CN106283209B - A kind of method and purposes preparing different scale nanometer fibril using coir fibre - Google Patents
A kind of method and purposes preparing different scale nanometer fibril using coir fibre Download PDFInfo
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Abstract
The present invention provides a kind of methods using native cellulose fibre preparation nanometer fibril, it is characterized in that, it include: to be totally submerged swelling and the unicellular tubular fiber of isolated native cellulose fibre and part in the mixed solution containing NaOH and NaClO than 1: 30~1: 50 by solid and liquid weight, the concentration of NaOH is 20-80g/L in the mixed solution containing NaOH and NaClO, the concentration of NaClO is 15-65g/L, after stirring and synchronous ultrasonic shake 1~20 hour at 60~98 DEG C, the mixed liquor of the fibril containing nanometer is obtained；After the mixed liquor of the resulting fibril containing nanometer is first carried out centrifuge separation removal of impurities for the first time with the revolving speed of 2000~4500rpm, lower liquid is taken to carry out step A, step B or step C.The present invention using targeting be swollen with dissolve the impact of fibril interstitial and ultrasonic wave microbubble expand and efficient, low damage separate the micro- fibril of acquisition and base fibre, facilitate the high-tech of coir fibre and recycling for fining, is conducive to the sustainable development of cellulose fibre resource.
Description
Technical field
The present invention relates to a kind of methods for preparing different scale nanometer fibril using coir fibre, especially a kind of to utilize oxygen
Change method prepares the method and purposes of different scale nanometer fibril.
Background technique
Cellulose is inexhaustible, nexhaustible, green, the free of contamination renewable resource of nature, is given birth to every year on the earth
Long plant cellulose is up to several hundred million tons, has been more than existing petroleum total reserve, but utilization is very little.The overwhelming majority is nature
It degrades and as fuel combustion, this inherently a kind of pollution.It is reported that being lost as caused by environmental pollution and ecological disruption
Account for the 15% of GDP total value, it means that be 9% economic growth on one side, be 15% loss late on one side.In human society face
When facing the problems such as natural resources shortage, energy crisis, environmental pollution, plant resources as widely distributed, abundance on the earth,
The fibre resources of sustainable use have huge developing and utilizingpotentiality, by global most attention, and have become and can hold
One of the utilization of continuous resource and new material and developing direction.And extraction prepares nano-cellulose fibril as opening up from plant fiber
A kind of approach for opening up fibre resources, obtains the extensive concern of people.
Coconut is one of main woody oleiferous plants crop in torrid areas, Hainan subtropical zone Di Shu and torrid areas, coconut money
Source very abundant.Coconut one can produce fruit every year, and producing fruit peak period is September to January next year, produce the fruit service life up to 80 years.Every plant of coconut palm
Set average annual output fruit 50~200 before 80 years age of trees.Existing 2000 history of cocoanut tree is cultivated in Hainan, until after liberation
Just start large-scale planting.Equal yield accounts for about the 99% of national total output up to 2.2~2.4 hundred million now.As coconut industry
Adjunct --- coir fibre, if each coconut produces coir fibre 200g/, the annual coir fibre resource in Hainan Province is reachable
4.4~4.8 ten thousand tons.
Coir fibre has toughness strong, anti-from separating in coconut husk, cleaning, removing the native cellulose fibre obtained after hide glue
The characteristics such as damp, ventilative, antibacterial.Current main application has cushion, rope, brush, indoor decoration (ethnic group or the foreigner
It is disposed with it to be made into various shape), preparing active carbon, fuel etc., be also taken as waste natural degradation or burning.As
Weaving is cushion, carpet, rope, net, doormat etc. with coir fibre major product.However, all these applications and product are all
It is with textile made of coir fibre itself and application.
Since native cellulose fibre is mostly multistage fibrillar structure, such as micro- fibril and base fibre are both less than 50nm, these
Nano-cellulose fibril attenuates with its thickness size, and crystallinity is higher, therefore also known as nano-cellulose whisker.Nano-cellulose
The extraction preparation method of fibril and research mainly have physical method, bioanalysis and chemical method.
Physical method is to have prepared tool after handling cellulose fibre by high pressure beating equipment or high pressure Refining apparatus
There is the cellulose of nano-scale.(Cellulose microfibrils:a novel method of preparation
using high shear relining and cryocrushing.Chakraborty.Holzforschung.2005,59:
102-107；Nano-fibrillation of pulp fibers for the processing of transparent
nanocomposites.Iwamoto S,Nakagaito AN,Yano H.2007,89:461-466；The effect of
morphological changes from pulp fiber towards nano-scale fibrillated
cellulose on the mechanical properties of high-strength plant fiber based
composites.Nakagaito AN,Yano H.2004,78:547-552.)
Cellulase treatment method is to handle cellulose by mild enzyme hydrolysis method, then passes through mechanical and high pressure homogeneous work
With the cellulose for preparing nano-scale size.(Structure and properties of cellulose
nanocompsite films containing melamine formaldehyde.Henriksson M,Berglund
LA.J ApplPolym Sci.2007,106:2817-2824；Cellulose nanopaper structures of high
toughness.Henriksson M,Berglund LA.Biomacromolecules.2008,9:1579-1585；
Isolation of cellulose microfibrils-An enzymatic approach.Janardhnan S,Sain
M.Bioresources.2006,1:176-188.)。
Chemical treatment is will be natural using the methods of DMSO or TEMPO by chemical reagent or the quick-fried preprocess method of sudden strain of a muscle
Cellulose fibre is purified, the method for preparing nano-cellulose whisker.(copper sulphate co-catalysis prepare nano-cellulose whisker and
Its enhancing aqueous polyurethane, Li Jinling, South China Science & Engineering University, 2010；Nano-cellulose whisker and its in nanocomposite
Application progress, Li Peiyao, Song Guojun, QiFeng etc., modern chemical industry, 2006:96-99；Pectin and preparation are extracted with Ramulus Mori
Application of the nano-cellulose whisker in silk fibroin composite membrane coating, Liu Lin, Fei Jianming, Zhan Pengfei etc., sericulture science, 2010 (1): 20-
24；The preparation and property of native cellulose nanoparticle, Shi Guang, Sun Lin, Chen Jinlong etc., South China Normal University's journal (natural section
Learn version), 2008 (4): 68-73.Structure,morphology and thermal characteristics of
banana nano fibers obtained by steam explosion[J].Deepa B,Abraham E,Cherian B
M,et al.BIORESOURCE TECHNOLOGY.2011,102:1988-1997；Physico-mechanical
properties of the jute micro/nanofibril reinforced starch/polyvinyl alcohol
biocomposite films.Das K,Ray D,Bandyopadhyay N R,et al.Composites part
B.2011,42:376-381.)。
Herein, physical method relies primarily on mechanical force, consumes energy larger.Condition needed for bioanalysis is normal temperature and pressure, not only may be used
To avoid a large amount of spent acid and impurity caused by acid-hydrolysis method, while the consumption of water and power resource can also be reduced, to experiment
Equipment requirement is low, but required time is very long, and the requirement to enzyme is very high.Preparation of most of researcher to nano-cellulose whisker
Mainly use chemical method.Chemical method has a pollution, corrosive equipment, but high-efficient.Acid-hydrolysis method in chemical method prepares nanometer
Cellulose whiskers can generate a large amount of spent acid and impurity, pollute environment, can corrode equipment, and the more difficult recycling of residue after reaction,
But preparation process comparative maturity, has been carried out industrialized production at present.Oxidizing process is just to begin one's study recent years, is avoided
Spent acid is generated in preparation process, reduces the requirement to equipment.
Currently, relevant article and patent introduction are prepared on nano-cellulose both at home and abroad, it is as a result as follows: such as: A
novel green approach for the preparation of cellulose nanowhiskers from white
coir,Diego M.Naschimento,Jessica S.Almeida,Amanda F.Dias et al.Carbohydrate
Polymers, 2014,110,456-463 be by acetic acid and salt low-kappa number, through hydrogen peroxide and alkali process, then by sulfuric acid
The coconut husk nano-cellulose whisker made after reason；Cell nanowhiskers from coconut husk fibers:Eeffect
of preparation conditions on their thermal and morphological behavior,
M.F.Rosa,E.S.Medeiros,J.A.Malmonge et al.Carbohydrate Polymers,2010,81,83-92
And Effect of pre-acid-hydrolysis treatment on morphology and properties of
cellulose nanowhiskers from coconut hust,Farah Fahma,Shinichiro Iwamoto,
Naruhito Hori et al.Cellulose, 2011,18,443-450 be all to handle by alkali and sodium chlorite, then pass through
The method that sulfuric acid treatment obtains coconut husk nano-cellulose.
Also there are more related patents to describe the manufacture craft of nano-cellulose whisker, relate generally to physics, enzyme process, chemistry
With oxidizing process etc., wherein the mode for mostly using two or more method to combine greatly.As patent CN104311675A,
CN105369663A, CN103938477A and CN103492637A mainly prepare nano-cellulose by the way of grinding.And it is special
Sharp CN105367670A, CN105175557A, CN104963228A, CN104846679A, CN104761648A,
CN104583492A, CN104099794A, CN103774481A, CN103193889A and CN104448007A etc. use a variety of sides
Method interaction achievees the purpose that extract nano-cellulose.But production method is different from the present invention.Wherein, mostly concerned
CN201210216631.8 is mentioned from coconut husk using the method for pretreatment, addition hydrogen peroxide inhibitor and ultrasonic wave auxiliary
The method for taking hemicellulose, but this patent focuses on the extraction for being composition.Patent CN201510171351.3,
CN201510172664.0, CN201510172902.8 are by pretreatment, biochemical treatment, mechanical crushing, DMSO and TEMPO oxygen
The method for changing processing extracts the method for Cellulose nanocrystal palpus from bracteal leaf of corn, cotton stalk bark and stalk.Wherein TEMPO is aoxidized
Method is to be aoxidized using TMPO/NaCLO/NaBr ternary system to native cellulose.Patent CN201510173982.9 is with low fibre
Dimension cellulose content plant fiber is the nanofiber made after raw material, preprocessed, etherification process and alkali process and TEMPO oxidation processes
The method of plain whisker；Patent CN201510050169.2 is the method mulberry skin by the quick-fried-ultrasonic wave degumming and bleaching of sudden strain of a muscle
The patent of nano-cellulose whisker.Patent CN201310033311 is a kind of utilization cellulose hydrolyzation moso bamboo fiber preparation nanometer
The method of microcrystalline cellulose.Patent CN201210165585 is to prepare to receive from flaxen fiber by alkali process and TEPO method for oxidation
The method of meter Jing Xu.Patent CN201280027973 is to be used as catalyst with heterocyclic nitroxyl radical, and hypochlorite is used as main oxygen
Method of the agent as oxygen source and tertiary amine or chlorine dioxide as the activator production cellulose products of heterocyclic nitroxyl radical.
Above-mentioned method for oxidation focuses on to be producing for cellulose fibre.These patents and the present invention are in pretreated mode, oxidation etc.
Processing mode on exist it is significantly different.Be mainly reflected in: one, there are dramatically different, coir fibres in process object
It is the biological cell wall film of double-layer structure, different from the cotton of single layer cell wall film or cell-free wall film, fiber crops, stalk, rice and kernel stalk fiber
Cellulose fiber.Secondly, the crystalline texture of pipe fiber (unicellular) in coir fibre be spiral crystal zone structure, crystal perfection is good,
Processing method and fibril discrete level are different, especially need to increase strength disposal step by step in oxidation process, make every effort to obtain pipe
Fibrillar structure body in fiber.
Summary of the invention
The object of the present invention is to provide a kind of methods for preparing different scale nanometer fibril using native cellulose fibre.
In order to achieve the above object, different scale nanometer original is prepared using native cellulose fibre the present invention provides a kind of
Fine method characterized by comprising
Step 1: native cellulose fibre is added in the NaOH solution that concentration is 5~12g/L, solid and liquid weight ratio is
1:15~1:30 is separated by solid-liquid separation after stirring and synchronous ultrasonic shake 0.2~3 hour at 60~98 DEG C, obtained solid is washed
It washs and is swollen at least once and the unicellular tubular fiber of isolated native cellulose fibre and part；
Step 2: solid-liquid weight is pressed in resulting swelling and the unicellular tubular fiber of isolated native cellulose fibre and part
Amount is totally submerged in the mixed solution containing NaOH and NaClO than 1:30~1:50, and the mixing containing NaOH and NaClO is molten
The concentration of NaOH is 20-80g/L in liquid, and the concentration of NaClO is 15-65g/L, stirring and synchronous ultrasonic shake at 60~98 DEG C
After swinging 1~20 hour, the mixed liquor of the fibril containing nanometer is obtained；
Step 3: by the mixed liquor of the resulting fibril containing nanometer first with the revolving speed of 2000~5000rpm carry out for the first time from
After heart separation, impurity removal, lower liquid is taken to carry out step A, step B or step C:
Step A: it directly carries out dialysis 0.5~3 day, obtains a nanometer fibril lotion, be dried to obtain a nanometer fibril；
Step B: second is carried out with revolving speed 9000-13000rpm and is centrifugated, supernatant liquid is dried to obtain micro- fibril
The mixture of boundling fibril and micro- fibril obtains a nanometer fibril lotion, is dried to obtain base by lower liquid through dialysis 0.5~3 day
Fibril；
Step C: second is carried out with revolving speed 5000-8000rpm and is centrifugated, supernatant liquid is dried to obtain micro- fibril collection
Beam fibril.
Preferably, the step C further include: resulting lower liquid will be centrifugated for the second time through dialysis 0.5~3
It, obtains a nanometer fibril lotion, is dried to obtain the mixture of base fibre Yu micro- fibril.
Preferably, the step C further include: resulting lower liquid will be centrifugated for the second time with revolving speed 9000-
13000rpm carries out third time centrifuge separation, and supernatant liquid is dried to obtain micro- fibril and micro- fibril boundling fibril；
It is highly preferred that the step C further include: resulting lower liquid will be centrifugated for the third time through dialysis 0.5~3
It, obtains a nanometer fibril lotion, is dried to obtain base fibre.
Preferably, the native cellulose fibre is coir fibre.
It is highly preferred that the preparation method of the coir fibre includes: that coconut husk shredding is obtained coma, it will be resulting
Coma carries out kiering, washing and extruding and removes water, dries, obtains coir fibre.
It is highly preferred that the kiering, washing and extruding go water circulation to carry out, cycle-index is 1~4 time.
It is highly preferred that the kiering includes that coma is immersed in water, it is placed in 60~98 DEG C of water-baths, kiering is swollen
Profit 0.2~3 hour.
It is highly preferred that at least one of drawing is hit, rubs and pulled to the shredding using mechanical.
It is highly preferred that the washing is to discharge water to wash or change trough washery.
It is highly preferred that the drying is to dry in 80 DEG C of baking ovens.
Preferably, the mixing speed in the first step be 300-1000rpm, ultrasonic oscillation frequency be 10~
50kHz。
It is highly preferred that the specific steps of " washing " in the first step include: to add deionization to wash obtained solid
It washs, be filtered by vacuum again, make filtrate in alkalescence or neutrality after " washing ".
Preferably, the mixing speed in the second step be 300-1000rpm, ultrasonic oscillation frequency be 10~
50kHz。
The present invention also provides nanometer prepared by the above-mentioned method using native cellulose fibre preparation nanometer fibril is former
Fibre prepares cellulose matrix or height in directly preparation nanometer~submicron thickness ultrathin nanometer fibril film or as reinforcing material
Effect in the nanometer~submicron thickness composite fibre or composite membrane of copolymer matrix.
Preferably, nanometer~submicron thickness ultrathin nanometer fibril film is filter membrane or bio-medical material.
Unicellular pipe fiber of the present invention refers to the unicellular pipe isolated in the coir fibre being made of many cells
Shape fiber.
Alkalescence of the present invention refers to that pH is 8-9.
The diameter of micro- fibril boundling fibril of the present invention is 60-200nm or so, the micro- fibril of the cellulose it is straight
Diameter is 20~60nm or so, and the diameter of the cellulose base fibril is 6~20nm or so.
Compared with prior art, the beneficial effects of the present invention are:
1, the present invention overcomes the randomnesss separated in traditional defibration method greatly, whisker is partially thick and thickness is discrete
Greatly, and be not easy to obtain high yield and the problem of whisker size is unable to control, using targeting be swollen with dissolve fibril interstitial with
The impact of ultrasonic wave microbubble expands and the separation of efficient, low damage ground obtains micro- fibril and base is fine, facilitates the height of coir fibre
Technology is recycled with fining, is conducive to the sustainable development of cellulose fibre resource.
2, the present invention can effective, high productivity preparing nano size fibril；
3, the gradable separation and Extraction base of the present invention fine (6~20nm), micro- fibril (20~60nm) and micro- fibril boundling are former
Slim (60~200nm), to carry out the application of the tunica fibrosa and composite fibre of different scale and skin effect；
4, the present invention prepares nanometer fibril compared to physical method and bioanalysis, has the characteristics that low energy consumption and high-efficient, phase
Than preparing nanometer fibril in acid-hydrolysis method, the present invention is smaller to the corrosivity of equipment, low energy consumption, low pollution.This is coir fibre
The top grade of resource cleans utilization, provides innovation practical technique for environmental protection and sustainable development.
Detailed description of the invention
Fig. 1 is transmission electron microscope (TEM) photo of coconut husk nanometer fibril body prepared by embodiment 1；
Fig. 2 is transmission electron microscope (TEM) photo of the micro- fibril of coconut husk nanometer prepared by embodiment 2；
Fig. 3 is transmission electron microscope (TEM) photo of coconut husk nanometer base fibre prepared by embodiment 3；
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
Embodiment 1
A method of different scale nanometer fibril, specific steps are prepared using coir fibre are as follows:
(1) adherency impurity is removed in shredding removal of impurities, kiering swelling and cleaning: by machinery strike, rubbing and pulls drawing and open coconut husk
Pine removes the coir fibre of adhesion and the impurity of root, obtains coma, and resulting coma is carried out kiering, washs and squeezes
Pressure removes water, and it includes that coma is placed in beaker that the specific steps of water are gone in the kiering, washing and extruding, is totally submerged in water
In, it is placed in 98 DEG C of water-baths and carries out kiering swelling 1 hour, stirred with the revolving speed of 500rpm while kiering, used after kiering
Multistage roller device, which squeeze to coma, removes water, is washed with water, then squeeze water；Kiering, washing and the extruding is gone
Water circulation carries out 4 times, to remove matrix between fiber, later, is placed in 80 DEG C of baking ovens to dry and arrives constant weight, and shearing length about 7~
20mm obtains coir fibre；
(2) dipping by lye swelling is separated with synchronous ultrasonic concussion: coir fibre is added to the NaOH that concentration is 8g/L
In solution, solid and liquid weight ratio is 1:30, is placed in ultrasonic washing instrument, the speed at 90 DEG C with 500rpm is stirred and synchronized super
Sound wave shock (20kHz) is after 1 hour, vacuum filtration, and obtained solid addition deionized water is washed and is filtered by vacuum 4 times, makes to filter
Liquid is neutrality, is swollen and the unicellular tubular fiber of isolated coir fibre and part (for yellow wadding body)；
(3) NaClO-NaOH mixed liquor oxidation dissolution is with ultrasonic separation: by resulting swelling and isolated coir fibre
And the unicellular tubular fiber in part is totally submerged in the mixed solution containing NaOH and NaClO by solid and liquid weight ratio 1:40, it is described
The mixed solution containing NaOH and NaClO in the concentration of NaOH be 30g/L, the concentration of NaClO is 18g/L, and solvent is deionization
Water is placed in ultrasonic washing instrument at 90 DEG C with the speed stirring of 500rpm and synchronous ultrasonic concussion (20kHz) 10 hours
Afterwards, the mixed liquor of the fibril containing nanometer is obtained；
(4) mixed liquor of the resulting fibril containing nanometer is first removed partial size with the revolving speed centrifuge separation of 5000rpm is 100nm
Above particle, salt and compared with impurity such as macrofibril bodies, directly adopt (the retention point of commercially available conventional dialysis film for remaining solution
Son amount is 6000) to carry out dialysis 2 days using deionized water, to remove deionization and low molecule impurity, obtains a nanometer fibril lotion,
80 DEG C of dry 1h obtain a nanometer fibril, can be used for making the fibril film of nano thickness and as filter membrane or bio-medical material
Material etc..
In 10-94nm, average diameter exists the diameter of the nanometer fibril nanometer fibril as shown in Figure 1: of present embodiment preparation
75nm, yield are survey crystallinity 34.5% 76.3%.
Embodiment 2
A method of different scale nanometer fibril, specific steps are prepared using coir fibre are as follows:
(1) adherency impurity is removed in shredding removal of impurities, kiering swelling and cleaning: by machinery strike, rubbing and pulls drawing and open coconut husk
Pine removes the coir fibre of adhesion and the impurity of root, obtains coma, and resulting coma is carried out kiering, washs and squeezes
Pressure removes water, and it includes that coma is placed in beaker that the specific steps of water are gone in the kiering, washing and extruding, is totally submerged in water
In, it is placed in 80 DEG C of water-baths and carries out kiering swelling 3 hours, stirred with the revolving speed of 500rpm while kiering, used after kiering
Multistage roller device, which squeeze to coma, removes water, is washed with water, then squeeze water；Kiering, washing and the extruding is gone
Water circulation carries out 3 times, to remove matrix between fiber, later, is placed in 80 DEG C of baking ovens to dry and arrives constant weight, and shearing length about 8~
15mm obtains coir fibre；
(2) dipping by lye swelling is separated with synchronous ultrasonic concussion: coir fibre is added to the NaOH that concentration is 10g/L
In solution, solid and liquid weight ratio is 1:30, is placed in ultrasonic washing instrument, the speed at 80 DEG C with 800rpm is stirred and synchronized super
Sound wave shock (30kHz) is after 2 hours, vacuum filtration, and obtained solid addition deionized water is washed and is filtered by vacuum 3 times, makes to filter
Liquid is neutrality, is swollen and the unicellular tubular fiber of isolated coir fibre and part (for yellow wadding body)；
(3) NaClO-NaOH mixed liquor oxidation dissolution is with ultrasonic separation: by resulting swelling and isolated coir fibre
And the unicellular tubular fiber in part is totally submerged in the mixed solution containing NaOH and NaClO by solid and liquid weight ratio 1:30, it is described
The mixed solution containing NaOH and NaClO in the concentration of NaOH be 50g/L, the concentration of NaClO is 30g/L, and solvent is deionization
Water is placed in ultrasonic washing instrument at 80 DEG C with the speed stirring of 800rpm and synchronous ultrasonic concussion (30kHz) 15 hours
Afterwards, the mixed liquor of the fibril containing nanometer is obtained；
(4) mixed liquor of the resulting fibril containing nanometer is first removed partial size with the revolving speed centrifuge separation of 5000rpm is 100nm
Above particle, salt and compared with impurity such as macrofibril bodies after, take lower liquid to carry out centrifugation point again with the revolving speed of 8000rpm
From, supernatant liquid is obtained into micro- fibril boundling fibril in 80 DEG C of dry 1h, by lower liquid using commercially available conventional dialysis film (cut
Staying molecular weight is 8000) to carry out dialysis 2 days using deionized water, to remove deionization and low molecule impurity, obtains a nanometer fibril cream
Liquid is dried to obtain a nanometer fibril, is the mixture of micro- fibril and base fibre, can be used as the fibril film of thinner nano thickness and
As filter membrane or bio-medical material etc..
The nanometer fibril of present embodiment preparation is as shown in Figure 2: the diameter of nanometer fibril exists in 6-55nm, average diameter
38.2nm, yield are survey crystallinity 32.6% 60.3%.
Embodiment 3
A method of different scale nanometer fibril, specific steps are prepared using coir fibre are as follows:
(1) adherency impurity is removed in shredding removal of impurities, kiering swelling and cleaning: by machinery strike, rubbing and pulls drawing and open coconut husk
Pine removes the coir fibre of adhesion and the impurity of root, obtains coma, and resulting coma is carried out kiering, washs and squeezes
Pressure removes water, and it includes that coma is placed in beaker that the specific steps of water are gone in the kiering, washing and extruding, is totally submerged in water
In, it is placed in 70 DEG C of water-baths and carries out kiering swelling 3 hours, stirred with the revolving speed of 500rpm while kiering, used after kiering
Multistage roller device, which squeeze to coma, removes water, is washed with water, then squeeze water；Kiering, washing and the extruding is gone
Water circulation carries out 3 times, to remove matrix between fiber, later, is placed in 80 DEG C of baking ovens to dry and arrives constant weight, and shearing length about 5~
8mm obtains coir fibre；
(2) dipping by lye swelling is separated with synchronous ultrasonic concussion: coir fibre is added to the NaOH that concentration is 12g/L
In solution, solid and liquid weight ratio is 1:40, is placed in ultrasonic washing instrument, the speed at 70 DEG C with 1000rpm is stirred and synchronized
Ultrasonic oscillation (50kHz) is after 2 hours, vacuum filtration, and obtained solid addition deionized water is washed and is filtered by vacuum 3 times, is made
Filtrate is neutrality, is swollen and the unicellular tubular fiber of isolated coir fibre and part (for yellow wadding body)；
(3) NaClO-NaOH mixed liquor oxidation dissolution is with ultrasonic separation: by resulting swelling and isolated coir fibre
And the unicellular tubular fiber in part is totally submerged in the mixed solution containing NaOH and NaClO by solid and liquid weight ratio 1:50, it is described
The mixed solution containing NaOH and NaClO in the concentration of NaOH be 80g/L, the concentration of NaClO is 65g/L, and solvent is deionization
Water is placed in ultrasonic washing instrument at 70 DEG C with the speed stirring of 1000rpm and synchronous ultrasonic concussion (50kHz) 20 hours
Afterwards, the mixed liquor of the fibril containing nanometer is obtained；
(4) mixed liquor of the resulting fibril containing nanometer is first removed partial size with the revolving speed centrifuge separation of 5000rpm is 100nm
Above particle, salt and compared with impurity such as macrofibril bodies after, take lower liquid to carry out primary centrifugation point with the revolving speed of 9000rpm
From, supernatant liquid is obtained into the mixture of micro- fibril boundling fibril and micro- fibril in 80 DEG C of dry 1h, by lower liquid use city
(molecular cut off 10000 carries out dialysis 2 days using deionized water, to go deionization and low molecule miscellaneous to the conventional dialysis film sold
Matter obtains a nanometer fibril lotion, obtains base fibre in 80 DEG C of dry 1h, can be as ultra-fine film.Present embodiment preparation
Nanometer fibril is as shown in Figure 3: the diameter of the base fibre is in 5-22nm, and for average diameter in 16.3nm, yield is actual measurement knot
The 57.9% of brilliant degree 34.1%.The diameter of the mixture of micro- fibril boundling fibril and micro- fibril is put down in 19.3-187nm
Equal diameter 88.2nm, yield 39.5%.
Claims (7)
1. a kind of method for preparing different scale nanometer fibril using native cellulose fibre characterized by comprising
Step 1: by native cellulose fibre be added to concentration be 5 ~ 12g/L NaOH solution in, solid and liquid weight ratio be 1:15 ~
1:30 is separated by solid-liquid separation after stirring and synchronous ultrasonic shake 0.2 ~ 3 hour at 60 ~ 98 DEG C, at least by obtained solid washing
Once, it is swollen and the unicellular tubular fiber of isolated native cellulose fibre and part；The native cellulose fibre
For coir fibre；The preparation method of the coir fibre includes: that coconut husk shredding is obtained coma, by resulting coma
It carries out kiering, washing and extruding and removes water, dry, obtain coir fibre；Kiering, washing and the extruding goes water circulation to carry out,
Cycle-index is 1 ~ 4 time, to remove matrix between fiber；
Step 2: solid and liquid weight ratio is pressed in resulting swelling and the unicellular tubular fiber of isolated native cellulose fibre and part
1:30 ~ 1:50 is totally submerged in the mixed solution containing NaOH and NaClO, in the mixed solution containing NaOH and NaClO
The concentration of NaOH is 20-80g/L, and the concentration of NaClO is 15-65g/L, at 60 ~ 98 DEG C stirring and synchronous ultrasonic concussion 1 ~
After 20 hours, the mixed liquor of the fibril containing nanometer is obtained；
Step 3: the mixed liquor of the resulting fibril containing nanometer is first carried out first time centrifuge separation with the revolving speed of 2000 ~ 4500rpm
After removal of impurities, lower liquid is taken to carry out step A, step B or step C:
Step A: it directly carries out dialysis 0.5 ~ 3 day, obtains a nanometer fibril lotion, be dried to obtain a nanometer fibril；
Step B: second is carried out with revolving speed 9000-13000rpm and is centrifugated, supernatant liquid is dried to obtain micro- fibril boundling
The mixture of fibril and micro- fibril obtains a nanometer fibril lotion by lower liquid through dialysis 0.5 ~ 3 day, is dried to obtain base fibre；
Step C: carrying out second with revolving speed 5000-8000rpm and be centrifugated, and it is former that supernatant liquid is dried to obtain micro- fibril boundling
It is fine.
2. the method for preparing different scale nanometer fibril using native cellulose fibre as described in claim 1, feature exist
In the step C further include: resulting lower liquid will be centrifugated for the second time through dialysis 0.5 ~ 3 day, obtain a nanometer fibril
Lotion is dried to obtain the mixture of base fibre Yu micro- fibril.
3. the method for preparing different scale nanometer fibril using native cellulose fibre as described in claim 1, feature exist
In the step C further include: resulting lower liquid will be centrifugated for the second time with revolving speed 9000-13000rpm and carry out the
It is centrifugated three times, supernatant liquid is dried to obtain micro- fibril and micro- fibril boundling fibril.
4. the method for preparing different scale nanometer fibril using native cellulose fibre as claimed in claim 3, feature exist
In the step C further include: resulting lower liquid will be centrifugated for the third time through dialysis 0.5 ~ 3 day, obtain a nanometer fibril
Lotion is dried to obtain base fibre.
5. the method for preparing different scale nanometer fibril using native cellulose fibre as described in claim 1, feature exist
In the mixing speed in the first step is 300-1000rpm, and ultrasonic oscillation frequency is 10 ~ 50kHz.
6. the method for preparing different scale nanometer fibril using native cellulose fibre as described in claim 1, feature exist
In the mixing speed in the second step is 300-1000rpm, and ultrasonic oscillation frequency is 10 ~ 50kHz.
7. the method institute of any of claims 1-6 for preparing different scale nanometer fibril using native cellulose fibre
The nanometer fibril of preparation is directly preparing the purposes in nanometer ~ submicron thickness ultrathin nanometer fibril film, or as strengthening material
Material and the purposes in cellulose matrix or other high polymer matrix preparation nanometer ~ submicron thickness composite membrane.
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