CN106832425A - High performance Graphene composite nano fiber element and preparation method thereof, application - Google Patents
High performance Graphene composite nano fiber element and preparation method thereof, application Download PDFInfo
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- CN106832425A CN106832425A CN201610835479.XA CN201610835479A CN106832425A CN 106832425 A CN106832425 A CN 106832425A CN 201610835479 A CN201610835479 A CN 201610835479A CN 106832425 A CN106832425 A CN 106832425A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
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Abstract
The invention provides a kind of high performance Graphene composite nano fiber element, mainly by nano-cellulose and graphite alkenes material composition, graphite alkenes material is mutually in situ with nano-cellulose to be carried；In the Graphene composite nano fiber element, the content of graphite alkenes material, in below 20wt%, is further below 10wt%, further between 0.5wt% 5wt%.Preparation method includes：(A) cellulose, graphite alkenes material and distilled water deionized water are mixed into ultrasonic disperse, grinding and obtains suspension；(B) by suspension ultrasound, centrifugation, freeze-drying shaping obtains final product Graphene composite nano fiber element.The Graphene composite nano fiber element of the embodiment of the present invention, graphite alkenes material can keep content higher, still dispersion ratio is more uniform for graphene particles, granular size is also than more uniform, agglomerated particle produces less, and also it is extra impart the excellent anti-microbial property of nano-cellulose, far infrared performance, excellent toughness, hot water resistance and antistatic property.
Description
Technical field
It is compound in particular to a kind of high performance Graphene the present invention relates to nano-cellulose processing preparation field
Nano-cellulose and preparation method thereof, application.
Background technology
Cellulose is to be widely present on the earth and reproducible resource.Nano micro crystal cellulose, is that native cellulose passes through
After treatment (such as sour water solution, biological enzyme hydrolysis), the crystal region of amorphous region and low-crystallinity in cellulose is abolished, and is obtained
A kind of cellulose crystallite body for arriving.The nano micro crystal cellulose prepared by native cellulose not only has the basic structure of cellulose
With performance, also with huge specific surface area (~70), high-crystallinity (>70%), high-hydrophilic, high Young's modulus, high intensity
(7500MPa), hyperfine structure and high transparency, good biodegradability is with biocompatibility and stabilization chemically
Energy.In addition, because cellulose surface exposes great amount of hydroxy group, reproducibility and non-reducing end group so that nano micro crystal cellulose
With huge chemical modification potentiality, promoting its application study in fields such as papermaking, medicine, food, composites to process hand can
Heat.
Graphene is a kind of two-dimensional material of the alveolate texture being made up of individual layer sp2 hydbridized carbon atoms, with many excellent
Different performance.It has been found since 2004, Graphene just becomes a big study hotspot of scientific circles.In the thing to Graphene
While Physicochemical property is studied, the composite related to Graphene also emerges in an endless stream.On nano science direction, stone
Black alkene is also used to prepare the nano composite material of correlation, especially the nanometer of Graphene/metal or graphene/metal oxide
Composite.Due to the excellent properties of Graphene, these nano composite materials are in novel energy, bio-sensing, catalysis, optics material
There are wide Research Prospects in the fields such as material.
In the prior art, the Related product of Graphene composite nano fiber element is relatively more, such as patent CN103937032A
In describe a kind of composite coloured film of Cellulose nanocrystal/Graphene and its fast preparation method, by the fiber that will be prepared
The nanocrystalline solution that is prepared into of element mixes with Graphene, and ultrasonic disperse, vacuum filtration obtains colour film.Also patent
A kind of method that graphene oxide co-catalysis sour water solution prepares nano micro crystal cellulose is described in CN104910394A, it is above-mentioned special
Graphene is described in profit can be combined to form the correlation technique of joint product with nano-cellulose, but problem exists
In while Graphene addition certain in ensure that joint product, there are graphene particles in nano-cellulose
Disperse uneven, granular size heterogeneity, be susceptible to the problem of interlayer reunion, so different piece footpath graphite alkenes materials
The stress concentration point for bringing can be easy to be broken, the performance of the product that influence is prepared.
In view of this, it is special to propose the present invention.
The content of the invention
The first object of the present invention is to provide a kind of with high performance Graphene composite nano fiber element, and this is compound
In cellulose, graphite alkenes material can keep content higher, and still dispersion ratio is more uniform for graphene particles, granular size
Than more uniform, agglomerated particle produces less, and graphite alkenes material is added during nano-cellulose is prepared so that stone
Black alkenes material is opened cellulose noncrystalline domain and is mutually carried with nano-cellulose by interspersed, realizes In-situ reaction, more has
What is imitated realizes scattered uniformity and holding Graphene and the respective performance of nano-cellulose, and also additionally imparts Nanowire
Dimension excellent anti-microbial property, the far infrared performance of element, excellent toughness, hot water resistance and antistatic property, the cost of material of use
Low, small investment thus further expands the market range of application of nano-cellulose, improves value-added content of product,
Be conducive to further genralrlization application.
The second object of the present invention is to provide a kind of preparation side of above-mentioned high performance Graphene composite nano fiber element
Method, step linking is tight before and after the preparation method, method simple and fast, no in whole preparation process to use anyization such as soda acid
Medicament is learned, environmental protection also without the generation of spent acid salkali waste, and has equally been reached using preparation method of the invention and employed
Acidifying prepares nano-cellulose and is had the advantage that, such as suitable draw ratio.And the preparation method has method simply easy
In operation, operating condition is gentle, and industrialized production, the economic benefit for being capable of achieving Graphene composite nano fiber element are good.
The third object of the present invention is to provide the above-mentioned application with high performance Graphene composite nano fiber element, should
Nano-cellulose products application widely, can be widely applied to industry-by-industry.
In order to realize above-mentioned purpose of the invention, spy uses following technical scheme：
A kind of high performance Graphene composite nano fiber element product is the embodiment of the invention provides, it is mainly by Graphene
Class material is constituted with nano-cellulose, and the graphite alkenes material is mutually in situ with nano-cellulose to be carried；
In the Graphene composite nano fiber element, the content of graphite alkenes material is further in below 20wt%
Below 10wt%, further between 0.5wt%-5wt%.
Wherein, the Graphene composite nano fiber element in, the content of graphite alkenes material in below 20wt% because graphite
If the alkene content Graphene that can be easily caused too high departs from nano-cellulose, there is group in graphene particles in nano-cellulose
It is poly-, poor dispersion, and then the performance of final products is had influence on, therefore the content of graphite alkenes material needs control suitable
In the range of to ensure excellent dispersiveness, this scope is also the comparing that inventor is gone out by substantial amounts of practical experience final optimization pass
Suitable content, the content of more excellent graphite alkenes material is controlled in below 10wt%, can also for 0.5wt%-5wt% it
Between, in addition for example, 1wt%, 1.5wt%, 2wt%, 2.5wt%, 3.5wt%, 4wt% etc..
In a word, in Graphene composite nano fiber element of the invention, Graphene content is higher in itself, but particle disperses
Than more uniform, the excellent anti-microbial property of nano cellulose material, excellent toughness, hot water resistance and antistatic are also additionally imparted
Performance, the cost of material of use is low, small investment, thus further expands the market range of application of fibrous material, improves
Value-added content of product, is also beneficial to further genralrlization application.
Further, nano-cellulose is prepared by corn cob fiber element, it is preferable that the nano-cellulose be by
The corn cob fiber element that purification bleaching is crossed is prepared.
The present invention prepares the raw material preferably corn cob fiber element of nano-cellulose, because corn cob fiber element itself is quite
In refuse reclamation, the reasonable redistribution of resource is realized, and the Graphene that can cause to prepare using this cellulose
The particle diameter of composite nano fiber element product is more homogeneous.
Corn cob fiber element included before nano-cellulose is prepared by the specific method of purification bleaching：
A. sour water solution is carried out to corn core raw material, pentose solution and sour hydrolytic residue is obtained after separation；It is used acid for sulfuric acid,
The conventional acid solution such as hydrochloric acid, phosphoric acid, sulfurous acid, the consumption of acid is the 1-10wt% of corn core raw material, and hydrolysis temperature is 100-150
DEG C, the time is 0.5-3h；
B. with the sour hydrolytic residue that alkaline solution treatment is above-mentioned, alkali solution liquid and alkaline hydrolysis residue are obtained after separation.Alkali used is hydrogen
Sodium oxide molybdena, the consumption of alkali is the 1-15wt% of corn core raw material, and treatment temperature is 40-100 DEG C, and the time is 1-6h；
C. bleaching is carried out to above-mentioned alkaline hydrolysis residue, processing mode includes sodium hypochlorite bleaching, hydrogen peroxide bleaching, alkali
One or more in the modes such as treatment, acid treatment.
By that after above-mentioned purification processes, can obtain corn cob fiber element, its main index is content of cellulose：80-
95%, whiteness 70-90%, ash content 0.1-2%, fibre length 0.05-0.5mm.
Further, the draw ratio of nano-cellulose is controlled at (5-1000)：1, preferably (10-300)：1, more preferably
It is (15-200)：1.
During practical operation, the minimum diameter of nano-cellulose is less than 20nm, preferably below 10nm, more preferably 5nm with
Under.
Graphite alkenes material of the present invention includes that Graphene, biomass Graphene, graphene oxide, Graphene spread out
One or more biological mixing, the Graphene derivative is the Graphene by being modified.
Preferably, the Graphene derives any a kind included in element doping Graphene or functional group's graphite alkene thing
Or at least 2 kinds of combination.
Preferably, the element doping Graphene is including in metal-doped Graphene or nonmetal doping Graphene
Any a kind or at least 2 kinds of combination.
The metal-doped metallic element it is typical but non-limiting including potassium, sodium, gold, silver, iron, copper, nickel, chromium titanium,
Vanadium or cobalt.
The nonmetal doping Graphene is typical but non-limiting including nitrogen, phosphorus, silicon, boron or silicon.
Preferably, the nonmetal doping Graphene includes nitrogen-doped graphene, phosphorus doping Graphene or sulfur doping
Any a kind or at least 2 kinds of combination in Graphene.
Preferably, functional group's graphite alkene includes being grafted with the Graphene of functional group.
Preferably, functional group's graphite alkene includes any a kind or at least 2 be grafted with hydroxyl, carboxyl or amino
The Graphene of the combination planted.
Hydroxyl of the present invention includes that-R1-OH, the R1 include alkyl, and typical but non-limiting hydroxyl can be
Methylhydroxy, ethyl hydroxy, propyl hydroxy, butylhydroxy, amyl group hydroxyl, hexyl hydroxyl etc..
Carboxyl of the present invention includes that-R2-COOH, the R2 include alkyl, and typical but non-limiting hydroxyl can be with
It is methylhydroxy, ethyl hydroxy, propyl hydroxy, butylhydroxy, amyl group hydroxyl, hexyl hydroxyl etc..
Carboxyl of the present invention includes-R3-NH3, the R3 includes alkyl, and typical but non-limiting hydroxyl can be
Methylhydroxy, ethyl hydroxy, propyl hydroxy, butylhydroxy, amyl group hydroxyl, hexyl hydroxyl etc..
In addition, biomass Graphene is to contain single-layer graphene, few layer graphene, graphite with biomass as prepared by raw material
Alkene nano-lamellar structure, and carried metal/nonmetallic compound, the number of plies are not more than 10 layers of two-dimensional nano Carbon Materials, or even can
Be more than on the basis of the carbon composite comprising graphitized charcoal, metal/non-metal compound.
The present invention is except there is provided a kind of high performance Graphene composite nano fiber element product, additionally providing the Graphene
The preparation method of composite nano fiber element, specifically includes following steps：
(A) cellulose, graphite alkenes material and deionized water are mixed into ultrasonic disperse, grinding and obtains suspension；
(B) by suspension ultrasound, centrifugation, freeze-drying shaping obtains final product Graphene composite nano fiber element.
In the prior art, the synthesis technique of nano-cellulose mainly has following several：
1st, Mechanical Method：Native cellulose is processed through high-pressure machinery, obtains a kind of colloidal Nanowire of novel high swollen
Dimension element, commonly referred to as fento cellulose (MFC).MFC by some wire microfibres grown constitute it is random netted
Thing, remains the profile of microfibre, and its fibre diameter is 10-50nm, and length is 10-20 times of diameter.By mechanical legal system
Standby MFC, without chemical reagent, effect on environment is small.But the MFC particle diameter distributions for preparing in this way are wide, and Preparation equipment
Special, energy ezpenditure is high, therefore the method is at present using less.High pressure homogenization method and chemical mechanical pulping belong to mechanical preparation
Method.
2nd, chemical method：After native cellulose is through sour water solution or enzymolysis, NCC is obtained.NCC be a kind of a diameter of 1~100nm,
Length is tens to hundreds of nanometers of rigid rod fiber element, and the general crystal formation with native cellulose I can form steady in water
Fixed suspension.Enzyme hydrolysis method, enzymatic isolation method and bioanalysis are specifically included, wherein enzyme hydrolysis method preparation NCC can produce substantial amounts of
Spent acid and impurity, it is high to consersion unit requirement, and the more difficult recovery of residue after reaction, but preparation technology comparative maturity, realize
Industrialized production.
3rd, bioanalysis：The cellulose commonly known as bacteria cellulose prepared by Microbe synthesis method, bacteria cellulose
Physics and chemical property it is close with native cellulose.The structure of controllable NCC, crystal formation and particle diameter point when bioanalysis prepares NCC
Cloth etc., therefore easily realize industrialization and be commercialized.But bacteria cellulose preparation process is complicated, time-consuming, high cost, price
Expensive, yield is low.
In the preparation technology of above-mentioned nano-cellulose commonly used in the prior art, it is uneven that size distribution easily occurs in Mechanical Method
Problem, chemical method in itself not environmentally, pollutes environment, also has a certain degree of infringement to the health of operating personnel, of the invention
The preparation method of Graphene composite nano fiber element had both solved the problems, such as that Mechanical Method size distribution was uneven, it is thus also avoided that useization
The serious problem of method environmental pollution, whole preparation method running cost is also than relatively low.
In the present invention, in step (A), the size indicator for adding graphite alkenes material is also have strict requirements, stone
Below 70 μm, D10 norm controllings are in below 20um for the D90 norm controllings of black alkenes material.Conventional Graphene composite Nano
Cellulose products have only carried out certain restriction to Graphene content, but have ignored graphite alkenes material size indicator in itself
This important parameter, the present inventor by substantial amounts of creative experiments, by by the content of graphite alkenes material, granularity
Index is limited in suitable scope, play a role jointly by being worked in coordination for these indexs, has been finally reached of the invention
Goal of the invention, solves the problems, such as that graphene particles dispersion is uneven really.
Preferably, in order to further improve Graphene composite nano fiber element in graphite alkenes material dispersive property, stone
The D90 indexs of black alkenes material are preferably controlled in less than 50 μm, more excellent D90 norm controllings below 30 μm, more preferably 5-25 μ
Between m, for example, can also be 45um, 40um, 35um, 30um etc..Here D90 norm controllings refer to 100um below 70 μm
Following particle diameter material accounts for overall 90%, i.e., this 90% the inside maximum particle diameter is 100um, so ensure that graphite alkenes material
Dispersiveness, while also ensure that the size homogeneity of graphene particles, it is to avoid the generation of particle agglomeration.
Further, the D90 indexs of graphite alkenes material are preferably controlled in less than 20 times of D10 indexs, preferably 10 times
Hereinafter, more preferably less than 5 times, can also for less than 8 times, less than 11 times, less than 12 times, less than 13 times, 14 times it is such as the following.This
The purpose of sample is the big chip architecture that graphite alkenes material is kept to try one's best, it is ensured that graphite alkenes material will not occur interlayer group
It is poly-, the problem that the stress concentration point for preventing different footpath graphite alkenes materials from bringing is broken, because granularity is too big or too small
It is unfavorable for forming homogeneous material with nano-cellulose, so that composite nano fiber element product various aspects of performance performance is all
It is good, therefore preferably control in suitable scope the size indicator of graphite alkenes material.
Certainly, during practical operation, specific control graphite alkenes material D90, D10 index is needed using classification pretreatment side
Method, including：Retain bottom after centrifugally operated after graphite alkenes material is mixed with deionized water, under the conditions of 2000-3000rpm to sink
Form sediment, supernatant respectively obtains secondary bottom precipitation and secondary supernatant after centrifugally operated under the conditions of 5000-7000rpm, wherein
The fractional centrifugation liquid is prepared including any one in bottom precipitation, secondary bottom precipitation, secondary supernatant, and preferably two
Secondary bottom precipitation.
The centrifugally operated speed ratio that the first step obtains bottom precipitation is relatively low, behind the further centrifugally operated of supernatant speed
It is then higher, because the material grainses degree in precipitation is general than larger, if the too fast electrodeposition substance for being unfavorable for bulky grain of speed,
Material grainses degree in follow-up supernatant is typically smaller, therefore speed needs soon, so that the small material of granularity floats
In there is supernatant.So granularity than more consistent graphite alkenes material by after classification in bottom precipitation or at secondary bottom
Portion is precipitated or in secondary supernatant, and fractional centrifugation liquid can select above-mentioned any one material by classification treatment, equal energy
Ensure that there is granularity than more consistent graphite alkenes material, and granularity size also than convenient, to have fully ensured that piece
The homogeneity in footpath, is conducive to subsequently ensureing the performance of product prepared.
Wherein, the time of centrifugally operated is preferably controlled between 20-40min under the conditions of 2000-3000rpm, 5000-
The time of centrifugally operated is preferably controlled between 10-30min under the conditions of 7000rpm, is controlled in preferably operating time Nei Gengli
In the more thorough of grain size grading treatment, so that particle diameter distribution is more uniform.
Wherein, in step (A), the main purpose of ultrasonic disperse treatment is to be imitated by mechanical dispersion and ultrasonic cavitation
Should cause that fiber reaches the effect for separating degraded, the time of general ultrasonic disperse treatment is preferably controlled in 15-60min, more preferably
Be 30-50min, the power of ultrasonic disperse treatment is preferably controlled between 500-1500kw, more preferably 1000-1200kw it
Between, in order to lift fiber separation, the effect of degraded, certain grinding operation was first typically carried out before ultrasonic disperse treatment, according to
Being reached by the mutual rubbing action between grinding bead and fiber makes fiber separation, the effect of degraded, is so also correspondingly improved
General work efficiency, the frequency of grinding is preferably controlled between 25-35Hz, and between more preferably 27-32Hz, the time of grinding is most
Control between 4-6h well, more preferably 5-5.5h.
In order to fully improve joint product dispersive property in itself, graphite alkenes material used with cellulose, go from
Certain grinding pretreatment is preferably first carried out before sub- water mixing, it is more excellent, only from residual on the pretreated chamber wall of grinding
The graphite alkenes material for staying, mixes with cellulose, deionized water.Because the Graphene on chamber wall has more preferable nano-meter characteristic
And lamellar structure, therefore more preferably select the graphite alkenes material on chamber wall.
In other suspension, the concentration of cellulose is preferably controlled between 1wt%-10wt%, and that more excellent is 2wt%-
In addition can also be 3wt%, 4wt%, 5wt%, 6wt%, 7wt% etc. between 8wt%.
The preparation method of the Graphene composite nano fiber element of the embodiment of the present invention, after it with the addition of grapheme material,
The efficiency of grinding itself is improve, the time of grinding is shortened, causes that nano-cellulose has in particular by biomass Graphene
There are the features such as antibacterial bacteriostatic, far infrared more prominent.
The further double lifting nanofiber of Graphene composite nano fiber element prepared using above-mentioned preparation method
The plain mechanical property of itself, and also the excellent anti-microbial property of nano-cellulose, far infrared performance additionally are imparted, excellent is tough
Property, hot water resistance and antistatic property, it is equal in medicine, environmental protection, packaging for foodstuff, composite multiple industries using widely
There is very wide application.
Compared with prior art, beneficial effects of the present invention are：
(1) high performance Graphene composite nano fiber element of the invention, graphite alkenes material can keep higher and contain
Amount, still dispersion ratio is more uniform for graphene particles, and also than more uniform, agglomerated particle produces less granular size, and properties are steady
It is fixed；
(2) preparation method of high performance Graphene composite nano fiber element of the invention, step before and after the preparation method
Linking is tight, method simple and fast, and without using any chemical agents such as soda acids in whole preparation process, environmental protection does not have yet
There is the generation of spent acid salkali waste, and equally reached using preparation method of the invention and employ acidifying and prepare nano-cellulose institute
Have the advantage that, such as suitable draw ratio.And the preparation method has method simply easily operated, operating condition is gentle,
Industrialized production, the economic benefit for being capable of achieving Graphene composite nano fiber element are good；
(3) high performance Graphene of the invention compound para-aramid fiber application widely, in medicine, environmental protection, is eaten
Product packaging, composite multiple industry have very wide application.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the present invention.It is unreceipted specific in embodiment
Condition person, the condition advised according to normal condition or manufacturer is carried out.Agents useful for same or the unreceipted production firm person of instrument, are
The conventional products that can be obtained by commercially available purchase.
Preparation example 1
The preparation method of bleaching corn cob fiber element is as follows：
1) sour water solution first is carried out to corn core raw material, pentose solution and sulphuric acid hydrolysis residue is obtained after separation；The consumption of acid
It is the 6wt% of corn core raw material, hydrolysis temperature is 130 DEG C, and the time is 2h；Then above-mentioned sour water is processed with sodium hydroxide solution
Solution residue, obtains alkali solution liquid and alkaline hydrolysis residue after separation, the consumption of alkali is the 7wt% of corn core raw material, and treatment temperature is 90 DEG C,
Time is 3h；
2) bleaching is carried out to above-mentioned alkaline hydrolysis residue, processing mode is hydrogen peroxide bleaching, and dioxygen water consumption accounts for alkaline hydrolysis
The 6wt% of residue oven dry weight, it is 10wt% to starch dense, and temperature is 90 DEG C, and bleaching time is 2h, by after above-mentioned purification processes,
Corn cob fiber element can be obtained, its main index is whiteness 75%, fibre length 0.16mm.
Embodiment 1
The preparation method of high performance Graphene composite nano fiber element is as follows：
1) the corn cob fiber element 80g for obtaining preparation example 1 mixes with 20g graphene oxides and 800ml deionized waters
Slurry is made into, 4h is ground with frequency 25Hz in grinder, obtain suspension；
2) ultrasound 60min, centrifugation, freeze-drying under 1500kw power by above-mentioned suspension, obtains composite Nano fine
Dimension element.
Embodiment 2
The preparation method of high performance Graphene composite nano fiber element is as follows：
1) after 10g graphene oxides first being ground into 4h, add preparation example 1 obtain 90g corn cob fibers element and
The mixing of 1000ml deionized waters is made into slurry, and 6h is ground with frequency 35Hz in grinder, obtains suspension；
2) ultrasound 30min, centrifugation, freeze-drying under 700kw power by above-mentioned suspension, obtains composite nano fiber
Element.
Embodiment 3
The preparation method of high performance Graphene composite nano fiber element is as follows：
1) after graphene oxide first being ground into 4h, in the 10g graphene oxides that selection remains in above chamber wall plus
Enter 90g corn cob fibers element that preparation example 1 obtains and the mixing of 1000ml deionized waters is made into slurry, with frequency in grinder
Rate 27Hz is ground 5h, obtains suspension；
2) ultrasound 15min, centrifugation, freeze-drying under 500kw power by above-mentioned suspension, obtains composite nano fiber
Element.
Embodiment 4
The preparation method of high performance Graphene composite nano fiber element is as follows：
1) graphene oxide is mixed with deionized water, is protected after centrifugally operated 20-40min under the conditions of 2000-3000rpm
First time bottom precipitation, supernatant is stayed to respectively obtain secondary bottom after centrifugally operated 10-30min under the conditions of 5000-7000rpm
Precipitation and secondary supernatant, (D90 is 50um, D10 to the 10g graphene oxide fractional centrifugations liquid that the secondary bottom precipitation of selection is obtained
It is 12um), the 190g corn cob fibers that are obtained with preparation example 1 element and 3800ml deionized waters mixs and are made into slurry, are grinding
5.5h is ground with frequency 32Hz in machine, suspension is obtained；
2) ultrasound 50min, centrifugation, freeze-drying under 1000kw power by above-mentioned suspension, obtains composite Nano fine
Dimension element.
Embodiment 5
Concrete technology step is substantially the same manner as Example 4, and the difference with embodiment 4 is that the graphene oxide of selection divides
Level centrifugate is first time bottom precipitation (D90 is 70um, and D10 is 30um).
Embodiment 6
Concrete technology step is substantially the same manner as Example 4, and the difference with embodiment 4 is that the graphene oxide of selection divides
Level centrifugate is first time bottom precipitation (D90 is 370um, and D10 is 120um).
Embodiment 7
Concrete technology step is substantially the same manner as Example 4, and the difference with embodiment 4 is that the graphene oxide of selection divides
Level centrifugate is second supernatant (D90 is 20um, and D10 is 0.5um).
Embodiment 8
Concrete technology step is substantially the same manner as Example 4, and the difference with embodiment 4 is that the graphene oxide of selection divides
Level centrifugate (D90 is 30um, and D10 is 10um).
Embodiment 9
Concrete technology step is substantially the same manner as Example 4, and the difference with embodiment 4 is that the graphene oxide of selection divides
Level centrifugate (D90 is 5um, and D10 is 0.25um).
Embodiment 10
Concrete technology step is substantially the same manner as Example 4, and the difference with embodiment 4 is that the graphene oxide of selection divides
Level centrifugate (D90 is 25um, and D10 is 5um).
Embodiment 11
Concrete technology step is substantially the same manner as Example 4, and the difference with embodiment 4 is that the graphene oxide of selection divides
Level centrifugate (D90 is 70um, and D10 is 20um).
Embodiment 12
It is step 1 with the distinctive points of embodiment 8) in, graphene oxide replaces with biomass Graphene.
Embodiment 13
It is step 1 with the distinctive points of embodiment 8) in, graphene oxide replaces with redox Graphene.
Embodiment 14
It is step 1 with the distinctive points of embodiment 8) in, graphene oxide replaces with nitrogen-doped graphene and graphite oxide
(quality is 1 to the mixture of alkene:1).
Embodiment 15
It is step 1 with the distinctive points of embodiment 4) in, graphene oxide 10g, corn cob fiber element 390g, deionized water
13L。
Embodiment 16
It is step 1 with the distinctive points of embodiment 4) in, graphene oxide 10g, corn cob fiber element 990g, deionized water
99L。
Embodiment 17
It is step 1 with the distinctive points of embodiment 4) in, graphene oxide 10g, corn cob fiber element 2000g, deionization
Water 40L.
Embodiment 18
Be step 1 with the distinctive points of embodiment 4) in, the corn cob fiber element that preparation example 1 is obtained replace with without
Purify the corn cob fiber element of bleaching.
Embodiment 19
It is step 1 with the distinctive points of embodiment 4) in, the corn cob fiber element that preparation example is obtained replaces with willow fiber
Element.
Embodiment 20
It is step 1 with the distinctive points of embodiment 4) in, the corn cob fiber element that preparation example is obtained replaces with reed fiber
Element.
Comparative example 1
In a kind of CN101509209B " preparation method of clubbed nano-cellulose " patent, what embodiment 1 was prepared receives
Rice cellulose products.
Comparative example 2
In a kind of CN102433786A " method of preparing micro nano-crystalline cellulose with mechanical force chemical " patent prepared by embodiment 1
The nano-cellulose product for obtaining.
Experimental example 1
The nano-cellulose product of embodiment of the present invention 1-20 and comparative example 1-2 is carried out into performance detection, concrete outcome
It is as shown in table 1 below：
The performance indications of table 1 are contrasted
Contrasted by embodiment data and comparative example 1,2, it can be seen that after addition graphite alkenes material, using purely mechanic side
Method can just reach the effect of chemical method, even better, which reduce the generation of spent acid alkali, be conducive to environmental protection；And lead to
Contrast is crossed, the length of nano-cellulose and the scope of diameter prepared by embodiment will much be narrower than comparative example 1 and 2, illustrate to prepare
The nano-cellulose particle diameter for obtaining is more uniform, and homogeneity is good.
After especially carrying out pre-treatment to graphite alkenes material so that the diameter of the nano-cellulose of preparation more plus nano
Change, and cause that draw ratio is bigger, and fluctuate within the specific limits, be more beneficial for follow-up application.
Application examples 1
The Graphene composite nano fiber element that the embodiment of the present invention 8 and 12 is prepared replaces patent publication No. respectively
CN102344685A, the embodiment 1- of entitled " a kind of method for preparing nano cellulose microfibril reinforced polymer composite material "
Nano cellulose material used or its preparation process in 6, test data are as follows：
The Graphene composite nano fiber element corresponding data that the embodiment of the present invention 8 is prepared is as follows：
Embodiment 1：The tensile strength of composite material film is 47MPa, and stretch modulus is 1.5GPa；
Embodiment 2：The intensity of composite fibre is:4.5cN/dtex；
Embodiment 3：The intensity of composite fibre is:5.5cN/dtex；
Embodiment 4：The tensile strength of composite material film reaches 150MPa, and stretch modulus reaches 4.6GPa；
Embodiment 5：The intensity of composite fiber is 4.3cN/dtex；
Embodiment 6：The intensity of composite fiber is:6.4cN/dtex.
The Graphene composite nano fiber element corresponding data that the embodiment of the present invention 12 is prepared is as follows：
Embodiment 1：The tensile strength of composite material film is 49MPa, and stretch modulus is 1.7GPa；
Embodiment 2：The intensity of composite fibre is:4.8cN/dtex；
Embodiment 3：The intensity of composite fibre is:5.9cN/dtex；
Embodiment 4：The tensile strength of composite material film reaches 160MPa, and stretch modulus reaches 4.9GPa；
Embodiment 5：The intensity of composite fiber is 4.6cN/dtex；
Embodiment 6：The intensity of composite fiber is:6.7cN/dtex.
Although illustrate and describing the present invention with specific embodiment, but will be appreciated that without departing substantially from of the invention
Many other changes and modification can be made in the case of spirit and scope.It is, therefore, intended that in the following claims
Including belonging to all such changes and modifications in the scope of the invention.
Claims (10)
1. a kind of high performance Graphene composite nano fiber is plain, it is characterised in that mainly by nano-cellulose and graphite alkenes
Material composition, the graphite alkenes material is mutually in situ with nano-cellulose to be carried；
In the Graphene composite nano fiber element, the content of graphite alkenes material is further in below 20wt%
Below 10wt%, further between 0.5wt%-5wt%.
2. Graphene composite nano fiber according to claim 1 is plain, it is characterised in that the nano-cellulose is by corn
Core cellulose is prepared；
Preferably, the nano-cellulose is that the corn cob fiber element crossed by purifying bleaching is prepared.
3. Graphene composite nano fiber according to claim 1 is plain, it is characterised in that the major diameter of the nano-cellulose
Than being (5-1000)：1, preferably (10-300)：1, more preferably (15-200)：1.
4. Graphene composite nano fiber according to claim any one of 1-3 is plain, it is characterised in that graphite alkenes material
Including Graphene, biomass Graphene, graphene oxide, Graphene derivative the mixing of one or more, the Graphene
Derivative includes the Graphene of element doping；
Preferably, the Graphene derives include in element doping Graphene or functional group's graphite alkene thing any a kind or extremely
Few 2 kinds combination；
Preferably, it is any during the element doping Graphene is including metal-doped Graphene or nonmetal doping Graphene
1 kind or at least 2 kinds of combination；
The metal-doped metallic element it is typical but non-limiting including potassium, sodium, gold, silver, iron, copper, nickel, chromium titanium, vanadium or
Cobalt；
The nonmetal doping Graphene is typical but non-limiting including nitrogen, phosphorus, silicon, boron or silicon；
Preferably, the nonmetal doping Graphene includes nitrogen-doped graphene, phosphorus doping Graphene or sulfur doping graphite
Any a kind or at least 2 kinds of combination in alkene；
Preferably, functional group's graphite alkene includes being grafted with the Graphene of functional group；
Preferably, functional group's graphite alkene includes any a kind or at least 2 kinds be grafted with hydroxyl, carboxyl or amino
The Graphene of combination；
Wherein, the hydroxyl include R1-OH, the R1 include alkyl, typical but non-limiting hydroxyl include methylhydroxy,
One of which in ethyl hydroxy, propyl hydroxy, butylhydroxy, amyl group hydroxyl, hexyl hydroxyl；
The carboxyl includes that R2-COOH, the R2 include alkyl, and typical but non-limiting hydroxyl includes methylhydroxy, second
One of which in base hydroxyl, propyl hydroxy, butylhydroxy, amyl group hydroxyl, hexyl hydroxyl；
The carboxyl includes R3-NH3, the R3 include alkyl, typical but non-limiting hydroxyl include methylhydroxy, ethyl
One of which in hydroxyl, propyl hydroxy, butylhydroxy, amyl group hydroxyl, hexyl hydroxyl.
5. the plain preparation method of Graphene composite nano fiber described in any one of claim 1-4, it is characterised in that main bag
Include following steps：
(A) cellulose, graphite alkenes material and deionized water are mixed into ultrasonic disperse, grinding and obtains suspension；
(B) by suspension ultrasound, centrifugation, freeze-drying shaping obtains final product Graphene composite nano fiber element；
Preferably, in the suspension, the concentration of cellulose is 1wt%-10wt%.
6. the preparation method of Graphene composite nano fiber according to claim 5 element, it is characterised in that the suspension
In, below 70 μm, D10 norm controllings are in below 20um for the D90 norm controllings of graphite alkenes material；
Preferably, the D90 norm controllings of graphite alkenes material are below 50 μm, preferably less than 30 μm, more preferably 5-25 μm
Between；
Preferably, D90 norm controllings are in less than 20 times of D10 indexs, more preferably preferably less than 10 times, less than 5 times.
7. the preparation method of Graphene composite nano fiber according to claim 6 element, it is characterised in that the Graphene
The control method of class material D90, D10 index includes：Obtained after graphite alkenes material is pre-processed with deionized water mixing-classifying
Fractional centrifugation liquid, then the fractional centrifugation liquid is obtained into suspension with nano-cellulose mixing ultrasonic disperse, grinding；
Preferably, the method for the classification pretreatment includes：After graphite alkenes material is mixed with deionized water, 2000-
Retain bottom precipitation under the conditions of 3000rpm after centrifugally operated, supernatant is distinguished after centrifugally operated under the conditions of 5000-7000rpm
Secondary bottom precipitation is obtained with secondary supernatant；
Wherein, the fractional centrifugation liquid is prepared into including any one in bottom precipitation, secondary bottom precipitation, secondary supernatant
Arrive, preferably secondary bottom precipitation；
Preferably, under the conditions of 2000-3000rpm the time control of centrifugally operated in 20-40min；
Preferably, under the conditions of 5000-7000rpm the time control of centrifugally operated in 10-30min.
8. the preparation method of Graphene composite nano fiber according to claim 5 element, it is characterised in that the step
(A) in, graphite alkenes material mixes with cellulose, deionized water again after being ground pretreatment；
Preferably, the graphite alkenes material remained on pretreated chamber wall will be ground to mix with cellulose, deionized water.
9. the preparation method of Graphene composite nano fiber according to claim 5 element, it is characterised in that the step
(A) in, the FREQUENCY CONTROL of grinding is in 25-35Hz, more preferably 27-32Hz；
Preferably, the time control of grinding is in 4-6h, more preferably 5-5.5h；
Preferably, the time control of ultrasonic disperse treatment is in 15-60min, more preferably 30-50min；
Preferably, the Power Control of ultrasonic disperse treatment is in 500-1500kw, more preferably 1000-1200kw.
10. the Graphene composite nano fiber element described in any one of claim 1-4 is in medicine, environmental protection, packaging for foodstuff, composite wood
Application in terms of material.
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| PCT/CN2017/100249 WO2018054212A1 (en) | 2016-09-20 | 2017-09-01 | Graphene composite, preparation method therefor and use thereof, method for preparing nanocellulose and resultant nanocellulose, and high-performance graphene composite nanocellulose and preparation method therefor |
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