EP0533005A2 - Fibrillen aus Zelluloseester mit an ihrer Oberfläche eingebetteten Additiven - Google Patents

Fibrillen aus Zelluloseester mit an ihrer Oberfläche eingebetteten Additiven Download PDF

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Publication number
EP0533005A2
EP0533005A2 EP92115235A EP92115235A EP0533005A2 EP 0533005 A2 EP0533005 A2 EP 0533005A2 EP 92115235 A EP92115235 A EP 92115235A EP 92115235 A EP92115235 A EP 92115235A EP 0533005 A2 EP0533005 A2 EP 0533005A2
Authority
EP
European Patent Office
Prior art keywords
additive
cellulose ester
dope
nozzle
fibril
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.)
Withdrawn
Application number
EP92115235A
Other languages
English (en)
French (fr)
Other versions
EP0533005A3 (en
Inventor
Clinton Dale Felton
George Allibone Serad
Baylor Dee Gibson
Samuel Scott Mcnair, Jr.
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.)
CNA Holdings LLC
Original Assignee
Hoechst Celanese Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hoechst Celanese Corp filed Critical Hoechst Celanese Corp
Publication of EP0533005A2 publication Critical patent/EP0533005A2/de
Publication of EP0533005A3 publication Critical patent/EP0533005A3/en
Withdrawn legal-status Critical Current

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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
    • D01F2/24—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives
    • D01F2/28—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives from organic cellulose esters or ethers, e.g. cellulose acetate
    • 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
    • D01D5/40—Formation of filaments, threads, or the like by applying a shearing force to a dispersion or solution of filament formable polymers, e.g. by stirring
    • 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

Definitions

  • Cellulose ester fibrillar material wherein additives are imbedded in or impregnated on the surface of the fibrillar material in such a manner as not to adversely impact the beneficial affects of those additives, and the method of making the same are disclosed herein.
  • Cellulose ester fibrillar material is known (see U. S. Patent Nos. 3,842,007 and 4,192,838).
  • Cellulose acetate fibrillar material is commercially available from the Hoechst Celanese Corporation of Charlotte, NC under the tradename of "Cellulose Acetate Fibrets". The chemical process by which these materials are made is also well known. Ibid .
  • several methods of manufacturing this fibrillar material have been proposed (see in U. S. Patent Nos. 3,842,007; 4,017,862; and 4,192,838).
  • Cellulose ester fibrillar material has application in a wide variety of end uses. Such end uses include, but are not limited to, filtration and nonwovens.
  • the fibrils can be used, alone, as a filter aid (see in U. S. Patent No. 3,842,007) or as a component in filter sheets (see U. S. Patent Nos. 4,283,186 and 5,002,964) or as a component in filter disks.
  • the fibrils can be used to bind components of the nonwoven (see in U. S. Patent No. 4,192,838).
  • Fibrets typically have a surface area of over 5 square meters per gram. Individual fibrets have a length of between 0.1 to 1,000 microns and a diameter ranging from 0.2 to 0.6 microns.
  • One scheme is the mixture of the additive into the cellulose ester precursor solution prior to fibril formation. Addition of an opacifier to fibrets is known. See U. S. Patent No. 4,460,647. This scheme is limited for filtration applications because the additive is embedded within the fibril and is blinded by the cellulose ester, so that the additive looses its efficacy for enhancing the fibril's affinity for the specified target material.
  • An alternate scheme is the combination of the additive and the fibril after fibril manufacture. This scheme is limited because the additive does not always adhere to the surface of the fibril, thus the additive can be dusted off or washed away from the fibril during use.
  • an adhesive could be used to prevent the loss of the additive (for example, see in U. S. Patent Nos. 4,007,114 and 4,647,324), but the use of the adhesive can be detrimental in two ways. First, the adhesive could blind the additive and thus dull its affinity for the target material. Second, the adhesive could bind fibrils together whereby the high surface area of the fibrils is lost.
  • non-related filter medias such as melt-blown nonwovens (see, for example, in U. S. Patent No. 4,797,318)
  • particles are blown against microfiber materials after formation but before solidification. The particles are then attached to the surface of the melt-blown microfibers forming the nonwoven.
  • This material does not suggest the invention disclosed herein because the microfibers must be melt processable, i.e. thermoplastic.
  • the cellulose esters used in this invention are not melt processable, instead, they are solution processable.
  • Cellulose ester fibrillar material having additives imbedded in or impregnated upon a surface of said fibrillar material is disclosed herein.
  • the method comprises the steps of: providing a polymer solution or "dope", coagulation liquid, and additive; mixing the polymer solution and coagulation liquid within the attenuation zone of a nozzle; adding the additive to the mixture within the attenuation zone of the nozzle; and thereby forming the fibrillar material.
  • Figure 1 is a schematic representation of a process wherein cellulose ester fibrillar material is made with additives disposed on the surface of the fibrillar material.
  • Figure 2 is a cross sectional representation of an attenuation nozzle used in one embodiment of the instant invention.
  • Figure 3 is a cross sectional representation of the attenuation nozzle used in an alternate embodiment of the instant invention.
  • Figure 4 is a photo micrograph (x500) of cellulose acetate fibrils with an additive (bentonite) that is made according to the instant invention.
  • cellulose ester fibrillar material as set forth above, is well known.
  • the manufacture of cellulose ester fibrils comprises the production of solvated cellulose ester material (also referred to as a "polymer solution"), commonly referred to as a "dope".
  • This dope is then injected through an attenuation nozzle, under conditions of high shear, where it is mixed with a coagulating liquid.
  • the cellulose ester solvent is leached from the cellulose ester whereby the fibrils are formed. Thereafter, the fibrils undergo a series of dewatering, homogenizing and drying steps.
  • the instant invention may be used with any of the known dope and/or coagulation liquid formulations or downstreaming dewatering, homogenizing and drying steps.
  • cellulose ester refers to, but is not limited to, cellulose acetate, cellulose triacetate, cellulose acetate butyrate, benzyl cellulose, or mixtures thereof.
  • fibril material or “fibril” refers to, but is not limited to, microfibers having surface areas in excess of 5.0 square meters per gram, length less than 1000 microns, and diameters from about 0.2 to 90 microns.
  • cellulose ester fibrils have a surface area of about 20 square meters per gram, lengths of about 20 - 200 microns, and diameters of about 0.5 - 5 microns.
  • additive refers to, but is not limited to, any material that has a particular affinity for another material or that has a special ability to entrap or absorb or adsorb another material (for example, bentonite, activated carbon, zeolites, etc.).
  • diope or “polymer solution” or “cellulose ester solution” refers to, but is not limited to, a 5-15% solution of cellulose ester (based upon the weight of the cellulose ester).
  • the solvent component of the dope or cellulose ester solution may comprise a solvent for the cellulose ester, alone, or a mixture of the solvent for the cellulose ester (comprising 80%-98% by weight) and a nonsolvent for cellulose ester (comprising 2-20% by weight) which is miscible in the solvent for the cellulose ester.
  • the term "coagulation liquid" refers to, but is not limited to, a mixture consisting essentially of the nonsolvent for the cellulose ester, but it may also include up to 10% by weight of the solvent.
  • the cellulose ester is cellulose acetate
  • the solvent is acetone
  • the nonsolvent is water.
  • additives can be affixed to the surface of a fibril without the loss of the additives' affinity for a particular target material, the loss of the high surface area of the fibril, by injecting the additive, typically in the form of a slurry, into the attenuation nozzle during fibril formation.
  • FIG. 1 there is shown schematic representation of a cellulose ester manufacturing scheme 10.
  • Dope is delivered to an attenuation nozzle 30 from dope supply 12 via an optional metering pump 16 and dope heater 14.
  • Coagulating liquid is delivered to nozzle 30 from supply 18 via high pressure pump 20.
  • Additive is delivered into nozzle 30 from additive tank 22 via metering pump 24.
  • additive may also be metered into the coagulation liquid and carried to nozzle 30 (as illustrated in phantom). Further details regarding attenuation nozzle 30 are set forth hereinafter.
  • Nozzle 30 comprises an inlet 32 for dope and inlet 34 for coagulation liquid and a capillary 40 through valve stem 42.
  • Additive is injected into an attenuation zone 38 through capillary 40.
  • Inlet 32 for dope is in fluid communication with an annular cavity 44 which opens into attenuation zone 38.
  • Coagulation liquid inlet 34 is in fluid communication with an annular conduit 46 which exits into attenuation zone 38.
  • coagulation liquid, dope and additive are intimately mixed in such a way that the additive is disposed upon the exterior surface of the fibret so that the additive's affinity for a particular target material is not diminished.
  • nozzle 30' is shown in use of an alternate process.
  • Nozzle 30' is essentially the same of nozzle 30 with the exception that additive can be introduced into the nozzle via the coagulation inlet 34' as well as capillary 40'.
  • additive is disposed upon the surface of the fibret in attenuation zone 38' so that the additive's affinity for a particular target material is not diminished.
  • FIG 4 there is shown cellulose ester fibrillar material made in accordance with the foregoing description.
  • the fibrils are the rope-like strands seen throughout the photomicrograph.
  • the additives (bentonite) are seen as the granular material on the surface of the fibrils.
  • a 0.03 inch capillary was drilled through the needle valve stem of a standard attenuation nozzle (See in U. S. Patent No. 4,192,838).
  • the capillary was attached through a 0.25 inch hose to a Cole Parmer Diaphragm Pump (80 to 800 ml/min, 50 psi max. pressure, set at 40% of full scale).
  • Bentonite was dispersed in acetone in a reservoir and continuously stirred to prevent the particulate from settling to the bottom.
  • Heated dope was supplied to the fibret nozzle from the preheater heated at a temperature of 60°C and a Zenith 58 pump speed of 40 rpm.
  • Precipitation water was pumped through the system from a 40 gallon hot water heater set at 170 degrees F and a pressure of 185 psi.
  • Fibrils were collected on a screen support over a 55 gallon drum. Solvent passed through the screen was collected in the drum. After startup with no additive, additive was injected into the dope stream through the capillary in the needle valve stem. Fibril formation was not interrupted by this event.
  • Bentonite was blended directly into a dope and extruded into fibril form.
  • the following zeta potential values were obtained by measuring streaming potentials with a Zeta Data instrument manufactured by Paper Chemistry Laboratory, Inc. of Carmel, NY.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Dispersion Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Artificial Filaments (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
EP19920115235 1991-09-16 1992-09-05 Cellulose ester fibrillar material having additives imbedded on a surface thereof Withdrawn EP0533005A3 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US76067491A 1991-09-16 1991-09-16
US760674 1991-09-16

Publications (2)

Publication Number Publication Date
EP0533005A2 true EP0533005A2 (de) 1993-03-24
EP0533005A3 EP0533005A3 (en) 1993-08-04

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP19920115235 Withdrawn EP0533005A3 (en) 1991-09-16 1992-09-05 Cellulose ester fibrillar material having additives imbedded on a surface thereof

Country Status (2)

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EP (1) EP0533005A3 (de)
JP (1) JPH07197314A (de)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0711512A3 (de) * 1994-10-21 1997-06-18 Daicel Chem Tabakrauchfiltermaterialen, Celluloseester Fasermaterialen und Verfahren zu deren Herstellung
EP0908541A1 (de) * 1996-03-06 1999-04-14 Mitsubishi Rayon Co., Ltd. Auf fibrillen basierende fasern, methode zu deren herstellung, dabei verwendete spinndüse und damit hergestellte formkörper
US6184373B1 (en) 1999-09-03 2001-02-06 Eastman Chemical Company Method for preparing cellulose acetate fibers

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6229927B2 (ja) * 2013-06-24 2017-11-15 国立大学法人 岡山大学 セルロースナノファイバーの製造方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1188342A (en) * 1966-03-16 1970-04-15 West Virginia Pulp & Paper Co Fiber Filler Matter and process of manufacture
GB2103637A (en) * 1981-07-02 1983-02-23 Courtaulds Plc Adsorptive material
DE3131073A1 (de) * 1981-08-05 1983-02-24 Institute für Textil- und Faserforschung Stuttgart, 7410 Reutlingen Verfahren zur herstellung von fasern fuer technische zwecke, nach dem verfahren hergestellte fasern fuer technische zwecke und ihre verwendung
US4460647A (en) * 1982-09-13 1984-07-17 Celanese Corporation Fibrets suitable for paper opacification

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1188342A (en) * 1966-03-16 1970-04-15 West Virginia Pulp & Paper Co Fiber Filler Matter and process of manufacture
GB2103637A (en) * 1981-07-02 1983-02-23 Courtaulds Plc Adsorptive material
DE3131073A1 (de) * 1981-08-05 1983-02-24 Institute für Textil- und Faserforschung Stuttgart, 7410 Reutlingen Verfahren zur herstellung von fasern fuer technische zwecke, nach dem verfahren hergestellte fasern fuer technische zwecke und ihre verwendung
US4460647A (en) * 1982-09-13 1984-07-17 Celanese Corporation Fibrets suitable for paper opacification

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0711512A3 (de) * 1994-10-21 1997-06-18 Daicel Chem Tabakrauchfiltermaterialen, Celluloseester Fasermaterialen und Verfahren zu deren Herstellung
US5863652A (en) * 1994-10-21 1999-01-26 Daicel Chemical Industries Ltd. Tobacco smoke filter materials, fibrous cellulose esters, and production processes
EP0908541A1 (de) * 1996-03-06 1999-04-14 Mitsubishi Rayon Co., Ltd. Auf fibrillen basierende fasern, methode zu deren herstellung, dabei verwendete spinndüse und damit hergestellte formkörper
EP0908541A4 (de) * 1996-03-06 1999-06-23 Mitsubishi Rayon Co Auf fibrillen basierende fasern, methode zu deren herstellung, dabei verwendete spinndüse und damit hergestellte formkörper
US6248267B1 (en) 1996-03-06 2001-06-19 Mitsubishi Rayon Co., Ltd. Method for manufacturing fibril system fiber
US6184373B1 (en) 1999-09-03 2001-02-06 Eastman Chemical Company Method for preparing cellulose acetate fibers

Also Published As

Publication number Publication date
JPH07197314A (ja) 1995-08-01
EP0533005A3 (en) 1993-08-04

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