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WO2012120071A1 - Procédé de fabrication d'une suspension stable de cellulose à haute teneur en solides - Google Patents

Procédé de fabrication d'une suspension stable de cellulose à haute teneur en solides Download PDF

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Publication number
WO2012120071A1
WO2012120071A1 PCT/EP2012/053985 EP2012053985W WO2012120071A1 WO 2012120071 A1 WO2012120071 A1 WO 2012120071A1 EP 2012053985 W EP2012053985 W EP 2012053985W WO 2012120071 A1 WO2012120071 A1 WO 2012120071A1
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Prior art keywords
cellulose
neutral
nanofibrils
anionically modified
suspension
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PCT/EP2012/053985
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English (en)
Inventor
Ian Graveson
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Sappi Netherlands Services BV
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Sappi Netherlands Services BV
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    • 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
    • D01D1/00—Treatment of filament-forming or like material
    • D01D1/02—Preparation of spinning solutions

Definitions

  • the present invention is directed towards a method for suspending neutral or anionically modified cellulose to obtain a stable, high solids suspension which is suitable for use in the formation of fibres.
  • Cellulose in particular in the form of fibres can be used for many applications and products, so e.g. for the making of paper or board structures, but also for making spun fibres such as viscose fibres or lyocell fibres which show excellent mechanical properties.
  • Due to the chemical nature of cellulose it is a very difficult material to dissolve directly, typically requiring either very polar solvents that are expensive and often toxic and hazardous or else that the cellulose is first derivatised to achieve dissolution in a more convenient solvent. Without a derivatising charge the maximum cellulose that may be suspended in water to obtain a gel composition is in the range of 6 to 9 % (percentage of cellulose nanofibrils in the total gel composition) dependent on particle size.
  • prior art systems added a high level to full derivatisation charge to achieve stable suspensions at solids levels of greater than 9%
  • the present invention is directed towards a method for suspending neutral or anionically modified cellulose to obtain a stable, high solids suspension which is suitable for use in the formation of fibres.
  • the invention provides a method for preparing a stable, high solids suspension of neutral or anionically modified cellulose nanofibrils comprising the steps of: (a) isolating neutral or anionic cellulose nanofibrils from cellulose-based material and (b) preparing a stable suspension of the neutral or anionic cellulose nanofibrils in a (viscous) continuous phase that is suitable for use as a basis for fibre spinning.
  • high solid(s) refers to the solid content of neutral or anionic cellulose nanofibrils in the suspension, which solid content refers to the weight ratio of the neutral or anionic cellulose nanofibrils to the continuous phase in the suspension expressed in percentage.
  • the solid content of neutral or anionically modified cellulose nanofibrils in the suspension is in the range of 7 to 80 % solids, preferably 9 to 60 %, more preferably 20 to 40 %.
  • continuous phase (as used in reference to the high solid suspension) is a viscous continuous state and refers to a liquid in which the anionically charged or neutral cellulose nanofibrils are dispersed, with or without, preferably with, the presence of additives or suspending agents (to obtain said viscous continuous phase).
  • disperse may include all states of dissolution, including suspend and dissolve, which are representative for the (lower and upper) limits of dispersing.
  • a suitable additive is typically a viscous agent and may be a natural gum (e.g. gum arabic, gum tragacanth, guar gum, locust bean gum, carrageenan) a pectin, an alginate, a cellulose derivative (e.g. hydroxypropylmethylcellulose, methyl cellulose, hydroxyethylcellulose, carboxymethylcellulose), preferably methyl cellulose (such as the methyl cellulose or hydroxyl propyl methyl cellulose supplied by Dow Wolff Cellulosics under the trade name Methocel).
  • a natural gum e.g. gum arabic, gum tragacanth, guar gum, locust bean gum, carrageenan
  • pectin e.g. hydroxypropylmethylcellulose, methyl cellulose, hydroxyethylcellulose, carboxymethylcellulose
  • a cellulose derivative e.g. hydroxypropylmethylcellulose, methyl cellulose, hydroxyethylcellulose, carboxymethylcellulose
  • a suitable liquid - into which said additive or suspending agent is dispersed (and finally dissolved) to obtain the (viscous) continuous phase - includes aqueous solvents, alcohols, ethers, ketones, preferably aqueous solvents, more preferably water.
  • aqueous solvent refers to a solvent comprising at least 50%, preferably at least 80%, more preferably at least 90% and optimally from 95 to 100% water by weight of the solvent.
  • the aqueous solvent may have a pH of from 2 to 10, more preferably from 4 to 8 and optimally from 5.5 to 7.5 at 20° C.
  • the invention provides a method for preparing a stable, high solids suspension of neutral or anionically modified cellulose nanofibrils (that is suitable for use as a basis for fibre spinning) comprising the steps of: (a) isolating neutral or anionic cellulose nanofibrils from cellulose-based material and (b) preparing a stable suspension of the neutral or anionic cellulose nanofibrils in a (viscous) continuous phase by dispersing the nanofibrils obtained in step (a) in a liquid in the presence of a (dispersed or dissolved) additive.
  • the invention provides a method for preparing a stable, high solids suspension of neutral or anionically modified cellulose nanofibrils, wherein the solid content of neutral or anionically modified cellulose nanofibrils in the suspension is in the range of 6 to 80 %, comprising the steps of: (a) isolating neutral or anionic cellulose nanofibrils from cellulose-based material and (b) preparing a stable suspension of the neutral or anionic cellulose nanofibrils in a (viscous) continuous phase by dispersing the nanofibrils obtained in step (a) in a liquid in the presence of a (dispersed or dissolved) additive .
  • stable suspension refers to a suspension of the neutral or anionically modified cellulose nanofibrils in a liquid (comprising the dissolved additive or suspending agent) in which (liquid or suspension) said cellulose is substantially insoluble, but wherein upon preparation the cellulose nanofibrils remain overtime, i.e. up to 48 hours, preferably up to 24 hours, evenly dispersed, i.e. not substantially agglomerated within the suspension without any separation (such as floating or sedimentation) is occurring.
  • substantially insoluble refers to such a small degree of solubility so as not to effect the nanofibrillar structure of the cellulose.
  • nanofibril or “nanofibrillar” in combination with cellulose refer to cellulose that is substantially completely in the form of nanofibrils, and those which may be substantially nanofibrillated while containing minor but not significant amounts of non- nanofibrillar structure, provided that the cellulose is in sufficient nanobrillar form to confer the benefits necessary for use in the methods of the present invention.
  • Nanofibrils obtained from anionically modified cellulose are referred to as anionic cellulose nanofibrils or nanofibrillar anionically modified cellulose.
  • Nanofibrils obtained from neutral cellulose are referred to as neutral cellulose nanofibrils or nanofibrillar neutral cellulose.
  • the cellulose nanofibrils may be extracted from nanofibril containing cellulose-based material, including hydrolyzed or mechanically disintegrated cellulose obtained from cotton linter, hard or soft wood pulp, purified wood pulp or the like, commercially available cellulose excipients, powdered cellulose, regenerated cellulose, microcrystalline and low crystallinity celluloses.
  • Preferred cellulose sources are derived primarily from wood pulp. Suitable wood pulp fibres include ground wood fibres, recycled or secondary wood pulp fibres, and bleached and unbleached wood pulp fibres. Both softwoods and hardwoods can be used. Details of the selection of wood pulp fibres are well known to those skilled in the art.
  • suitable wood pulp fibres can be obtained from well known chemical processes such as the kraft and sulfite processes, with or without subsequent bleaching. Pulp fibres can also be processed by thermomechanical, chemi- thermomechanical methods, or combinations thereof. Preferably the cellulose is obtained by chemical pulping and extraction.
  • the anionic charge is preferably provided by derivatisation with suitable groups carrying a negative charge, such as sulfur-containing groups (e.g. sulfate, sulfonate, alkylsulfate, alkylsulfonate), carboxyl & carboxymethyl groups, phosphor- containing groups (e.g. phosphate, phosphonate), nitro groups or the like, or combinations thereof.
  • the average thickness is preferably in the range of 3-300 nm, preferably in the range of 3-200 nm, more preferably in the range of 10- 100 nm.
  • the anionically modified cellulose nanofibril is a cellulose nanofibril derivatized with sulfur containing groups, such as sulfated or sulfonated cellulose nanofibrils.
  • the anionically modified cellulose is sulfur- derivatized cellulose, more specifically sulfur-derivatized cellulose nanofibril.
  • sulfur-derivatized cellulose nanofibril refers to a cellulose nanofibril that has been derivatized with anionically charged sulfur groups by reaction of a cellulose nanofibril with a suitable sulfating agent. It will be appreciated that sulfur-derivatized cellulose nanofibril includes free acid and salt forms where appropriate.
  • a sulfur-derivatized cellulose nanofibril can be produced by reacting a sulfating agent with a hydroxyl group of the cellulose nanofibril to provide a cellulose sulfate ester according to literature procedures (see e.g. Cellulose (1998) 5, 19-32 by Dong, Re vol and Gray).
  • the degree of substitution of anionically modified groups on the cellulose nanofibril should be sufficiently low such that the derivatized cellulose nanofibril will be substantially insoluble (as indicated above) in the continuous phase (or liquid) that is present in the intended methods of the invention.
  • the anionically modified cellulose nanofibril of the invention can be characterized as having an average degree of substitution by an anionic group of from about 0.001 to about 2.
  • the modified cellulose nanofibil has an average degree of substitution by an anionic group of less than 1.0, preferably less than 0.5, more preferably less than 0.1, and at a level where the anionic cellulose cannot form a stable suspension in water without the use of addition additives or chemicals.
  • the average degree of substitution by an anionic group refers to the average number of moles of the respective anionic group per mole of glucose unit in the modified nanofibril.
  • the average degree of e.g. sulfate group substitution refers to the average number of moles of sulfate groups per mole of glucose unit in the modified nanofibril.
  • the degree of substitution can be determined according to methods known in the art (see for example Zhang K et al, Cellulose 17: 427-435, 2010 and references cited therein).
  • the suspension of the anionically modified cellulose i.e. the anionic cellulose suspension
  • the anionically modified cellulose is prepared in liquid to obtain a (viscous) continuous phase in which the anionically modified cellulose is substantially insoluble. It is understood that the solubility of the anionically modified cellulose depends on the degree of substitution with the anionically charged groups.
  • the neutral cellulose is preferably a (neutral) cellulose nanofibril isolated by use of chemical or mechanical degradation or a combination of both process stages on the starting cellulose-based material as defined hereinabove.
  • the neutral cellulose nanofibrils may be obtained by mixing finely shredded cellulose-based starting material as defined hereinabove with a non-derivatising mineral acid, for example hydrochloric acid, boiling said mixture for between 10 minutes and 5 hours.
  • a non-derivatising mineral acid for example hydrochloric acid
  • concentration of the non-derivatising mineral acid is between 0.1 to 90%, preferably 10 to 60%.
  • the obtained mixture is filtered and the extracted cellulosic material with or without prior drying is subject to mechanical shear for example using a ball mill or au hor device to obtain the neutral cellulose nanofibrils.
  • the neutral cellulose nanofibril is characterized by having an elongated form, having an average length in the range of 15-300 nm, preferably in the range of 50-200 nm.
  • the average thickness is preferably in the range of 3-300 nm, preferably in the range of 3-200 nm, more preferably in the range of 10-100 nm.
  • the neutral cellulose may then be suspended in a fluid medium or liquid comprising an additive or a suspending agent as defined hereinabove to obtain a (viscous) continuous phase as defined hereinabove.
  • a suitable suspending agent (or additive) may be a natural gum (e.g. gum arabic, gum tragacanth, guar gum, locust bean gum, carrageenan) a pectin, an alginate, a cellulose derivative (e.g.
  • a suitable liquid or continuous phase may be selected from aqueous solvents, e.g. water, or organic solvents, e.g. methylene chloride, methanol, propanol and dimethyl sulfoxide and the like, or as defined hereinabove.
  • the suspension of the anionically modified cellulose is provided in a concentration range of between about 0.01 % and about 100 % (i.e. ⁇ 100%), more specifically between about 0.01 % and about 80 %, preferably between about 1.0 % and 75 %, more preferably between about 1.0% up to about 60 %, more preferably between about 5.0% up to about 60 %, most preferably between about 7.0% up to about 60 %.
  • Cellulose nanofibrils extracted using hydrochloric acid followed by mechanical grinding are suspended with mixing in a 3 % solution of a Dow Wolff Methocel A grade (methyl cellulose) having a number average molecular weight of 180,000 and a solution viscosity of 40,000 mP.s (measured as a 2 % solution at 20 °C using an Ubbelohde viscometer).
  • the concentration of the neutral nanofibrils in the suspension is 30 %w/w.
  • Cellulose nanofibrils extracted using hydrochloric acid followed by mechanical grinding are suspended with mixing in a 1.2 % solution of a Dow Wolff Methocel J grade (hydroxyl propyl methyl cellulose) having a number average molecular weight of 220,000 and a solution viscosity of 75,000 mP.s (measured as a 1% solution at 20 °C using a Brookfield viscometer).
  • the concentration of the neutral nanofibrils in the suspension is 27%w/w.
  • Example 3 Cellulose nanofibrils extracted using sulfuric acid and having a degree of substitution of ⁇ 0.5 is mechanically processed to break-up the cellulose structure in order to release the nanofibrils.
  • the nanofibrils are dried and fractionated to recover the fraction 100-200 nm in length.
  • These nanofibrils are dispersed, with mixing in a 2.5 % solution of hydroxyl propyl methyl cellulose having a solution viscosity of 40,000 mP.s.
  • the cellulose concentration is 28% w/w
  • Anionic cellulose nanofibrils derived from the sulfuric acid hydrolysis of microcrystalline cellulose are purified via dialysis against reverse osmosis purified/deionized water for three days.
  • an aqueous solution of Methocel A methyl cellulose, supplier Dow Wolff, Mw ca. 180 kDa
  • Methocel A methyl cellulose, supplier Dow Wolff, Mw ca. 180 kDa
  • the composite cellulose-cellulose ether powder (88g) is then reconstituted into a highly concentrated, viscous, aqueous gel by mixing with aqueous sodium chloride solution (O.OOIM, 163g) in a 0.25 litre screw topped jar and subjecting to resonant acoustic mixing (LabRam mixer, ResoDyn Inc) for 5 minutes.
  • aqueous sodium chloride solution O.OOIM, 163g
  • Neutral cellulose nanofibrils derived from the hydrochloric acid hydrolysis of microcrystalline cellulose are purified via dialysis against reverse osmosis purified/deionized water for three days.
  • an aqueous solution of Methocel A methyl cellulose, supplier Dow Wolff, Mw - 180 kDa
  • the composite cellulose-cellulose ether powder (88g) is then reconstituted into a highly concentrated, viscous, aqueous gel by mixing with water (88g) in a 0.25 litre screw topped jar and subjecting to resonant acoustic mixing (LabRam mixer, ResoDyn Inc) for 6 minutes.
  • Neutral cellulose nanofibrils derived from the hydrochloric acid hydrolysis of microcrystalline cellulose are purified via dialysis against reverse osmosis purified/deionized water for three days.
  • an aqueous solution of hydroxypropylmethyl cellulose, supplier Dow Wolff) 400g, 2% solids by weight and system rendered visually homogeneous via gentle mechanical agitation.
  • the resultant viscous, composite gel is then dehydrated by freeze drying to yield a finally divided powder.
  • the composite cellulose-cellulose ether powder is then reconstituted into a highly concentrated, viscous, aqueous gel by mixing with water in a screw topped jar and subjecting to resonant acoustic mixing (LabRam mixer, ResoDyn Inc) for 6 minutes.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Textile Engineering (AREA)
  • Artificial Filaments (AREA)

Abstract

La présente invention concerne un procédé de préparation d'une suspension stable et à haute teneur en solides de nanofibrilles de cellulose neutres ou ayant subi une modification anionique, présentant de préférence une teneur en solides de nanofibrilles de cellulose neutres ou ayant subi une modification anionique de 6 à 80 %, le procédé comportant les étapes consistant à : (a) isoler des nanofibrilles de cellulose neutres ou anioniques d'un matériau à base de cellulose ; et (b) préparer une suspension stable des nanofibrilles de cellulose neutres ou anioniques dans une phase continue (visqueuse) adaptée à une utilisation en tant que matière première pour le filage de fibres.
PCT/EP2012/053985 2011-03-08 2012-03-08 Procédé de fabrication d'une suspension stable de cellulose à haute teneur en solides Ceased WO2012120071A1 (fr)

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EP11157313 2011-03-08
EP11157313.5 2011-03-08

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WO2012120071A1 true WO2012120071A1 (fr) 2012-09-13

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160333116A1 (en) * 2014-01-17 2016-11-17 Nippon Paper Industries Co., Ltd. Dry solids of anionically modified cellulose nanofibers and processes for preparing them
US12285731B2 (en) 2019-09-12 2025-04-29 United States Of America, As Represented By The Secretary Of The Army Acoustic mixing system for creating propellant mixture

Citations (3)

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US6231657B1 (en) * 1996-07-15 2001-05-15 Rhodia Chimie Supplementation of cellulose nanofibrils with carboxycellulose with low degree of substitution
US6485767B1 (en) * 1997-10-29 2002-11-26 Rhodia Chimie Use of cellulose microfibrils in dry form in food formulations
JP2010242063A (ja) * 2009-03-17 2010-10-28 Kuraray Co Ltd セルロースナノファイバー複合ポリビニルアルコール系重合体組成物

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6231657B1 (en) * 1996-07-15 2001-05-15 Rhodia Chimie Supplementation of cellulose nanofibrils with carboxycellulose with low degree of substitution
US6485767B1 (en) * 1997-10-29 2002-11-26 Rhodia Chimie Use of cellulose microfibrils in dry form in food formulations
JP2010242063A (ja) * 2009-03-17 2010-10-28 Kuraray Co Ltd セルロースナノファイバー複合ポリビニルアルコール系重合体組成物

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Title
CH EYHOLZER ET AL: "Reinforcing effect of carboxymethylated nanofibrillated cellulose powder on hydroxypropyl cellulose", CELLULOSE, KLUWER ACADEMIC PUBLISHERS, DO, vol. 17, no. 4, 8 May 2010 (2010-05-08), pages 793 - 802, XP019815403, ISSN: 1572-882X *
DONG; REVOL; GRAY, CELLULOSE, vol. 5, 1998, pages 19 - 32
ELITON S. MEDEIROS ET AL: "Electrospun Nanofibers of Poly(vinyl alcohol) Reinforced with Cellulose Nanofibrils", JOURNAL OF BIOBASED MATERIALS AND BIOENERGY, vol. 2, no. 3, 1 September 2008 (2008-09-01), pages 231 - 242, XP055031138, ISSN: 1556-6560, DOI: 10.1166/jbmb.2008.411 *
PULLAWAN T ET AL: "Discrimination of matrix-fibre interactions in all-cellulose nanocomposites", COMPOSITES SCIENCE AND TECHNOLOGY, ELSEVIER, UK, vol. 70, no. 16, 31 December 2010 (2010-12-31), pages 2325 - 2330, XP027491454, ISSN: 0266-3538, [retrieved on 20101020], DOI: 10.1016/J.COMPSCITECH.2010.09.013 *
ZHANG K ET AL., CELLULOSE, vol. 17, 2010, pages 427 - 435

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160333116A1 (en) * 2014-01-17 2016-11-17 Nippon Paper Industries Co., Ltd. Dry solids of anionically modified cellulose nanofibers and processes for preparing them
US11603415B2 (en) * 2014-01-17 2023-03-14 Nippon Paper Industries Co., Ltd. Dry solids of anionically modified cellulose nanofibers and processes for preparing them
US12152090B2 (en) * 2014-01-17 2024-11-26 Nippon Paper Industries Co., Ltd. Dry solids of anionically modified cellulose nanofibers and processes for preparing them
US12285731B2 (en) 2019-09-12 2025-04-29 United States Of America, As Represented By The Secretary Of The Army Acoustic mixing system for creating propellant mixture

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