WO2009126106A1 - Method for providing a nanocellulose involving modifying cellulose fibers - Google Patents

Method for providing a nanocellulose involving modifying cellulose fibers Download PDF

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Publication number
WO2009126106A1
WO2009126106A1 PCT/SE2009/050371 SE2009050371W WO2009126106A1 WO 2009126106 A1 WO2009126106 A1 WO 2009126106A1 SE 2009050371 W SE2009050371 W SE 2009050371W WO 2009126106 A1 WO2009126106 A1 WO 2009126106A1
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WO
WIPO (PCT)
Prior art keywords
pulp
cmc
approximately
cellulose
nanocellulose
Prior art date
Application number
PCT/SE2009/050371
Other languages
French (fr)
Inventor
Mikael Ankerfors
Tom Lindström
Original Assignee
Stfi-Packforsk Ab
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 Stfi-Packforsk Ab filed Critical Stfi-Packforsk Ab
Priority to CA2721056A priority Critical patent/CA2721056C/en
Priority to US12/936,916 priority patent/US8911591B2/en
Priority to AU2009234498A priority patent/AU2009234498B2/en
Priority to RU2010145477/04A priority patent/RU2519257C2/en
Priority to JP2011503940A priority patent/JP2011522902A/en
Priority to ES09729526.5T priority patent/ES2485302T3/en
Priority to EP09729526.5A priority patent/EP2265760B1/en
Priority to NZ588539A priority patent/NZ588539A/en
Priority to BRPI0911507A priority patent/BRPI0911507B8/en
Publication of WO2009126106A1 publication Critical patent/WO2009126106A1/en
Priority to ZA2010/07250A priority patent/ZA201007250B/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
    • B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
    • B82B3/0095—Manufacture or treatments or nanostructures not provided for in groups B82B3/0009 - B82B3/009
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
    • D21H11/16—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
    • D21H11/20—Chemically or biochemically modified fibres
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/001—Modification of pulp properties
    • D21C9/002—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
    • D21H11/16—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
    • D21H11/18—Highly hydrated, swollen or fibrillatable fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/02—Cellulose; Modified cellulose
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/001—Modification of pulp properties
    • D21C9/007—Modification of pulp properties by mechanical or physical means
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H15/00—Pulp or paper, comprising fibres or web-forming material characterised by features other than their chemical constitution
    • D21H15/02—Pulp or paper, comprising fibres or web-forming material characterised by features other than their chemical constitution characterised by configuration

Definitions

  • This invention concerns the technical field of treatment of cellulose containing material for the manufacturing of nanocellulose (microfibrillated cellulose). Also disclosed is nanocellulose manufactured in accordance with said method and uses of said cellulose.
  • WO2005080678 a method for the modification of lignocellulosic materials is disclosed.
  • Cellulose fibres are treated with an aqueous electrolyte-containing solution of an amphoteric cellulose derivative for at least 5 minutes at a temperature of at least 50 °C.
  • the pH during the treatment is approximately 1.5-4.5 or higher than 1 1 ; or the concentration of the electrolyte is approximately 0.0001 -0.05 M if the electrolyte has monovalent cations, or approximately 0.0002-0.1 M if the electrolyte has divalent cations.
  • said document relates to products obtained by the above mentioned method and uses of said products for manufacturing paper with a high wet strength.
  • the present invention solves the above problem by providing according to a first aspect a method for providing a nanocellulose involving modifying cellulose fibers wherein the method comprises the following steps: i) treating cellulose fibers for at least 5 minutes with an aqueous electrolyte-containing solution of an amphoteric carboxymethyl cellulose (amphoteric CMC) or a derivative thereof, preferably a low molecular amphoteric CMC or a CMC derivative thereof, whereby the temperature during the treatment is at least 50 9 C, and at least one of the following conditions apply:
  • the pH of the aqueous solution during the treatment lies in the interval of approximately 1 .5 - 4.5, preferably in the region 2 - 4;
  • the pH of the aqueous solution during the treatment is higher than approximately 1 1 ; or C) the concentration of the electrolyte in the aqueous solution lies in the interval of approximately 0.0001 -0.5 M, preferably approximately 0.001 -0.4 M, if the electrolyte has monovalent cations (such as Na 2 SO 4 ), or in the range of approximately 0.0001 - 0.1 M, preferably approximately 0.0005-0.05 M, if the electrolyte has divalent cations (such as CaCI 2 ), ii) adjusting the pH by using a basic and/or an acidic liquid into a pH range of from about 5 to about 13, preferably the pH is adjusted to a pH from about 6 to about 12, and iii) treating said material in a mechanical comminution device, thus providing said nanocellulose.
  • a basic and/or an acidic liquid into a pH range of from about 5 to about 13, preferably the pH is adjusted to a pH from about 6 to about 12, and iii) treating said material in
  • This invention thereby involves attachment of amphoteric CMC polymers to lignocellulosic fibres as a pre-treatment before homogenization with the purpose of manufacturing nanocellulose.
  • the attachment of amphoteric CMC polymers has proven to have several benefits, as outlined below.
  • the attachment of amphoteric CMC polymers decreases the energy consumption considerably and makes it possible to avoid clogging problems. Furthermore, it increases the anionic charge density of the fibres, which facilitates the delamination and, furthermore, enables delamination at much lower charge densities than if the charges would have been introduced by for instance any carboxymethylation reaction. Moreover, the CMC attachment process is aqueous based, which is beneficial since no other solvents than water is needed.
  • amphoteric CMC polymers By using amphoteric CMC polymers, the attachment is easier and the attachment degree is increased as compared to anionic CMC.
  • Condition C is preferably combined with either of conditions A or B in step i), when applicable.
  • the treated cellulose fibers may also after step i) be washed first with an acidic liquid and thereupon an essentially neutral liquid, preferably water.
  • the present invention also provides, according to a second aspect, a modified lignocellulosic material (nanocellulose) obtained by the method according to the first aspect.
  • the attached amount of amphoteric CMC to lignocellulosic fibres is in the interval of from 5 to 250 milligram amphoteric CMC/gram dry fibre, preferably from 7 to 200 milligram amphoteric CMC/gram dry fibre and more preferably from 10 to 150 milligram amphoteric CMC/gram dry fibre.
  • amphoteric CMC as described herein advantageously enables an aqueous pre-treatment process for the manufacture of nanocellulose with less energy consumption and without the risk of clogging. This effect is attained by attachment of relatively small amounts of amphoteric CMC which results in lower charge densities than if a carboxymethylation reaction would have been used.
  • the anionic charge density of the amphoteric CMC used in the method influences the amount of CMC needed. CMC of high anionic charge density lowers the amount of CMC needed.
  • the present invention also provides according to a third aspect use of the lignocellulosic material (nanocellulose) of the second aspect in cosmetic products, pharmaceutical products, food products, paper products, composite materials, coatings, hygiene/absorbent products, films, emulsion/dispersing agents, drilling muds and to enhance the reactivity of cellulose in the manufacture of regenerated cellulose or cellulose derivatives or in rheology modifiers.
  • CMC carboxymethyl cellulose
  • This CMC derivative may further have been cationized in a, for the skilled person, well known manner to a substitution degree between 0.00001 and 1 .0, preferably 0.00001 and 0.4.
  • the cationization is preferably performed by the introduction of at least one ammonium function; most preferred a secondary, tertiary or quaternary ammonium function (or a mixture thereof) into the derivative.
  • mechanical comminution device means any device which may be suitable for providing a nanocellulose (a microfibrillated cellulose) as set out above, and said device may e.g. be a refiner, a fluidizer, a homogenizer or a microfluidizer.
  • cellulose fibres cellulose material
  • a pulp which may be chemical pulp, mechanical pulp, thermomechanical pulp or chemi(thermo)mechanical pulp (CMP or CTMP).
  • Said chemical pulp is preferably a sulphite pulp or a kraft pulp.
  • the pulp may consist of pulp from hardwood, softwood or both types.
  • the pulp may e.g. contain a mixture of pine and spruce or a mixture of birch and spruce.
  • the chemical pulps that may be used in the present invention include all types of chemical wood-based pulps, such as bleached, half-bleached and unbleached sulphite, kraft and soda pulps, and mixtures of these.
  • the consistency of the pulp during manufacture of nanocellulose may be any consistency, ranging from low consistency through medium consistency to high consistency.
  • the preferred concentration of amphoteric cellulose derivative is approximately 0.02
  • a more preferred concentration is approximately 0.04 - 2 % w/w, and the most preferred concentration of additive is approximately 0.08 - 1% w/w.
  • the temperature during the treatment is in excess of approximately 50 °C, preferably at least approximately 100 °C, and most preferred up to approximately 120 °C.
  • the method according to the invention may thus be carried out at a pressure in excess of atmospheric pressure. Suitable equipment and working conditions for this will be obvious for one skilled in the arts.
  • condition C applies together of either condition A or condition B in step i).
  • a method wherein said cellulose fibers is contained in a pulp, preferably a sulphite pulp or a kraft pulp.
  • the preferred concentration of pulp is approximately 0.5 - 50%, a more preferred concentration interval is approximately 5 - 50%, and the most preferred concentration interval is approximately 10 - 30%.
  • Such high concentration mixes are known to one skilled in the arts within the relevant technical field, and are suitable for use in association with the present invention.
  • Fig. 1 shows Case C which gave rise to an MFC gel.
  • Fig. 2 shows Case D which gave rise to an MFC gel.
  • Fig. 3 shows Case E which gave rise to an MFC gel.
  • Fig. 4 shows Case F which gave rise to an MFC gel.
  • Fig. 5 shows Case H which gave rise to an MFC gel.
  • Fig. 6 shows Case K which did not give rise to an MFC gel.
  • Fig. 7 shows Case L which gave rise to an MFC gel.
  • Pulp Commercial never dried bleached sulphite pulp (Domsj ⁇ ECO Bright, Domsj ⁇ Fabriker) Procedure:
  • the pulp was then ion-exchanged into its hydrogen counter-ion form. Firstly, the HCI was added to the pulp to a concentration of 10 2 M (pH is 2). The pH was held at 2 for 30 minutes. Then the pulp was washed with deionised water on a b ⁇ chner funnel until the conductivity of the filtrate was below 5 ⁇ S/cm. 3. The pulp was then ion-exchanged into its sodium counter-ion form. Firstly, the NaHCO 3 was added to the pulp to a concentration of 10 ⁇ 3 M and NaOH was then added to reach a pH of 9. The pH was held at 9 for 30 minutes. Then the pulp was washed with deionised water on a b ⁇ chner funnel until the conductivity of the filtrate was below 5 ⁇ S/cm.
  • Amphoteric-CMC with an anionic degree of substitution of 0.64, cationic degree of substitution of 0.048 and an intrinsic viscosity of 2.0 was dissolved in deionised water.
  • the pulp was then ion-exchanged into its sodium counter-ion form as described above in step 2 and 3. 8.
  • the pulps (2 % concentration in deionised water) were then homogenised with one pass through a Microfluidizer M-1 10EH (Microfluidics Corp.) at an operating pressure of 1750 bar.
  • the chambers that were used had an inner diameter of 200 ⁇ m and 100 ⁇ m.
  • Pulp Commercial never dried bleached sulphite dissolving pulp (Domsj ⁇ Dissolving plus,
  • the pulp was then ion-exchanged into its hydrogen counter-ion form. Firstly, the HCI was added to the pulp to a concentration of 10 '2 M (pH is 2). The pH was held at 2 for 30 minutes. Then the pulp was washed with deionised water on a b ⁇ chner funnel until the conductivity of the filtrate was below 5 ⁇ S/cm. 3. The pulp was then ion-exchanged into its sodium counter-ion form. Firstly, the NaHCO 3 was added to the pulp to a concentration of 10 ⁇ 3 M and NaOH was then added to reach a pH of 9. The pH was held at 9 for 30 minutes. Then the pulp was washed with deionised water on a b ⁇ chner funnel until the conductivity of the filtrate was below 5 ⁇ S/cm.
  • Amphoteric-CMC with an anionic degree of substitution of 0.64, cationic degree of substitution of 0.048 and an intrinsic viscosity of 2.0 was dissolved in deionised water.
  • the pulps (2 % concentration in deionised water) were then homogenised with one pass through a Microfluidizer M-1 10EH (Microfluidics Corp.) at an operating pressure of 1750 bar.
  • the chambers that were used had an inner diameter of 200 ⁇ m and 100 ⁇ m.
  • the pulp was then ion-exchanged into its sodium counter-ion form. Firstly, the NaHCO 3 was added to the pulp to a concentration of 10 ⁇ 3 M and NaOH was then added to reach a pH of 9. The pH was held at 9 for 30 minutes. Then the pulp was washed with deionised water on a b ⁇ chner funnel until the conductivity of the filtrate was below 5 ⁇ S/cm. 4. Amphoteric-CMC with an anionic degree of substitution of 0.65, cationic degree of substitution of 0.048 and an intrinsic viscosity of 2.0 was dissolved in tap water. 5. The CMC-attachment was carried out in accordance to Laine et al. (Laine, J. et al.
  • the pulps (2 % concentration in deionised water) were then homogenised with one pass through a Microfluidizer M-1 10EH (Microfluidics Corp.) at an operating pressure of 1700 bar.
  • the chambers that were used had an inner diameter of 200 ⁇ m and 100 ⁇ m.
  • the pulp was then ion-exchanged into its sodium counter-ion form. Firstly, the NaHCO 3 was added to the pulp to a concentration of 10 '3 M and NaOH was then added to reach a pH of 9. The pH was held at 9 for 30 minutes. Then the pulp was washed with deionised water on a b ⁇ chner funnel until the conductivity of the filtrate was below 5 ⁇ S/cm.
  • the pulp was then ion-exchanged into its sodium counter-ion form as described above in step 2 and 3. 8.
  • the pulps (2 % concentration in deionised water) were then homogenised with one pass through a Microfluidizer M-1 10EH (Microfluidics Corp.) at an operating pressure of 1750 bar.
  • the chambers that were used had an inner diameter of 200 ⁇ m and 100 ⁇ m.
  • Pulp Commercial never dried bleached sulphite dissolving pulp (Domsj ⁇ Dissolving plus,
  • the pulp was then ion-exchanged into its hydrogen counter-ion form. Firstly, the HCI was added to the pulp to a concentration of 10 '2 M (pH is 2). The pH was held at 2 for 30 minutes. Then the pulp was washed with deionised water on a b ⁇ chner funnel until the conductivity of the filtrate was below 5 ⁇ S/cm.
  • the pulp was then ion-exchanged into its sodium counter-ion form. Firstly, the NaHCO 3 was added to the pulp to a concentration of 10 '3 M and NaOH was then added to reach a pH of 9. The pH was held at 9 for 30 minutes. Then the pulp was washed with deionised water on a b ⁇ chner funnel until the conductivity of the filtrate was below 5 ⁇ S/cm.
  • Anionic-CMC with an anionic degree of substitution of 0.57 and an intrinsic viscosity of 1.4 was dissolved in deionised water.
  • the pulps (2 % concentration in deionised water) were then homogenised with one pass through a Microfluidizer M-1 10EH (Microfluidics Corp.) at an operating pressure of 1750 bar.
  • the chambers that were used had an inner diameter of 200 ⁇ m and 100 ⁇ m.
  • Pulp Commercial never dried bleached sulphite pulp (Domsj ⁇ ECO Bright, Domsj ⁇ Fabriker)
  • the pulp was then ion-exchanged into its hydrogen counter-ion form. Firstly, the HCI was added to the pulp to a concentration of 10 '2 M (pH is 2). The pH was held at 2 for 30 minutes. Then the pulp was washed with deionised water on a b ⁇ chner funnel until the conductivity of the filtrate was below 5 ⁇ S/cm.
  • the pulp was then ion-exchanged into its sodium counter-ion form. Firstly, the NaHCO 3 was added to the pulp to a concentration of 10 '3 M and NaOH was then added to reach a pH of 9. The pH was held at 9 for 30 minutes. Then the pulp was washed with deionised water on a b ⁇ chner funnel until the conductivity of the filtrate was below 5 ⁇ S/cm.
  • Anionic-CMC with an anionic degree of substitution of 0.4 and an intrinsic viscosity of 15 was dissolved in deionised water.
  • the pulps (2.6 % concentration in deionised water) were then homogenised with one pass through a Microfluidizer M-1 10EH (Microfluidics Corp.) at an operating pressure of 1750 bar.
  • the chambers that were used had an inner diameter of 200 ⁇ m and 100 ⁇ m.
  • the attached amount of anionic CMC on the fibres was determined by conductometric titration.
  • the conductometric titration measures the total amounts of anionic groups, e.g. carboxyl acid groups, in the pulps. Prior to the titration, the pulp was washed to different counter-ion form as follows.
  • the pulp was set to its sodium counter-ion form.
  • the pulp was dispersed in deionised water and then 0.001 M NaHCO 3 was added, pH was set to 9 using NaOH. After 30 more minutes the excessive NaOH and the NaHCO 3 were washed away with deionised water on a b ⁇ chner funnel until the conductivity was below 5 ⁇ S/cm.
  • the amount of attached CMC was evaluated by comparing the result from the anionic CMC pulps with the result from reference pulp, the amount of attached CMC could be determined.
  • amphoteric CMC the nitrogen content in the pulps were measured. This was done since the amphoteric CMC's cationic groups contained nitrogen.
  • the intrinsic viscosity of the CMCs was measured in deionised water with 0.1 M NaCI at a temperature of 25 °C.

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Abstract

The present invention provides a method for the manufacturing of nanocellulose. The method includes a first modification of the cellulose material, where the cellulose fibres are treated with an aqueous electrolyte-containing solution of an amphoteric cellulose derivative. The modification is followed by a mechanical treatment. By using this method for manufacturing nanocellulose, clogging of the mechanical apparatus is avoided. Also disclosed is nanocellulose manufactured in accordance with said method and uses of said cellulose.

Description

Method for providing a nanocellulose involving modifying cellulose fibers
Field of invention
This invention concerns the technical field of treatment of cellulose containing material for the manufacturing of nanocellulose (microfibrillated cellulose). Also disclosed is nanocellulose manufactured in accordance with said method and uses of said cellulose.
Background
In WO2005080678 a method for the modification of lignocellulosic materials is disclosed. Cellulose fibres are treated with an aqueous electrolyte-containing solution of an amphoteric cellulose derivative for at least 5 minutes at a temperature of at least 50 °C. The pH during the treatment is approximately 1.5-4.5 or higher than 1 1 ; or the concentration of the electrolyte is approximately 0.0001 -0.05 M if the electrolyte has monovalent cations, or approximately 0.0002-0.1 M if the electrolyte has divalent cations. Further said document relates to products obtained by the above mentioned method and uses of said products for manufacturing paper with a high wet strength.
However nothing is mentioned in the above document about manufacturing of nanocellulose or similar. In Wagberg et al (2008) the reaction between chloroacetic acid and lignocellulose fibres is described as a pre-treatment to ease delamination in a homogenizer in order to create nanocellulose or microfibrillar cellulose. However, attachment of carboxymethylcellulose polymers to the lignocellulosic fibres is not described.
Through US 4,341 ,807 further a method for manufacturing a microfibrillated cellulose or nanocellulose is disclosed by using homogenization. A problem when manufacturing nanocellulose from pulp is however the clogging of the homogenizer, when the pulp is pumped through high pressure fluidizers/homogenizers. Another problem is the excessive energy consumption during homogenization, unless the pulp before refining is subjected to some type of physiochemical pretreatment. Thus there is a need for a process wherein the clogging problem and the excessive energy consumption can be alleviated and/or avoided.
Summary of the invention
The present invention solves the above problem by providing according to a first aspect a method for providing a nanocellulose involving modifying cellulose fibers wherein the method comprises the following steps: i) treating cellulose fibers for at least 5 minutes with an aqueous electrolyte-containing solution of an amphoteric carboxymethyl cellulose (amphoteric CMC) or a derivative thereof, preferably a low molecular amphoteric CMC or a CMC derivative thereof, whereby the temperature during the treatment is at least 509C, and at least one of the following conditions apply:
A) the pH of the aqueous solution during the treatment lies in the interval of approximately 1 .5 - 4.5, preferably in the region 2 - 4; or
B) the pH of the aqueous solution during the treatment is higher than approximately 1 1 ; or C) the concentration of the electrolyte in the aqueous solution lies in the interval of approximately 0.0001 -0.5 M, preferably approximately 0.001 -0.4 M, if the electrolyte has monovalent cations (such as Na2SO4), or in the range of approximately 0.0001 - 0.1 M, preferably approximately 0.0005-0.05 M, if the electrolyte has divalent cations (such as CaCI2), ii) adjusting the pH by using a basic and/or an acidic liquid into a pH range of from about 5 to about 13, preferably the pH is adjusted to a pH from about 6 to about 12, and iii) treating said material in a mechanical comminution device, thus providing said nanocellulose.
This invention thereby involves attachment of amphoteric CMC polymers to lignocellulosic fibres as a pre-treatment before homogenization with the purpose of manufacturing nanocellulose. The attachment of amphoteric CMC polymers has proven to have several benefits, as outlined below.
The attachment of amphoteric CMC polymers decreases the energy consumption considerably and makes it possible to avoid clogging problems. Furthermore, it increases the anionic charge density of the fibres, which facilitates the delamination and, furthermore, enables delamination at much lower charge densities than if the charges would have been introduced by for instance any carboxymethylation reaction. Moreover, the CMC attachment process is aqueous based, which is beneficial since no other solvents than water is needed.
By using amphoteric CMC polymers, the attachment is easier and the attachment degree is increased as compared to anionic CMC.
Condition C is preferably combined with either of conditions A or B in step i), when applicable. The treated cellulose fibers may also after step i) be washed first with an acidic liquid and thereupon an essentially neutral liquid, preferably water. The present invention also provides, according to a second aspect, a modified lignocellulosic material (nanocellulose) obtained by the method according to the first aspect. The attached amount of amphoteric CMC to lignocellulosic fibres is in the interval of from 5 to 250 milligram amphoteric CMC/gram dry fibre, preferably from 7 to 200 milligram amphoteric CMC/gram dry fibre and more preferably from 10 to 150 milligram amphoteric CMC/gram dry fibre. The attachment of amphoteric CMC as described herein advantageously enables an aqueous pre-treatment process for the manufacture of nanocellulose with less energy consumption and without the risk of clogging. This effect is attained by attachment of relatively small amounts of amphoteric CMC which results in lower charge densities than if a carboxymethylation reaction would have been used. Naturally, the anionic charge density of the amphoteric CMC used in the method influences the amount of CMC needed. CMC of high anionic charge density lowers the amount of CMC needed.
The present invention also provides according to a third aspect use of the lignocellulosic material (nanocellulose) of the second aspect in cosmetic products, pharmaceutical products, food products, paper products, composite materials, coatings, hygiene/absorbent products, films, emulsion/dispersing agents, drilling muds and to enhance the reactivity of cellulose in the manufacture of regenerated cellulose or cellulose derivatives or in rheology modifiers.
Detailed description of the invention
It is intended throughout the present description that the expression "amphoteric cellulose derivative" embraces any cellulose derivative comprising simultaneously both cationic and anionic moieties. Further said amphoteric cellulose derivative is preferably an amphoteric cellulose derivative which still is net, negatively charged, but comprises a less amount of cationically active groups. Still further preferred said cellulose derivative is an amphoteric CMC (CMC=carboxymethyl cellulose) derivative, especially preferred is an amphoteric CMC derivative with a preferred anionic molar substitution degree between 0.3 and 1 .2, i.e. D. S = 0.3 - 1 .2 and the viscosity may be approximately 25-8,000 mPa at a concentration of 4%.
This CMC derivative may further have been cationized in a, for the skilled person, well known manner to a substitution degree between 0.00001 and 1 .0, preferably 0.00001 and 0.4. The cationization is preferably performed by the introduction of at least one ammonium function; most preferred a secondary, tertiary or quaternary ammonium function (or a mixture thereof) into the derivative.
It is intended throughout the present description that the expression "mechanical comminution device" means any device which may be suitable for providing a nanocellulose (a microfibrillated cellulose) as set out above, and said device may e.g. be a refiner, a fluidizer, a homogenizer or a microfluidizer.
According to a preferred embodiment of the first aspect of the present invention there is provided a method wherein said cellulose fibres (cellulose material) is present in the form of a pulp, which may be chemical pulp, mechanical pulp, thermomechanical pulp or chemi(thermo)mechanical pulp (CMP or CTMP). Said chemical pulp is preferably a sulphite pulp or a kraft pulp.
The pulp may consist of pulp from hardwood, softwood or both types. The pulp may e.g. contain a mixture of pine and spruce or a mixture of birch and spruce. The chemical pulps that may be used in the present invention include all types of chemical wood-based pulps, such as bleached, half-bleached and unbleached sulphite, kraft and soda pulps, and mixtures of these. The consistency of the pulp during manufacture of nanocellulose may be any consistency, ranging from low consistency through medium consistency to high consistency. The preferred concentration of amphoteric cellulose derivative is approximately 0.02
- 4 % w/w, calculated on the dry weight of the fiber material. A more preferred concentration is approximately 0.04 - 2 % w/w, and the most preferred concentration of additive is approximately 0.08 - 1% w/w.
According to a preferred embodiment of the first aspect of the present invention there is provided a method wherein the cellulose fibres are treated for approximately 5 - 180 minutes; a preferred treatment (adsorption) period is approximately 10 - 120 min.
According to a preferred embodiment of the first aspect of the present invention there is provided a method wherein the temperature during the treatment is in excess of approximately 50 °C, preferably at least approximately 100 °C, and most preferred up to approximately 120 °C. The method according to the invention may thus be carried out at a pressure in excess of atmospheric pressure. Suitable equipment and working conditions for this will be obvious for one skilled in the arts.
According to a preferred embodiment of the first aspect of the present invention there is provided a method wherein condition C applies together of either condition A or condition B in step i).
According to a preferred embodiment of the first aspect of the present invention there is provided a method wherein said cellulose fibers is contained in a pulp, preferably a sulphite pulp or a kraft pulp.
The preferred concentration of pulp is approximately 0.5 - 50%, a more preferred concentration interval is approximately 5 - 50%, and the most preferred concentration interval is approximately 10 - 30%. Such high concentration mixes are known to one skilled in the arts within the relevant technical field, and are suitable for use in association with the present invention.
Preferred features of each aspect of the invention are as for each of the other aspects mutatis mutandis. The prior art documents mentioned herein are incorporated to the fullest extent permitted by law. The invention is further described in the following examples in conjunction with the appended figures, which do not limit the scope of the invention in any way. Embodiments of the present invention are described in more detail with the aid of examples of embodiments and figures, the only purpose of which is to illustrate the invention and are in no way intended to limit its extent.
Figures
In the appended figures 1 -7, resulting products after homogenisation are shown as set out in the examples part below. More specifically: Fig. 1 shows Case C which gave rise to an MFC gel.
Fig. 2 shows Case D which gave rise to an MFC gel.
Fig. 3 shows Case E which gave rise to an MFC gel.
Fig. 4 shows Case F which gave rise to an MFC gel.
Fig. 5 shows Case H which gave rise to an MFC gel. Fig. 6 shows Case K which did not give rise to an MFC gel.
Fig. 7 shows Case L which gave rise to an MFC gel.
Examples
Cases A-F
Pulp: Commercial never dried bleached sulphite pulp (Domsjό ECO Bright, Domsjό Fabriker) Procedure:
1 . The never dried pulp was first dispersed in deionised water. Two litres of deionised water was added to 30 grams of pulp and was then dispersed with 10000 revolutions in a laboratory disintegrator in accordance to (ISO 5263-1 :2004).
2. The pulp was then ion-exchanged into its hydrogen counter-ion form. Firstly, the HCI was added to the pulp to a concentration of 10 2 M (pH is 2). The pH was held at 2 for 30 minutes. Then the pulp was washed with deionised water on a bϋchner funnel until the conductivity of the filtrate was below 5 μS/cm. 3. The pulp was then ion-exchanged into its sodium counter-ion form. Firstly, the NaHCO3 was added to the pulp to a concentration of 10~3 M and NaOH was then added to reach a pH of 9. The pH was held at 9 for 30 minutes. Then the pulp was washed with deionised water on a bϋchner funnel until the conductivity of the filtrate was below 5 μS/cm.
4. Amphoteric-CMC with an anionic degree of substitution of 0.64, cationic degree of substitution of 0.048 and an intrinsic viscosity of 2.0 was dissolved in deionised water.
5. The CMC-attachment was carried out in accordance to Laine et al. (Laine, J. et al. (2000) Nordic Pulp and Paper Research Journal 15(5), page 520-526). Conditions during attachment: pulp concentration=20 gram/litre; temperature=120 °C; treatment time=2 hours; CaCI2-concentration=0.05 M; water=deionised water. Different amounts of CMC was added for the different cases, A-F (Case A=O mg CMC/g fibre, Case B=10 mg CMC/g fibre, Case C=20 mg CMC/g fibre, Case D=40 mg CMC/g fibre, Case E=80 mg CMC/g fibre, Case F=120 mg CMC/g fibre).
6. After the CMC-attachment treatment, the pulp was washed with deionised water on a bϋchner funnel until the conductivity of the filtrate was below 5 μS/cm.
7. The pulp was then ion-exchanged into its sodium counter-ion form as described above in step 2 and 3. 8. The pulps (2 % concentration in deionised water) were then homogenised with one pass through a Microfluidizer M-1 10EH (Microfluidics Corp.) at an operating pressure of 1750 bar. The chambers that were used had an inner diameter of 200 μm and 100 μm.
Cases G-H
Pulp: Commercial never dried bleached sulphite dissolving pulp (Domsjό Dissolving plus,
Domsjό Fabriker)
Procedure:
1. The never dried pulp was first dispersed in deionised water. Two litres of deionised water was added to 30 grams of pulp and was then dispersed with 10000 revolutions in a laboratory disintegrator in accordance to (ISO 5263-1 :2004).
2. The pulp was then ion-exchanged into its hydrogen counter-ion form. Firstly, the HCI was added to the pulp to a concentration of 10'2 M (pH is 2). The pH was held at 2 for 30 minutes. Then the pulp was washed with deionised water on a bϋchner funnel until the conductivity of the filtrate was below 5 μS/cm. 3. The pulp was then ion-exchanged into its sodium counter-ion form. Firstly, the NaHCO3 was added to the pulp to a concentration of 10~3 M and NaOH was then added to reach a pH of 9. The pH was held at 9 for 30 minutes. Then the pulp was washed with deionised water on a bϋchner funnel until the conductivity of the filtrate was below 5 μS/cm.
4. Amphoteric-CMC with an anionic degree of substitution of 0.64, cationic degree of substitution of 0.048 and an intrinsic viscosity of 2.0 was dissolved in deionised water.
5. The CMC-attachment was carried out in accordance to Laine et al. (Laine, J. et al. (2000) Nordic Pulp and Paper Research Journal 15(5), page 520-526). Conditions during attachment: pulp concentration=20 gram/litre; temperature=120 °C; treatment time=2 hours; CaCI2-concentration=0.05 M; water=deionised water. Different amounts of CMC was added for the different cases G-H (Case G=O mg CMC/g fibre, Case H=80 mg CMC/g fibre). 6. After the CMC-attachment treatment, the pulp was washed with deionised water on a bϋchner funnel until the conductivity of the filtrate was below 5 μS/cm.
7. The pulp was then ion-exchanged into its sodium counter-ion form as described above in step 2 and 3.
8. The pulps (2 % concentration in deionised water) were then homogenised with one pass through a Microfluidizer M-1 10EH (Microfluidics Corp.) at an operating pressure of 1750 bar. The chambers that were used had an inner diameter of 200 μm and 100 μm.
Case I Pulp: Commercial never dried bleached sulphite pulp (Domsjό ECO Bright, Domsjό Fabriker) Procedure:
1 . The never dried pulp was first dispersed in deionised water. Two litres of deionised water was added to 30 grams of pulp and was then dispersed with 10000 revolutions in a laboratory disintegrator in accordance to (ISO 5263-1 :2004). 2. The pulp was then ion-exchanged into its hydrogen counter-ion form. Firstly, the HCI was added to the pulp to a concentration of 10'2 M (pH is 2). The pH was held at 2 for 30 minutes. Then the pulp was washed with deionised water on a bϋchner funnel until the conductivity of the filtrate was below 5 μS/cm.
3. The pulp was then ion-exchanged into its sodium counter-ion form. Firstly, the NaHCO3 was added to the pulp to a concentration of 10~3 M and NaOH was then added to reach a pH of 9. The pH was held at 9 for 30 minutes. Then the pulp was washed with deionised water on a bϋchner funnel until the conductivity of the filtrate was below 5 μS/cm. 4. Amphoteric-CMC with an anionic degree of substitution of 0.65, cationic degree of substitution of 0.048 and an intrinsic viscosity of 2.0 was dissolved in tap water. 5. The CMC-attachment was carried out in accordance to Laine et al. (Laine, J. et al.
(2000) Nordic Pulp and Paper Research Journal 15(5), page 520-526). Conditions during attachment: pulp concentration=20 gram/litre; temperature=room temperature (around 20 °C); treatment time=2 hours; water=tap water; CMC addition=10 mg CMC/g fibre, no addition of extra electrolytes. 6. After the CMC-attachment treatment, the pulp was washed with deionised water on a bϋchner funnel until the conductivity of the filtrate was below 5 μS/cm.
7. The pulp was then ion-exchanged into its sodium counter-ion form as described above in step 2 and 3.
8. The pulps (2 % concentration in deionised water) were then homogenised with one pass through a Microfluidizer M-1 10EH (Microfluidics Corp.) at an operating pressure of 1700 bar. The chambers that were used had an inner diameter of 200 μm and 100 μm.
Case J Pulp: Commercial never dried bleached sulphite pulp (Domsjό ECO Bright, Domsjό Fabriker) Procedure:
1 . The never dried pulp was first dispersed in deionised water. Two litres of deionised water was added to 30 grams of pulp and was then dispersed with 10000 revolutions in a laboratory disintegrator in accordance to (ISO 5263-1 :2004). 2. The pulp was then ion-exchanged into its hydrogen counter-ion form. Firstly, the HCI was added to the pulp to a concentration of 102 M (pH is 2). The pH was held at 2 for 30 minutes. Then the pulp was washed with deionised water on a bϋchner funnel until the conductivity of the filtrate was below 5 μS/cm.
3. The pulp was then ion-exchanged into its sodium counter-ion form. Firstly, the NaHCO3 was added to the pulp to a concentration of 10'3 M and NaOH was then added to reach a pH of 9. The pH was held at 9 for 30 minutes. Then the pulp was washed with deionised water on a bϋchner funnel until the conductivity of the filtrate was below 5 μS/cm.
4. Anionic-CMC with an anionic degree of substitution of 0.57 and an intrinsic viscosity of 1.4 was dissolved in deionised water. 5. The CMC-attachment was carried out in accordance to Laine et al. (Laine, J. et al. (2000) Nordic Pulp and Paper Research Journal 15(5), page 520-526). Conditions during attachment: pulp concentration=20 gram/litre; temperature=120 °C; treatment time=2 hours; CaCI2-concentration=0.05 M; water=deionised water; CMC-dosage=80 mg CMC/g fibre.
6. After the CMC-attachment treatment, the pulp was washed with deionised water on a bϋchner funnel until the conductivity of the filtrate was below 5 μS/cm.
7. The pulp was then ion-exchanged into its sodium counter-ion form as described above in step 2 and 3. 8. The pulps (2 % concentration in deionised water) were then homogenised with one pass through a Microfluidizer M-1 10EH (Microfluidics Corp.) at an operating pressure of 1750 bar. The chambers that were used had an inner diameter of 200 μm and 100 μm.
Case K
Pulp: Commercial never dried bleached sulphite dissolving pulp (Domsjό Dissolving plus,
Domsjό Fabriker)
Procedure:
1. The never dried pulp was first dispersed in deionised water. Two litres of deionised water was added to 30 grams of pulp and was then dispersed with 10000 revolutions in a laboratory disintegrator in accordance to (ISO 5263-1 :2004).
2. The pulp was then ion-exchanged into its hydrogen counter-ion form. Firstly, the HCI was added to the pulp to a concentration of 10'2 M (pH is 2). The pH was held at 2 for 30 minutes. Then the pulp was washed with deionised water on a bϋchner funnel until the conductivity of the filtrate was below 5 μS/cm.
3. The pulp was then ion-exchanged into its sodium counter-ion form. Firstly, the NaHCO3 was added to the pulp to a concentration of 10'3 M and NaOH was then added to reach a pH of 9. The pH was held at 9 for 30 minutes. Then the pulp was washed with deionised water on a bϋchner funnel until the conductivity of the filtrate was below 5 μS/cm.
4. Anionic-CMC with an anionic degree of substitution of 0.57 and an intrinsic viscosity of 1.4 was dissolved in deionised water.
5. The CMC-attachment was carried out in accordance to Laine et al. (Laine, J. et al. (2000) Nordic Pulp and Paper Research Journal 15(5), page 520-526). Conditions during attachment: pulp concentration=20 gram/litre; temperature=120 0C; treatment time=2 hours; CaCI2-concentration=0.05 M; water=deionised water; CMC-dosage=80 mg CMC/g fibre. 6. After the CMC-attachment treatment, the pulp was washed with deionised water on a bϋchner funnel until the conductivity of the filtrate was below 5 μS/cm. 7. The pulp was then ion-exchanged into its sodium counter-ion form as described above in step 2 and 3. 8. The pulps (2 % concentration in deionised water) were then homogenised with one pass through a Microfluidizer M-1 10EH (Microfluidics Corp.) at an operating pressure of 1750 bar. The chambers that were used had an inner diameter of 200 μm and 100 μm.
Case L
Pulp: Commercial never dried bleached sulphite pulp (Domsjό ECO Bright, Domsjό Fabriker)
Procedure: 1. The never dried pulp was first dispersed in deionised water. Two litres of deionised water was added to 30 grams of pulp and was then dispersed with 10000 revolutions in a laboratory disintegrator in accordance to (ISO 5263-1 :2004).
2. The pulp was then ion-exchanged into its hydrogen counter-ion form. Firstly, the HCI was added to the pulp to a concentration of 10'2 M (pH is 2). The pH was held at 2 for 30 minutes. Then the pulp was washed with deionised water on a bϋchner funnel until the conductivity of the filtrate was below 5 μS/cm.
3. The pulp was then ion-exchanged into its sodium counter-ion form. Firstly, the NaHCO3 was added to the pulp to a concentration of 10'3 M and NaOH was then added to reach a pH of 9. The pH was held at 9 for 30 minutes. Then the pulp was washed with deionised water on a bϋchner funnel until the conductivity of the filtrate was below 5 μS/cm.
4. Anionic-CMC with an anionic degree of substitution of 0.4 and an intrinsic viscosity of 15 was dissolved in deionised water.
5. The CMC-attachment was carried out in accordance to Laine et al. (Laine, J. et al. (2000) Nordic Pulp and Paper Research Journal 15(5), page 520-526). Conditions during attachment: pulp concentration=20 gram/litre; temperature=120 °C; treatment time=2 hours; CaCI2-concentration=0.05 M; water=deionised water; CMC-dosage=80 mg CMC/g fibre.
6. After the CMC-attachment treatment, the pulp was washed with deionised water on a bϋchner funnel until the conductivity of the filtrate was below 5 μS/cm. 7. The pulp was then ion-exchanged into its sodium counter-ion form as described above in step 2 and 3.
8. The pulps (2.6 % concentration in deionised water) were then homogenised with one pass through a Microfluidizer M-1 10EH (Microfluidics Corp.) at an operating pressure of 1750 bar. The chambers that were used had an inner diameter of 200 μm and 100 μm.
Analysis
Conductometric Titration The attached amount of anionic CMC on the fibres was determined by conductometric titration. The conductometric titration measures the total amounts of anionic groups, e.g. carboxyl acid groups, in the pulps. Prior to the titration, the pulp was washed to different counter-ion form as follows.
1 . First the pulp was set to its hydrogen counter-ion form. A sample containing 2 g of dry pulp was dispersed in 1000 ml of deionised water and then 0.01 M HCI was added, fixing pH to 2. The excessive HCI was washed away after 30 minutes with deionised water on a bϋchner funnel until the conductivity was below 5 μS/cm.
2. Secondly, the pulp was set to its sodium counter-ion form. The pulp was dispersed in deionised water and then 0.001 M NaHCO3 was added, pH was set to 9 using NaOH. After 30 more minutes the excessive NaOH and the NaHCO3 were washed away with deionised water on a bϋchner funnel until the conductivity was below 5 μS/cm.
3. After this, the sample was once more set to its hydrogen counter ion form (se step 1 ) and washed to a conductivity below 5 μS/cm.
4. Finally, the total charge density of the pulps were determined with conductometric titration according to the procedure described by Katz et al. "The determination of strong and acidic groups in sulfite pulps", svensk papperstidning no. 6/1984, page R48-R53.
The amount of attached CMC was evaluated by comparing the result from the anionic CMC pulps with the result from reference pulp, the amount of attached CMC could be determined.
Nitrogen Analysis
In order to evaluate the attached amount of amphoteric CMC, the nitrogen content in the pulps were measured. This was done since the amphoteric CMC's cationic groups contained nitrogen. The apparatus used was an Antek 7000 (Antek Instruments, Inc.) and the method was Pyro-chemiluminescence (combustion temperature = 1050 °C). Before the actual measurements, a calibration curve was made with the amphoteric CMC in order to know how much nitrogen was present per mg CMC.
Intrinsic Viscosity of CMC
The intrinsic viscosity of the CMCs was measured in deionised water with 0.1 M NaCI at a temperature of 25 °C.
Results
Figure imgf000013_0001
As can be seen in the table, it was not possible to homogenise the pulps without any CMC attachment due to clogging (Cases A and G). With the aid of amphoteric CMC it was possible to homogenise the pulp without clogging when the attachment level was above 23.6 mg/g (Cases C-F and H) and this resulted in an MFC gel. Lower attachment levels resulted in clogging (Case B). If the temperature during the CMC-attachment procedure was lowered to room temperature (Case I), no CMC was attached to the pulp and as a result it was not possible to homogenise due to clogging. In Cases J and K, anionic CMC was attached to the pulps. However, since the CMC was anionic the attachment level was lower and this made it impossible to make MFC. In Case J, sulphite pulp was used and this sample was possible to homogenise but did not result in a MFC gel. The dissolving pulp in Case K was not possible to homogenise due to clogging. All conditions in Case L, were the same as in Case J, but another anionic CMC was used instead. This CMC was easier to attach and as a result the attachment level was as high as 61 .6 mg/g. Since the amount of CMC was higher it was possible to homogenise this sample and thereby produce an MFC gel. However, to reach this level three times more CMC was needed than if amphoteric CMC was used (compare with Case C). In the appended figures 1 -7, the resulting products after homogenisation are shown.
Various embodiments of the present invention have been described above but a person skilled in the art realizes further minor alterations, which would fall into the scope of the present invention. The breadth and scope of the present invention should not be limited by any of the above-described exemplary embodiments, but should be defined only in accordance with the following claims and their equivalents. For example, any of the above- noted methods can be combined with other known methods. Other aspects, advantages and modifications within the scope of the invention will be apparent to those skilled in the art to which the invention pertains.
List of documents appearing in the description
WO2005080678
US 4,341 ,807
Laine et al. (Laine, J. et al. (2000) Nordic Pulp and Paper Research Journal 15(5), page 520- 526) and
Katz et al. "The determination of strong and acidic groups in sulfite pulps", svensk papperstidning no. 6/1984, page R48-R53.
Wagberg et al. "The Build-Up of Polyelectrolyte Multilayers of Microfibrillated Cellulose and Cationic Polyelectrolytes". Langmuir (2008), 24(3), 784-795.

Claims

Claims
1. Method for providing a nanocellulose involving modifying cellulose fibers wherein the method comprises the following steps: i) treating cellulose fibers for at least 5 minutes with an aqueous electrolyte-containing solution of an amphoteric carboxymethyl cellulose or a derivative thereof, preferably a low molecular amphoteric CMC or a CMC derivative thereof, whereby the temperature during the treatment is at least 509C, and at least one of the following conditions apply: A) the pH of the aqueous solution during the treatment lies in the interval of approximately 1 .5 - 4.5, preferably in the region 2 - 4; or
B) the pH of the aqueous solution during the treatment is higher than approximately 1 1 ; or
C) the concentration of the electrolyte in the aqueous solution lies in the interval of approximately 0.0001 -0.5 M, preferably approximately 0.001 -0.4 M, if the electrolyte has monovalent cations, or in the range of approximately 0.0001 -0.1 M, preferably approximately 0.0005-0.05 M, if the electrolyte has divalent cations, ii) adjusting the pH by using a basic and/or an acidic liquid into a pH range of from about 5 to about 13, preferably the pH is adjusted to a pH from about 6 to about 12, and iii) treating said material in a mechanical comminution device, thus providing said nanocellulose.
2. Method according to claim 1 , wherein condition C applies together of either condition A or condition B in step i).
3. Method according to claim 1 , wherein the amphoteric CMC derivative has an anionic molar substitution degree between 0.3 and 1.2.
4. Method according to claim 1 , wherein the CMC derivative has been cationized to a substitution degree between 0.00001 and 1.0, preferably 0.00001 and 0.4.
5. Method according to claim 4, wherein the cationization has been performed by the introduction of at least one ammonium function, preferably a secondary, tertiary or quaternary ammonium function, into the derivative.
6. Method according to claim 1 , wherein the cellulose fibres are treated for approximately 5 - 180 minutes.
7. Method according to claim 1 , wherein the temperature during the treatment is in excess of approximately 50 °C, preferably at least approximately 100 °C, and most preferred up to approximately 120 °C.
8. A method according to claim 1 wherein said cellulose fibres are contained in a pulp, preferably a sulphite pulp or kraft pulp.
9. A nanocellulose obtained by a method according to any one of claims 1 - 8.
10. Use of said nanocellulose according to claim 9 in cosmetic products, pharmaceutical products, food products, paper products, composite materials, coatings, hygiene/absorbent products, films, emulsion/dispersing agents, drilling muds and to enhance the reactivity of cellulose in the manufacture of regenerated cellulose or cellulose derivatives or in rheology modifiers.
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