation and crystallinity. Moreover, the tensile strength and modulus of the fibre may be further augmented by the incorporation of reinforcing particles - thus forming a modified or composite fibre, in which the regenerated cellulose is the matrix.
  • the degree of orientation/crystallinity and particle content that can be achieved through existing process technologies and hence the extent of fibre strength that is possible. It would therefore be highly desirable to design a process that enables the manufacture of cellulose-based fibres having a comparatively higher degree of crystallinity, in order to achieve stronger cellulose-based fibres.
  • CNC nanocrystalline cellulose
  • CNC may be used as a reinforcement particles in man-made cellulose fibres, but because of the economic cost and the intricacies of successfully incorporation of CNC into the spinning dope, it is desirable to utilise alternative reinforcement particles which can be handled more conveniently in the production process of cellulose-based fibres and which are obtainable at lower cost, while at the same time yielding a considerable enhancement in tenacity and/or tensile modulus increase, when compared to unreinforced man-made cellulose fibres.
  • the present invention provides for a method for spinning a reinforced cellulosic fibre or filament, comprising the steps of: a. forming a composite spinning solution comprising inorganic reinforcing particles, a cellulosic base material and a process solvent, b. extruding the composite spinning solution through an orifice into a regeneration fluid such as to form the reinforced cellulosic fibre or filament, wherein the composite spinning solution is formed by dissolving the cellulosic base material in the process solvent and distributively dispersing the inorganic reinforcing particles in the process solvent and wherein the inorganic reinforcing particles have an aspect ratio of 1.25:1 or more, preferably of 1.5 or more and more preferably of 10:1 1 or more.
  • the present invention also provides for a cellulosic fibre or filament optionally obtainable by the method as described above, comprising a cellulosic base material and inorganic reinforcing particles, wherein the inorganic reinforcing particles are distributively dispersed throughout the cellulosic base material and wherein the inorganic reinforcing particles have an aspect ratio of 1.25:1 or more, preferably of 1.5 or more and more preferably of 10:1 1 or more.
  • the present invention further provides for the use of inorganic particles having an aspect ratio of 1.25:1 or more, preferably of 1.5 or more, and more preferably of 10:1 or more for reinforcing a cellulosic fibre or filament comprising a cellulosic base material, wherein the inorganic particles are distributively dispersed throughout the cellulosic base material.
  • the present invention even further provides for a processing and spinning apparatus for producing the reinforced cellulosic filament as above, said apparatus comprising: a. a temperature-controlled mixing compartment for dissolving a cellulosic base material in a process solvent and distributively dispersing the reinforcing particles in a process solvent such as to form a spinning solution, b. a spinneret or spinning nozzle connected to the temperature-controlled mixing compartment, for extruding the spinning solution into a temperature-controlled regeneration compartment, c. a temperature-controlled regeneration compartment comprising a regeneration fluid suitable for forming the reinforced cellulosic filament from the extruded spinning solution and d. an optional orientation compartment connected to, or comprised in, the temperature-controlled regeneration compartment, comprising a means for drawing the formed reinforced cellulosic filament by a factor of from 1 to 20, preferably from 5 to 15 and most preferably from 8 to 14.
  • the present invention provides for a method for spinning a reinforced cellulosic fibre or filament, comprising the steps of: a. forming a composite spinning solution comprising inorganic reinforcing particles, a cellulosic base material and a process solvent, b. extruding the composite spinning solution through an orifice into a regeneration fluid such as to form the reinforced cellulosic fibre or filament, wherein the composite spinning solution is formed by dissolving the cellulosic base material in the process solvent and distributively dispersing the inorganic reinforcing particles in the process solvent and wherein the inorganic reinforcing particles have an aspect ratio of 1.25:1 or more, preferably of 1.5 or more and more preferably of 10:1 1 or more.
  • the composite spinning solution comprises an inorganic reinforcing particle, a cellulosic base material and a process solvent.
  • distributedly dispersed particles refers to solid particles in a solid or liquid phase which are dispersed in a spatially homogeneous manner throughout the bulk of the liquid or solid.
  • the term "aspect ratio of a particle” refers to the ratio between the average length of a particle and the average width of a particle.
  • nanocellulose as used herein also encompasses the (interchangeably used) term “nanofibrillated cellulose” and refers to cellulose particles which are characterized by having an elongated form, having an aspect ratio of at least 2:1, and having an average length in the range of 15-900 nm, preferably in the range of 50-700 nm, more preferably 70-700nm.
  • the average diameter is preferably in the range of 3-200 nm, preferably in the range of 5-100 nm, more preferably in the range of 5-30 nm.
  • the inorganic reinforcing particles useful in the method of the present invention can be chosen from particles comprising or consisting of a mineral chosen from chemical compounds of aluminium and oxygen, such as ⁇ -alumina; wollastonite whiskers, asbestos fibre, titanium dioxide fibres, glass fibre, metal oxides particles chosen from zinc oxide (ZnO), alumina (Al 2 O 3 ), magnetite (Fe 3 O 4 ) or titanium dioxide (TiO 2 ) particles; silicon oxide particles such as fumed silica (Si02) particles; nitride particles such as boron nitride (BN), titanium nitride (TiN) or silicon nitride (eg.
  • a mineral chosen from chemical compounds of aluminium and oxygen, such as ⁇ -alumina
  • wollastonite whiskers asbestos fibre, titanium dioxide fibres, glass fibre, metal oxides particles chosen from zinc oxide (ZnO), alumina (Al 2 O 3 ), magnetite (Fe 3 O 4 ) or titanium dioxide (
  • Si 3 N 4 particles; natural or synthetic silicate particles such as particles of calcium silicate (CaSiO 3 ), wollastonite, magadiite, clay particles; natural and synthetic phyllosilicate particles such as kaolinite, halloysite or talc particles; smectite particles such as montmorillonite (MT), bentonite, hectorite, synthetic hectorite or laponite particles; mica particles such as illite particles; sepiolite particles; palygorskite particles such as attapulgite or imogolite particles; or organically modified derivatives thereof such as modified montmorillonite (MMTs), hydrated oxides such as brucite, gibbsite), layered double hydroxides (eg.
  • MMTs modified montmorillonite
  • MMTs modified montmorillonite
  • hydrated oxides such as brucite, gibbsite
  • layered double hydroxides eg.
  • Oxifluorides carbonate particles such as precipitated or ground calcium carbonate particles; sulphates particles such as for example barite (BaSO 4 ) particles; phosphate particles; phosphonate particles such as hydroxyapatite, zirconium phosphate or alumino-phosphate particles; chloride particles; metal nanoparticles such as silver, gold or copper nanoparticles; and mixtures of two or more such particles; or mixtures thereof.
  • the inorganic reinforcing particles useful in the method of the present invention may be treated by the applying a metal oxide, metal nitride, metal carbide, metal sulphide, or mixtures thereof, preferably of silica, alumina, zirconia, or mixtures thereof, and more preferably of silica to the surface of the inorganic reinforcing particle.
  • a metal oxide, metal nitride, metal carbide, metal sulphide, or mixtures thereof preferably of silica, alumina, zirconia, or mixtures thereof, and more preferably of silica to the surface of the inorganic reinforcing particle.
  • Such particles are hereinafter referred to as "interfacially modified inorganic particles"
  • the surface treatment consisting of preferably silica, alumina or mixtures thereof improves (i) the dispersibility of the reinforcing particles in the spinning solution via promotion of preferential absorption of cellulose chains at the particle - liquid medium interface and also (ii) the interfacial compatibility between the inorganic reinforcing particles and the cellulosic base material, thus enabling enhanced stress transfer between cellulose matrix and the reinforcing particles in the composite fibres of the present invention.
  • said interfacial modification of the particles via application of an inorganic surface treatment consisting of a metal oxide, metal nitride, metal carbide, metal sulphide, or mixtures thereof, preferably of silica, alumina, zirconia, or mixtures thereof, and more preferably of silica, is afforded by precipitation of a thin layer of the chosen inorganic compound or mixture of compounds from a suitable precursor or precursors, mediated by a controlled change in temperature, pressure, pH, ionic environment or a related physicochemical parameter.
  • Suitable precursors as known by those skilled in the art are selected from, but not limited to, metal alkoxides, metal acetates or other lower carboxylate salts, complex metal oxoanions and metal amine complexes.
  • the fluid medium in which the interfacial modification of the particles is conducted may be an aqueous liquid, organic liquid, mixtures of such liquids, a gas or a plasma.
  • the surface treatment might optionally be further modified by subsequent calcination of the treated particles by heating at a elevated temperature, between 100 °C and 800 °C , preferably between 450 °C and 650 °C.
  • the inorganic surface treatment may be a continuous or semi-continuous layer having a thickness from 2 nm to 10 nm, preferably from 4 nm to 6 nm.
  • the interfacially modified inorganic particles useful in the method of the present invention are selected in cases where the dispersibility of the particles is deemed to be poor.
  • poor dispersibility is defined as the presence of phase separation and/or agglomeration of the reinforcing particles when they are incorporated into the cellulose spinning solution or spinning dope according to the method of the present invention.
  • the presence of phase separation and/or aggregation is readily detected via the technique of optical microscopy, as will be known by those skilled in the art.
  • Said interfacially modified particles have an inorganic surface treatment that promotes preferential absorption of cellulose chains at the particle-liquid medium interface, thus preventing phase separation/aggregation and thus enhancing dispersibility.
  • the inorganic reinforcing particles useful in the method of the present invention can be chosen from inorganic reinforcing particles having an inorganic surface treatment applied thereto, wherein the surface treatement consists of metal oxides, metal nitrides, metal carbides, metal sulphides, or mixtures thereof, preferably of silica, alumina, zirconia, or mixtures thereof, and more preferably of silica.
  • Such surface treatment may be applied to the inorganic reinforcing particles, namely particles comprising or consisting of an inorganic material, preferably of a mineral chosen from chemical compounds of aluminium and oxygen, such as ⁇ -alumina; wollastonite whiskers, asbestos fibre, titanium dioxide fibres, glass fibre, metal oxides particles chosen from zinc oxide (ZnO), alumina (Al 2 O 3 ), magnetite (Fe 3 O 4 ) or titanium dioxide (TiO 2 ) particles; silicon oxide particles such as fumed silica (SiO 2 ) particles; nitride particles such as boron nitride (BN), titanium nitride (TiN) or silicon nitride (eg.
  • an inorganic material preferably of a mineral chosen from chemical compounds of aluminium and oxygen, such as ⁇ -alumina
  • wollastonite whiskers asbestos fibre, titanium dioxide fibres, glass fibre, metal oxides particles chosen from zinc oxide (ZnO), alumina (Al 2 O 3
  • Si 3 N 4 particles; natural or synthetic silicate particles such as particles of calcium silicate (CaSiO 3 ), wollastonite, magadiite, clay particles; natural and synthetic phyllosilicate particles such as kaolinite, halloysite or talc particles; smectite particles such as montmorillonite (MT), bentonite, hectorite, synthetic hectorite or laponite particles; mica particles such as illite particles; sepiolite particles; palygorskite particles such as attapulgite or imogolite particles; or organically modified derivatives thereof such as modified montmorillonite (MMTs), hydrated oxides such as brucite, gibbsite), layered double hydroxides (eg.
  • MMTs modified montmorillonite
  • MMTs modified montmorillonite
  • hydrated oxides such as brucite, gibbsite
  • layered double hydroxides eg.
  • Oxifluorides carbonate particles such as precipitated or ground calcium carbonate particles; sulphates particles such as for example barite (BaSO 4 ) particles; phosphate particles; phosphonate particles such as hydroxyapatite, zirconium phosphate or alumino-phosphate particles; chloride particles; metal nanoparticles such as silver, gold or copper nanoparticles; and mixtures of two or more such particles.; or mixtures thereof.
  • the inorganic reinforcing particles having an inorganic surface treatment applied thereto may obtained by treatment of the inorganic reinforcing particles with sodium silicate solution as described in Colloids and Surfaces A: Physicochemical and Engineering Aspects, 80 (1993) 203-210 by A. Philipse , and then subsequently freeze drying the wet, surface treated particles and calcining them at 600°C for at least 6 hours.
  • the inorganic reinforcing particles having an inorganic surface treatment applied thereto are nanorods of ⁇ -alumina derived from the calcination of boehmite (aluminium oxide hydroxide) precursor particles, having silica applied thereto.
  • the production of such inorganic reinforcing particles may be achieved by first obtaining boehmite nanorods by hydrothermal treatment of an aluminium tri-alkoxide in acidic aqueous solution and subsequent sodium silicate solution treatment of the thus obtained boehmite rods or needles as described in Colloids and Surfaces A: Physicochemical and Engineering Aspects, 80 (1993) 203-210 by A. Philipse .
  • interfacially modified particles are then freeze-dried, and calcined at 600°C for at least 6 hours, thus yielding particles having an inner core of ⁇ -alumina and an surface treated wiith silica.
  • Such particles are shown to exhibit enhanced dispersibility in solutions of the cellulosic base materials of the present invention as evidenced via the absence of phase separation or aggregation on observation via optical microscopy.
  • the inorganic reinforcing particles useful in the method of the present invention are hollow metal oxide or silica nanorods made of for example silica, alumina, zirconia or or mixtures thereof, synthesized using nanocrystalline cellulose (CNC) as a template particle.
  • CNC nanocrystalline cellulose
  • hollow silica nanorods may be achieved by treating an aqueous dispersion of nanocrystalline cellulose (CNC) with a tetraalkoxysilane such as tetraethoxysilane as described in BioResources 7(2), 2319-2329 by Fu et al., and subsequently freeze-drying and calcining the silica-coated CNC at 600°C for at least 6 hours, such that the inner CNC core combusts, leaving only the silica outer surface as hollow silica nanorods.
  • CNC nanocrystalline cellulose
  • the inorganic reinforcing particles useful in the method of the present invention are particles of fumed metal oxide such as or fumed alumina or fumed titania, fumed silica, or mixtures thereof.
  • the inorganic reinforcing particles useful in the method of the present invention are particles of fumed metal oxides such as fumed alumina or fumed titania, or fumed silica
  • the particles can have a specific surface area of from 50 m 2 /g to 500 m 2 /g, more preferably of from 100 m 2 /g to 400m 2 /g, when measured according to the BET methodology.
  • the high specific surface area is due to the unique particle structure in which primary particles having a diameter of 7 to 40 nm in size are aggregated into structures having a median aggregate size of from 70 to 200 nm.
  • the inorganic reinforcing particles useful in the method of the present invention can be incorporated in the composite spinning solution at a concentration between 0.01 to 10 weight percent, preferably from 0.1 to 5 weight percent, more preferably of from 1 to 3 weight percent, based on the dry weight of the cellulosic base material.
  • the composite spinning solution may further comprise organic reinforcing particles chosen from nanographite particles, chopped aramid fibre, graphene or graphene oxide nanosheets, lignin nanoparticles, chitin-derived particles, carbon nanotubes or mixtures thereof.
  • the organic reinforcing particles are preferably carbon nanotubes or graphene nanosheets.
  • the process solvent may be chosen from solvents or mixtures of solvents capable of solubilizing the cellulosic base material, in particular cuprammonium solutions; amine oxides or ionic liquids.
  • Suitable ionic liquid are salts of 1-alkyl-3-methylimidazolium such as 1-alkyl-3-methylimidazolium halides, 1-alkyl-3-methylimidazolium thiocyanates, 1-alkyl-3-methylimidazolium carboxylates, 1-alkyl-3-methylimidazolium dialkylphosphates; salts of 1-(hydroxyalkyl)-3-methylimidazolium such as 1-(hydroxyalkyl)-3-methylimidazolium halides, 1-(hydroxyalkyl)-3-methylimidazolium thiocyanates, 1-(hydroxyalkyl)-3-methylimidazolium carboxylates, 1-(hydroxyalkyl)-3-methylimidazolium dialkylphosphates; salts of 1-alkenyl-3-methylimidazolium such as 1-alkenyl-3-methylimidazolium halides, 1-alkenyl-3-methylimidazolium thiocyanates, 1-alkeny
  • the process solvent is preferably a mixture of solvents, such as mixtures of an ionic liquid with dimethyl sulfoxide (DMSO), more preferably mixtures of one or more salts of 1-(hydroxyalkyl)-3-methylimidazolium or 1-alkyl-3-methylimidazolium with dimethyl sulfoxide (DMSO).
  • DMSO dimethyl sulfoxide
  • the composite spinning solution may comprise of from 70 to 99 weight percent, preferably of from 85 to 95 weight percent of a suitable process solvent, based on the total weight of the composite spinning solution.
  • the regeneration fluid is a gas or a liquid and serves the purpose of coagulating the composite spinning solution exiting the spinneret, in order to yield a solid filament or fibre that can be further processed.
  • Suitable regeneration media for cellulosic fibres or filament are known to the person skilled in the art and may be in liquid or gaseous form, and may be at a temperature of from 10 to 130°C, preferably between 15 to 60°C and most conveniently at room temperature. From a safety and cost point of view, liquid water is the most preferred regeneration medium.
  • the term "cellulosic base material” may refers to microcrystalline cellulose (MCC), microbial cellulose, cellulose derived from marine organisms or other invertebrates, cellulose derived from mechanically generated wood pulp or from chemical wood pulp; cellulose derived from man-made cellulose-based materials such as tyre cord, viscose, cellulose acetate or triacetate, lyocell, rayon, modal rayon, mercerized cotton fibre and other cellulose II sources.
  • MCC microcrystalline cellulose
  • microbial cellulose cellulose derived from marine organisms or other invertebrates, cellulose derived from mechanically generated wood pulp or from chemical wood pulp
  • cellulose derived from man-made cellulose-based materials such as tyre cord, viscose, cellulose acetate or triacetate, lyocell, rayon, modal rayon, mercerized cotton fibre and other cellulose II sources.
  • the cellulosic base material may further be chemically modified by, but not limited to, carboxylation, oxidation, xanthation, carbamation, sulphation or esterification of the polysaccharide backbone.
  • the most readily available commercial cellulosic base material is sourced from ground wood fibres, recycled or secondary wood pulp fibres, bleached and unbleached wood fibres.
  • the wood may be from softwoods and hardwoods alike.
  • other vegetable biomass materials such as bagasse, bamboo, cotton, ramie, jute, bamboo, bagasse, and similar plants may be used as sources of cellulosic material.
  • the cellulosic base material may be available in the form of a dried cellulose powder, aqueous cellulose suspension or paste, or a solution of readily dissolved cellulosic base material in a process solvent.
  • cellulosic base materials include, for example, Avicel PH-101, obtainable from the FMC Corporation.
  • the cellulosic base material is dissolved in the process solvent and the inorganic reinforcing particles are distributively dispersed in the process solvent to form the composite spinning solution by a. first combining the inorganic reinforcing particles with the process solvent such as to form a distributively dispersed suspension of inorganic reinforcing particles in the process solvent, and b. subsequently adding the cellulosic base material, and optionally additional process solvent, to said suspension of inorganic reinforcing particles to form the composite spinning solution.
  • the cellulosic base material is dissolved in the process solvent and the inorganic reinforcing particles are distributively dispersed in the process solvent to form the composite spinning solution by a. first combining the cellulosic base material with the process solvent such as to form a solution of cellulosic base material, and b. subsequently adding the inorganic reinforcing particles, and optionally additional process solvent, to said solution of cellulosic base material to form the composite spinning solution having the inorganic reinforcing particles distributively dispersed therein.
  • the present invention also provides for a reinforced cellulosic fibre or filament optionally obtainable by the method as described above, comprising a cellulosic base material and inorganic reinforcing particles, wherein the inorganic reinforcing particles are distributively dispersed throughout the cellulosic base material and wherein the inorganic reinforcing particles have an aspect ratio of 1.25:1 or more, preferably of 1.5 or more and more preferably of 10:1 1 or more.
  • the reinforced cellulosic fibre or filament according to the present invention may comprise the inorganic reinforcing particles of from 0.01 to 10 by weight percent, preferably between 0.1 to 5 by weight percent, more preferably from 1 to 3 by weight percent, based on the dry weight of the cellulosic base material.
  • the reinforced cellulosic fibre or filament according to the present invention may further comprise organic reinforcing particles, preferably of from 0.1 to 5 by weight percent, more preferably of from 1 to 3 by weight percent based on the dry weight of the cellulosic base material.
  • the organic reinforcing particles may be chosen from particles having an aspect ratio of 1.25:1 or more, preferably of 1.5 or more, more preferably of 10:1 or more.
  • the organic reinforcing particles can be chosen from nanocrystalline cellulose (CNC) nanographite particles, chopped aramid fibre, graphene or graphene oxide nanosheets, lignin nanoparticles, chitin-derived particles, carbon nanotubes or mixtures thereof.
  • the organic reinforcing particles are preferably nanocrystalline cellulose (CNC), carbon nanotubes or graphene nanosheets.
  • the cellulosic base material is dissolved in the process solvent and the organic and inorganic reinforcing particles are distributively dispersed in the process solvent to form the composite spinning solution by a. first combining the inorganic and organic reinforcing particles with the process solvent such as to form a distributively dispersed suspension of inorganic reinforcing particles in the process solvent, and b. subsequently adding the cellulosic base material, and optionally additional process solvent, to said suspension of inorganic reinforcing particles to form the composite spinning solution.
  • Suitable process solvents for when both inorganic and organic reinforcing particles are comprised in the composite spinning solution are ionic liquids pertaining to the group of salts of 1-(hydroxyalkyl)-3-methylimidazolium or mixtures thereof.
  • the cellulosic base material is dissolved in the process solvent and the inorganic reinforcing particles are distributively dispersed in the process solvent to form the composite spinning solution by a. first combining the cellulosic base material with the process solvent such as to form a solution of cellulosic base material, and b. subsequently adding the inorganic reinforcing particles, and optionally additional process solvent, to said solution of cellulosic base material to form the composite spinning solution having the inorganic reinforcing particles distributively dispersed therein.
  • the process solvent such as to form a solution of cellulosic base material
  • Suitable process solvents for when both inorganic and organic reinforcing particles are comprised in the composite spinning solution are ionic liquids pertaining to the group of salts of 1-(hydroxyalkyl)-3-methylimidazolium or mixtures thereof with DMSO.
  • the reinforced cellulosic fibre or filament according to the present invention may a diameter of from 3 to 350, preferably of from 3 to 50, and more preferably of from 2 to 25 microns.
  • the reinforced cellulosic fibre or filament according to the present invention has superior mechanical properties, such as a tenacity of from 50 to 200 cN/tex, preferably of from 55 to 200 cN/tex, more preferably 60 to 150 cN/tex, and a tensile modulus of from 2300 to 5000 cN/tex, preferably of from 2400 to 3500 cN/Tex, more preferably of from 2500 to 3500 cN/tex, when measured according to the International Bureau for the Standardisation of Man-Made Fibres (BISFA) Test method - 'Testing methods viscose, modal, lyocell and acetate staple fibres and tows', 2004 Edition.
  • a tenacity of from 50 to 200 cN/tex preferably of from 55 to 200 cN/tex, more preferably 60 to 150 cN/tex
  • a tensile modulus of from 2300 to 5000 cN/tex, preferably of from 2400 to 3500
  • the reinforced cellulosic fibre or filament according to the present invention may further display a linear density of said fibre or filament is in the range of 0.1 to 5, preferably of from 0.3 to 2 dtex.
  • the present invention further provides for a reinforced cellulosic fibre or filament, obtainable by the method described above, comprising a cellulosic base material and a first or mixture of first and second reinforcing particle.
  • the reinforced cellulosic fibre or filament obtainable by the method described above is characterized in that the reinforcing particles are distributively dispersed throughout the bulk of the cellulosic base material.
  • the reinforced cellulosic fibre or filament obtainable by the method described above is a monolithic reinforced cellulosic fibre or filament, in opposition to the subdivided structure core-shell fibres or filaments.
  • the present invention even further provides for a spinning apparatus for producing the reinforced cellulosic filament as above, said apparatus comprising: a. a temperature-controlled mixing compartment for dissolving a cellulosic base material in a process solvent and distributively dispersing the reinforcing particles in a process solvent such as to form a spinning solution, b. a spinneret or spinning nozzle connected to the temperature-controlled mixing compartment, for extruding the spinning solution into a temperature-controlled regeneration compartment, c. a temperature-controlled regeneration compartment comprising a regeneration fluid suitable for forming the reinforced cellulosic filament from the extruded spinning solution and d. an optional orientation compartment connected to, or comprised in, the temperature-controlled regeneration compartment, comprising a means for drawing the formed reinforced cellulosic filament by a factor of from 1 to 20, preferably from 5 to 15 and most preferably from 8 to 14.
  • the temperature-controlled mixing compartment preferably comprises a mixing means of the static mixer type, designed to achieve distributive mixing of the reinforcement particles.
  • the spinneret or spinning nozzle comprises one or more channels having a tri- or quadriconical profile, having preferably having a length of from 200 to 300 microns and an exit diameter of from 40 to 250 microns, preferably of 90 microns.
  • the composite spinning solution is heated in the temperature-controlled mixing compartment of the spinning apparatus to a temperature of at least its melting point
  • the spinneret may be equipped with a heating means such as for example an external oil circulator jacket in order to heat the spinning solution to a temperature of at least its melting point.
  • the composite spinning solution Prior to being extruded through the spinneret or spinning nozzle into a regeneration medium, the composite spinning solution is preferably degassed by submitting the composite spinning solution to reduced pressure, to avoid bubble formation during the spinning process.
  • the spinneret or spinning nozzle may have one or more channels, for example between 25 and 75, of preferably tri- or quadriconical profile, having preferably having a length of from 200 to 300 microns and an exit diameter of from 40 to 250 microns, preferably of 90 microns.
  • Example 1 (synthesis of high aspect ratio alumina nanorods, with a silica surface coating for enhanced dispersibility in cellulose/IL solutions, and use in spinning of regenerated cellulosic fibres with enhanced tensile properties - particles incorporated in spinning solution).
  • Boehmite nanorods were first synthesized via the hydrothermal treatment of an aluminium tri-alkoxide in acidic aqueous solution.
  • An aqueous solution containing aluminium tri- sec -butoxide (concentration 0.25M) and hydrochloric acid (concentration 0.192M) was charged into a 2 litre stainless steel autoclave with facilities for mechanical stirring. This acidic solution was then heated under pressure to a temperature of 150°C and stirring maintained at 20rpm for 12 hours.
  • the resultant product - a bluish, turbid dispersion - was transferred to a 2 litre glass reactor with impeller stirrer and condenser.
  • the suspension of silica coated boehmite rods was then stirred for a further hour and the pH then adjusted to 7.0 via addition of further acid. On cooling, dissolved electrolytes were removed via multiple high-speed centrifugation/decanting/reconstitution with purified water. The particulate product was isolated via freeze drying and then calcined at 600°C in a Carbolite furnace for 6 hours. The product - silica coated ⁇ -alumina nanorods - was obtained as a white powder. TEM analysis indicated that the rod-like habit and aspect ratio of the alumina 'cores' of the final product were maintained on calcination and the silica treatment was present as a dense, continuous layer on the particle surfaces of typical thickness ⁇ 5nm.
  • a sample of alumina nanorods was prepared without a silica surface treatment for comparative purposes.
  • one litre of an aqueous solution containing aluminium tri- sec -butoxide (concentration 0.25M) and hydrochloric acid (concentration 0.192M) was charged into a 2 litre stainless steel autoclave with facilities for mechanical stirring. This acidic solution was then heated under pressure to a temperature of 150°C and stirring maintained at 20rpm for 12 hours.
  • the resultant product was purified via multiple high-speed centrifugation/decanting/reconstitution with purified water in order to remove residual acid and hydrolysis products.
  • the boehmite precursor particles were analysed via SEM (average length ⁇ 395 nm, average width 14 nm - image analysis).
  • the precursor particles were calcined at 600°C in a Carbolite furnace for 6 hours.
  • the product - ⁇ -alumina nanorods - was obtained as a white powder. Subsequent microscopic analysis indicated that the high aspect ratio of the precursor particles was maintained on calcination.
  • the above composite spinning solution was subsequently degassed and conveyed to a fibre spinning apparatus by means of a co-rotating twin screw extruder (screw diameter 21mm, L/D 25) terminated with a gear pump, filter pack and spinning device.
  • a co-rotating twin screw extruder screw diameter 21mm, L/D 25
  • Each zone of the extruder barrel was maintained at a controlled temperature of 40°C by means of integrated electric heating elements.
  • the spinning device was terminated in a spinneret containing a plurality of channels (50) of quadriconical profile (45°, 30°, 20°, 10°), length 250 microns and exit diameter 90 microns.
  • the temperature of the spinning device was maintained at 40°C by means of an external oil circulator jacket.
  • the volumetric flow rate of the composite spinning dope through the spinning device was controlled to give an extrusion velocity of 8m/min at the spinneret orifice.
  • Spinning was conducted by extrusion through an air gap of 10mm into a coagulation bath containing water maintained at 18°C.
  • a system of motorized godets was employed to maintain a take up velocity of 64m/min, giving a draw ratio of 8.
  • the fibre tow was rinsed by conveying through two further water baths maintained at 60°C, passed through a forced convection drying system and wound onto a spool.
  • a second comparative multifilament tow, prepared in an identical manner to the above, but with inclusion of uncoated alumina nanorods was found to have tenacity 36cN/tex and tensile modulus 1600cN/tex.
  • optical microscopy of the composite spinning solution showed the presence of phase separation, with discrete agglomerates of particles visible.
  • Example 2 Introduction of reinforcing particles into a pre-prepared cellulose spinning solution using a compounding device and use in the preparation of regenerated cellulose fibres with enhanced tensile properties
  • a cellulosic base solution was prepared by dissolving cellulose pulp (61g, DP 1150, 96% ⁇ -cellulose) in a mixture of dimethyl sulphoxide (469.5g) and 1-ethyl-3-methylimidazolium acetate (EMIMAc, 469.5g), by compounding in a Z-blade mixer for 60 minutes at 80°C, removing any water present under reduced pressure, yielding a visually transparent and homogeneous solution.
  • cellulose pulp 61g, DP 1150, 96% ⁇ -cellulose
  • EMIMAc 1-ethyl-3-methylimidazolium acetate
  • the cellulosic base solution was subsequently degassed and conveyed to a fibre spinning apparatus by means of a co-rotating twin screw extruder (screw diameter 21mm, L/D 25) terminated with a gear pump and filter pack.
  • a co-rotating twin screw extruder screw diameter 21mm, L/D 25
  • Each zone of the extruder barrel was maintained at a controlled temperature of 50°C by means of integrated electric heating elements.
  • Fumed silica (specific surface area ⁇ 200 m 2 g -1 ) was metered into the extruder barrel through a port equidistant between the cellulose solution feed hopper and barrel terminus, by means of a gravimetric powder feeder.
  • the feed rate of these reinforcing particles was set so as to give a final particle concentration of 2%, on the weight of cellulose in the final dried fibre.
  • the spinning assembly was terminated in a spinneret containing a plurality of channels (50) of quadriconical profile (45°, 30°, 20°, 10°), length 250microns and exit diameter 90microns.
  • the temperature of the spinning device was maintained at 50°C by means of an external oil circulator jacket.
  • Composite reinforced regenerated cellulose fibres were spun by simultaneously metering the cellulosic base solution and reinforcing particle suspension into the mixing chamber of the spinning assembly. The two components were then subjected to effective distributive mixing by passing through the static mixer assembly, prior to extrusion through the spinnerets. The total volumetric flow rate through the spinning assembly was controlled to give an extrusion velocity of 8m/min at the spinneret. Spinning was conducted by extrusion through an air gap of 10mm into a coagulation bath containing water maintained at 18°C. A system of motorized godets was employed to maintain a take up velocity of 72m/min, giving a draw ratio of 9. The fibre tow was rinsed by conveying through two further water baths maintained at 60°C, passed through a forced convection drying system and wound onto a spool.
  • Example 3 Preparation of high aspect ratio silica nanotubes using cellulose nanocrystals as a template and subsequent use in the spinning of regenerated cellulose fibres with enhanced tensile properties - reinforcing particles introduced as a non-aqueous suspension, injected separately into the spinning device and distributive mixing afforded by means of a static mixer assembly
  • CNC sulphated cellulose nanocrystals
  • sulphated CNC is readily prepared via the hydrolysis of cellulose pulp in the presence of sulphuric acid (64% wt/wt), quenching in excess water, then purifying via dialysis, ion exchange and filtration, adjusting the pH to ⁇ 8 with ammonia solution (28%) and freeze drying.
  • the average length of such particles is typically ⁇ 210nm, with an average width ⁇ 20nm.
  • the resultant suspension of silica coated cellulose nanocrystals was then purified via multiple high-speed centrifugation/decanting/reconstitution with purified water, prior to freeze drying and subsequent calcination of the solid product at 600°C for 6 hours.
  • the product - hollow silica nanotubes - was obtained as a white powder. SEM analysis confirmed that the aspect ratio ( ⁇ 7) and rod-like habit of the original template particles was maintained in the final product.
  • a cellulosic base solution was then prepared by dissolving cellulose pulp (61g, DP 1150, 96% ⁇ -cellulose) in 1-ethyl-3-methylimidazolium acetate (EMIMAc, 939 g) by compounding in a Z-blade mixer for 60 minutes at 80°C, removing any water present under reduced pressure, yielding a visually transparent and homogeneous solution.
  • cellulose pulp 61g, DP 1150, 96% ⁇ -cellulose
  • EMIMAc 1-ethyl-3-methylimidazolium acetate
  • a separate reinforcing particle suspension was prepared by suspending a portion (5.0g) of the above silica nanotubes in dimethyl sulphoxide (95.0g) by means of an ultrasonic probe, yielding a stable, visually transparent and fluid dispersion.
  • the cellulosic base solution was subsequently degassed and conveyed to a fibre spinning apparatus by means of a co-rotating twin screw extruder (screw diameter 21mm, L/D 25) terminated with a gear pump and filter pack.
  • a co-rotating twin screw extruder screw diameter 21mm, L/D 25
  • the spinning apparatus comprised a cylindrical member containing sequentially: a mixing chamber for introduction of the above silica nanotube reinforcing particle suspension from an injector assembly affixed perpendicular to the main flow direction, a static mixing zone containing a fused array of 10 smxs static mixers, and a final steel mesh filter pack of nominal mesh size 5microns.
  • the injector assembly was used to meter the previously prepared reinforcing particle suspension into the mixing chamber by means of a high-pressure syringe driver (Cetoni) fitted with a 100ml stainless steel syringe.
  • the spinning assembly was terminated in a spinneret containing a plurality of channels (50) of quadriconical profile (45°, 30°, 20°, 10°), length 250microns and exit diameter 90microns.
  • the temperature of the spinning device was maintained at 50°C by means of an external oil circulator jacket.
  • Composite reinforced regenerated cellulose fibres were spun by simultaneously metering the cellulosic base solution and reinforcing particle suspension into the mixing chamber of the spinning assembly. The two components were then subjected to effective distributive mixing by passing through the static mixer assembly, prior to extrusion through the spinnerets. The total flow rate through the spinning assembly was controlled to give an extrusion velocity of 8m/min at the spinneret and the ratio of the volumetric flow rates of cellulose solution and cellulose nanocrystal suspension respectively were fixed at a ratio of 20:1. Spinning was conducted by extrusion through an air gap of 10mm into a coagulation bath containing water maintained at 18°C.
  • a system of motorized godets was employed to maintain a take up velocity of 72m/min, giving a draw ratio of 9.
  • the fibre tow was rinsed by conveying through two further water baths maintained at 60°C, passed through a forced convection drying system and wound onto a spool.
  • a multifilament tow of "control" fibres prepared in an identical manner without the addition of reinforcing particles (reinforcing particle suspension replaced by an injection of DMSO), was found to have tenacity 44 cN/tex and tensile modulus 2275 cN/tex.

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WO2018086149A1 (zh) * 2016-11-11 2018-05-17 海安县恒业制丝有限公司 一种纳米氧化锌/SiO2/石墨烯复合纤维
CN108570722A (zh) * 2018-04-18 2018-09-25 浙江梵彼斯特轻纺发展有限公司 一种空心凤梨麻复合纤维及其制备工艺
JP2018536102A (ja) * 2015-11-20 2018-12-06 済南聖泉集団股▲ふん▼有限公司Ｊｉｎａｎ Ｓｈｅｎｇｑｕａｎ Ｇｒｏｕｐ Ｓｈａｒｅ Ｈｏｌｄｉｎｇ Ｃｏ．， Ｌｔｄ 機能性再生セルロース繊維及びその調製方法と使用
CN109897235A (zh) * 2019-01-31 2019-06-18 华南理工大学 一种甲壳素/石墨烯复合海绵及制备方法与应用
CN109913965A (zh) * 2019-01-25 2019-06-21 复旦大学 一种共碱体系原位自组装纤维素/石墨烯复合纤维及其制备方法
WO2019229030A1 (en) * 2018-06-01 2019-12-05 Climeworks Ag Process for the preparation of homogeneous hybrid materials
CN111485418A (zh) * 2020-03-18 2020-08-04 哈尔滨工业大学 一种表面接枝氧化石墨烯-二氧化硅的植物纤维布的制备方法
CN113215822A (zh) * 2021-04-30 2021-08-06 杭州师范大学 一种基于取向纳米纤维的多功能可拉伸透气传感材料
CN113417024A (zh) * 2021-06-25 2021-09-21 南通强生石墨烯科技有限公司 一种白石墨烯发光再生纤维素纤维及其制备方法
US11127510B2 (en) * 2017-03-17 2021-09-21 University Of Kwazulu-Natal Electroconductive composite
CN114210692A (zh) * 2021-11-05 2022-03-22 新疆冠农果茸股份有限公司 一种全料发酵中废弃秸秆预处理工艺
CN114507910A (zh) * 2022-02-22 2022-05-17 西安工程大学 一种纳米芳纶增强再生纤维素纤维材料、制备方法及应用
CN114517338A (zh) * 2022-04-21 2022-05-20 潍坊潍森纤维新材料有限公司 一种纤维素粘胶的制备方法及其在纤维素肠衣中的应用
CN114591518A (zh) * 2020-12-02 2022-06-07 固特异轮胎和橡胶公司 制备二氧化硅/纤维素混合物的方法
CN114907687A (zh) * 2022-05-27 2022-08-16 福州大学 用于mjr3d打印的二氧化硅包裹碳纳米管增强尼龙12复合材料及其制备方法和应用
CN116084043A (zh) * 2022-11-30 2023-05-09 芯安健康科技(广东)有限公司 一种阻燃抗菌防螨多功能纤维及其制备方法和应用
CN117777981A (zh) * 2024-02-27 2024-03-29 山东海嘉石油化工有限公司 一种黏土稳定剂的制备方法

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JP2018536102A (ja) * 2015-11-20 2018-12-06 済南聖泉集団股▲ふん▼有限公司Ｊｉｎａｎ Ｓｈｅｎｇｑｕａｎ Ｇｒｏｕｐ Ｓｈａｒｅ Ｈｏｌｄｉｎｇ Ｃｏ．， Ｌｔｄ 機能性再生セルロース繊維及びその調製方法と使用
WO2018086149A1 (zh) * 2016-11-11 2018-05-17 海安县恒业制丝有限公司 一种纳米氧化锌/SiO2/石墨烯复合纤维
US11127510B2 (en) * 2017-03-17 2021-09-21 University Of Kwazulu-Natal Electroconductive composite
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US11845060B2 (en) 2018-06-01 2023-12-19 Climeworks Ag Process for the preparation of homogeneous hybrid materials
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