CN104945517B - It is a kind of to prepare cellulose nano-fibrous method - Google Patents
It is a kind of to prepare cellulose nano-fibrous method Download PDFInfo
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Abstract
The invention discloses a kind of method for preparing cellulose nano-fibrous dispersion liquid, cellulosic material is disperseed in pH is 4~5 water system buffer solution systems, laccase, TEMPO is added, prepares laccase TEMPO oxidation systems；Oxygen, oxidation reaction 24~130 hours are persistently pumped into reaction system；After reaction terminates, centrifugation filters out supernatant, and supernatant is reused；The insoluble oxycellulose of water is precipitated as, is cleaned with deionized water to neutrality；Then add deionized water stirring and obtain oxycellulose water slurry, carry out homogenate and ultrasonically treated, it is oxidized cellulose nanofibers dispersion liquid that centrifugation, which obtains supernatant,.The present invention not only avoids pollution of the halogen to environment while oxidation efficiency is ensured, and the reaction system may be reused, the utilization rate of oxidation system is improved, oxidation effectiveness is homogeneous, cellulose nano-fibrous yield is improved, the nanofiber of high length-diameter ratio is can obtain.
Description
Technical field
The present invention relates to cellulose nano-fibrous preparation method technical field, and in particular to uses a kind of selective oxidation
System selective oxidation cellulose, and the method for preparing cellulose nano-fibrous dispersion liquid with reference to mechanical treatment, it is possible to enter one
Step prepares the materials such as nano-fiber film, gel by cellulose nano-fibrous dispersion liquid.
Background technology
Cellulose is content most abundant renewable organic substance on the earth, is converting light energy into of photosynthesis of plant
Learn the primary product of energy.The yield of worldwide inner cellulose is huge, wherein 89% native cellulose resource quilt
Various microbial degradation consumption, are eventually converted into carbon dioxide and water in nature.Followed although this is important carbon in nature
Ring, but for economic angle, this is undoubtedly the huge wasting of resources.
Cellulose is primarily present in the secondary wall of plant cell walls, such as timber and cotton-wool.In biosynthesis
Cheng Zhong, elongated nanoscale microfibre of the cellulose by diameter in 2-20nm is constituted.The elementary cell molecule of cellulose
Synthesis is strictly controlled by synthesis mechanism, and it is not the simply parallel surface for being distributed in cell, and accurately controlling
Certain anglec of rotation is formed under making mechanism.Due to planting species specific biosynthesis pattern, cellulosic molecule forms almost complete
Beautiful crystalline arrangement.These microfibres are mutually closely connected by hydrogen bond, so as to constitute the multilayered structure of cell membrane.From one
The doughnut of a spindle-type is presented in the cellulose that cell factory is extracted, and about 20-30 μm of diameter is about several millimeters.
Modern biotechnology research application
Cellulose is done modification to expand the application of cellulose products by different disposal technology.Wherein utilize fiber
It is a very promising direction that element, which is prepared cellulose nano-fibrous,.
Nanofiber, refers to diameter and reaches the larger filamentary material of nanoscale length, its diameter is generally less than 100nm.By
To with nanometer length is discussed in nanofiber is small, and the more typical material of physical and chemical properties of its own has had larger change,
Predominantly the following aspects：
1st, skin effect.The size of particle is smaller, and its surface area is bigger, and surface atom number, surface can increase sharply.Due to
Surface particle lacks the coordination of adjacent atom, there is many dangling bonds, thus surface can increase after become extremely unstable, it is easy to it
He combines atom, thus shows very strong activity.
2nd, small-size effect.The de Broglie wavelength of electronics is arrived with the wavelength of light wave, conducted when the size of particulate is small and super
Lead state coherence length transmission depth is approximate or more hour, its periodic boundary condition will be destroyed, sound, light, the electricity of particle
Magnetic, macroscopic property will all change, such as fusing point reduction, color separation discoloration, absorption ultraviolet, shielding electromagnetic wave.
3rd, quantum size effect.When particle size it is small to a certain extent when, the electron energy level near fermi level by standard even
It is continuous to be changed into discrete energy level, it was that the material of conductor is possible to be changed into insulator originally now, breeding, insulator is also possible to be changed into super
Conductor.
4th, the brass speculum, placed in the sun to generate enough heat to ignite dry gass channel effect of macroscopic quantum.Tunnel-effect refers to fine particle has the energy for running through potential barrier in any case
Power.
Prepare at present cellulose nano-fibrous main method have chemical hydrolysis, physicomechanical processes, biological bacterium synthesis,
Chemical artificial synthesized and five kinds of methods of electrostatic spinning.Wherein chemical method can be while surface-modified nano cellulose, imparting be received
Meter level cellulose crystals are with new function and characteristic；The structure of controllable nano-cellulose, crystalline form, particle diameter when bacterium living beings are synthesized
Distribution etc., easily realizes industrialization and commercialization；Physical mechanical method technique, equipment are simple, and nanofiber can be obtained simultaneously
Element and nano-cellulose compound；Artificial synthesized nano-cellulose is easiest to the structure, crystalline form, particle diameter point of nano-cellulose
Cloth etc.；Electrospinning process can prepare most thin nano-scale fiber at present.
Although nanofiber have many preparation methods, also there are many limitations：Chemical method needs to use strong acid hydrolysis,
High is required to consersion unit, reacted residue is reclaimed and handle difficult；It is complicated, time-consuming that bioanalysis prepares bacteria cellulose
Long, cost is high, price；Physical, which prepares fibrillation nano-cellulose, to be needed using special equipment and uses high pressure, energy
Consumption is higher, and the nano-cellulose particle diameter distribution of preparation is wide；Artificial synthesized molecular weight cellulose is small；Electrostatic spinning prepares micro-
Fine fibre cross section is big, and cross-sectional distribution is also very wide.Therefore research and development go out new simple, green, low energy consumption, it is quick, high
Effect to prepare nano-cellulose method very urgent.
Nearby, a kind of new method for preparing cellulose nano dispersion fluid is widely used.It applies a kind of nitre of stabilization
Acyl compounds (such as 2,2,6,6- tetramethyl piperidine -1- oxygen radicals, TEMPO) are used as oxidant selective oxidation primary hydroxyl
For aldehyde radical or carboxyl.In TEMPO medium oxidation systems, the oxidation performance of cellulose has gone out the oxidation effectiveness of high selectivity.
Need to utilize two kinds of compounds containing halogen of NaClO and NaBr in whole oxidation system, this is a drawback.
With the development of science and technology, the method for preparing cellulose nano-fibrous dispersion liquid can be more ripe, and is used as one
Emerging nano meter biomaterial is planted, nano-cellulose is increasingly subject to the extensive concern of all circles.It is expected that in the near future, Nanowire
Dimension element will develop into one big industry.
The content of the invention
Goal of the invention：For the deficiencies in the prior art, it is an object of the invention to provide one kind using laccase-
TEMPO oxidation system selective oxidation celluloses, the method that cellulose nano dispersion fluid is then prepared by mechanical treatment, to subtract
Pollution of the halogen to environment in few original oxidation system (TEMPO-NaBr-NaClO), improves recycling for oxidation system
Rate, it is cost-effective.
Technical scheme：For achieving the above object, the technical solution adopted by the present invention is as follows：
It is a kind of to prepare cellulose nano-fibrous method, comprise the following steps：
(1) cellulosic material is disperseed in pH is 4~5 water system buffer solution systems；
(2) laccase, TEMPO are added in the water slurry of cellulosic material, laccase-TEMPO oxidation systems are prepared；
(3) oxygen is persistently pumped into reaction system to ensure that oxygen-supply quantity can promote oxidation reaction to continue fully to enter
OK, reaction temperature is room temperature, oxidation reaction 24-130 hours；
(4) after reaction terminates, whole reaction system is placed in terminating reaction in frozen water；Centrifugation filters out supernatant, preserves to 4
DEG C refrigerator is to reuse；The insoluble oxycellulose of water is precipitated as, the insoluble oxidized fibre of eccentric cleaning water is carried out with deionized water
Element, until oxycellulose is cleaned to neutrality；
(5) insoluble oxycellulose of fetching water is added in deionized water, is stirred, is obtained oxycellulose aqueous suspension
Liquid；Repeat homogenate and ultrasonically treated, number of repetition 4-6 times to oxycellulose water slurry；It is outstanding after will be ultrasonically treated
Supernatant liquid is placed in a centrifuge centrifugation, and supernatant is oxidized cellulose nanofibers dispersion liquid.
In step (2), in the laccase-TEMPO oxidation systems of preparation, the enzyme activity amount ranges of laccase are 100~1000U/g
Cellulosic material.
Described laccase is laccase enzyme system, including fungal laccase and plant laccase etc..
Described cellulosic material is adopted to be prepared with the following method：
Paper pulp raw material is taken, is cleaned with distilled water to neutrality；Preparation mass fraction is 0.5%NaClO2Solution, by paper pulp plus
Enter NaClO2It is submerged completely to paper pulp in solution；To the NaClO for being soaked with paper pulp2Acetum is added in solution, by the pH of system
It is adjusted to less than 5；Then whole system is placed in water bath processing 2 hours in 70 DEG C of water-baths, during which entered in the ranks every 15-20 minutes
Have a rest stirring；Bleaching terminates, and bleached pulp is washed till into neutrality with distilled water, the paper pulp after being bleached.
Described cellulosic material source is bagasse pulp, bardwood pulp or softwood pulp etc..
The method for building up of laccase-TEMPO oxidation systems is as follows：
The a certain amount of distilled water for boiling more than 5 minutes is taken, the 0.1M water system buffer solutions for preparing that pH is 4-5 after room temperature are cooled to
(such as citric acid-sodium citrate buffer solution)；100mL buffer solutions are taken, 5mM TEMPO is added and is configured to TEMPO solution；It is separately added into
1g cellulosic materials and 100~1000U laccases；System is stirred with magnetic stirring apparatus, being pumped into oxygen makes reaction persistently enter
OK；Reaction temperature is room temperature, and the reaction time is 24~130 hours.
Compared with prior art, biology enzyme is combined by the present invention with conventional chemical oxidation system, proposes biology enzyme oxygen
The method that change system prepares cellulose nano-fibrous dispersion liquid, not only avoids halogen pair while oxidation efficiency is ensured
The pollution of environment, and the reaction system may be reused, and improve the utilization rate of oxidation system, oxidation effectiveness is homogeneous, carries
The yield of high-cellulose nanofiber, the degradation to cellulose is low, can obtain the nanofiber of high length-diameter ratio；For cellulose
The preparation of nanofiber provides new approaches and new method.
Brief description of the drawings
Fig. 1 is cellulose nano-fibrous atomic force microscopy diagram；Wherein, left figure is bardwood pulp, and right figure is bagasse pulp；
Fig. 2 is cellulosic material and oxycellulose X-ray diffractogram；
Fig. 3 is cellulose and the infrared figure of oxycellulose.
Embodiment：
Below in conjunction with specific embodiment, the invention will be further elaborated.Embodiment is for illustrative and not limiting hair
It is bright.Any those of ordinary skill in this area can do appropriate it will be appreciated that these embodiments do not limit the present invention in any way
Modification and without prejudice to the present invention essence and deviate the scope of the present invention.
In following examples, used assay method is as follows：
Determine the carboxyl-content of oxycellulose：The cellulose for weighing the oxidation of dry weight 0.1g laccase-TEMPO oxidation systems adds
Enter in 60mL distilled water, the pH of system is adjusted to more than 9 by addition 0.5mmol/L NaOH solution, is then continuously stirred 30 minutes
More than, cellulose is more preferably dispersed in system.System pH is adjusted to 2.5 by addition 0.5mol/L HCl solution, continuously stirs 10
Minute.Then the number of 0.05mol/L NaOH solution, every 30 seconds record pH and electric conductivity value is continuously added dropwise using pH titration systems
According to.When pH rises to more than 11, stop reaction.
Determine laccase activity：Prepare the 0.1mmol/L HAc-NaAc buffer solutions that pH is 4.5.Then ABTS is weighed to be dissolved in
0.5mmol/L ABTS solution is made in HAc-NaAc buffer solutions.3mL 0.5mmol/L ABTS solution is pipetted with liquid-transfering gun in rule
Lattice for 1cm cuvette in, be immediately placed in 50 DEG C of water-baths preheat 5 minutes.By the cuvette paper containing ABTS after preheating
Dry, 0.1mL (to be diluted guarantee curve in advance according to the height of enzyme activity in measurement range) enzyme liquid pipetted with liquid-transfering gun,
Pipette tips are stretched into inside ABTS and got after enzyme liquid, will be shaken 3-4 times above and below cuvette, after being allowed to uniform, be immediately placed in light splitting light
In degree meter, the change of 6 minutes internal absorbances (p) is determined at wavelength 420nm, absorbance per minute is recorded (with 0.1mmol/L
On the basis of HAc-NaAc buffer solutions).Enzyme activity is calculated：
That is laccase=Δs p × n × 0.21528
N represents the extension rate of enzyme liquid, extinction coefficient epsilon=3.6 × 104(M-1·cm-1)。
Embodiment 1：Bleach the preparation of bagasse pulp
Sulphite bagasse pulp is taken, is cleaned with distilled water to neutrality.Preparation mass fraction is 0.5%NaClO2
(sodium chlorite) solution, NaClO is added by paper pulp2It is submerged completely to paper pulp in solution.To the NaClO for being soaked with paper pulp2In solution
Acetum is added, the pH of system is adjusted to less than 5.Then whole system is placed in water bath processing 2 hours in 70 DEG C of water-baths,
Period carried out intermittent stirring every 15-20 minutes.After the completion of bleaching, bleached pulp is washed till neutrality with distilled water, bleached
Bagasse pulp afterwards, is placed in 4 DEG C of refrigerators and preserves.
Embodiment 2：Laccase-TEMPO systems aoxidize paper cellulose
Configure 0.1mol/L citric acid-sodium citrate buffer solutions.Weigh 5mM TEMPO and be dissolved in citric acid-sodium citrate
TEMPO solution is configured in buffer solution.Weigh dry weight 1g bleaching bagasse pulps to add in TEMPO solution, addition 100U laccases (come from
Trametes versicolor) add system.Room temperature lower open mouth is placed, and is continuously stirred with 200rpm rotating speed.React 130h
Afterwards, stirring is stopped.Reaction system is centrifuged 8 minutes with 10000 rpms, supernatant is poured onto in reagent bottle and collected, no
Molten thing addition distilled water continues eccentric cleaning 7 times, collects water-insoluble, as laccase-TEMPO oxidation systems oxycellulose.
The carboxyl-content for determining oxycellulose is 0.365mmol/g celluloses.After oxidation terminates, contained laccase activity is in system
9.3U。
Embodiment 3：Laccase-TEMPO systems aoxidize paper cellulose
Configure 0.1mol/L citric acid-sodium citrate buffer solutions.Weigh 5mM TEMPO and be dissolved in citric acid-sodium citrate
TEMPO solution is configured in buffer solution.Weigh dry weight 1g bleaching bagasse pulps to add in TEMPO solution, addition 1000U laccases (come
From Trametes versicolor) add system.Room temperature lower open mouth is placed, and is continuously stirred with 200rpm rotating speed.React 24h
Afterwards, stirring is stopped.Reaction system is centrifuged 8 minutes with 10000 rpms, supernatant is poured onto in reagent bottle and collected, no
Molten thing addition distilled water continues eccentric cleaning 7 times, collects water-insoluble, as laccase-TEMPO oxidation systems oxycellulose.
The carboxyl-content for determining oxycellulose is 0.637mmol/g celluloses.After oxidation terminates, contained laccase activity is in system
156.4U。
Embodiment 4：Laccase-TEMPO systems aoxidize paper cellulose
Configure 0.1mol/L citric acid-sodium citrate buffer solutions.Weigh 5mM TEMPO and be dissolved in citric acid-sodium citrate
TEMPO solution is configured in buffer solution.Weigh dry weight 1g bleached hardwoods paper pulp (preparation method be the same as Example 1) and add TEMPO solution
In, addition 100U laccases (coming from Rhus vernicfera) add system.Room temperature lower open mouth is placed, and is connected with 200rpm rotating speed
Continuous stirring.React after 130h, stop stirring.Reaction system is centrifuged 8 minutes with 10000 rpms, supernatant is poured onto
Collected in reagent bottle, insoluble matter addition distilled water continues eccentric cleaning 7 times, collect water-insoluble, as laccase-TEMPO oxidations
System oxycellulose.The carboxyl-content for determining oxycellulose is 0.348mmol/g celluloses.After oxidation terminates, in system
Contained laccase activity is 8.7U.
Embodiment 5：Laccase-TEMPO systems aoxidize paper cellulose
Configure 0.1mol/L citric acid-sodium citrate buffer solutions.Weigh 5mM TEMPO and be dissolved in citric acid-sodium citrate
TEMPO solution is configured in buffer solution.Weigh dry weight 1g bleached hardwoods paper pulp to add in TEMPO solution, addition 500U laccases (come from
Rhus vernicfera) add system.Room temperature lower open mouth is placed, and is continuously stirred with 200rpm rotating speed.React after 72h, stop
Stirring.Reaction system is centrifuged 8 minutes with 10000 rpms, supernatant is poured onto in reagent bottle and collected, insoluble matter addition
Distilled water continues eccentric cleaning 7 times, collects water-insoluble, as laccase-TEMPO oxidation systems oxycellulose.Determine oxidation
The carboxyl-content of cellulose is 0.523mmol/g celluloses.After oxidation terminates, contained laccase activity is 93.4U in system.
Embodiment 6：Laccase-TEMPO systems aoxidize paper cellulose
Configure 0.1mol/L citric acid-sodium citrate buffer solutions.Weigh 5mM TEMPO and be dissolved in citric acid-sodium citrate
TEMPO solution is configured in buffer solution.Weigh dry weight 1g bleached softwood pulps to add in TEMPO solution, addition 500U laccases (come from
Pleuratus ostreatus) add system.Room temperature lower open mouth is placed, and is continuously stirred with 200rpm rotating speed.React after 72h,
Stop stirring.Reaction system is centrifuged 8 minutes with 10000 rpms, supernatant is poured onto in reagent bottle and collected, insoluble matter
Add distilled water and continue eccentric cleaning 7 times, collect water-insoluble, as laccase-TEMPO oxidation systems oxycellulose.Determine
The carboxyl-content of oxycellulose is 0.596mmol/g celluloses.After oxidation terminates, contained laccase activity is 87.6U in system.
Embodiment 7：The preparation of cellulose nano dispersion fluid
Take dry weight 0.2g laccase-TEMPO oxidation systems to aoxidize paper cellulose to add in 100mL distilled water, continuously stir
Cellulose is set to be uniformly dispersed.Then use carried out after refiner homogenized, processing it is ultrasonically treated.Recycle at homogenate and ultrasound
Reason 6 times.The cellulose suspension handled is centrifuged 8 minutes with 10000 rpms of rotating speed, is toppled over supernatant, is as aoxidized
The nano dispersion fluid of cellulose.
Embodiment 8
Laccase-TEMPO systems oxidation paper cellulose prepared by optional above-described embodiment carries out performance measurement, as a result such as
Under：
1) cellulose nano-fibrous atomic force microscopy diagram is as shown in figure 1, left figure is bardwood pulp, and right figure is bagasse
Slurry.As shown in Figure 1, the nanofiber dispersion that prepared by this oxidation system is uniform, and nanofibers of dimensions has very high point with fibrous raw material
System.Left figure is the nanofiber prepared by raw material of bardwood pulp, and length reaches micron level, a diameter of 4-20 nanometers；Right figure
The nanofiber prepared by raw material of bagasse pulp, length is more than 1 micron, and even up to tens microns having, diameter exists
3-16 nanometers.
2) cellulosic material and oxycellulose X ray diffracting spectrum are as shown in Figure 2, it is seen that cellulose is sent out in oxidizing process
Raw degraded, amorphous region short texture is more easy to degrade, therefore the crystallinity of cellulose increases after oxidation.
3) cellulose and oxycellulose infared spectrum are as shown in figure 3, in 1740cm-1There is carboxyl in place, oxycellulose
Absworption peak, it was demonstrated that the feasibility of laccase-TEMPO oxidation systems.
Claims (5)
1. a kind of method for preparing cellulose nano-fibrous dispersion liquid, it is characterised in that comprise the following steps：
(1) cellulosic material is disperseed in pH is 4~5 water system buffer solution systems；
(2) water slurry, laccase, TEMPO of cellulosic material are taken, laccase-TEMPO oxidation systems are prepared；
(3) oxygen is persistently pumped into reaction system to ensure that oxygen-supply quantity can promote oxidation reaction to continue abundant progress, instead
It is room temperature, oxidation reaction 24~130 hours to answer temperature；
(4) after reaction terminates, whole reaction system is placed in terminating reaction in frozen water；Centrifugation filters out supernatant, preserves to 4 DEG C of ice
Case is to reuse；The insoluble oxycellulose of water is precipitated as, the insoluble oxycellulose of eccentric cleaning water is carried out with deionized water, directly
Extremely oxycellulose is cleaned to neutrality；
(5) insoluble oxycellulose of fetching water is added in deionized water, is stirred, is obtained oxycellulose water slurry；
Repeat homogenate and ultrasonically treated, number of repetition 4-6 times to oxycellulose water slurry；Suspension after will be ultrasonically treated
Centrifugation is placed in a centrifuge, supernatant is oxidized cellulose nanofibers dispersion liquid.
2. the method according to claim 1 for preparing cellulose nano-fibrous dispersion liquid, it is characterised in that：In step (2),
In the laccase-TEMPO oxidation systems of preparation, the enzyme activity amount ranges of laccase are 100~1000U/g cellulosic materials.
3. the method according to claim 1 or 2 for preparing cellulose nano-fibrous dispersion liquid, it is characterised in that：Described
Laccase is laccase enzyme system, including fungal laccase and plant laccase.
4. the method according to claim 1 for preparing cellulose nano-fibrous dispersion liquid, it is characterised in that：In step (1),
Described cellulosic material is adopted to be prepared with the following method：
Sulfite pulp is taken, is cleaned with distilled water to neutrality；Preparation mass fraction is 0.5%NaClO2Solution, paper pulp is added
NaClO2It is submerged completely to paper pulp in solution；To the NaClO for being soaked with paper pulp2Acetum is added in solution, the pH of system is adjusted
To less than 5；Then whole system is placed in water bath processing 2 hours in 70 DEG C of water-baths, during which carries out interval every 15-20 minutes
Stirring；Bleaching terminates, and bleached pulp is washed till into neutrality with distilled water, the bagasse pulp after being bleached.
5. the method according to claim 1 for preparing cellulose nano-fibrous dispersion liquid, it is characterised in that：Described fiber
Plain raw material sources are bagasse pulp, bardwood pulp or softwood pulp.
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| CN105254903A (en) * | 2015-11-13 | 2016-01-20 | 南京林业大学 | Method for preparing oxidated chitin nanofiber dispersion liquid |
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| CN107286259B (en) * | 2016-03-31 | 2019-08-02 | 新材料与产业技术北京研究院 | A kind of preparation method of nano-cellulose |
| CN106638088B (en) * | 2016-11-11 | 2018-03-16 | 南京林业大学 | A kind of method for preparing nano-cellulose using neutral sulfite hydrogen salt preprocessing plant fibre |
| CN106521667A (en) * | 2016-11-15 | 2017-03-22 | 青岛大学 | Cellulose filament and preparation method thereof |
| CN106758263B (en) * | 2017-04-13 | 2019-03-01 | 江南大学 | A kind of method that bioanalysis prepares easy decontamination cotton products |
| CN107236049A (en) * | 2017-06-29 | 2017-10-10 | 东北农业大学 | A kind of nano-cellulose and preparation method thereof |
| RU2708307C1 (en) * | 2019-06-13 | 2019-12-05 | Федеральное государственное бюджетное учреждение науки Институт высокомолекулярных соединений Российской академии наук | Method of producing bacterial cellulose nanofibers |
| CN111019193A (en) * | 2019-11-19 | 2020-04-17 | 南开大学 | Preparation method of modified nanofiber silk aqueous solution |
| CN111122429B (en) * | 2019-12-31 | 2022-04-22 | 华南理工大学 | Rapid detection method for nanocellulose conversion degree |
| CN111763266A (en) * | 2020-02-28 | 2020-10-13 | 南京理工大学 | Based on TEMPO/laccase/O2Method for preparing bacterial cellulose nano-fiber by oxidation system |
| CN112079935B (en) * | 2020-08-26 | 2023-01-31 | 广东工业大学 | Preparation method of nano-cellulose |
| CN115197467A (en) * | 2021-04-13 | 2022-10-18 | 香港纺织及成衣研发中心 | Method for separating polyester and cotton in blended fabric |
| CN113845667A (en) * | 2021-11-01 | 2021-12-28 | 江南大学 | Preparation method and application of oxidized nano cellulose pickering emulsion |
| CN114671958B (en) * | 2022-04-02 | 2022-12-16 | 华南理工大学 | Dialdehyde nanocellulose with high degree of substitution and preparation method thereof |
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| CN101874043A (en) * | 2007-11-26 | 2010-10-27 | 国立大学法人东京大学 | Cellulose nanofiber and process for production thereof, and cellulose nanofiber dispersion |
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