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WO2015112894A1 - Nanofibres polymères cisaillées de faibles longueurs de coupe pour dispersions liquides - Google Patents

Nanofibres polymères cisaillées de faibles longueurs de coupe pour dispersions liquides Download PDF

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Publication number
WO2015112894A1
WO2015112894A1 PCT/US2015/012744 US2015012744W WO2015112894A1 WO 2015112894 A1 WO2015112894 A1 WO 2015112894A1 US 2015012744 W US2015012744 W US 2015012744W WO 2015112894 A1 WO2015112894 A1 WO 2015112894A1
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WO
WIPO (PCT)
Prior art keywords
polymeric
nano fiber
length
fiber
nanofibers
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US2015/012744
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English (en)
Inventor
Peter GEISEN
Sumit GANGWAL
Miles C. Wright
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
XANOFI Inc
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XANOFI Inc
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Filing date
Publication date
Application filed by XANOFI Inc filed Critical XANOFI Inc
Publication of WO2015112894A1 publication Critical patent/WO2015112894A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • D01D5/423—Formation of filaments, threads, or the like by cutting films into narrow ribbons or filaments or by fibrillation of films or filaments by fibrillation of films or filaments
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21D—TREATMENT OF THE MATERIALS BEFORE PASSING TO THE PAPER-MAKING MACHINE
    • D21D1/00—Methods of beating or refining; Beaters of the Hollander type
    • D21D1/20—Methods of refining

Definitions

  • the present invention relates to shearing polymeric nano fibers to short cut lengths in liquids to control the length of the nano fiber to allow the nano fiber to be dispersed in liquids.
  • Nanofibers are increasingly being investigated for use in various applications. Nanofibers may attain a high surface area comparable with the finest nanoparticle powders, yet are fairly flexible, and retain one macroscopic dimension which makes them easy to handle, orient and organize.
  • the present invention comprises a method to shear long nanofibers to staple nanofibers of short cut lengths in liquids to improve how the nanofibers disperse in liquids.
  • a wide variety of methods may be utilized to shear the nanofibers to short cut lengths including, but not limited to, shearing achieved by a colloid mill, shear homogenizer, shear mixer, etc.
  • nanofiber refers generally to an elongated fiber structure having an average diameter ranging from less than 50 nm - 5 ⁇ in some examples, in other examples ranging from less than 100 nm - 5 ⁇ , and in other examples ranging from 200 nm - 5 ⁇ .
  • the average diameter ranges from 40 nm - 5 ⁇ , 40 nm - 2 ⁇ , 50 nm - 5 ⁇ , 50 nm - 2 ⁇ , 100 nm - 5 ⁇ , 100 nm - 2 ⁇ , 200 nm - 5 ⁇ , or 200 nm - 2 ⁇ .
  • the "average" diameter may take into account not only that the diameters of individual nanofibers making up a plurality of nanofibers formed by implementing the presently disclosed method may vary somewhat, but also that the diameter of an individual nanofiber may not be uniform over its length in some implementations of the method.
  • the average length of the nanofibers may range from 100 nm or greater. In other examples, the average length may range from 100 nm to millions of nm.
  • the aspect ratio (length/diameter) of the nanofibers may range from 100 or greater. In other examples, the aspect ratio may range from 20 to millions. In some specific examples, we have demonstrated nanofibers with aspect ratios of at least 10,000. Insofar as the diameter of the nanofiber may be on the order of a few microns or less, for convenience the term "nanofiber” as used herein encompasses both nano-scale fibers and micro-scale fibers (microfibers).
  • Short cut length is defined herein as fibers with lengths in the range of 10 to 2000 ⁇ . In some cases the length can be as high as 1000-5000 ⁇ . These may be termed “staple nanofibers”.
  • the fibers are of standardized length and may be of any chemical composition.
  • the staple length may refer to an average length of a group of fibers, or a range of lengths in each sample containing fibers.
  • fibril refers generally to a fine, filamentous non-uniform structure in animals or plants having an average diameter ranging from about 1 nm - 1 ,000 nm in some examples, in other examples ranging from about 1 nm - 500 nm, and in other examples ranging from about 25 nm - 250 nm.
  • fibrils are formed by phase separation from nanofibers.
  • a fibril may be composed of an inorganic precursor or an inorganic compound.
  • the term "fibrils" distinguishes these structures from the polymer nanofibers utilized to form the inorganic fibrils.
  • Polymers encompassed by the present disclosure generally may be any naturally- occurring or synthetic polymers capable of being fabricated into nano fibers.
  • Examples of polymers include many high molecular weight (MW) solution-processable polymers such as polyethylene (more generally, various polyolefms), polystyrene, cellulose, cellulose acetate, poly(L-lactic acid) (PLA), polyacrylonitrile (PAN), polyvinylidene difluoride (PVDF), conjugated organic semiconducting and conducting polymers, biopolymers such as polynucleotides (DNA) and polypeptides, etc.
  • MW molecular weight
  • PVDF polyvinylidene difluoride
  • Suitable polymers to form nanofibers include vinyl polymers such as, but not limited to, cellulose acetate propionate, cellulose acetate butyrate, polyethylene, polypropylene, poly(vinyl chloride), polystyrene, polytetrafluoroethylene, poly(a- methylstyrene), poly(acrylic acid), poly(isobutylene), poly(acrylonitrile), poly(methacrylic acid), poly(methyl methacrylate), poly(l-pentene), poly( 1,3 -butadiene), poly(vinyl acetate), poly(2- vinyl pyridine), 1 ,4-polyisoprene, and 3,4-polychloroprene.
  • vinyl polymers such as, but not limited to, cellulose acetate propionate, cellulose acetate butyrate, polyethylene, polypropylene, poly(vinyl chloride), polystyrene, polytetrafluoroethylene, poly(a- methylstyren
  • nonvinyl polymers such as, but not limited to, poly(ethylene oxide), polyformaldehyde, polyacetaldehyde, poly(3-propionate), poly(lO-decanoate), poly(ethylene terephthalate), polycaprolactam, poly(l 1-undecanoamide), poly(hexamethylene sebacamide), poly(m-phenylene terephthalate), poly(tetramethylene-m-benzenesulfonamide).
  • nonvinyl polymers such as, but not limited to, poly(ethylene oxide), polyformaldehyde, polyacetaldehyde, poly(3-propionate), poly(lO-decanoate), poly(ethylene terephthalate), polycaprolactam, poly(l 1-undecanoamide), poly(hexamethylene sebacamide), poly(m-phenylene terephthalate), poly(tetramethylene-m-benzenesulfonamide).
  • Additional polymers include those falling within one of the following polymer classes: polyolefm, poly ether (including all epoxy resins, polyacetal, polyetheretherketone, polyetherimide, and poly(phenylene oxide)), polyamide (including polyureas), polyamideimide, polyarylate, polybenzimidazole, polyester (including polycarbonates), polyurethane, polyimide, polyhydrazide, phenolic resins, polysilane, polysiloxane, polycarbodiimide, polyimine, azo polymers, polysulfide, and polysulfone.
  • polyolefm poly ether (including all epoxy resins, polyacetal, polyetheretherketone, polyetherimide, and poly(phenylene oxide)), polyamide (including polyureas), polyamideimide, polyarylate, polybenzimidazole, polyester (including polycarbonates), polyurethane, polyimide, polyhydrazide, phenolic resins, polysilane, polysiloxane
  • the polymer used to form nanofibers can be synthetic or naturally- occurring.
  • natural polymers include, but are not limited to, polysaccharides and derivatives thereof such as cellulosic polymers (e.g., cellulose and derivatives thereof as well as cellulose production byproducts such as lignin) and starch polymers (as well as other branched or non-linear polymers, either naturally occurring or synthetic).
  • exemplary derivatives of starch and cellulose include various esters, ethers, and graft copolymers.
  • the polymer may be crosslinkable in the presence of a multifunctional crosslinking agent or crosslinkable upon exposure to actinic radiation or other type of radiation.
  • the polymer may be homopolymers of any of the foregoing polymers, random copolymers, block copolymers, alternating copolymers, random tripolymers, block tripolymers, alternating tripolymers, derivatives thereof (e.g., graft copolymers, esters, or ethers thereof), and the like.
  • Polymeric nanofibers can be sheared to short cut lengths in liquids to control their length to diameter aspect ratio using wet grinding processes and equipment.
  • colloid mill equipment with a milling head, or rotor and stator head can be used to mill polymeric nanofibers in liquid solutions.
  • key processing parameters including shearing revolution per minute [RPM], liquid residence time, liquid flow rate, rotor/stator gap distance, etc.
  • the final chopped / sheared length of the nanofibers can be controlled.
  • Nanofibers can be sheared in aqueous liquids mainly comprised of water or other liquids containing organic solvents and viscous mediums (glycerol, glycols, aqueous glycerin solutions, etc.).
  • aqueous liquids mainly comprised of water or other liquids containing organic solvents and viscous mediums (glycerol, glycols, aqueous glycerin solutions, etc.).
  • L:D length-to-diameter
  • optimum L:D ratios are about 500. In some cases this optimal ratio can range from 100 to 1000. In other instances the L:D ratio can range more broadly from 20 to 3000. This L:D ratio is also preferred for nanofibers to allow them to more easily disperse in liquids.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Textile Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une fine nanofibre polymère cisaillée d'une faible longueur de coupe et un procédé de cisaillement de la nanofibre polymère. Dans certains modes de réalisation, la nanofibre polymère comprend : une plage de longueur allant de 10 à 2000 μm ; un rapport d'aspect de longueur sur diamètre (L:D) allant de 20 à 10 000 ; une plage de diamètre moyen allant de 1 nm à 2 μm ; et/ou deux polymères différents ou plus et/ou un ou plusieurs additifs. La longueur raccourcie de la nanofibre polymère permet une dispersion aisée dans certains liquides par comparaison avec la même fibre fine de longueurs importantes. Le procédé de cisaillement des nanofibres polymères comprend le broyage de la fibre polymère dans une solution liquide, exécuté avec des procédés et un équipement de concassage humide.
PCT/US2015/012744 2014-01-24 2015-01-23 Nanofibres polymères cisaillées de faibles longueurs de coupe pour dispersions liquides Ceased WO2015112894A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201461931396P 2014-01-24 2014-01-24
US61/931,396 2014-01-24

Publications (1)

Publication Number Publication Date
WO2015112894A1 true WO2015112894A1 (fr) 2015-07-30

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2015/012744 Ceased WO2015112894A1 (fr) 2014-01-24 2015-01-23 Nanofibres polymères cisaillées de faibles longueurs de coupe pour dispersions liquides

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WO (1) WO2015112894A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3455403A4 (fr) * 2016-05-09 2020-12-23 North Carolina State University Particules polymères de type fractal et leur utilisation dans diverses applications

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0592542A1 (fr) * 1991-07-02 1994-04-20 Du Pont Agents epaississants a base de fibrides.
EP1743975A1 (fr) * 2004-02-19 2007-01-17 Toray Industries, Inc. Solution mixte, emulsion et gelifiant a base de nanofibres et leur procede de production, et papier synthetique a base de nanofibres et son procede de production
JP2013104142A (ja) * 2011-11-11 2013-05-30 Daicel Corp セルロース系不織布及びその製造方法並びにセパレータ
WO2013188657A1 (fr) * 2012-06-13 2013-12-19 University Of Maine System Board Of Trustees Procédé écoénergétique pour la préparation de fibres de nanocellulose

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0592542A1 (fr) * 1991-07-02 1994-04-20 Du Pont Agents epaississants a base de fibrides.
EP1743975A1 (fr) * 2004-02-19 2007-01-17 Toray Industries, Inc. Solution mixte, emulsion et gelifiant a base de nanofibres et leur procede de production, et papier synthetique a base de nanofibres et son procede de production
JP2013104142A (ja) * 2011-11-11 2013-05-30 Daicel Corp セルロース系不織布及びその製造方法並びにセパレータ
WO2013188657A1 (fr) * 2012-06-13 2013-12-19 University Of Maine System Board Of Trustees Procédé écoénergétique pour la préparation de fibres de nanocellulose

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ALARGOVA R G ET AL: "Formation of Polymer Microrods in Shear Flow by Emulsification - Solvent Attrition Mechanism", INTERNET CITATION, 1 January 2006 (2006-01-01), pages 765 - 774, XP002492443, ISSN: 0743-7463, Retrieved from the Internet <URL:http://pubs.acs.org/cgi-bin/article.cgi/langd5/2006/22/i02/pdf/la051825v.pdf> [retrieved on 20080805] *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3455403A4 (fr) * 2016-05-09 2020-12-23 North Carolina State University Particules polymères de type fractal et leur utilisation dans diverses applications
EP3940032A1 (fr) * 2016-05-09 2022-01-19 North Carolina State University Particules polymères de type fractal et leur utilisation dans diverses applications
US11306214B2 (en) 2016-05-09 2022-04-19 North Carolina State University Fractal-like polymeric particles and their use in diverse applications
US12209203B2 (en) 2016-05-09 2025-01-28 North Carolina State University Fractal-like polymeric particles and their use in diverse applications

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