CN103060937A - Preparation method of cellulose nanofiber - Google Patents
Preparation method of cellulose nanofiber Download PDFInfo
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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 the natural polymer field, also belong to agricultural engineering field.
Technical background
Cellulose is renewable plant resources the abundantest on the earth, by the natural polymer that β-(1 → 4)-D-Glucose forms, is the main component of plant cell wall.Cellulose has the characteristics such as hydrophily, chemical reactivity, biocompatibility and biological degradability.And nano-cellulose also has very high specific area, degree of crystallinity and modulus except inheriting cellulosic above-mentioned character, is deemed to be for a long time the natural polymer subbundle of excellent combination property always.Cellulose nano-fibrous and general inorganic nano reinforcing material is compared, the characteristics such as they have renewable, wide material sources, power consumption is low, cost is low, density is low, and the surface has many hydroxyls can participate in graft reaction.The maximum Young's modulus value of natural plant cellulose is higher than the 70GPa of metallic aluminium and the 76Gpa of glass fibre up to 128GPa.Its ultimate tensile strength is about 17.8GPa, is 7 times of iron and steel.Usually, cellulose nano whisker and nanofiber directly or be scattered in natural polymer or the synthetic high polymer are widely used in improving (Biomacromolecules, 2009,10,425 such as the mechanical property of polymeric material and thermal property after surface modification; Macromolecules, 1995,28,6365; Prog.Polym.Sci., 1999,24,221).In addition, the cellulose nano-fibrous fields such as food, cosmetics, water treatment, packing, construction material that also can be used for.Because it has good biocompatibility, also has potential application prospect in fields such as biological medicine, organizational projects.
Cellulose macromolecule is joined together to form primary fibrillation by hydrogen bond, and it has crystal region and amorphous area.Several primary fibrillation form microfibril, and further forming fibrillation, diameter is tens of microns, and their insoluble and water and common organic solvents, therefore owing to there is strong intermolecular hydrogen bonding effect, can not easily it be dispersed into the state of nanofiber.Cellulose nano-fibrous preparation can be taked biological synthesis method, be that bacterium is under the condition that oxygen exists, synthetic diameter is the gel of the continuous nano-fibre cellulose fiber composition of 20-100nm take the low molecular weight D-Glucose as carbon source, be called Nano bacteria cellulose (bacterial nanocellulose) (Prog.Polym.Sci., 2001,26,1561).Yet, because the source of bacterial strain greatly affects its productive rate in the bacteria cellulose incubation, and strict to nutrient solution source, composition and cultivation temperature, and need the above times in two weeks, and be not suitable for producing and using in a large number.Obtain nano-cellulose more cellulose nano-fibrous mainly the separation from timber and agriculture and forestry organic waste material by enzyme, chemistry and physical means.To adopt the mechanical treatment modes such as high pressure homogenization, microjet or extra-fine grinding such as fibrillation cellulose (microfibrillated cellulose), 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 that 100nm arrives several microns cellulose nano-fibrous (Biomacromolecules, 2004,5,1983; Cellulose, 2005,12,305; Biomacromolecules, 2006,7,1687; Biomacromolecules, 2009,10,1992); Nanocrystalline cellulose (nanocrystalline cellulose) is in mechanical agitation and ultrasonic auxiliary lower, remove polysaccharide and the cellulosic amorphous portion that is combined in fiber surface by acid hydrolysis, obtaining width is that 5-70nm, length are the bar-shaped avicel cellulose (J.Mater.Sci. of 100-300nm, 2010,45,1-33).In addition, can also be with cellulose dissolution at N-methylmorpholine-oxide (NMMO), N, among N-dimethylacetylamide/lithium chloride (LiCl/DMAc), 1-allyl-3-methylimidazole villaumite (BmimCl)/DMSO and 1-butyl-3-methylimidazole villaumite (the AmimCl)/DMSO, then utilize the method for electrostatic spinning to obtain cellulose nano-fibrous (Polymer, 2006,47,5097; J.Appl.Polym.Sci., 2005,98,1855; Cellulose, 2010,17,223; Polymer, 2008,49,2911).Yet in said method, the processing of high pressure homogenizer need to consume a large amount of energy, is disadvantageous aspect cost.And the diameter of the cellulose fento of acquisition is heterogeneity also, the crude fibre that common residual diameter 1 μ m is above.On the other hand, the cellulosic fiber lengths that acid hydrolysis process obtains can shorten, and is difficult to keep the shape of fiber.The TEMPO method for oxidation relates to expensive TEMPO and reclaims, and produces Cl
2Etc. chloride noxious material.Electrospinning process is produced nanofiber and is subjected to the restriction of stability and production efficiency to be difficult to a large amount of productions.Because the difference of source difference and processing method, cellulose nano-fibrous size is also different.Therefore, effectively reduce energy consumption, the shortening production cycle of nanofiber preparation process, obtain simultaneously the focus that stable nanofiber always is concern.
The inventor herein has proposed to utilize the method for NaOH/ urea, NaOH/ thiocarbamide, LiOH/ urea and the quick dissolving cellulos of LiOH/ thiourea solution of low temperature precooling in the patent No. is the patent of ZL03128386.1, ZL200310111567.8, ZL200410012682.4 and 200310111447.8.The method is that cellulose macromolecule and small solvent molecule form the vermiform semi-rigid chain conformation of surrounding cellulose and NaOH compound take urea as shell under the low temperature by the hydrogen bond action self assembly, destroy in the cellulosic molecule and dissolve (Macromolecules with the intermolecular hydrogen bonding effect, 2008,41,9345; ChemPhysChem, 2007,8,1572; J.Polym.Sci.Pol.Phys., 2006,44,3093; Macromol.Biosci., 2005,5,539).Cellulose solution be can access according to the method, and (Adv.Mater., 2007,19,821 such as regenerated celulose fibre (the tens of microns of diameter), film, intermingling material, composite prepared 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 mutual mat of cellulose macromolecule in the solution, in said method, the process that cellulose is regenerated from solution is very fast, all can't 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 preparation is cellulose nano-fibrous.
The cellulose nano-fibrous method of preparation provided by the present invention is:
Cellulose dissolution is made cellulose aqueous solution, under agitation adding water-soluble non-solvent in the cellulose solution makes cellulose born again from solution gradually, then the separating substances beyond cellulose and the water is removed, again disperse to obtain cellulose nano-fibrous suspension, drying is removed decentralized medium and just can be obtained cellulose nano-fibrous.
As above-mentioned cellulose source, can be to separate paper pulp from trees, bamboo, cotton, careless class, crudefiber crop and other higher plant, bamboo pulp, cotton pulp, straw pulp, jute pulp etc., and separate 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 to have no particular limits.For example, described cellulose solution is to be 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 preferred, cellulose solution is made in NaOH/ aqueous solution of urea or LiOH/ aqueous solution of urea by cellulose dissolution.
Preferred as another, described cellulose solution is to be cooled to 15 ° of C of 0～– with the dicyandiamide solution that the water of 5～10wt%NaOH, 0.1～20wt% urea and surplus consists of, dissolving cellulos and obtaining.
Preferred as another, described cellulose solution is to be cooled to 15 ° of C of 0～– with the dicyandiamide solution that the water of 3～8wt%LiOH, 0.1～20wt% urea and surplus consists of, 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 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 solvents.In the solvent of enumerating, preferably make water and water-soluble alcohols, acids, ammoniac compounds in the above, more preferably make 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 cellulose regenerated process is processed.
In preparation method of the present invention, between regeneration and dispersion steps, the separating substances beyond cellulose nano-fibrous and the water is excluded outside the system, so long as can realize the unit operations of this purpose, then can use arbitrarily method, such as centrifugal, dialysis, filtration etc.
To can obtain cellulose nano-fibrous suspension by cellulose nano-fibrous being dispersed in the medium that dissolving, regeneration obtain.
Be used for the again medium of dispersion, water is preferred usually.Except water, can also use as required water-soluble organic solvent, such 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 solvents.
Can use various dispersal devices as the dispersal device that is used for dispersion steps.For example, can use the dispersal devices such as domestic stirrer, cell crushing instrument, ultrasonic homogenizer, high pressure homogenizer, screw extruder, stone mill.If the device that uses such powerful of homogenizer and have the making beating ability then can obtain less cellulose nano-fibrous of size more efficiently.
Removing decentralized medium in the cellulose nano-fibrous suspension that obtains 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.For example, remove liquid medium and obtain cellulose nano-fibrous by utilizing freeze drying plant, roller drier, spray dryer to carry out constant pressure and dry and freeze drying.Perhaps carrying out critical point drying or supercritical drying with carbon dioxide, methyl alcohol, ethanol, acetone etc. as supercritical fluid removes liquid medium and obtains cellulose nano-fibrous.
For making dry rear cellulose nano-fibrous can being more prone to that obtains again be distributed in the decentralized medium, can also sneak into water-soluble high-molecular compound (especially can form synthetic high polymer, carbohydrate, polysaccharide, protein of hydrogen bond etc.) in the 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.
Cellulose nano-fibrous can again being distributed in the decentralized medium that obtains after dry.
It is a kind of new cellulose nano-fibrous that the present invention also provides, and the diameter of fiber and has the cellulose II type crystal structure below 50nm.
Of the present invention cellulose nano-fibrous through finishing and with the polymeric material compound tense such as resin, in polymeric material, show good dispersiveness.In composite, the cellulose nano-fibrous enhancing effect that plays can significantly be improved mechanical property and the thermal property of polymer composites.The cellulose nano-fibrous fields such as food, cosmetics, water treatment, packing, construction material, biological medicine, organizational project that also can be used for of the inventive method preparation.
Among the preparation method of the present invention, utilize first cellulose solvent to destroy the interior and intermolecular hydrogen bonding of molecule of cellulose macromolecule, in solution, form the cellulosic molecule chain conformation of nanoscale owing to solvation, slowly adding non-solvent can be so that the nanometer cellulosic molecule chain conformation in the solution be kept, so can not form large aggregation.The cellulose nano-fibrous diameter of the present invention's preparation is below 50nm, and has the cellulose II type crystal structure, cellulose nano-fibrously having a visibly different crystal structure with bacteria cellulose, TEMPO oxidizing process and acid hydrolysis process obtain, is unexistent in the prior art.
Description of drawings
Fig. 1 left side is the photo of cellulose nano-fibrous aqueous dispersions;
Fig. 1 right side is the cellulose nano-fibrous photo of gel that obtains after centrifugal.
Fig. 2 is cellulose nano-fibrous electron scanning micrograph.
Fig. 3 is cellulose nano-fibrous X-ray diffraction spectrogram.
The specific embodiment
Below will specify the present invention by embodiment, but the protection domain that these specific embodiments do not limit the present invention in any way.The used raw material of the present embodiment is known compound, can buy in market.
Embodiment 1
The dicyandiamide solution that will consist of with the water of 5～10wt%NaOH, 0.1～20wt% urea and surplus is cooled to 15 ° of C of 0～–, adds the cellulose stirring and dissolving and obtains the 50g0.5wt% cellulose solution.Under agitation in cellulose solution, slowly drip distilled water until cellulose holomorphosis from solution out obtains cellulose nano-fibrous suspension.Place the bag filter dialysis to neutral cellulose nano-fibrous suspension, then continue to process 10 minutes with cell crushing instrument, namely obtain cellulose nano-fibrous aqueous dispersions.It is cellulose nano-fibrous to obtain white puffy through freeze drying.
Embodiment 2
The dicyandiamide solution that will consist of with the water of 5～10wt%NaOH, 0.1～20wt% urea and surplus is cooled to 15 ° of C of 0～–, adds the cellulose stirring and dissolving and obtains the 1wt% cellulose solution.Under agitation in cellulose solution, slowly drip methyl alcohol until cellulose holomorphosis from solution out obtains cellulose nano-fibrous suspension.Place the bag filter dialysis to neutral cellulose nano-fibrous suspension, then continue to process 10 minutes with homogenizer, namely obtain cellulose nano-fibrous aqueous dispersions.It is cellulose nano-fibrous to obtain white puffy through freeze drying.
Embodiment 3
The dicyandiamide solution that will consist of with the water of 5～10wt%NaOH, 0.1～20wt% urea and surplus is cooled to 15 ° of C of 0～–, adds the cellulose stirring and dissolving and obtains the 1wt% cellulose solution.Under agitation in cellulose solution, slowly drip hydrochloric acid until cellulose holomorphosis from solution out obtains cellulose nano-fibrous suspension.Place the bag filter dialysis to neutral cellulose nano-fibrous suspension, then continue to process 10 minutes with homogenizer, namely obtain cellulose nano-fibrous aqueous dispersions.Water is replaced into to obtain white puffy through critical point drying again behind the ethanol cellulose nano-fibrous.
Embodiment 4
The dicyandiamide solution that will consist of with the water of 5～10wt%NaOH, 0.1～20wt% urea and surplus is cooled to 15 ° of C of 0～–, adds the cellulose stirring and dissolving and obtains the 3wt% cellulose solution.Under agitation in cellulose solution, slowly drip ethanol until cellulose holomorphosis from solution out obtains cellulose nano-fibrous suspension.Remove supernatant after cellulose nano-fibrous suspension is centrifugal, add again the distilled water washing.Repeated centrifugation-washing step is until suspension is neutral.Then continue to 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 is left), through cellulose nano-fibrous precipitating after centrifugal, obtains gel cellulose nano-fibrous (Fig. 1 is right).Sem observation finds that cellulose nano-fibrous diameter is (Fig. 2) below 50nm.The native cellulose cellulose nano-fibrous and as raw material that obtains by preparation method of the present invention has diverse crystal structure.Learn that from the X-ray diffraction spectrogram cellulose nano-fibrous crystal structure is the cellulose II type, and degree of crystallinity obviously descend (Fig. 3).
Embodiment 5
The dicyandiamide solution that will consist of with the water of 5～10wt%NaOH, 0.1～20wt% urea and surplus is cooled to 15 ° of C of 0～–, adds the cellulose stirring and dissolving and obtains the 3wt% cellulose solution.Under agitation in cellulose solution, slowly drip hydrochloric acid until cellulose holomorphosis from solution out obtains cellulose nano-fibrous suspension.With cellulose nano-fibrous suspension sand core funnel filtration under diminished pressure, the distilled water washing is until neutral.Then continue to process 10 minutes with cell crushing instrument, namely obtain cellulose nano-fibrous aqueous dispersions.
Embodiment 6
The dicyandiamide solution that will consist of with the water of 5～10wt%NaOH, 0.1～20wt% urea and surplus is cooled to 15 ° of C of 0～–, adds the cellulose stirring and dissolving and obtains the 3wt% cellulose solution.Under agitation in cellulose solution, slowly drip ammoniacal liquor until cellulose holomorphosis from solution out obtains cellulose nano-fibrous suspension.With cellulose nano-fibrous suspension sand core funnel filtration under diminished pressure, the distilled water washing is until neutral.Then continue to process 10 minutes with cell crushing instrument, namely obtain cellulose nano-fibrous aqueous dispersions.
Embodiment 7
The dicyandiamide solution that will consist of with the water of 3～8wt%LiOH, 0.1～20wt% urea and surplus is cooled to 15 ° of C of 0～–, adds the cellulose stirring and dissolving and obtains the 2wt% cellulose solution.Under agitation in cellulose solution, slowly drip ethanol until cellulose holomorphosis from solution out obtains cellulose nano-fibrous suspension.Remove supernatant after cellulose nano-fibrous suspension is centrifugal, add again the distilled water washing.Repeated centrifugation-washing step is until suspension is neutral.Then continue to process 10 minutes with cell crushing instrument, obtain cellulose nano-fibrous aqueous dispersions.Add the 3wt% polyvinyl alcohol in cellulose nano-fibrous aqueous dispersions, it is cellulose nano-fibrous to obtain white puffy through freeze drying.
Embodiment 8
The dicyandiamide solution that will consist of with the water of 3～8wt%LiOH, 0.1～20wt% urea and surplus is cooled to 15 ° of C of 0～–, adds the cellulose stirring and dissolving and obtains the 3wt% cellulose solution.Under agitation in cellulose solution, slowly drip acetic acid until cellulose holomorphosis from solution out obtains cellulose nano-fibrous suspension.Remove supernatant after cellulose nano-fibrous suspension is centrifugal, add again the distilled water washing.Repeated centrifugation-washing step is until suspension is neutral.Add ethanol and continue processing 10 minutes with cell crushing instrument, obtain cellulose nano-fibrous alcohol dispersion liquid.
Embodiment 9
The dicyandiamide solution that will consist of with the water of 3～8wt%LiOH, 0.1～20wt% urea and surplus is cooled to 0～-15 ° of C, adds the cellulose stirring and dissolving and obtains the 3wt% cellulose solution.Under agitation in cellulose solution, slowly drip sulfuric acid until cellulose holomorphosis from solution out obtains cellulose nano-fibrous suspension.Remove supernatant after cellulose nano-fibrous suspension is centrifugal, add again the distilled water washing.Repeated centrifugation-washing step is until suspension is neutral.Then continue to process 10 minutes with cell crushing instrument, obtain cellulose nano-fibrous aqueous dispersions.It is cellulose nano-fibrous to obtain white puffy through freeze drying.
Embodiment 10
The dicyandiamide solution that will consist of with the water of 3～8wt%LiOH, 0.1～20wt% urea and surplus is cooled to 15 ° of C of 0～–, adds the cellulose stirring and dissolving and obtains the 5wt% cellulose solution.Under agitation in cellulose solution, slowly drip ammoniacal liquor until cellulose holomorphosis from solution out obtains cellulose nano-fibrous suspension.Remove supernatant after cellulose nano-fibrous suspension is centrifugal, add again the distilled water washing.Repeated centrifugation-washing step is until suspension is neutral.Then continue to process 20 minutes with cell crushing instrument, obtain cellulose nano-fibrous aqueous dispersions.It is cellulose nano-fibrous to obtain white puffy through freeze drying.
Claims (9)
1. cellulose nano-fibrous preparation method, it is characterized in that: cellulose dissolution is made cellulose aqueous solution, under agitation adding water-soluble non-solvent in the cellulose solution makes cellulose born again from solution gradually, then the separating substances beyond cellulose and the water is removed, again disperse to obtain cellulose nano-fibrous suspension, drying is removed decentralized medium and just can be obtained cellulose nano-fibrous.
2. preparation method according to claim 1, it is characterized in that: described cellulose aqueous solution is to be obtained in aqueous alkali, alkali-aqueous solution of urea, alkali-thiourea solution or alkali-urea-thiourea solution by cellulose dissolution, and described alkali refers to one or both of NaOH and LiOH.
3. preparation method according to claim 2, it is characterized in that: described cellulose aqueous solution is made in NaOH/ aqueous solution of urea or LiOH/ aqueous solution of urea by cellulose dissolution.
4. preparation method according to claim 3 is characterized in that: described cellulose aqueous solution is that the dicyandiamide solution that the water with 5～10 wt% NaOH, 0.1～20 wt% urea and surplus consists of is cooled to 0～– 15
oC, dissolving cellulos and obtaining.
5. preparation method according to claim 3 is characterized in that: described cellulose aqueous solution is that the dicyandiamide solution that the water with 3～8 wt% LiOH, 0.1～20 wt% urea and surplus consists of is cooled to 0～– 15
oC, dissolving cellulos and obtaining.
6. preparation method according to claim 1, it is characterized in that: described water-soluble non-solvent refers to water or water-soluble salt, alcohols, ketone, acids, anhydrides, Ammonia or ester class, or the mixture of aforementioned various solvents.
7. preparation method according to claim 6, it is characterized in that: described water-soluble non-solvent refers to water, methyl alcohol, ethanol, hydrochloric acid, sulfuric acid, acetic acid or ammoniacal liquor.
8. preparation method according to claim 1 is characterized in that: be used for the medium that again disperses, for water or water-soluble alcohols, ethers, ketone, ester class,
N, NThe – dimethyl formamide,
N, N– dimethylacetylamide, methyl-sulfoxide, or the mixture of aforementioned various solvents.
One kind cellulose nano-fibrous, it is characterized in that: the described cellulose nano-fibrous cellulose II type crystal structure that has, fibre diameter is below 50 nm.
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