CN106283209A - A kind of method utilizing coir fibre to prepare different scale nanometer fibril and purposes - Google Patents
A kind of method utilizing coir fibre to prepare different scale nanometer fibril and purposes Download PDFInfo
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Abstract
The invention provides a kind of method utilizing native cellulose fibre to prepare nanometer fibril, it is characterized in that, including: native cellulose fibre that is swelling and that separate and the unicellular tubular fiber of part are totally submerged in the mixed solution containing NaOH and NaClO by solid-liquid weight ratio 1: 30～1: 50, in the described mixed solution containing NaOH and NaClO, the concentration of NaOH is 20 80g/L, the concentration of NaClO is 15 65g/L, after stirring synchronous ultrasonic shake 1～20 hour at 60～98 DEG C, obtain the mixed liquor containing nanometer fibril；After the mixed liquor containing nanometer fibril of gained is first carried out centrifugation remove impurity for the first time with the rotating speed of 2000～4500rpm, take off layer liquid and carry out step A, step B or step C.The present invention use targeting swelling with dissolve the impact of fibril interstitial and ultrasound wave microbubble expand and damage efficient, low separate the micro-fibril of acquisition and base is fine, contribute to the high-tech of coir fibre and recycling of becoming more meticulous, the beneficially sustainable development of cellulose fibre resource.
Description
Technical field
The present invention relates to a kind of method utilizing coir fibre to prepare different scale nanometer fibril, particularly one utilizes oxygen
Change method prepares method and the purposes of different scale nanometer fibril.
Background technology
Cellulose is nature Renewable resource inexhaustible, nexhaustible, green, free of contamination, and the earth is given birth to every year
Long plant cellulose is up to several hundred million ton, has exceeded existing petroleum total reserve, but utilization is very little.The overwhelming majority is nature
Degrade and as fuel combustion, this inherently a kind of pollution.It is reported that the loss caused by environmental pollution and ecological disruption is
Account for the 15% of GDP total value, it means that be the economic growth of 9%, while being the loss rate of 15%.In human society face
When facing the problems such as natural resources shortage, energy crisis, environmental pollution, plant resources as widely distributed on the earth, abundance,
The fibre resources of sustainable use, has huge developing and utilizingpotentiality, by global most attention, and has become and can hold
The utilization of continuous resource and new material and one of developing direction.And extraction prepares nano-cellulose fibril as opening up from Plant fiber
A kind of approach of exhibition fibre resources, obtains the extensive concern of people.
Cortex cocois radicis is one of main woody oleiferous plants crop in torrid areas, Di Shu subtropical zone, Hainan and torrid areas, and Cortex cocois radicis provides
Source is the abundantest.Cortex cocois radicis one can produce really every year, and producing fruit peak period is that JIUYUE was up to 80 years to January next year, product fruit life-span.Every strain coconut palm
Average before 80 years age of trees of tree produces fruit 50～200 per year.Hainan cultivation cocoanut tree history of existing 2000, until after liberation
Just start implantation in large scale.All yield is up to 2.2～2.4 hundred million now, accounts for the 99% of whole nation total output.As coconut industry
Appurtenance coir fibre, if each Cortex cocois radicis produces coir fibre 200g/, the annual coir fibre resource in Hainan Province up to
4.4～4.8 ten thousand tons.
Coir fibre separates from coconut husk, remove impurity, remove hide glue after the native cellulose fibre that obtains, there is toughness strong, anti-
The characteristic such as damp, ventilative, antibacterial.Current main uses has medicated cushion, rope, brush, indoor decoration (ethnic groups or foreigner
Can make variously-shaped disposed within it), preparing active carbon, fuel etc., be also taken as garbage natural degradation or burning.As
Weaving coir fibre major product is mat, carpet, rope, net, doormat etc..But, all these application and product are all
It is the textile and application made with coir fibre itself.
Owing to native cellulose fibre is mostly multistage fibrillar structure, as micro-fibril and base fibre are both less than 50nm, these
Nano-cellulose fibril attenuates with its thickness size, and its degree of crystallinity is the highest, therefore is also called nano-cellulose whisker.Nano-cellulose
The extraction preparation method of fibril and research, mainly have Physical, bioanalysis and chemical method.
Physical is to have prepared tool by high pressure beating equipment or high pressure Refining apparatus after cellulose fibre process
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 process cellulose, then by machinery and the homogeneous work of high pressure by gentle enzyme hydrolysis method
With the cellulose 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 by chemical reagent or to dodge quick-fried preprocess method, then through methods such as DMSO or TEMPO, by natural
Cellulose fibre purifies, the method preparing nano-cellulose whisker.(copper sulfate co-catalysis prepare nano-cellulose whisker and
It strengthens aqueous polyurethane, Li Jinling, South China Science & Engineering University, and 2010；Nano-cellulose whisker and in nano composite material
Application progress, Li Peiyao, Song Guojun, QiFeng etc., modern chemical industry, 2006:96-99；Pectin and preparation is extracted with Ramulus Mori
The application in silk fibroin composite membrane coating of the nano-cellulose whisker, Liu Lin, Fei Jianming, Zhan Pengfei etc., silkworm industry science, 2010 (1): 20-
24；The preparation of native cellulose nanoparticle and character, 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.)。
Here, Physical relies primarily on mechanical force, consumes energy bigger.Needed for bioanalysis, condition is normal temperature and pressure, not only may be used
To avoid a large amount of spent acid and impurity produced by acid-hydrolysis method, the consumption of water and power resource can also be reduced, to experiment simultaneously
Equipment requirements is low, but required time is the longest, and the requirement to enzyme is the highest.The major part researcher preparation to nano-cellulose whisker
Mainly use chemical method.Chemical method has pollution, corrosive equipment, but efficiency is high.Acid-hydrolysis method in chemical method prepares nanometer
Cellulose whiskers can produce substantial amounts of spent acid and impurity, pollutes environment, understands the more difficult recovery of residue after etching apparatus, and reaction,
But preparation technology comparative maturity, has been carried out industrialized production at present.Oxidizing process is just to begin one's study recent years, it is to avoid
Preparation process produces spent acid, decreases the requirement to equipment.
At present, the article and patent introduction that preparing on nano-cellulose is correlated with both at home and abroad, result is 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 is by acetic acid and salt low-kappa number, processes through hydrogen peroxide and alkali, then by sulphuric acid
The coconut husk nano-cellulose whisker of system 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 is all to process through alkali and sodium chlorite, then passes through
Sulfuric acid treatment obtains the method for coconut husk nano-cellulose.
Also there is more Patents to describe the processing technology of nano-cellulose whisker, relate generally to physics, enzyme process, chemistry
With oxidizing process etc., the most mostly use the mode that two or more method combines.As patent CN104311675A,
CN105369663A, CN103938477A and CN103492637A mainly use the mode of grinding to prepare nano-cellulose.And it is special
Profit CN105367670A, CN105175557A, CN104963228A, CN104846679A, CN104761648A,
CN104583492A, CN104099794A, CN103774481A, CN103193889A and CN104448007A etc. use multiple side
Method interacts, and reaches to extract the purpose of nano-cellulose.But manufacture method is all different from the present invention.Wherein, mostly concerned
CN201210216631.8 is to utilize pretreatment, interpolation hydrogen peroxide inhibitor and the method for ultrasonic assistant, carries from coconut husk
The method taking hemicellulose, but this patent is emphatically the extraction of composition.Patent CN201510171351.3,
CN201510172664.0, CN201510172902.8 are by pretreatment, biochemical treatment, mechanical activation comminution, DMSO and TEMPO oxygen
The method that change processes, the method extracting Cellulose nanocrystal palpus from bracteal leaf of corn, cotton stalk bark and straw.Wherein TEMPO oxidation
Method is to utilize TMPO/NaCLO/NaBr ternary system to aoxidize native cellulose.Patent CN201510173982.9 is with low fibre
Dimension cellulose content Plant fiber is raw material, and preprocessed, etherificate processes and alkali processes and the nanofiber of system after TEMPO oxidation processes
The method of element whisker；Patent CN201510050169.2 is by dodging quick-fried-ultrasound wave degumming and the method for bleaching Cortex Mori
The patent of nano-cellulose whisker.Patent CN201310033311 is that one utilizes cellulase hydrolysis Phyllostachys pubescens Mazei ex H.de Lebaie fiber to prepare nanometer
The method of microcrystalline Cellulose.Patent CN201210165585 is to process to prepare from flaxen fiber with TEPO method for oxidation by alkali to receive
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
Agent is as oxygen source, and the method that tertiary amine or chlorine dioxide make cellulose products as the activator of heterocyclic nitroxyl radical.
Above-mentioned method for oxidation is emphatically producing of cellulose fibre.These patents and the present invention are at the mode of pretreatment, Oxidation etc.
Processing mode on all exist significantly different.Be mainly reflected in: one, process exist on object dramatically different, coir fibre
It is the biological cell wall film of double-layer structure, is different from monolayer cell wall film or the cotton of acellular wall film, fiber crops, straw, rice Wheat straw fiber
Cellulose fiber.Two, the crystalline texture of the pipe fiber (unicellular) in coir fibre is spiral crystal zone structure, and crystal perfection is good,
Processing method is different with defibrillation energy level, especially needs to strengthen strength disposal step by step in oxidizing process, makes every effort to be managed
Fibrillar structure body in fiber.
Summary of the invention
It is an object of the invention to provide a kind of method utilizing native cellulose fibre to prepare different scale nanometer fibril.
In order to achieve the above object, the invention provides one, to utilize native cellulose fibre to prepare different scale nanometer former
Fine method, it is characterised in that including:
The first step: being joined by native cellulose fibre in the NaOH solution that concentration is 5～12g/L, solid-liquid weight ratio is 1
: 15～1: 30, after at 60～98 DEG C, stirring synchronous ultrasonic shake 0.2～3 hour, solid-liquid separation, gained solid is washed
Wash at least one times, obtain native cellulose fibre that is swelling and that separate and the unicellular tubular fiber of part；
Second step: the swelling of gained and native cellulose fibre and the unicellular tubular fiber of part separated are pressed solid-liquid weight
Amount is totally submerged in the mixed solution containing NaOH and NaClO than 1: 30～1: 50, and the described mixing containing NaOH and NaClO is molten
In liquid the concentration of NaOH be the concentration of 20-80g/L, NaClO be 15-65g/L, at 60～98 DEG C stirring and synchronous ultrasonic
After shaking 1～20 hour, obtain the mixed liquor containing nanometer fibril；
3rd step: by the mixed liquor containing nanometer fibril of gained first with the rotating speed of 2000～5000rpm carry out for the first time from
After heart separation, impurity removal, take off layer liquid and carry out step A, step B or step C:
Step A: directly carry out dialysing 0.5～3 day, obtains nanometer fibril emulsion, is dried to obtain nanometer fibril；
Step B: carry out second time centrifugation with rotating speed 9000-13000rpm, supernatant liquid is dried to obtain micro-fibril
Boundling fibril and the mixture of micro-fibril, by lower floor's liquid through dialysis 0.5～3 day, obtain nanometer fibril emulsion, be dried to obtain base
Fibril；
Step C: carry out second time centrifugation with rotating speed 5000-8000rpm, supernatant liquid is dried to obtain micro-fibril collection
Bundle fibril.
Preferably, described step C also includes: by lower floor's liquid of second time centrifugation gained through dialysis 0.5～3
My god, obtain nanometer fibril emulsion, be dried to obtain the fine mixture with micro-fibril of base.
Preferably, described step C also includes: by lower floor's liquid of second time centrifugation gained with rotating speed 9000-
13000rpm carries out third time centrifugation, and supernatant liquid is dried to obtain micro-fibril and micro-fibril boundling fibril；
It is highly preferred that described step C also includes: by lower floor's liquid of third time centrifugation gained through dialysis 0.5～3
My god, obtain nanometer fibril emulsion, be dried to obtain base fine.
Preferably, described native cellulose fibre is coir fibre.
It is highly preferred that the preparation method of described coir fibre includes: by coconut husk shredding, it is thus achieved that coma, by gained
Coma carries out kiering, washs and extrude and anhydrate, and dries, obtains coir fibre.
It is highly preferred that described kiering, wash and extrude circulation of anhydrating and carry out, cycle-index is 1～4 time.
It is highly preferred that described kiering includes being immersed in water coma, being placed in 60～98 DEG C of water-baths, kiering is swollen
Moisten 0.2～3 hour.
It is highly preferred that described shredding use machinery to hit, rub and pull in drawing at least one.
It is highly preferred that described washing is washed for discharging water or changes trough washery.
It is highly preferred that described drying is to dry in 80 DEG C of baking ovens.
Preferably, the described mixing speed in the first step is 300-1000rpm, ultrasonic wave concussion frequency be 10～
50kHz。
It is highly preferred that the concrete steps of " washing " in the described first step including: gained solid to be added deionization washing
Wash, vacuum filtration again, making filtrate after " washing " is alkalescence or neutrality.
Preferably, the described mixing speed in second step is 300-1000rpm, ultrasonic wave concussion frequency be 10～
50kHz。
Present invention also offers the nanometer prepared by the above-mentioned method utilizing native cellulose fibre to prepare nanometer fibril former
Fibre at directly preparation nanometer～the ultrathin nanometer fibril film of submicron thickness or prepares cellulose matrix or height as reinforcing material
Effect in the nanometer of copolymer matrix～the composite fibre of submicron thickness or composite membrane.
Preferably, the ultrathin nanometer fibril film of described nanometer～submicron thickness is filter membrane or bio-medical material.
Unicellular pipe fiber of the present invention refers to isolated unicellular pipe in the coir fibre being made up of many cells
Shape fiber.
Alkalescence of the present invention refers to that pH is 8-9.
A diameter of about 60-200nm of micro-fibril boundling fibril of the present invention, the micro-fibril of described cellulose straight
Footpath is 20～about 60nm, a diameter of the 6～about 20nm of described cellulose base fibril.
Compared with prior art, the invention has the beneficial effects as follows:
1, instant invention overcomes that the randomness separated in traditional defibration method is big, whisker is partially thick and thickness is discrete
Greatly, and be difficult to obtain high yield and the uncontrollable problem of whisker size, use targeting swelling with dissolve fibril interstitial with
The impact of ultrasound wave microbubble expands and damage ground separation efficient, low obtains micro-fibril and base is fine, contributes to the height of coir fibre
Technology and recycling of becoming more meticulous, the beneficially sustainable development of cellulose fibre resource.
2, the present invention can effectively, the fibril of high productivity preparing nano size；
3, the present invention gradable separation and Extraction base fine (6～20nm), micro-fibril (20～60nm) and micro-fibril boundling are former
Slim (60～200nm), the application of fibrous membrane and composite fibre to carry out different scale and skin effect；
4, the present invention prepares nanometer fibril compared to Physical and bioanalysis, has the feature that energy consumption is low and efficiency is high, phase
Ratio prepares nanometer fibril in acid-hydrolysis method, and the present invention is less to the corrosivity of equipment, low energy consumption, low stain.This is coir fibre
The top grade of resource, clean utilization, provide innovation practical technique for environmental conservation and sustainable development.
Accompanying drawing explanation
Fig. 1 is transmission electron microscope (TEM) photo of the coconut husk nanometer fibril body of embodiment 1 preparation；
Fig. 2 is transmission electron microscope (TEM) photo of the micro-fibril of coconut husk nanometer of embodiment 2 preparation；
Fig. 3 is transmission electron microscope (TEM) photo of the coconut husk nanometer base fibre of embodiment 3 preparation；
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is expanded on further.Should be understood that these embodiments are merely to illustrate the present invention
Rather than restriction the scope of the present invention.In addition, it is to be understood that after having read the content that the present invention lectures, people in the art
The present invention can be made various changes or modifications by member, and these equivalent form of values fall within the application appended claims equally and limited
Scope.
Embodiment 1
A kind of method utilizing coir fibre to prepare different scale nanometer fibril, concretely comprises the following steps:
(1) stuck foreign matter is removed in shredding remove impurity, kiering swelling and cleaning: is hit by machinery, is rubbed and pull to draw and opened by coconut husk
Pine, removes coir fibre and the impurity of root of adhesion, it is thus achieved that coma, the coma of gained carries out kiering, washs and squeeze
Pressure is anhydrated, and described kiering, washs and extrudes the concrete steps anhydrated and include being placed in beaker coma, is totally submerged in water
In, it being placed in 98 DEG C of water-baths and carry out kiering swelling 1 hour, while kiering, the rotating speed with 500rpm stirs, and uses after kiering
Multistage roller device carries out extruding to coma and anhydrates, and washes with water, then extruding is anhydrated；Described kiering, wash and extrude
Water circulation is carried out 4 times, to remove substrate between fiber, afterwards, is placed in 80 DEG C of baking ovens drying to constant weight, shearing length about 7～
20mm, obtains coir fibre；
(2) dipping by lye is swelling separates with synchronous ultrasonic concussion: coir fibre joins the NaOH that concentration is 8g/L
In solution, solid-liquid weight ratio is 1:30, is placed in ultrasonic washing instrument, stirs with the speed of 500rpm and synchronize super at 90 DEG C
Sound wave shock (20kHz) is after 1 hour, vacuum filtration, gained solid adds deionized water wash vacuum filtration 4 times, makes filter
Liquid is neutral, obtains coir fibre that is swelling and that separate and the unicellular tubular fiber of part (for yellow flco)；
(3) NaClO-NaOH mixed liquor oxidation dissolution separates with ultrasound wave: by the swelling of gained and the coir fibre of separation
And the unicellular tubular fiber of part is totally submerged in the mixed solution containing NaOH and NaClO by solid-liquid weight ratio 1: 40, described
The mixed solution containing NaOH and NaClO in the concentration that concentration is 30g/L, NaClO of NaOH be 18g/L, solvent is deionization
Water, is placed in ultrasonic washing instrument at 90 DEG C and stirs also synchronous ultrasonic concussion (20kHz) 10 hours with the speed of 500rpm
After, obtain the mixed liquor containing nanometer fibril；
(4) mixed liquor containing nanometer fibril of gained is first removed particle diameter as 100nm with the rotating speed centrifugation of 5000rpm
The impurity such as above granule, salt and relatively macrofibril body, directly use commercially available conventional dialysis film (to retain by remaining solution
Molecular weight is 6000) use deionized water to carry out dialysing 2 days, to remove deionization and low molecule impurity, obtain nanometer fibril emulsion,
Obtain nanometer fibril at 80 DEG C of dry 1h, its may be used for make nano thickness fibril film and as filter membrane or bio-medical
Material etc..
Nanometer fibril prepared by present embodiment is as shown in Figure 1: the diameter of nanometer fibril exists in 10-94nm, average diameter
75nm, its productivity is the 76.3% of actual measurement degree of crystallinity 34.5%.
Embodiment 2
A kind of method utilizing coir fibre to prepare different scale nanometer fibril, concretely comprises the following steps:
(1) stuck foreign matter is removed in shredding remove impurity, kiering swelling and cleaning: is hit by machinery, is rubbed and pull to draw and opened by coconut husk
Pine, removes coir fibre and the impurity of root of adhesion, it is thus achieved that coma, the coma of gained carries out kiering, washs and squeeze
Pressure is anhydrated, and described kiering, washs and extrudes the concrete steps anhydrated and include being placed in beaker coma, is totally submerged in water
In, it being placed in 80 DEG C of water-baths and carry out kiering swelling 3 hours, while kiering, the rotating speed with 500rpm stirs, and uses after kiering
Multistage roller device carries out extruding to coma and anhydrates, and washes with water, then extruding is anhydrated；Described kiering, wash and extrude
Water circulation is carried out 3 times, to remove substrate between fiber, afterwards, is placed in 80 DEG C of baking ovens drying to constant weight, shearing length about 8～
15mm, obtains coir fibre；
(2) dipping by lye is swelling separates with synchronous ultrasonic concussion: coir fibre joins the NaOH that concentration is 10g/L
In solution, solid-liquid weight ratio is 1: 30, is placed in ultrasonic washing instrument, stirs with the speed of 800rpm and synchronize super at 80 DEG C
Sound wave shock (30kHz) is after 2 hours, vacuum filtration, gained solid adds deionized water wash vacuum filtration 3 times, makes filter
Liquid is neutral, obtains coir fibre that is swelling and that separate and the unicellular tubular fiber of part (for yellow flco)；
(3) NaClO-NaOH mixed liquor oxidation dissolution separates with ultrasound wave: by the swelling of gained and the coir fibre of separation
And the unicellular tubular fiber of part is totally submerged in the mixed solution containing NaOH and NaClO by solid-liquid weight ratio 1: 30, described
The mixed solution containing NaOH and NaClO in the concentration that concentration is 50g/L, NaClO of NaOH be 30g/L, solvent is deionization
Water, is placed in ultrasonic washing instrument at 80 DEG C and stirs also synchronous ultrasonic concussion (30kHz) 15 hours with the speed of 800rpm
After, obtain the mixed liquor containing nanometer fibril；
(4) mixed liquor containing nanometer fibril of gained is first removed particle diameter as 100nm with the rotating speed centrifugation of 5000rpm
After the impurity such as above granule, salt and relatively macrofibril body, take off layer liquid and be centrifuged again point with the rotating speed of 8000rpm
From, supernatant liquid is obtained micro-fibril boundling fibril at 80 DEG C of dry 1h, lower floor's liquid is used commercially available conventional dialysis film
(molecular cut off is 8000) uses deionized water to carry out dialysing 2 days, to remove deionization and low molecule impurity, obtains nanometer fibril
Emulsion, is dried to obtain nanometer fibril, and it is micro-fibril and the mixture of base fibre, can be as the fibril film of thinner nano thickness
And as filter membrane or bio-medical material etc..
Nanometer fibril prepared by present embodiment is as shown in Figure 2: the diameter of nanometer fibril exists in 6-55nm, average diameter
38.2nm, its productivity is the 60.3% of actual measurement degree of crystallinity 32.6%.
Embodiment 3
A kind of method utilizing coir fibre to prepare different scale nanometer fibril, concretely comprises the following steps:
(1) stuck foreign matter is removed in shredding remove impurity, kiering swelling and cleaning: is hit by machinery, is rubbed and pull to draw and opened by coconut husk
Pine, removes coir fibre and the impurity of root of adhesion, it is thus achieved that coma, the coma of gained carries out kiering, washs and squeeze
Pressure is anhydrated, and described kiering, washs and extrudes the concrete steps anhydrated and include being placed in beaker coma, is totally submerged in water
In, it being placed in 70 DEG C of water-baths and carry out kiering swelling 3 hours, while kiering, the rotating speed with 500rpm stirs, and uses after kiering
Multistage roller device carries out extruding to coma and anhydrates, and washes with water, then extruding is anhydrated；Described kiering, wash and extrude
Water circulation is carried out 3 times, to remove substrate between fiber, afterwards, is placed in 80 DEG C of baking ovens drying to constant weight, shearing length about 5～
8mm, obtains coir fibre；
(2) dipping by lye is swelling separates with synchronous ultrasonic concussion: coir fibre joins the NaOH that concentration is 12g/L
In solution, solid-liquid weight ratio is 1:40, is placed in ultrasonic washing instrument, stirs with the speed of 1000rpm and synchronize at 70 DEG C
Ultrasonic wave concussion (50kHz) is after 2 hours, vacuum filtration, gained solid adds deionized water wash vacuum filtration 3 times, makes
Filtrate is neutral, obtains coir fibre that is swelling and that separate and the unicellular tubular fiber of part (for yellow flco)；
(3) NaClO-NaOH mixed liquor oxidation dissolution separates with ultrasound wave: by the swelling of gained and the coir fibre of separation
And the unicellular tubular fiber of part is totally submerged in the mixed solution containing NaOH and NaClO by solid-liquid weight ratio 1: 50, described
The mixed solution containing NaOH and NaClO in the concentration that concentration is 80g/L, NaClO of NaOH be 65g/L, solvent is deionization
Water, is placed in ultrasonic washing instrument at 70 DEG C and stirs also synchronous ultrasonic concussion (50kHz) 20 hours with the speed of 1000rpm
After, obtain the mixed liquor containing nanometer fibril；
(4) first with the rotating speed centrifugation of 5000rpm, the mixed liquor containing nanometer fibril of gained being removed particle diameter is
After the impurity such as the granule of more than 100nm, salt and relatively macrofibril body, take off layer liquid with the rotating speed of 9000rpm carry out once from
The heart separates, and at 80 DEG C of dry 1h, supernatant liquid is obtained micro-fibril boundling fibril and the mixture of micro-fibril, is adopted by lower floor's liquid
With commercially available conventional dialysis film, (molecular cut off is 10000, uses deionized water to carry out dialysing 2 days, to remove deionization and low point
Sub-impurity, obtains nanometer fibril emulsion, obtains base at 80 DEG C of dry 1h fine, can be as ultra-fine film.Present embodiment system
Standby nanometer fibril is as shown in Figure 3: the fine diameter of described base is at 5-22nm, and average diameter is at 16.3nm, and its productivity be reality
Survey the 57.9% of degree of crystallinity 34.1%.Described micro-fibril boundling fibril and the diameter of the mixture of micro-fibril are at 19.3-
187nm, average diameter 88.2nm, its yield is 39.5%.
Claims (10)
1. one kind utilizes the method that native cellulose fibre prepares different scale nanometer fibril, it is characterised in that including:
The first step: being joined by native cellulose fibre in the NaOH solution that concentration is 5～12g/L, solid-liquid weight ratio is 1: 15
～1: 30, after at 60～98 DEG C, stirring synchronous ultrasonic shake 0.2～3 hour, solid-liquid separation, gained solid is washed extremely
The most once, native cellulose fibre that is swelling and that separate and the unicellular tubular fiber of part are obtained；
Second step: the swelling of gained and native cellulose fibre and the unicellular tubular fiber of part separated are pressed solid-liquid weight ratio
1: 30～1: 50 is totally submerged in the mixed solution containing NaOH and NaClO, in the described mixed solution containing NaOH and NaClO
The concentration of NaOH be the concentration of 20-80g/L, NaClO be 15-65g/L, at 60～98 DEG C stirring and synchronous ultrasonic concussion 1
～after 20 hours, obtain the mixed liquor containing nanometer fibril；
3rd step: the mixed liquor containing nanometer fibril of gained is first carried out the most centrifugal point with the rotating speed of 2000～4500rpm
After remove impurity, take off layer liquid and carry out step A, step B or step C:
Step A: directly carry out dialysing 0.5～3 day, obtains nanometer fibril emulsion, is dried to obtain nanometer fibril；
Step B: carry out second time centrifugation with rotating speed 9000-13000rpm, supernatant liquid is dried to obtain micro-fibril boundling
Fibril and the mixture of micro-fibril, by lower floor's liquid through dialysis 0.5～3 day, obtain nanometer fibril emulsion, be dried to obtain base
Fine；
Step C: carry out second time centrifugation with rotating speed 5000-8000rpm, supernatant liquid is dried to obtain micro-fibril boundling former
Fine.
Utilizing the method that native cellulose fibre prepares different scale nanometer fibril the most as claimed in claim 1, its feature exists
In, described step C also includes: by lower floor's liquid of second time centrifugation gained through dialysis 0.5～3 day, obtain nanometer former
Fine emulsion, is dried to obtain the fine mixture with micro-fibril of base.
Utilizing the method that native cellulose fibre prepares different scale nanometer fibril the most as claimed in claim 1, its feature exists
In, described step C also includes: with rotating speed 9000-13000rpm, lower floor's liquid of second time centrifugation gained is carried out
Three centrifugations, are dried to obtain micro-fibril and micro-fibril boundling fibril by supernatant liquid.
Utilizing the method that native cellulose fibre prepares different scale nanometer fibril the most as claimed in claim 3, its feature exists
In, described step C also includes: by lower floor's liquid of third time centrifugation gained through dialysis 0.5～3 day, obtain nanometer former
Fine emulsion, is dried to obtain base fine.
Utilizing the method that native cellulose fibre prepares different scale nanometer fibril the most as claimed in claim 1, its feature exists
In, described native cellulose fibre is coir fibre.
Utilizing the method that native cellulose fibre prepares different scale nanometer fibril the most as claimed in claim 5, its feature exists
In, the preparation method of described coir fibre includes: by coconut husk shredding, it is thus achieved that coma, the coma of gained is carried out kiering,
Wash and extrude and anhydrate, dry, obtain coir fibre.
Utilizing the method that native cellulose fibre prepares different scale nanometer fibril the most as claimed in claim 6, its feature exists
In, described kiering, washing and extrude circulation of anhydrating and carry out, cycle-index is 1～4 time.
Utilizing the method that native cellulose fibre prepares different scale nanometer fibril the most as claimed in claim 1, its feature exists
In, the described mixing speed in the first step is 300-1000rpm, and ultrasonic wave concussion frequency is 10～50kHz.
Utilizing the method that native cellulose fibre prepares different scale nanometer fibril the most as claimed in claim 1, its feature exists
In, the described mixing speed in second step is 300-1000rpm, and ultrasonic wave concussion frequency is 10～50kHz.
10. utilize, according to any one of claim 1-9, the method that native cellulose fibre prepares different scale nanometer fibril
Prepared nanometer fibril at directly preparation nanometer～the ultrathin nanometer fibril film of submicron thickness or is prepared as reinforcing material
Effect in cellulose matrix or the nanometer of high polymer substrate～the composite fibre of submicron thickness or composite membrane.
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