CN106279443B - The method and purposes of fibril film are prepared with native cellulose fibre separation nanometer fibril - Google Patents
The method and purposes of fibril film are prepared with native cellulose fibre separation nanometer fibril Download PDFInfo
- Publication number
- CN106279443B CN106279443B CN201610673472.2A CN201610673472A CN106279443B CN 106279443 B CN106279443 B CN 106279443B CN 201610673472 A CN201610673472 A CN 201610673472A CN 106279443 B CN106279443 B CN 106279443B
- Authority
- CN
- China
- Prior art keywords
- fibril
- cellulose
- film
- mixed liquor
- micro
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
- C08B15/08—Fractionation of cellulose, e.g. separation of cellulose crystallites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/08—Polysaccharides
- B01D71/12—Cellulose derivatives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
- C08B15/02—Oxycellulose; Hydrocellulose; Cellulosehydrate, e.g. microcrystalline cellulose
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/02—Cellulose; Modified cellulose
- C08L1/04—Oxycellulose; Hydrocellulose, e.g. microcrystalline cellulose
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2401/02—Cellulose; Modified cellulose
- C08J2401/04—Oxycellulose; Hydrocellulose
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- Analytical Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Artificial Filaments (AREA)
Abstract
The present invention provides a kind of in the native cellulose fibre separation nanometer fibril method for preparing fibril film characterized by comprising unicellular pipe fiber wadding body is immersed in 60~98 DEG C by solid-to-liquid ratio 1: 30~1: 50 and contains NaOH and H2O2Mixed solution in, stir and synchronous ultrasonic shake 1~10 hour after, obtain the mixed liquor of the fibril containing nano-cellulose；The mixed liquor of the resulting fibril containing nano-cellulose is subjected to first-stage centrifugal separation, obtains the mixed liquor of cellulose fibril；The mixed liquor of resulting cellulose fibril is subjected to two-stage centrifugal separation, collects sub-micron fibers element fibril bulk；Resulting sub-micron fibers element fibril bulk is cleaned to obtain cellulose fibril bulk clear liquid with deionized water, forms a film, obtains a nanometer fibril film.Targeting of the present invention swelling and dissolution fibril interstitial and the impact of ultrasonic wave microbubble expand and efficient, low damage separate the micro- fibril bulk of acquisition, micro- fibril and base fibre.
Description
Technical field
The present invention relates to a kind of in the coir fibre separation nanometer fibril method for preparing fibril film, it is especially a kind of using from
The method that heart separation method prepares coconut husk nano-cellulose fibril film.
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 micro- and micro-.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.It is receiving both at home and abroad
Relevant article and patent introduction are prepared on rice cellulose, it is as a result as follows: such as: A novel green approach for
The preparation of cellulose nanowhiskers from white coir, DiegoM.Naschimento,
Jessica S.Almeida, Amanda F.Dias et al.Carbohydrate Polymers, 2014,110,456-463
It is by acetic acid and salt low-kappa number, through hydrogen peroxide and alkali process, then the coconut husk nano-cellulose by making after sulfuric acid treatment is brilliant
Palpus；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, Namhito Hori et
Al.Cellulose, 2011,18,443-450 be all to handle by alkali and sodium chlorite, then obtain coconut husk by sulfuric acid treatment and receive
The method of rice 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 mechanically pulverized by pretreatment, biochemical treatment, DMSO processing,
The method of TEMPO oxidation processes extracts the method for Cellulose nanocrystal palpus from bracteal leaf of corn, cotton stalk bark and stalk.Wherein
TEMPO oxidizing process is to be aoxidized using TMPO/NaCLO/NaBr ternary system to native cellulose.Patent CN201510173982.9
It is to be made after preprocessed, etherification process and alkali process and TEMPO oxidation processes using low content of cellulose plant fiber as raw material
The method of nano-cellulose whisker；Patent CN201510050169.2 is mulberry skin by dodging quick-fried-ultrasonic wave degumming and bleaching
The patent of the nano-cellulose whisker of method.Patent CN201310033311 is a kind of utilization cellulose hydrolyzation moso bamboo fiber
The method for preparing nano micro crystal cellulose.Patent CN201210165585 is by alkali process and TEPO method for oxidation from flaxen fiber
The middle method for preparing nano whisker.Patent CN201280027973 is to be used as catalyst with heterocyclic nitroxyl radical, and hypochlorite is used
Make primary oxidizers as oxygen source and tertiary amine or chlorine dioxide and makes cellulose products as the activator of heterocyclic nitroxyl radical
Method.Above-mentioned method for oxidation focuses on to be producing for cellulose fibre.Also patent introduces producing for nano-cellulose film, patent
CN105384957A is reacted in quaternary ammonium salt ethanol solution using the hydroxyl on NaOH activated in water solution bacteria cellulose surface,
Sample obtains ordered nano-fibers film through washes of absolute alcohol and vacuum drying.Patent CN103387685A and
CN103387688A is that nano-cellulose and other materials are mixed with composite membrane, directlys adopt oxidizing process with this patent and separates
To nanometer fibril prepare fibril film mode it is different, the present invention be mainly using centrifuge separation method, will centrifugation gained
To the nanometer fibril of different stage be collected, then dialysed by deionized water, obtain fibril clear liquid, its processing
Method and fibril discrete level are different, especially need to increase strength disposal step by step during preparing nano fibril, make every effort to
Obtain the nanometer fibril of different stage.Innovation and technical characteristic of the invention is to provide a kind of with coir fibre separation nanometer fibril
The method for preparing fibril film.This will be helpful to the high-tech of coir fibre and recycling for fining, be conducive to cellulose fiber
Tie up the sustainable development of resource.
Summary of the invention
Simple and effective fibril film is prepared the purpose of the present invention is to provide a kind of with coir fibre separation nanometer fibril
Method and application thereof.
In order to achieve the above object, the present invention provides one kind prepares fibril with native cellulose fibre separation nanometer fibril
The method of film characterized by comprising
Step 1: by solid-liquid bath raio being to be placed in temperature be 60~98 DEG C contain at 1: 30~1: 50 by native cellulose fibre
NaOH and H2O2Mixed solution in, it is described to contain NaOH and H2O2Mixed solution in, the concentration of NaOH is 20~80g/L,
H2O2Concentration be 80~200ml/L, solvent is deionized water, stir and synchronous ultrasonic shake 0.2~2 hour after, through squeezing
Dehydration, washing, filtering, obtain unicellular pipe fiber wadding body；
Contain step 2: the unicellular pipe fiber wadding body is immersed in 60~98 DEG C by solid-to-liquid ratio 1: 30~1: 50
In the mixed solution of NaOH and NaClO, in the mixed solution containing NaOH and NaClO, the concentration of NaOH is 10~60g/
The concentration of L, NaClO are 15-65g/L, and solvent is deionized water, and stirring simultaneously after synchronous ultrasonic concussion 1~10 hour, is contained
The mixed liquor of nano-cellulose fibril；
It separates step 3: the mixed liquor of the resulting fibril containing nano-cellulose is carried out first-stage centrifugal to remove granule foreign
And fragment, obtain the mixed liquor of cellulose fibril；The mixed liquor of resulting cellulose fibril is subjected to two-stage centrifugal separation, is collected
Sub-micron fibers element fibril bulk, remaining nano-cellulose fibril mixed liquor；
Step 4: resulting sub-micron fibers element fibril bulk is cleaned to obtain cellulose fibril boundling with deionized water
Body clear liquid, film forming, obtains a nanometer fibril film；
Alternatively, the nano-cellulose fibril mixed liquor is carried out three-level centrifuge separation, the micro- fibril collection of cellulose is collected
Shu Ti, the mixed liquor of remaining cellulose base fibril and micro- fibril are clear with deionized water by the micro- fibril bulk of resulting cellulose
It washes to obtain the micro- fibril bulk clear liquid of cellulose, forms a film, obtain a nanometer fibril film；
Alternatively, the nano-cellulose fibril mixed liquor is carried out three-level centrifuge separation, the micro- fibril collection of cellulose is collected
Shu Ti, the mixed liquor of remaining cellulose base fibril and micro- fibril, by the mixed liquor of the cellulose base fibril and micro- fibril into
The centrifuge separation of row level Four, collects the micro- fibril of cellulose, remaining cellulose base fibril mixed liquor；By the micro- fibril of cellulose with
Deionized water cleans to obtain the micro- fibril clear liquid of cellulose, and film forming obtains a nanometer fibril film, alternatively, by resulting cellulose base
After fine mixed liquor carries out dialysis 0.5~3 day, cellulose base fibril clear liquid is obtained, forms a film, obtains a nanometer fibril film.
Preferably, the film build method includes that evaporation, sedimentation at least one of are gathered with Multiple depositions coating.
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 in the first step go water circulation to carry out, cycle-index is 1~3
It is secondary.
It is highly preferred that the kiering be by coma kiering 0.2~2 hour in 60~98 DEG C of water.
Preferably, the mixing speed of the stirring in the first step and synchronous ultrasonic concussion is 300-1000rpm, is surpassed
Sound wave shock frequency is 10~50kHz.
Preferably, the mixing speed of the stirring in the second step and synchronous ultrasonic concussion is 300-1000rpm, is surpassed
Sound wave shock frequency is 10~50kHz.
Preferably, the centrifugal rotational speed of the described first-stage centrifugal separation is 2000-3500rpm, centrifugation time 5-15min,
The centrifugal rotational speed of the two-stage centrifugal separation is 3500-8000rpm, centrifugation time 5-15min, the three-level centrifugation point
From centrifugal rotational speed be 8000-10000rpm, centrifugation time 5-15min, the centrifugal rotational speed of the level Four centrifuge separation is
10000-13000rpm, centrifugation time 5-15min.
Preferably, the dialysis uses commercially available conventional dialysis film, molecular cut off 6000-8000.
The present invention also provides the nanometer fibril films prepared by the above method as filter membrane or bio-medical material, or
As reinforcing material with cellulose matrix is compound prepares pure cellulose composite membrane, or as reinforcing material and other high polymer matrix
The compound purposes prepared in composite membrane.
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 the sub-micron fibers element fibril bulk in the present invention is 100-300nm or so.The fibre
The diameter of the micro- fibril bulk of dimension element is 40-100nm or so, and the diameter of the micro- fibril of the cellulose is 20~40nm or so,
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, basic principle of the invention be targeting swelling with dissolution fibril interstitial and ultrasonic wave microbubble impact expansion and
Efficiently, it is fine to obtain micro- fibril bulk, micro- fibril and base for the separation of low damage ground.By the method for centrifuge separation, directly obtain
Required nanometer fibril has the characteristics that low energy consumption and high-efficient；The fibril clear liquid of obtained four kinds of different-diameters can be with
Directly gathered by large surface expansion evaporation, sedimentation and form nanometer fibril film with Multiple depositions coating, be it is a kind of efficiently, simplicity
Method.
2, fibril bulk of the present invention can prepare the fibril film or fibril enhancing film of 0.4~10 μ m thick；Institute
The micro- fibril bulk stated can prepare the fibril film or fibril enhancing film of 0.2~10 μ m thick；Micro- fibril can be prepared
The fibril film or fibril of the μ m thick of 80nm~5 enhance film；The base fibre can prepare the μ m thick of 40nm~5 fibril film or
Person's fibril enhances film.
3, the resulting nanometer fibril film of the present invention can be used for filter membrane or the biology doctor of the i.e. different efficiency of different-diameter range
Use material；Or the different-diameter range fibril for cellulose matrix enhances and prepares pure cellulose composite membrane.It can also be used for increasing
Other strong high polymer matrix prepare the fibril film of the different-diameter range of composite membrane.And coir fibre is resourceful, and price is low
Honest and clean, waste is serious, and preparing coconut husk nano-cellulose fibril helps to be conducive to human society to the utilization of coir fibre resource
Sustainable development.
Detailed description of the invention
Fig. 1 is transmission electron microscope (TEM) photo of the micro- fibril bulk film of coconut husk nanometer of embodiment 1
Fig. 2 is the micro- fibril of transmission electron microscope (TEM) photo of the micro- fibril film of coconut husk nanometer of embodiment 2
Fig. 3 is transmission electron microscope (TEM) photo-based fibril of the coconut husk nanometer base fibre film of embodiment 3
Fig. 4 is the shooting photo in kind of the coconut husk nanometer fibril tunica fibrosa of embodiment 4.
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.
Dialysis in various embodiments of the present invention is carried out using deionized water.
Embodiment 1
A method of fibril film, specific steps are prepared with coir fibre separation nanometer fibril are as follows:
(1) it shredding removal of impurities, kiering swelling and cleaning impurity elimination: by machinery strike, rubs and pulls drawing for coconut husk shredding, remove
Particulate contaminant obtains loose coma；Resulting coma is subjected to kiering, washing and squeezes and removes water, the kiering,
The specific steps for washing and squeezing water include that coma is placed in beaker, are totally submerged Yu Shuizhong, are placed in 60 DEG C of water-baths
Middle progress kiering swelling 2 hours is stirred with the revolving speed of 500rpm while kiering, using multistage roller device to fiber after kiering
Group, which squeeze, removes water, is washed with water, then squeeze water；Kiering, washing and the extruding goes water circulation to carry out 3 times, to go
Except matrix between removal fiber, later, drying is placed in 80 DEG C of baking ovens to constant weight, obtain fiber surface without visible adherency impurity but wet
The clean coir fibre of state；
(2) synchronous to be swollen, bleach and separate: the clean coir fibre, which is placed in temperature by solid-liquid bath raio for 1: 30, is
90 DEG C contain NaOH and H2O2Mixed solution in, it is described to contain NaOH and H2O2Mixed solution in by NaOH, H2O2With go from
Sub- water composition, the concentration of NaOH are 20g/L, H2O2Concentration be 120ml/L, solvent is deionized water, stir and synchronous ultrasonic
Concussion 2 hours, mixing speed 500rpm, ultrasonic oscillation frequency are that 20kHz is obtained through 2 slot extrusion dehydrations, washing, filtering
Subalkaline high swelling and the isolated unicellular pipe fiber wadding body of milky；
(3) the unicellular pipe fiber wadding body oxidation dissolution and ultrasonic separation: is immersed in 90 by solid-to-liquid ratio 1: 30
DEG C containing in NaOH and NaClO mixed solution, by NaOH, NaClO deionization in the mixed solution containing NaOH and NaClO
Water forms, and in the mixed solution containing NaOH and NaClO, the concentration of NaOH is 10g/L, and the concentration of NaClO is 15g/L,
Solvent is deionized water, is stirred simultaneously after synchronous ultrasonic concussion 4 hours, mixing speed 500rpm, and ultrasonic oscillation frequency is
20kHz obtains the mixed liquor of the fibril containing nano-cellulose；
(4) fractional centrifugation separation is collected with dialysis: by the mixed liquor of the resulting fibril containing nano-cellulose carry out level-one from
The heart is separated to remove granule foreign and fragment, centrifugal rotational speed 3500rpm, and centrifugation time 10min obtains cellulose fibril
Mixed liquor；The mixed liquor of resulting cellulose fibril is subjected to two-stage centrifugal separation, centrifugal rotational speed 7000rpm, centrifugation time
For 10min, sub-micron fibers element fibril bulk, remaining nano-cellulose fibril mixed liquor are collected；Resulting sub-micron is fine
Plain fibril bulk is tieed up, cleans to obtain cellulose fibril bulk clear liquid with deionized water, through using commercially available conventional dialysis film
Dialysis is carried out 1 day to remove cellulose macromolecule and all ions and low molecule class impurity, and the molecular cut off of dialysis membrane is
6000, by sprawling evaporation mode film forming, obtain a nanometer fibril film.
The nano-cellulose fibril of present embodiment preparation is tested using transmission electron microscope, as shown in Figure 1.It is available
The thickness average out to 190nm of nano thin-film, in 98~230nm, average diameter becomes the diameter of cellulose fibril in 182nm, diameter
Different coefficient value 42.89%.
Embodiment 2:
A method of fibril film, specific steps are prepared with coir fibre separation nanometer fibril are as follows:
(1) it shredding removal of impurities, kiering swelling and cleaning impurity elimination: by machinery strike, rubs and pulls drawing for coconut husk shredding, remove
Particulate contaminant obtains loose coma；Resulting coma is subjected to kiering, washing and squeezes and removes water, the kiering,
The specific steps for washing and squeezing water include that coma is placed in beaker, are totally submerged Yu Shuizhong, are placed in 60 DEG C of water-baths
Middle progress kiering swelling 2 hours is stirred with the revolving speed of 700rpm while kiering, using multistage roller device to fiber after kiering
Group, which squeeze, removes water, is washed with water, then squeeze water；Kiering, washing and the extruding goes water to recycle progress 3 times, later,
It is placed in drying in 80 DEG C of baking ovens and obtains clean coir fibre of the fiber surface without visible adherency impurity but hygrometric state to constant weight；
(2) synchronous to be swollen, bleach and separate: the clean coir fibre, which is placed in temperature by solid-liquid bath raio for 1: 40, is
80 DEG C contain NaOH and H2O2Mixed solution in, it is described to contain NaOH and H2O2Mixed solution in by NaOH, H2O2With go from
Sub- water composition, the concentration of NaOH are 40g/L, H2O2Concentration be 150ml/L, solvent is deionized water, stir and synchronous ultrasonic
Concussion 1.5 hours, mixing speed 700rpm, ultrasonic oscillation frequency are that 30kHz is obtained through 3 slot extrusion dehydrations, washing, filtering
To subalkaline high swelling and the isolated unicellular pipe fiber wadding body of milky；
(3) the unicellular pipe fiber wadding body oxidation dissolution and ultrasonic separation: is immersed in 80 by solid-to-liquid ratio 1: 40
DEG C the mixed solution containing NaOH and NaClO in, by NaOH, NaClO and gone in the mixed solution containing NaOH and NaClO
Ionized water forms, and in the mixed solution containing NaOH and NaClO, the concentration of NaOH is 50g/L, and the concentration of NaClO is
30g/L, solvent are deionized water, are stirred simultaneously after synchronous ultrasonic concussion 5 hours, mixing speed 700rpm, ultrasonic oscillation
Frequency is 30kHz, obtains the mixed liquor of the fibril containing nano-cellulose；
(4) fractional centrifugation separation is collected with dialysis: by the mixed liquor of the resulting fibril containing nano-cellulose carry out level-one from
The heart is separated to remove granule foreign and fragment, centrifugal rotational speed 3000rpm, and centrifugation time 15min obtains cellulose fibril
Mixed liquor；The mixed liquor of resulting cellulose fibril is subjected to two-stage centrifugal separation, centrifugal rotational speed 6000rpm, centrifugation time
For 15min, sub-micron fibers element fibril bulk, remaining nano-cellulose fibril mixed liquor are collected；By the nanofiber
Plain fibril mixed liquor carries out three-level centrifuge separation, and centrifugal rotational speed 9000rpm, centrifugation time 10min collect the micro- original of cellulose
Fine bulk, the mixed liquor of remaining cellulose base fibril and micro- fibril, by the micro- fibril bulk of resulting cellulose with no ion
Water cleans to obtain the micro- fibril bulk clear liquid of cellulose, and commercially available conventional dialysis film is used to carry out dialysis 2 days to remove cellulose
Macromolecular and all ions and low molecule class impurity, the molecular cut off of dialysis membrane are 7000, by sprawling evaporation mode film forming,
Obtain a nanometer fibril film.
The nano-cellulose fibril of present embodiment preparation is tested using transmission electron microscope, as shown in Figure 2.It is available
The thickness average out to 90nm of nano thin-film, the diameter of the micro- fibril of cellulose is in 35~112nm, and average diameter is in 86nm, variation lines
Numerical value 40.78%.
Embodiment 3:
A method of fibril film, specific steps are prepared with coir fibre separation nanometer fibril are as follows:
(1) it shredding removal of impurities, kiering swelling and cleaning impurity elimination: by machinery strike, rubs and pulls drawing for coconut husk shredding, remove
Particulate contaminant obtains loose coma；Resulting coma is subjected to kiering, washing and squeezes and removes water, the kiering,
The specific steps for washing and squeezing water include that coma is placed in beaker, are totally submerged Yu Shuizhong, are placed in 60 DEG C of water-baths
Middle progress kiering swelling 2 hours is stirred with the revolving speed of 800rpm while kiering, using multistage roller device to fiber after kiering
Group, which squeeze, removes water, is washed with water, then squeeze water；Kiering, washing and the extruding goes water to recycle progress 3 times, later,
It is placed in drying in 80 DEG C of baking ovens and obtains clean coir fibre of the fiber surface without visible adherency impurity but hygrometric state to constant weight；
(2) synchronous to be swollen, bleach and separate: the clean coir fibre, which is placed in temperature by solid-liquid bath raio for 1: 40, is
70 DEG C contain NaOH and H2O2Mixed solution in, it is described to contain NaOH and H2O2Mixed solution in by NaOH, H2O2With go from
Sub- water composition, the concentration of NaOH are 60g/L, H2O2Concentration be 200ml/L, solvent is deionized water, stir and synchronizing ultrasound
Wave shakes 1 hour, mixing speed 800rpm, and ultrasonic oscillation frequency is that 40kHz is obtained through 4 slot extrusion dehydrations, washing, filtering
To subalkaline high swelling and the isolated unicellular pipe fiber wadding body of milky；
(3) the unicellular pipe fiber wadding body oxidation dissolution and ultrasonic separation: is immersed in 70 by solid-to-liquid ratio 1: 30
DEG C the mixed solution containing NaOH and NaClO in, by NaOH, NaClO and gone in the mixed solution containing NaOH and NaClO
Ionized water forms, and in the mixed solution containing NaOH and NaClO, the concentration of NaOH is 80g/L, and the concentration of NaClO is
48g/L, solvent are deionized water, are stirred simultaneously after synchronous ultrasonic concussion 8 hours, mixing speed 800rpm, ultrasonic oscillation
Frequency is 40kHz, obtains the mixed liquor of the fibril containing nano-cellulose；
(4) fractional centrifugation separation is collected with dialysis: by the mixed liquor of the resulting fibril containing nano-cellulose carry out level-one from
The heart is separated to remove granule foreign and fragment, centrifugal rotational speed 2500rpm, and centrifugation time 15min obtains cellulose fibril
Mixed liquor；The mixed liquor of resulting cellulose fibril is subjected to two-stage centrifugal separation, centrifugal rotational speed 8000rpm, centrifugation time
For 10min, sub-micron fibers element fibril bulk, remaining nano-cellulose fibril mixed liquor are collected；By the nanofiber
Plain fibril mixed liquor carries out three-level centrifuge separation, and it is micro- to collect cellulose by centrifugal rotational speed 10000rpm, centrifugation time 10min
Fibril bulk, the mixed liquor of remaining cellulose base fibril and micro- fibril, by the mixed of the cellulose base fibril and micro- fibril
It closes liquid and carries out level Four centrifuge separation, centrifugal rotational speed 12000rpm, centrifugation time 10min collect the micro- fibril of cellulose, remaining
Cellulose base fibril mixed liquor；The micro- fibril of cellulose is cleaned to obtain the micro- fibril clear liquid of cellulose with deionized water, is adopted
Dialysis is carried out 3 days to remove cellulose macromolecule and all ions and low molecule class impurity with commercially available conventional dialysis film, is dialysed
The molecular cut off of film is 8000, by sprawling evaporation mode film forming, obtains a nanometer fibril film.
The nano-cellulose fibril of present embodiment preparation is tested using transmission electron microscope, as shown in Figure 3.It is available
The minimum average thickness of nano thin-film is 48nm, the diameter of cellulose sub-micron fibril in 16~46nm, average diameter in 32nm,
Value for coefficient of variation 35.56%.
Embodiment 4
A method of fibril film, specific steps are prepared with coir fibre separation nanometer fibril are as follows:
(1) it shredding removal of impurities, kiering swelling and cleaning impurity elimination: by machinery strike, rubs and pulls drawing for coconut husk shredding, remove
Particulate contaminant obtains loose coma；Resulting coma is subjected to kiering, washing and squeezes and removes water, the kiering,
The specific steps for washing and squeezing water include that coma is placed in beaker, are totally submerged Yu Shuizhong, are placed in 60 DEG C of water-baths
Middle progress kiering swelling 2 hours is stirred with the revolving speed of 1000rpm while kiering, using multistage roller device to fibre after kiering
Dimension group, which squeeze, removes water, is washed with water, then squeeze water；Kiering, washing and the extruding goes water circulation to carry out 3 times, it
Afterwards, it is placed in drying in 80 DEG C of baking ovens and obtains clean coir fibre of the fiber surface without visible adherency impurity but hygrometric state to constant weight；
(2) synchronous to be swollen, bleach and separate: the clean coir fibre, which is placed in temperature by solid-liquid bath raio for 1: 30, is
60 DEG C contain NaOH and H2O2Mixed solution in, it is described to contain NaOH and H2O2Mixed solution in by NaOH, H2O2With go from
Sub- water composition, the concentration of NaOH are 50g/L, H2O2Concentration be 150ml/L, solvent is deionized water, stir and synchronous ultrasonic
Concussion 1 hour, mixing speed 1000rpm, ultrasonic oscillation frequency are that 50kHz is obtained through 2 slot extrusion dehydrations, washing, filtering
To subalkaline high swelling and the isolated unicellular pipe fiber wadding body of milky；
(3) the unicellular pipe fiber wadding body oxidation dissolution and ultrasonic separation: is immersed in 60 by solid-to-liquid ratio 1: 50
DEG C the mixed solution containing NaOH and NaClO in, by NaOH, NaClO and gone in the mixed solution containing NaOH and NaClO
Ionized water forms, and in the mixed solution containing NaOH and NaClO, the concentration of NaOH is 40g/L, and the concentration of NaClO is
38g/L, solvent are deionized water, are stirred simultaneously after synchronous ultrasonic concussion 5 hours, mixing speed 1000rpm, ultrasonic oscillation
Frequency is 50kHz, obtains the mixed liquor of the fibril containing nano-cellulose；
(4) fractional centrifugation separation is collected with dialysis: by the mixed liquor of the resulting fibril containing nano-cellulose carry out level-one from
Heart separation is to remove granule foreign and fragment, centrifugal rotational speed 3500rpm, centrifugation time 10mi, obtain cellulose fibril
Mixed liquor；The mixed liquor of resulting cellulose fibril is subjected to two-stage centrifugal separation, centrifugal rotational speed 6000rpm, centrifugation time
For 15min, sub-micron fibers element fibril bulk, remaining nano-cellulose fibril mixed liquor are collected；
The nano-cellulose fibril mixed liquor is subjected to three-level centrifuge separation, centrifugal rotational speed 9000rpm, when centrifugation
Between be 15min, collect the micro- fibril bulk of cellulose, the mixed liquor of remaining cellulose base fibril and micro- fibril, by the fibre
The mixed liquor for tieing up plain base fibre and micro- fibril carries out level Four centrifuge separation, centrifugal rotational speed 13000rpm, and centrifugation time is
15min collects the micro- fibril of cellulose, remaining cellulose base fibril mixed liquor；Resulting cellulose base fibril mixed liquor is used
Commercially available dialysis membrane carries out dialysis 1 day to remove cellulose macromolecule and all ions and low molecule class impurity, and dialysis membrane is cut
Staying molecular weight is 8000, is cleaned with deionized water, obtains cellulose base fibril clear liquid, carries out dialysis 3 using commercially available dialysis membrane
It is to remove cellulose macromolecule and all ions and low molecule class impurity, and condition is that molecular cut off is 8000, by sprawling
Evaporation mode film forming, obtains a nanometer fibril film.
The nano-cellulose fibril of present embodiment preparation is tested using transmission electron microscope, fiber as shown in Figure 4
The appearance images of film, wherein fibrillar size and distribution are similar with Fig. 2, and size does not change.The thickness of nano thin-film can be obtained
Average out to 26nm, the diameter of cellulose fibril is in 6~28nm, and average diameter is in 18.3nm, diameter variation coefficient value 42.89%.
Claims (7)
1. a kind of method for preparing fibril film with native cellulose fibre separation nanometer fibril characterized by comprising
Step 1: by native cellulose fibre by solid-liquid bath raio be 1:30 ~ 1:50 be placed in temperature be 60 ~ 98 DEG C containing NaOH and
H2O2Mixed solution in, it is described to contain NaOH and H2O2Mixed solution in, the concentration of NaOH is 20 ~ 80g/L, H2O2It is dense
Degree is 80 ~ 200ml/L, and solvent is deionized water, is stirred simultaneously after synchronous ultrasonic concussion 0.2 ~ 2 hour, through extrusion dehydration, water
It washes, filter, obtain unicellular pipe fiber wadding body；The native cellulose fibre is coir fibre；The coir fibre
Preparation method includes: that coconut husk shredding is obtained coma, and resulting coma is carried out kiering, washing and extruding and removes water, is dried
It is dry, obtain coir fibre；Kiering, washing and the extruding goes water circulation to carry out, and cycle-index is 1 ~ 3 time, to remove fiber
Between matrix；
Step 2: by the unicellular pipe fiber wadding body by solid-to-liquid ratio 1:30 ~ 1:50 be immersed in 60 ~ 98 DEG C containing NaOH and
In the mixed solution of NaClO, in the mixed solution containing NaOH and NaClO, the concentration of NaOH is 10 ~ 60g/L, NaClO
Concentration be 15 ~ 65g/L, solvent is deionized water, is stirred and after synchronous ultrasonic shakes 1 ~ 10 hour, is obtained containing nanofiber
The mixed liquor of plain fibril；
Step 3: the mixed liquor of the resulting fibril containing nano-cellulose is carried out first-stage centrifugal separation to remove granule foreign and broken
Piece obtains the mixed liquor of cellulose fibril；The mixed liquor of resulting cellulose fibril is subjected to two-stage centrifugal separation, collects sub-micro
Rice cellulose fibril bulk, remaining nano-cellulose fibril mixed liquor；
Step 4: resulting sub-micron fibers element fibril bulk with deionized water is cleaned to obtain cellulose fibril bulk clear
Liquid, film forming, obtains a nanometer fibril film；
Alternatively, the nano-cellulose fibril mixed liquor is carried out three-level centrifuge separation, the micro- fibril bulk of cellulose is collected,
The micro- fibril bulk of resulting cellulose is cleaned to obtain by the mixed liquor of remaining cellulose base fibril and micro- fibril with deionized water
The micro- fibril bulk clear liquid of cellulose, film forming, obtains a nanometer fibril film；
Alternatively, the nano-cellulose fibril mixed liquor is carried out three-level centrifuge separation, the micro- fibril bulk of cellulose is collected,
The mixed liquor of the cellulose base fibril and micro- fibril is carried out level Four by the mixed liquor of remaining cellulose base fibril and micro- fibril
The micro- fibril of cellulose, remaining cellulose base fibril mixed liquor are collected in centrifuge separation；By the micro- fibril of cellulose with no ion
Water cleans to obtain the micro- fibril clear liquid of cellulose, and film forming obtains a nanometer fibril film, alternatively, resulting cellulose base fibril is mixed
After liquid carries out dialysis 0.5 ~ 3 day, cellulose base fibril clear liquid is obtained, forms a film, obtains a nanometer fibril film.
2. the method for preparing fibril film as described in claim 1 with native cellulose fibre separation nanometer fibril, feature exist
It include that evaporation, sedimentation at least one of are gathered with Multiple depositions coating in, the film build method.
3. the method for preparing fibril film as described in claim 1 with native cellulose fibre separation nanometer fibril, feature exist
In, the kiering be by coma kiering 0.2 ~ 2 hour in 60 ~ 98 DEG C of water.
4. the method for preparing fibril film as described in claim 1 with native cellulose fibre separation nanometer fibril, feature exist
In the mixing speed of stirring and synchronous ultrasonic concussion in the first step is 300-1000rpm, and ultrasonic oscillation frequency is
10~50kHz。
5. the method for preparing fibril film as described in claim 1 with native cellulose fibre separation nanometer fibril, feature exist
In the mixing speed of stirring and synchronous ultrasonic concussion in the second step is 300-1000rpm, and ultrasonic oscillation frequency is
10~50kHz。
6. the method for preparing fibril film as described in claim 1 with native cellulose fibre separation nanometer fibril, feature exist
In, the centrifugal rotational speed of the described first-stage centrifugal separation be 2000-3500rpm, centrifugation time 5-15min, the second level from
The centrifugal rotational speed of heart separation is 3500-8000rpm, centrifugation time 5-15min, the centrifugal rotational speed of the three-level centrifuge separation
For 8000-10000rpm, centrifugation time 5-15min, the centrifugal rotational speed of the level Four centrifuge separation is 10000-
13000rpm, centrifugation time 5-15min.
7. the method institute of any of claims 1-6 for preparing fibril film with native cellulose fibre separation nanometer fibril
The nanometer fibril film of preparation is as filter membrane or bio-medical material, or as reinforcing material and the compound preparation of cellulose matrix
Pure cellulose composite membrane, or the purposes in composite membrane is prepared as reinforcing material and other high polymer matrix composites.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610673472.2A CN106279443B (en) | 2016-08-16 | 2016-08-16 | The method and purposes of fibril film are prepared with native cellulose fibre separation nanometer fibril |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610673472.2A CN106279443B (en) | 2016-08-16 | 2016-08-16 | The method and purposes of fibril film are prepared with native cellulose fibre separation nanometer fibril |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106279443A CN106279443A (en) | 2017-01-04 |
| CN106279443B true CN106279443B (en) | 2019-07-23 |
Family
ID=57672130
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610673472.2A Active CN106279443B (en) | 2016-08-16 | 2016-08-16 | The method and purposes of fibril film are prepared with native cellulose fibre separation nanometer fibril |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106279443B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113073485B (en) * | 2021-04-09 | 2022-08-12 | 黑龙江八一农垦大学 | Preparation method of nano cellulose fiber and product thereof |
| CN115012052A (en) * | 2022-04-29 | 2022-09-06 | 北华大学 | Method for preparing micro-nano cellulose fibers by taking corn straws as raw materials |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102675475A (en) * | 2012-05-24 | 2012-09-19 | 东华大学 | Method for preparing fibrilia carboxylation cellulose nanowhiskers |
-
2016
- 2016-08-16 CN CN201610673472.2A patent/CN106279443B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102675475A (en) * | 2012-05-24 | 2012-09-19 | 东华大学 | Method for preparing fibrilia carboxylation cellulose nanowhiskers |
Non-Patent Citations (1)
| Title |
|---|
| "椰壳纳米纤维素晶须的氧化法制备";谢文雅等;《成都纺织高等专科学校学报》;20160430;第33卷(第2期);第21-25页 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106279443A (en) | 2017-01-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | Reuse of waste cotton cloth for the extraction of cellulose nanocrystals | |
| JP5500842B2 (en) | Method for producing cellulose nanofiber | |
| KR100754315B1 (en) | Manufacturing method of bamboo chip for manufacturing a natural fiber and bamboo fiber using thereof | |
| CN103255662B (en) | Preparation method of nanometer fibril enteromorpha cellulose | |
| CN105568744B (en) | A kind of cornstalk nano-cellulose whisker and preparation method and application | |
| CN103396572A (en) | Lignocellulose nano-fiber/acrylic resin composite film preparation method | |
| CN100395384C (en) | Method for fabricating fiber of regenerative bamboo cellulose | |
| JP2010104768A (en) | Polysaccharide nanofiber, method for manufacturing the same, and ionic liquid solution and composite material containing polysaccharide nanofiber | |
| CN107236049A (en) | A kind of nano-cellulose and preparation method thereof | |
| CN101353826A (en) | Mulberry bark nano cellulose fibre and preparation thereof | |
| CN106317466A (en) | Method for preparing lithium battery diaphragm by compounding nano-cellulose and nano-silicon dioxide | |
| WO2007037711A1 (en) | The method of fibrous plant degumming | |
| CN106279443B (en) | The method and purposes of fibril film are prepared with native cellulose fibre separation nanometer fibril | |
| CN105648816A (en) | Method for extracting plant cellulose nanowhisker | |
| CN106149433A (en) | Nano-cellulose and preparation method thereof | |
| CN106283935B (en) | The method and purposes of separating pipe fiber from coir fibre | |
| CN105316770A (en) | Physical preparation method for bamboo fibers | |
| CN106758447B (en) | A kind of method that biology ultrasonic wave prepares textile fabric | |
| CN109485737A (en) | A method of Cellulose nanocrystal is prepared using moso bamboo | |
| Fauziyah et al. | Bagasse nanocellulose (Saccharum officinarum L.): process optimization and characterization | |
| CN106283209B (en) | A kind of method and purposes preparing different scale nanometer fibril using coir fibre | |
| CN106279444B (en) | method for preparing nano cellulose fibril by using natural cellulose fiber and application | |
| Sheltami et al. | Structural characterisation of cellulose and nanocellulose extracted from mengkuang leaves | |
| CN106188600B (en) | The method and purposes of heterogeneous composite membrane are prepared with coir fibre nanometer fibril enhancing | |
| CN104988779A (en) | Preparation method and application of Salix cheilophila nanocellulose |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |