CN103060937B - Preparation method of cellulose nanofiber - Google Patents
Preparation method of cellulose nanofiber Download PDFInfo
- Publication number
- CN103060937B CN103060937B CN201310034133.6A CN201310034133A CN103060937B CN 103060937 B CN103060937 B CN 103060937B CN 201310034133 A CN201310034133 A CN 201310034133A CN 103060937 B CN103060937 B CN 103060937B
- Authority
- CN
- China
- Prior art keywords
- cellulose
- solution
- fibrous
- water
- nano
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention discloses a preparation method of cellulose nanofiber. The method comprises the following steps of: dissolving cellulose to obtain a cellulose solution; slowly adding a nonsolvent into the cellulose solution under stirring, thus enabling the cellulose to gradually regenerate from the solution; removing substances except for the cellulose and water, and re-dispersing the solution to obtain cellulose nanofiber dispersion liquid; and removing dispersion media, thus obtaining the cellulose nanofiber. The cellulose nanofiber has a cellulose II type crystal structure, and the diameter of the nanofiber is less than 50 nanometers. The cellulose nanofiber prepared by the method is long and is high in strength.
Description
Technical field
The present invention relates to a kind of cellulose nano-fibrous preparation method and by the method obtain cellulose nano-fibrous, belong to natural polymer field, also belong to agricultural engineering field.
Technical background
Cellulose is renewable plant resources the abundantest on the earth, the natural polymer be made up of β-(1 → 4)-D-Glucose, is the main component of plant cell wall.Cellulose has the features such as hydrophily, chemical reactivity, biocompatibility and biological degradability.And nano-cellulose is except inheriting cellulosic above-mentioned character, also there is very high specific area, degree of crystallinity and modulus, be deemed to be the natural polymer subbundle of excellent combination property for a long time always.Compared with cellulose nano-fibrous and general inorganic nano reinforcing material, the feature such as they have renewable, wide material sources, power consumption is low, cost is low, density is low, and surface has many hydroxyls to participate in graft reaction.The maximum Young's modulus value of natural plant cellulose up to 128GPa, higher than the 70GPa of metallic aluminium and the 76Gpa of glass fibre.Its ultimate tensile strength is about 17.8GPa, is 7 times of iron and steel.Usually, Cellulose nanocrystal must and nanofiber directly or after surface modification, be scattered in natural polymer or synthesize in macromolecule, be widely used in improving (Biomacromolecules, 2009,10,425 such as the mechanical property of polymeric material and thermal property; Macromolecules, 1995,28,6365; Prog.Polym.Sci., 1999,24,221).In addition, cellulose nano-fibrously also can be used for the fields such as food, cosmetics, water treatment, packaging, construction material.Because it has good biocompatibility, in the field such as biological medicine, organizational project, also there is potential application prospect.
Cellulose macromolecule is joined together to form proto-fibrils dimension by hydrogen bond, and it has crystal region and amorphous area.Several proto-fibrils dimension forms microfibril, and forming fibrillation further, diameter is some tens of pm, and they are insoluble with water and common organic solvents, therefore owing to there is strong intermolecular hydrogen bonding effect, the state of nanofiber can not be dispersed into easily.Cellulose nano-fibrous preparation can take biological synthesis method, namely bacterium in the presence of oxygen, the gel of the continuous nano-fibre cellulose fiber composition being 20-100nm for carbon source synthesis diameter with low molecular weight D-Glucose, be called Nano bacteria cellulose (bacterial nanocellulose) (Prog.Polym.Sci., 2001,26,1561).But, due to its productive rate of source extreme influence of bacterial strain in bacteria cellulose incubation, and require strict to nutrient solution source, composition and cultivation temperature, and need the time of more than two weeks, and be not suitable for a large amount of production and application.More cellulose nano-fibrous separation from timber and agriculture and forestry organic waste material mainly through enzyme, chemistry and physical means obtains nano-cellulose.If fibrillation cellulose (microfibrillated cellulose) adopts the mechanical treatment modes such as high pressure homogenization, microjet or extra-fine grinding; desmoenzyme treatment technology or 2; 2; 6; the width that 6-tetramethyl piperidine oxygen radical (TEMPO) method for oxidation obtains is 5-60nm, and length is cellulose nano-fibrous (Biomacromolecules, 2004 that 100nm arrives several microns; 5,1983; Cellulose, 2005,12,305; Biomacromolecules, 2006,7,1687; Biomacromolecules, 2009,10,1992); Nanocrystalline cellulose (nanocrystalline cellulose) is under mechanical agitation and ultrasonic wave added, the polysaccharide of fiber surface and cellulosic amorphous portion is combined in by acid hydrolysis removing, obtain the bar-shaped avicel cellulose (J.Mater.Sci. that width is 5-70nm, length is 100-300nm, 2010,45,1-33).In addition; can also by cellulose dissolution at N-methylmorpholine-oxide (NMMO), N; in N-dimethylacetylamide/lithium chloride (LiCl/DMAc), 1-allyl-3-methylimidazole villaumite (BmimCl)/DMSO and 1-butyl-3-methylimidazole villaumite (AmimCl)/DMSO; then the method for electrostatic spinning is utilized to obtain cellulose nano-fibrous (Polymer; 2006; 47,5097; J.Appl.Polym.Sci., 2005,98,1855; Cellulose, 2010,17,223; Polymer, 2008,49,2911).But in the above-mentioned methods, the process of high pressure homogenizer needs to consume a large amount of energy, is disadvantageous in cost.Further, the diameter also heterogeneity of the cellulose fento of acquisition, the usually crude fibre of residual diameter more than 1 μm.On the other hand, the cellulosic fiber lengths that acid hydrolysis process obtains can shorten, and is difficult to the shape keeping fiber.TEMPO method for oxidation relates to expensive TEMPO and reclaims, and produces Cl
2etc. chloride noxious material.Electrospinning process production nanofiber is difficult to a large amount of production by the restriction of stability and production efficiency.Due to the difference of originate difference and processing method, cellulose nano-fibrous size is also different.Therefore, effectively reduce the energy consumption of nanofiber preparation process, shorten the production cycle, obtain the focus that stable nanofiber always is concern simultaneously.
Inventor herein the patent No. be ZL03128386.1, ZL200310111567.8, ZL200410012682.4 and 200310111447.8 patent in propose the NaOH/ urea, NaOH/ thiocarbamide, LiOH/ urea and the cellulosic method of LiOH/ thiourea solution rapid solution that utilize low temperature precooling.The method is that under low temperature, cellulose macromolecule and small solvent molecule are formed by hydrogen bond action self assembly with urea is the vermiform semi-rigid chain conformation that shell surrounds cellulose and NaOH compound; destroy in cellulosic molecule and intermolecular hydrogen bonding effect and dissolve (Macromolecules; 2008; 41,9345; ChemPhysChem, 2007,8,1572; J.Polym.Sci.Pol.Phys., 2006,44,3093; Macromol.Biosci., 2005,5,539).Can cellulose solution be obtained according to the method, and prepare (Adv.Mater., 2007,19,821 such as regenerated celulose fibre (diameter some tens of pm), film, intermingling material, composite by the tape casting, wet spinning process; Macromol.Rapid Commun., 2004,25,1558; Biomacromolecules, 2009,10,1597; J.Membr.Sci., 2006,279,246).But because the cellulose macromolecule in solution is mutually entangled, in the above-mentioned methods, the process that cellulose regenerates from solution is very fast, all cannot obtain cellulose nano-fibrous.
Summary of the invention
Technical problem to be solved by this invention is to overcome the deficiencies in the prior art, provides a kind of fast and stable to prepare cellulose nano-fibrous method, and the method prepare cellulose nano-fibrous.
The cellulose nano-fibrous method of preparation provided by the present invention is:
Cellulose dissolution is obtained cellulose aqueous solution, in cellulose solution, under agitation add water-soluble non-solvent makes cellulose born again from solution gradually, then by the separating substances removing beyond cellulose and water, again dispersion obtains cellulose nano-fibrous suspension, and dry removing decentralized medium just can obtain cellulose nano-fibrous.
As above-mentioned cellulose origin, can be separated the paper pulp, bamboo pulp, cotton pulp, straw pulp, jute pulp etc. from trees, bamboo, cotton, careless class, crudefiber crop and other higher plant, and be separated from one or more of the refined cellulose of animal, bacterium.
The preparation method of above-mentioned cellulose solution, can adopt the method according to known technology and have no particular limits.Such as, described cellulose solution is obtained in aqueous alkali, Jian – aqueous solution of urea, Jian – thiourea solution Huo Jian – Niao Su – thiourea solution by cellulose dissolution, and described alkali refers to one or both of NaOH and LiOH.
As one preferably, cellulose solution is obtained in NaOH/ aqueous solution of urea or LiOH/ aqueous solution of urea by cellulose dissolution.
Preferred as another, described cellulose solution is cooled to 0～–, 15 ° of C with the dicyandiamide solution that the water of 5 ~ 10wt%NaOH, 0.1 ~ 20wt% urea and surplus is formed, dissolving cellulos and obtaining.
Preferred as another, described cellulose solution is cooled to 0～–, 15 ° of C with the dicyandiamide solution that the water of 3 ~ 8wt%LiOH, 0.1 ~ 20wt% urea and surplus is formed, dissolving cellulos and obtaining.
In the step of dissolving cellulos, the concentration of cellulose aqueous solution has no particular limits, as long as solvent can fully dissolve.Usually, preferably make its concentration at below 5wt%.
Described water-soluble non-solvent refers to water or water-soluble salting liquid, alcohols, ketone, acids, anhydrides, Ammonia, ester class, or the mixture of aforementioned various solvent.In above-named solvent, preferably use water and water-soluble alcohols, acids, ammoniac compounds, more preferably use water, methyl alcohol, ethanol, hydrochloric acid, sulfuric acid, acetic acid or ammoniacal liquor.
Above-mentioned stirring is preferably mechanicalness and stirs, according to such method, and can high efficiency and at low cost to cellulose regenerated process process.
In the preparation process in accordance with the present invention, between regeneration and dispersion steps, the separating substances beyond cellulose nano-fibrous and water is excluded outside system, as long as the unit operations of this object can be realized, then can use arbitrary method, such as centrifugal, dialysis, filtration etc.
Cellulose nano-fibrous suspension can be obtained in media as well by by the cellulose nano-fibrous dispersion of dissolving, regeneration obtains.
For the medium again disperseed, usual water is preferred.Water-soluble organic solvent can also be used as required in addition to water, as alcohols (methyl alcohol, ethanol, isopropyl alcohol, isobutanol, sec-butyl alcohol, the tert-butyl alcohol, ethylene glycol, glycerol etc.), ethers (oxolane, 1,4-dioxane etc.), ketone (acetone), ester class (ethyl acetate), N, dinethylformamide, N, N-dimethylacetylamide, methyl-sulfoxide etc., or the mixture of aforementioned various solvent.
Various dispersal device can be used as the dispersal device for dispersion steps.Such as, the dispersal device such as domestic stirrer, cell crushing instrument, ultrasonic homogenizer, high pressure homogenizer, screw extruder, stone mill can be used.If use the such brute force of homogenizer and there is the device of making beating ability, then can obtain less cellulose nano-fibrous of size more efficiently.
Removing decentralized medium in the cellulose nano-fibrous suspension obtained by dispersion steps again just can obtain involved in the present invention cellulose nano-fibrous.Can adopt and remove decentralized medium according to the method for known technology and drying device and have no particular limits.Such as, by utilize freeze drying plant, roller drier, spray dryer carry out constant pressure and dry and freeze drying removing liquid medium obtain cellulose nano-fibrous.Or carry out using carbon dioxide, methyl alcohol, ethanol, acetone etc. as supercritical fluid critical point drying or supercritical drying removing liquid medium obtain cellulose nano-fibrous.
Again be distributed in decentralized medium for making dry rear cellulose nano-fibrous can being more prone to obtained, can also be mixed into water-soluble high-molecular compound (especially can form the synthesis macromolecule, carbohydrate, polysaccharide, protein etc. of hydrogen bond) in cellulose nano-fibrous suspension, water-soluble high-molecular compound can comprise polyvinyl alcohol, polyethylene glycol, polyacrylamide, Carboxymethyl Cellulose, hydroxyethylcellulose, hydroxypropyl cellulose, methylcellulose, ethyl cellulose, starch, alginic acid etc.
After dry, the cellulose nano-fibrous of acquisition can be distributed in decentralized medium again.
Present invention also offers a kind of newly cellulose nano-fibrous, the diameter of fiber at below 50nm, and has cellulose II type crystal structure.
Of the present invention cellulose nano-fibrous through finishing and with the polymeric material compound tenses such as resin, show excellent dispersiveness in the polymeric material.In the composite, cellulose nano-fibrously play enhancing effect, significantly can improve mechanical property and the thermal property of polymer composites.Prepared by the inventive method cellulose nano-fibrously also can be used for the fields such as food, cosmetics, water treatment, packaging, construction material, biological medicine, organizational project.
In preparation method of the present invention, first utilize cellulose solvent destroy cellulose macromolecule molecule in and intermolecular hydrogen bonding, in the solution because solvation forms the cellulosic molecule chain conformation of nanoscale, slow interpolation non-solvent can make the nanometer cellulosic molecule chain conformation in solution be kept, so can not form large aggregation.Cellulose nano-fibrous diameter prepared by the present invention is at below 50nm, and there is cellulose II type crystal structure, what obtain with bacteria cellulose, TEMPO oxidizing process and acid hydrolysis process cellulose nano-fibrously has visibly different crystal structure, is unexistent in prior art.
Accompanying drawing explanation
Fig. 1 left side is the photo of cellulose nano-fibrous aqueous dispersions;
Fig. 1 right side be centrifugal after the photo of gelatinous cellulose nanofiber that obtains.
Fig. 2 is cellulose nano-fibrous electron scanning micrograph.
Fig. 3 is cellulose nano-fibrous X-ray diffraction spectrogram.
Detailed description of the invention
Below will illustrate the present invention by embodiment, but the protection domain that these specific embodiments do not limit the present invention in any way.The present embodiment raw material used is known compound, can commercially buy.
Embodiment 1
The dicyandiamide solution formed with the water of 5 ~ 10wt%NaOH, 0.1 ~ 20wt% urea and surplus is cooled to 0～–, 15 ° of C, adds cellulose stirring and dissolving and obtain 50g0.5wt% cellulose solution.In cellulose solution, under agitation slowly drip distilled water until cellulose holomorphosis from solution out, obtains cellulose nano-fibrous suspension.Cellulose nano-fibrous suspension is placed in bag filter dialysis to neutral, then continues process 10 minutes with cell crushing instrument, namely obtain cellulose nano-fibrous aqueous dispersions.White fluffy is obtained cellulose nano-fibrous through freeze drying.
Embodiment 2
The dicyandiamide solution formed with the water of 5 ~ 10wt%NaOH, 0.1 ~ 20wt% urea and surplus is cooled to 0～–, 15 ° of C, adds cellulose stirring and dissolving and obtain 1wt% cellulose solution.In cellulose solution, under agitation slowly drip methyl alcohol until cellulose holomorphosis from solution out, obtains cellulose nano-fibrous suspension.Cellulose nano-fibrous suspension is placed in bag filter dialysis to neutral, then continues process 10 minutes with homogenizer, namely obtain cellulose nano-fibrous aqueous dispersions.White fluffy is obtained cellulose nano-fibrous through freeze drying.
Embodiment 3
The dicyandiamide solution formed with the water of 5 ~ 10wt%NaOH, 0.1 ~ 20wt% urea and surplus is cooled to 0～–, 15 ° of C, adds cellulose stirring and dissolving and obtain 1wt% cellulose solution.In cellulose solution, under agitation slowly drip hydrochloric acid until cellulose holomorphosis from solution out, obtains cellulose nano-fibrous suspension.Cellulose nano-fibrous suspension is placed in bag filter dialysis to neutral, then continues process 10 minutes with homogenizer, namely obtain cellulose nano-fibrous aqueous dispersions.White fluffy is obtained through critical point drying more cellulose nano-fibrous after water being replaced into ethanol.
Embodiment 4
The dicyandiamide solution formed with the water of 5 ~ 10wt%NaOH, 0.1 ~ 20wt% urea and surplus is cooled to 0～–, 15 ° of C, adds cellulose stirring and dissolving and obtain 3wt% cellulose solution.In cellulose solution, under agitation slowly drip ethanol until cellulose holomorphosis from solution out, obtains cellulose nano-fibrous suspension.After centrifugal for cellulose nano-fibrous suspension, remove supernatant, then add distilled water washing.Repeated centrifugation-washing step is until suspension is neutral.Then continue process 10 minutes with cell crushing instrument, obtain cellulose nano-fibrous aqueous dispersions.As shown in Figure 1, cellulose nano-fibrous aqueous dispersions is even milk-white coloured suspension (Fig. 1 left), cellulose nano-fibrously after centrifugal precipitates, and obtains gelatinous cellulose nanofiber (Fig. 1 is right).Sem observation finds, cellulose nano-fibrous diameter is at below 50nm (Fig. 2).Cellulose nano-fibrous and the native cellulose as raw material obtained by preparation method of the present invention has diverse crystal structure.Learn from X-ray diffraction spectrogram, cellulose nano-fibrous crystal structure is cellulose II type, and degree of crystallinity obviously declines (Fig. 3).
Embodiment 5
The dicyandiamide solution formed with the water of 5 ~ 10wt%NaOH, 0.1 ~ 20wt% urea and surplus is cooled to 0～–, 15 ° of C, adds cellulose stirring and dissolving and obtain 3wt% cellulose solution.In cellulose solution, under agitation slowly drip hydrochloric acid until cellulose holomorphosis from solution out, obtains cellulose nano-fibrous suspension.By cellulose nano-fibrous suspension sand core funnel filtration under diminished pressure, distilled water washing is until neutral.Then continue process 10 minutes with cell crushing instrument, namely obtain cellulose nano-fibrous aqueous dispersions.
Embodiment 6
The dicyandiamide solution formed with the water of 5 ~ 10wt%NaOH, 0.1 ~ 20wt% urea and surplus is cooled to 0～–, 15 ° of C, adds cellulose stirring and dissolving and obtain 3wt% cellulose solution.In cellulose solution, under agitation slowly drip ammoniacal liquor until cellulose holomorphosis from solution out, obtains cellulose nano-fibrous suspension.By cellulose nano-fibrous suspension sand core funnel filtration under diminished pressure, distilled water washing is until neutral.Then continue process 10 minutes with cell crushing instrument, namely obtain cellulose nano-fibrous aqueous dispersions.
Embodiment 7
The dicyandiamide solution formed with the water of 3 ~ 8wt%LiOH, 0.1 ~ 20wt% urea and surplus is cooled to 0～–, 15 ° of C, adds cellulose stirring and dissolving and obtain 2wt% cellulose solution.In cellulose solution, under agitation slowly drip ethanol until cellulose holomorphosis from solution out, obtains cellulose nano-fibrous suspension.After centrifugal for cellulose nano-fibrous suspension, remove supernatant, then add distilled water washing.Repeated centrifugation-washing step is until suspension is neutral.Then continue process 10 minutes with cell crushing instrument, obtain cellulose nano-fibrous aqueous dispersions.In cellulose nano-fibrous aqueous dispersions, add 3wt% polyvinyl alcohol, obtain white fluffy through freeze drying cellulose nano-fibrous.
Embodiment 8
The dicyandiamide solution formed with the water of 3 ~ 8wt%LiOH, 0.1 ~ 20wt% urea and surplus is cooled to 0～–, 15 ° of C, adds cellulose stirring and dissolving and obtain 3wt% cellulose solution.In cellulose solution, under agitation slowly drip acetic acid until cellulose holomorphosis from solution out, obtains cellulose nano-fibrous suspension.After centrifugal for cellulose nano-fibrous suspension, remove supernatant, then add distilled water washing.Repeated centrifugation-washing step is until suspension is neutral.Add ethanol and continue process 10 minutes with cell crushing instrument, obtaining cellulose nano-fibrous alcohol dispersion liquid.
Embodiment 9
The dicyandiamide solution formed with the water of 3 ~ 8wt%LiOH, 0.1 ~ 20wt% urea and surplus is cooled to 0 ~-15 ° of C, adds cellulose stirring and dissolving and obtain 3wt% cellulose solution.In cellulose solution, under agitation slowly drip sulfuric acid until cellulose holomorphosis from solution out, obtains cellulose nano-fibrous suspension.After centrifugal for cellulose nano-fibrous suspension, remove supernatant, then add distilled water washing.Repeated centrifugation-washing step is until suspension is neutral.Then continue process 10 minutes with cell crushing instrument, obtain cellulose nano-fibrous aqueous dispersions.White fluffy is obtained cellulose nano-fibrous through freeze drying.
Embodiment 10
The dicyandiamide solution formed with the water of 3 ~ 8wt%LiOH, 0.1 ~ 20wt% urea and surplus is cooled to 0～–, 15 ° of C, adds cellulose stirring and dissolving and obtain 5wt% cellulose solution.In cellulose solution, under agitation slowly drip ammoniacal liquor until cellulose holomorphosis from solution out, obtains cellulose nano-fibrous suspension.After centrifugal for cellulose nano-fibrous suspension, remove supernatant, then add distilled water washing.Repeated centrifugation-washing step is until suspension is neutral.Then continue process 20 minutes with cell crushing instrument, obtain cellulose nano-fibrous aqueous dispersions.White fluffy is obtained cellulose nano-fibrous through freeze drying.
Claims (3)
1. a cellulose nano-fibrous preparation method, is characterized in that:
Cellulose dissolution is obtained cellulose aqueous solution, and described cellulose aqueous solution is cooled to 0～– 15 with the dicyandiamide solution that the water of 5 ~ 10 wt% NaOH, 0.1 ~ 20 wt% urea and surplus is formed
oc, dissolving cellulos and obtaining, or described cellulose aqueous solution is cooled to 0～– 15 with the dicyandiamide solution that the water of 3 ~ 8 wt% LiOH, 0.1 ~ 20 wt% urea and surplus is formed
oc, dissolving cellulos and obtaining;
In cellulose solution, under agitation add water or water-soluble salt, alcohols, ketone, acids, anhydrides, Ammonia or ester class, or the mixture of aforementioned various material, make cellulose born again from solution gradually, then by the separating substances removing beyond cellulose and water, again dispersion obtains cellulose nano-fibrous suspension, and dry removing decentralized medium just can obtain cellulose nano-fibrous.
2. preparation method according to claim 1, is characterized in that: in cellulose solution, add water, methyl alcohol, ethanol, hydrochloric acid, sulfuric acid, acetic acid or ammoniacal liquor, makes cellulose born again from solution gradually.
3. preparation method according to claim 1, is characterized in that: for the medium again disperseed, for water or water-soluble alcohols, ethers, ketone, ester class,
n,N– dimethyl formamide,
n,N– dimethylacetylamide, methyl-sulfoxide, or the mixture of aforementioned various material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310034133.6A CN103060937B (en) | 2013-01-29 | 2013-01-29 | Preparation method of cellulose nanofiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310034133.6A CN103060937B (en) | 2013-01-29 | 2013-01-29 | Preparation method of cellulose nanofiber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103060937A CN103060937A (en) | 2013-04-24 |
| CN103060937B true CN103060937B (en) | 2015-06-10 |
Family
ID=48103821
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310034133.6A Active CN103060937B (en) | 2013-01-29 | 2013-01-29 | Preparation method of cellulose nanofiber |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103060937B (en) |
Families Citing this family (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103230355B (en) * | 2013-05-06 | 2015-01-28 | 珠海市红旌发展有限公司 | Sunscreen cream cosmetic composition containing nano crystal cellulose |
| AT515174B1 (en) * | 2013-10-15 | 2019-05-15 | Chemiefaser Lenzing Ag | Cellulose suspension, process for its preparation and use |
| CN103757729B (en) * | 2013-12-28 | 2015-10-28 | 复旦大学 | A kind of silk protein nano-microfiber and preparation method thereof |
| CN103866487B (en) * | 2014-03-27 | 2016-03-02 | 同济大学 | The preparation method of a kind of nano micro crystal cellulose/chitosan/polyvinyl alcohol composite nanometer film |
| CN104558639B (en) * | 2015-01-15 | 2017-02-22 | 四川大学 | Regenerated cellulose nano-particles and preparation method thereof |
| CN104651964A (en) * | 2015-01-28 | 2015-05-27 | 南通联海维景生物有限公司 | Preparation method of cellulose nanofiber |
| JP2017008176A (en) * | 2015-06-19 | 2017-01-12 | 日本製紙株式会社 | Dry solid article of cellulose nanofiber and manufacturing method thereof |
| CN105297283B (en) * | 2015-09-21 | 2018-07-13 | 武汉纺织大学 | A kind of p-aramid fiber nanofiber/non-woven fabric compounded filtrate of polyphenylene sulfide and preparation method thereof |
| CN106435831B (en) * | 2016-09-23 | 2018-07-06 | 青岛大学 | A kind of preparation method of the sodium alginate nano fiber based on self-assembly process |
| CN106633126B (en) * | 2016-10-15 | 2019-06-18 | 浙江金龙纸业有限公司 | Utilize the method for cation nanometer microcrystalline cellulose enhancing hemicellulose membrane |
| CN106591975B (en) * | 2016-12-08 | 2020-02-28 | 新乡化纤股份有限公司 | Centrifugal spinning process for regenerated cellulose filament fibers |
| CN106883301B (en) * | 2017-02-22 | 2019-05-14 | 中国科学院理化技术研究所 | It is a kind of while preparing Cellulose nanocrystal and cellulose nano-fibrous method |
| CN107057127A (en) * | 2017-05-02 | 2017-08-18 | 上海海洋大学 | A kind of preparation method of pH responsive nanos cellulose antibacterial controlled release membranes |
| CN107573762A (en) * | 2017-09-15 | 2018-01-12 | 东华大学 | A kind of water paint of the anti-sagging agent containing regenerated cellulose and its preparation method and application |
| CN107604454A (en) * | 2017-09-21 | 2018-01-19 | 成都新柯力化工科技有限公司 | A kind of environment-protecting clean preparation method of textile dedicated fiber cellulose fiber |
| CN108004829B (en) * | 2017-11-01 | 2019-11-15 | 华南理工大学 | A kind of high intensity nano fibre sill and the preparation method and application thereof |
| CN109096406B (en) * | 2018-10-25 | 2020-12-25 | 河北农业大学 | II type nano crystal cellulose ester and its preparation process and use |
| 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 |
| CN111138719A (en) * | 2019-11-25 | 2020-05-12 | 中国制浆造纸研究院有限公司 | Preparation method of powder containing nano-cellulose |
| CN111206317B (en) * | 2020-03-17 | 2021-01-29 | 阜阳恒泰纺织有限公司 | Modified flax/viscose blended yarn and preparation method thereof |
| CN111793223B (en) * | 2020-08-14 | 2022-08-19 | 中国科学院青岛生物能源与过程研究所 | Method for preparing nano-grade regenerated cellulose by adopting molten salt system |
| CN114272762B (en) * | 2021-09-15 | 2022-10-25 | 浙江泰林生命科学有限公司 | Preparation method of dust-free cellulose nitrate filter membrane |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1142185C (en) * | 2001-02-13 | 2004-03-17 | 中国科学院广州化学研究所 | Nano microcrystal cellulose with crystal form of cellulose II and its preparing process |
| CN1168767C (en) * | 2002-07-09 | 2004-09-29 | 武汉大学 | Prepn. process of intermingled chitin/cellulose material in sodium hydroxide/urea water solution system |
| CN1252163C (en) * | 2003-12-12 | 2006-04-19 | 武汉大学 | Lithium hydrate and carbamide composition solvent for dissolving cellulous fiber and its use |
| CN1289587C (en) * | 2004-01-18 | 2006-12-13 | 武汉大学 | Cellosolve and its use |
| CN101037479B (en) * | 2007-04-13 | 2010-05-19 | 武汉大学 | Method for dissolving cellulos |
| CN100542658C (en) * | 2007-08-22 | 2009-09-23 | 武汉大学 | A kind of preparation method of cellulose gel film |
| CN102146594A (en) * | 2011-05-09 | 2011-08-10 | 张家港耐尔纳米科技有限公司 | Oxidized cellulose nanofibers and preparation method thereof |
-
2013
- 2013-01-29 CN CN201310034133.6A patent/CN103060937B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN103060937A (en) | 2013-04-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103060937B (en) | Preparation method of cellulose nanofiber | |
| Farooq et al. | Cellulose from sources to nanocellulose and an overview of synthesis and properties of nanocellulose/zinc oxide nanocomposite materials | |
| Rol et al. | Pilot-scale twin screw extrusion and chemical pretreatment as an energy-efficient method for the production of nanofibrillated cellulose at high solid content | |
| Soni et al. | Chemical isolation and characterization of different cellulose nanofibers from cotton stalks | |
| Gupta et al. | Lignocellulosic biomass for the synthesis of nanocellulose and its eco-friendly advanced applications | |
| CN103059319B (en) | Preparation method of chitin nano fiber | |
| Chowdhury et al. | Preparation and characterization of nanocrystalline cellulose using ultrasonication combined with a microwave-assisted pretreatment process | |
| Khalil et al. | Production and modification of nanofibrillated cellulose using various mechanical processes: a review | |
| Rebouillat et al. | State of the art manufacturing and engineering of nanocellulose: a review of available data and industrial applications | |
| Visakh et al. | Preparation of bionanomaterials and their polymer nanocomposites from waste and biomass | |
| Kamel | Nanotechnology and its applications in lignocellulosic composites, a mini review | |
| JP5676860B2 (en) | Polysaccharide nanofibers and production method thereof, ionic liquid solution containing polysaccharide nanofibers and composite material | |
| Hu et al. | Preparation and characterization of nanofibrillated cellulose from bamboo fiber via ultrasonication assisted by repulsive effect | |
| Chen et al. | Individual cotton cellulose nanofibers: pretreatment and fibrillation technique | |
| El Seoud et al. | Cellulose regeneration and chemical recycling: closing the “cellulose gap” using environmentally benign solvents | |
| Li et al. | All-cellulose composites based on the self-reinforced effect | |
| JP4874930B2 (en) | Method for producing starch fiber | |
| WO2010090026A1 (en) | Chitin nanofiber and manufacturing method therefor, chitin nanofiber dispersion liquid, nanofibril structure, and chitin complex | |
| Chen et al. | High strength gelatin-based nanocomposites reinforced by surface-deacetylated chitin nanofiber networks | |
| Ren et al. | The effect of chemical and high-pressure homogenization treatment conditions on the morphology of cellulose nanoparticles | |
| Mao et al. | Progress in nanocellulose preparation and application | |
| JP6286131B2 (en) | Fine cellulose fiber, production method thereof and dispersion | |
| Hirota et al. | Cellulose II nanoelements prepared from fully mercerized, partially mercerized and regenerated celluloses by 4-acetamido-TEMPO/NaClO/NaClO 2 oxidation | |
| Gong et al. | Controlled production of spruce cellulose gels using an environmentally “green” system | |
| Lv et al. | Overview of preparation, modification, and application of tunicate-derived nanocellulose |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |