CN107163298A - A kind of chiral nematic nano-cellulose redox graphene laminated film and its preparation method and application - Google Patents
A kind of chiral nematic nano-cellulose redox graphene laminated film and its preparation method and application Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/04—Oxycellulose; Hydrocellulose
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
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Abstract
The invention provides a kind of chiral nematic nano-cellulose redox graphene laminated film and its preparation method and application.Convection drying film forming after the preparation method that the present invention is provided mixes chiral nematic nano-cellulose liquid crystal phase material and redox graphene water slurry, destruction will not be produced to the chiral nematic structure of nano-cellulose, and step is simple, abundant raw material is easy to get, and cost is low.The laminated film that the present invention is provided not only has the good characteristic of nano-cellulose, the electric conductivity of optical characteristics and graphene also with chiral nematic structure.
Description
Technical field
The present invention relates to the technical field of composite, more particularly to a kind of chiral nematic nano-cellulose-reduction-oxidation
Graphene composite film and its preparation method and application.
Background technology
Nano-cellulose (NCC) is the high polymer material with biological degradability most abundant in nature, manufacturing cost
It is cheap, nontoxic, excellent in mechanical performance, with advantages, particularly NCC such as huge specific surface area, preferable heat endurances
With very high Young's modulus and biocompatibility, mutually tied by the evaporation-induced self-assembly formation chiral nematic liquid crystal of itself
Structure, can impart the more morphological features of conductive composite film as matrix material.What nano-cellulose and graphene were constituted answers
Condensation material can show the performance of uniqueness, get more and more people's extensive concerning in recent years.
The method for preparing nano-cellulose-graphene composite film at present is a lot, in Publication No. CN103937032A
Using the method for vacuum filtration in state's patent, the colour that Cellulose nanocrystal graphene has been prepared in the presence of field of flow is answered
Close film.Publication No. CN105860143A Chinese patent disclose a kind of flexible nano cellulose-graphene composite film and its
Preparation method, wherein will be reduced after graphene oxide dispersion and nano-cellulose dispersion liquid ultrasound, obtains nanofiber flat band
The dispersion liquid of black alkene, then obtain composite membrane by centrifuging degassing and vacuum filtration.
But, the method operation that nano-cellulose-graphene composite film is prepared at present is complex, and can be to nanometer
The chiral nematic structure of cellulose produces certain destruction, and laminated film can not retain the particularity of chiral nematic nano-cellulose
Energy.
The content of the invention
In view of this, present invention aims at provide a kind of chiral nematic nano-cellulose-redox graphene to be combined
Film and its preparation method and application.The preparation method that the present invention is provided will not be produced to the chiral nematic structure of nano-cellulose
Destruction, step is simple, and gained laminated film not only has the good characteristic of nano-cellulose, the also light with chiral nematic structure
Learn characteristic and the electric conductivity of graphene.
In order to realize foregoing invention purpose, the present invention provides following technical scheme：
The invention provides a kind of preparation method of chiral nematic nano-cellulose-redox graphene laminated film,
Comprise the following steps：
Fiber and sulfuric acid are mixed reaction is hydrolyzed, obtain nano-cellulose suspension；
The nano-cellulose suspension is centrifuged, dialysed and concentrated successively, chiral nematic nano-cellulose is obtained
Liquid crystal phase material；
Dried after the chiral nematic nano-cellulose liquid crystal phase material and redox graphene water slurry are mixed
Film forming, obtains chiral nematic nano-cellulose-redox graphene laminated film.
It is preferred that, the mass concentration of the sulfuric acid is 90~98%；
The quality of the fiber and the volume ratio of sulfuric acid are 10~30g：100~200ml.
It is preferred that, the temperature of the hydrolysis is 30~70 DEG C；The time of hydrolysis is 1~3h.
It is preferred that, it is 6.5~7.5 that the dialysis, which specially dialyses nano-cellulose suspension to pH value,；
The concentration is specially that the mass concentration of nano-cellulose suspension is concentrated into 2~5%.
It is preferred that, the mass concentration of the redox graphene water slurry is 10~20%；
The mass ratio of the chiral nematic nano-cellulose liquid crystal phase material and redox graphene water slurry be 1~
5：1~5.
It is preferred that, the preparation method of the redox graphene water slurry comprises the following steps：
Graphene oxide and reducing agent are subjected to reduction reaction in water, the reaction containing redox graphene is obtained
Liquid；
It is 6.5~7.5 that the reaction solution containing redox graphene, which is centrifuged to pH value, obtains reduction-oxidation graphite
Alkene water slurry.
It is preferred that, the reducing agent is vitamin C and/or Tea Polyphenols；
The mass ratio of the graphene oxide and reducing agent is 0.1~0.5：0.3~1.
The invention provides chiral nematic nano-cellulose-reduction prepared by preparation method described in such scheme any one
Graphene composite thin film.
Exist the invention provides the nano-cellulose of the chiral nematic described in such scheme-redox graphene laminated film
Application in conductive material.
Exist the invention provides the nano-cellulose of the chiral nematic described in such scheme-redox graphene laminated film
Wet sensitive indicates the application in material.
The invention provides a kind of preparation method of chiral nematic nano-cellulose-redox graphene laminated film,
Comprise the following steps：Fiber and sulfuric acid are mixed reaction is hydrolyzed, obtain the reaction solution containing nano-cellulose；Contain described
The reaction solution for having nano-cellulose is centrifuged, dialysed and concentrated successively, obtains chiral nematic nano-cellulose liquid crystal phase material；
Drying and forming-film after the chiral nematic nano-cellulose liquid crystal phase material and redox graphene water slurry are mixed, is obtained
Chiral nematic nano-cellulose-redox graphene laminated film.The preparation method that the present invention is provided by chiral nematic nanometer
Convection drying film forming after cellulose solution crystalline phase material and the mixing of redox graphene water slurry, will not be to nano-cellulose
Chiral nematic structure produces destruction, and step is simple, and abundant raw material is easy to get, and cost is low.
The chiral nematic nano-cellulose prepared present invention also offers preparation method described in such scheme any one-also
Former graphene composite thin film.The laminated film that the present invention is provided not only has the good characteristic of nano-cellulose, also has
The optical characteristics of chiral nematic structure and the electric conductivity of graphene.Embodiment result shows, in the laminated film that the present invention is provided
When graphene content is 10wt%, the electrical conductivity of film can reach more than 0.8sm, and electric conductivity is excellent；And the present invention
Laminated film has the iris feature of nano-cellulose liquid crystalline phase, and the response to light is different in different humidity conditions, can
Indicated applied to wet sensitive in material.
Brief description of the drawings
Fig. 1 is chiral nematic nano-cellulose-redox graphene laminated film prepared by the embodiment of the present invention 1
SEM schemes；
Fig. 2 is chiral nematic nano-cellulose-reduction-oxidation of the different redox graphene contents of the embodiment of the present invention 3
The optical photograph of graphene composite film；
Fig. 3 is chiral nematic nano-cellulose-reduction-oxidation of the different redox graphene contents of the embodiment of the present invention 3
The electric conductivity of graphene composite film；
Fig. 4 is chiral nematic nano-cellulose-reduction-oxidation of the different redox graphene contents of the embodiment of the present invention 3
Spectrum change figure of the graphene composite film under different relative humidity.
Embodiment
The invention provides a kind of preparation method of chiral nematic nano-cellulose-redox graphene laminated film,
Comprise the following steps：
Fiber and sulfuric acid are mixed reaction is hydrolyzed, obtain nano-cellulose suspension；
The nano-cellulose suspension is centrifuged, dialysed and concentrated successively, chiral nematic nano-cellulose is obtained
Liquid crystal phase material；
Dried after the chiral nematic nano-cellulose liquid crystal phase material and redox graphene water slurry are mixed
Film forming, obtains chiral nematic nano-cellulose-redox graphene laminated film.
Fiber and sulfuric acid are mixed and reaction are hydrolyzed by the present invention, obtain nano-cellulose suspension.In the present invention, institute
It is preferably cotton fiber, flaxen fiber or silk fiber, more preferably cotton fiber to state fiber；The mass concentration of the sulfuric acid is preferably 90
~98%, more preferably 93~95%；The quality of the fiber and the volume ratio of sulfuric acid are preferably 10~30g：100~200ml,
More preferably 20g：120~180ml.
In the present invention, the temperature of the hydrolysis is preferably 30~70 DEG C, more preferably 40~60 DEG C；The hydrolysis
The time of reaction is preferably 1~3h, more preferably 1.5~2.5h；Reaction, institute is preferably hydrolyzed in the present invention under agitation
The speed for stating stirring is preferably 800~1000rpm, more preferably 850~950rpm.
Reach after the reaction time, the present invention preferably adds water into hydrolysis liquid, stops hydrolysis, obtains nanometer
Cellulose suspension.In the present invention, the addition volume of the water is preferably 8~10 times, more preferably 10 times of sulfuric acid volume.
Obtain after nano-cellulose suspension, the nano-cellulose suspension is centrifuged, dialysed by the present invention successively
And concentration, obtain chiral nematic nano-cellulose liquid crystal phase material.In the present invention, preferably by nano-cellulose before the centrifugation
Suspension removes supernatant liquor after standing, and is then centrifuged remaining turbidity screen；The time of the standing is preferably 10~
24h, more preferably 12~20h.In the present invention, the rotating speed of the centrifugation is preferably 4000~6000rpm, and more preferably 4500
~5500rpm, most preferably 5000rpm；The number of times of the centrifugation is preferably 3~4 times；The time of the single spin is preferably
8~12min, more preferably 9~11min, most preferably 10min.The present invention is by centrifuging to residual in nano-cellulose suspension
The sulfuric acid stayed carries out primary wash, and the pH value of gained suspension is preferably 2~3 after centrifugation.
After centrifugation, the present invention is dialysed centrifugation gained suspension.In the present invention, the endpoint pH of the dialysis is excellent
Elect 6.5~7.5, more preferably 6.8~7.2, most preferably 7.0 as；The dialysis is preferably with the molecular cut off of dialysis membrane
8000~12000, more preferably 9000~11000；The time of the dialysis is preferably 7~10 days, more preferably 8~9 days.This
The reaction solution containing nano-cellulose is further purified by centrifugation and dialysis for invention, removes the sulfuric acid wherein remained.
After dialysis, the present invention concentrates dialysis gained suspension, obtains chiral nematic nano-cellulose liquid crystal phase material.
In the present invention, the concentration is preferably that the mass concentration of nano-cellulose in suspension is concentrated into 2~5%, more preferably
3%；The present invention preferably concentrates suspension by drying, and the temperature of the drying is preferably 60~105 DEG C, more preferably 70~
90℃；The present invention does not have particular/special requirement to the time of the drying, can be concentrated into suspension and require concentration.In this hair
In bright, the mass concentration of suspension obtained by the dialysis is 1% or so, and the present invention makes the nanofiber in suspension by concentration
Plain mass concentration reaches 2~5%, so as to obtain chiral nematic nano-cellulose liquid crystal phase material.The present invention is using sulfuric acid to fibre
Dimension is hydrolyzed, and a certain amount of negative electrical charge is contained on the nano-cellulose surface obtained after hydrolysis, is 2~5% in mass concentration
Under the conditions of, nano-cellulose is carried out self assembly arrangement by active forces such as electrostatic repulsions, obtains chiral nematic nano-cellulose liquid
Crystalline phase material.
Obtain after chiral nematic nano-cellulose liquid crystal phase material, it is of the invention by the chiral nematic nano-cellulose liquid crystal
Chiral nematic nano-cellulose-reduction-oxidation is obtained after phase material and the mixing of redox graphene water slurry, drying and forming-film
Graphene composite film.In the present invention, the mass concentration of the redox graphene water slurry is preferably 10~20%,
More preferably 12~18%, most preferably 15%；The chiral nematic nano-cellulose liquid crystal phase material and reduction-oxidation graphite
The mass ratio of alkene water slurry is preferably 1~5：1~5, more preferably 1：2~4；Mixing of the present invention is preferably to stir mixed
Close, the time of the stirring mixing is preferably 2~4h；The stirring mixing is preferably magnetic agitation mixing；The magnetic agitation
Rotating speed be preferably 800~1000rpm, more preferably 850~950rpm.
The present invention will preferably hang with redox graphene water again after chiral nematic nano-cellulose liquid crystal phase material ultrasound
Supernatant liquid is mixed, and the ultrasonic time is preferably 10~30min, more preferably 15~25min；The ultrasonic power is preferably
300~500W, more preferably 350~450W；The present invention makes the particle of nano-cellulose suspension more disperse by ultrasound.
In the present invention, the preparation method of the redox graphene water slurry preferably includes following steps：
Graphene oxide and reducing agent are subjected to reduction reaction in water, the reaction containing redox graphene is obtained
Liquid；
It is 6.5~7.5 that the reaction solution containing redox graphene, which is centrifuged to pH value, obtains reduction-oxidation graphite
Alkene water slurry.
Graphene oxide and reducing agent are carried out reduction reaction by the present invention in water, are obtained containing redox graphene
Reaction solution.In the present invention, the reducing agent is preferably vitamin C and/or Tea Polyphenols；The graphene oxide and reducing agent
Mass ratio is preferably 0.1~0.5：0.3~1, more preferably 0.2~0.4：0.5~0.8；The time of the reduction reaction is preferred
For 1~3h, more preferably 1.5~2.5h；The temperature of the reduction reaction is preferably 80~100 DEG C, more preferably 85~95 DEG C；
The present invention preferably carries out reduction reaction under agitation, and the speed of the stirring is preferably 800~1000rpm, more preferably
850~950rpm.
Graphene oxide and water are preferably mixed and carry out ultrasound by the present invention, obtain graphene oxide aqueous suspensions, then again and
Reducing agent mixing carries out reduction reaction.In the present invention, the ultrasonic time is preferably 10~30min, more preferably 15~
25min；The ultrasonic power is preferably 300~500W, more preferably 350~450W；The graphene oxide aqueous suspensions
Mass concentration is preferably 5~10%, and more preferably 6~8%.
After reduction reaction, the present invention by the reaction solution containing redox graphene centrifuge to pH value be 6.5~
7.5, obtain redox graphene water slurry.The present invention preferably first mixes reaction solution and water containing redox graphene
Stand, centrifuged again after removing supernatant liquor after conjunction；The time of the standing is preferably 1~10h, more preferably 3~5h；This
Invention is by being diluted with water the reaction solution containing redox graphene into the reaction solution containing redox graphene, after making
Continuous centrifugation is more prone to carry out, and is easy to remove reducing agent by centrifuging.
It is 6.5~7.5, preferably 7.0 that the present invention, which centrifuges the reaction solution containing redox graphene to pH value,；
The rotating speed of the centrifugation is preferably 4000~6000rpm, more preferably 4500~5500rpm, most preferably 5000rpm；This hair
The bright number of times to the centrifugation is preferably 3~4 times；The time of the single spin is preferably 8~12min, more preferably 9~
11min, most preferably 10min.The reducing agent that the present invention is remained by centrifuging in the reaction solution containing redox graphene is gone
Remove.
In the present invention, after the centrifugation mass concentration of gained redox graphene water slurry be preferably 5~
10%, the present invention preferably makes the mass concentration of redox graphene water slurry reach 10~20% by concentration.The present invention
It is preferred that being concentrated by drying to evaporate the water, the temperature of the drying is preferably 60~105 DEG C, more preferably 70~90 DEG C；
The present invention does not have particular/special requirement to the time of the drying, can be concentrated into and require concentration.
After the completion of mixing, the mixture drying and forming-film is obtained chiral nematic nano-cellulose-reduction-oxidation by the present invention
Graphene composite film.In the present invention, the temperature of the drying is preferably room temperature, without carrying out extra heating and cooling；
The present invention does not have particular/special requirement to dry environment, is dried under air condition；The present invention does not have to the dry time
There is specific requirement, solvent can completely be removed；Of the invention preferably pour the mixture into is dried in polystyrene box,
The present invention does not have particular/special requirement to the size and area of the polystyrene box, specifically according to required film size and thickness
Spend to determine.The present invention makes the solvent in mixture volatilize naturally, so as at utmost protect by being dried under air room temperature state
Stay the chiral nematic structure of nano-cellulose.
The invention provides chiral nematic nano-cellulose-reduction prepared by preparation method described in such scheme any one
Graphene composite thin film.The laminated film that the present invention is provided includes chiral nematic nano-cellulose base material and oxygen reduction fossil
Black alkene strengthens phase.In the present invention, the mass content of redox graphene is preferably 1~20% in the laminated film, more
Preferably 5~15%；The thickness of the laminated film is preferably 15~25 μm, more preferably 18~22 μm.
Exist the invention provides the nano-cellulose of the chiral nematic described in such scheme-redox graphene laminated film
Application in conductive material.The laminated film that the present invention is provided has excellent electric conductivity, can be applied in conductive material.
Exist the invention provides the nano-cellulose of the chiral nematic described in such scheme-redox graphene laminated film
Wet sensitive indicates the application in material.The laminated film that the present invention is provided has the iris feature of nano-cellulose liquid crystalline phase, not
It is different to the response of light under same damp condition, with excellent wet sensitive optical property, wet sensitive can be applied to and indicated in material.
Chiral nematic nano-cellulose-redox graphene the laminated film provided with reference to embodiment the present invention
And its preparation method and application be described in detail, but they can not be interpreted as limiting the scope of the present invention.
Embodiment 1
Weigh 10g cotton fibers to add in 100mL round-bottomed flasks, add the 100ml concentrated sulfuric acid (H2SO4), control speed of agitator
For 800rpm, in 30 DEG C of stirred in water bath 3 hours, nano-cellulose suspension is obtained；Gained nano-cellulose suspension is used
Distilled water water dilution (distilled water volume is 10 times of the volume of the concentrated sulfuric acid used), stops hydrolysis, and standing sedimentation 12h, will be clear
Clear top layer liquid is poured out, and remaining turbidity screen is centrifuged into 3~5 times, and (centrifugal rotational speed is 4000rpm, and the single spin time is
8min), until suspension pH value 2.5, last time is centrifuged to the nano-cellulose suspension obtained and is placed in dialysis membrane (retention point
Son amount is 8000) interior, is dialysed 7 days with distilled water, until reaching that suspension pH value is 7.0, the gained suspension that then will dialyse is 60
It is 3% that mass concentration is concentrated into DEG C baking oven, obtains chiral nematic nano-cellulose liquid crystal phase material.
0.5g graphene oxides are weighed, deionized water 10ml, ultrasonic vibration 10min (ultrasonic power is 300W) is added, obtains
To graphene oxide suspension (mass concentration is 5%), graphene oxide suspension is put into three-necked flask, added
0.3gVC, 3h (speed of agitator is 800rpm) is stirred under 80 DEG C of water bath conditions, the reaction containing redox graphene is obtained
Liquid；Distilled water 10ml is added to the reaction solution containing redox graphene, supernatant liquor is outwelled after standing 5h, will be remaining muddy
The turbid leafing heart 3 times (centrifugal rotational speed is 4000rpm, and the single spin time is 8min), until centrifuging to pH value 7.0, is reduced
Graphene oxide suspension；It is 10% that redox graphene suspension is concentrated into mass concentration at 60 DEG C.
Chiral nematic structure nano cellulose solution crystalline phase material 6g, ultrasonic vibration 10min (ultrasonic power is 300W) are weighed,
Weigh redox graphene suspension 0.2g to add in the chiral nematic structure nano cellulose solution after ultrasound, in 800rpm
Magnetic agitation under the conditions of stir 2h, obtain mixture, pour the mixture into polystyrene square box, make at ambient temperature molten
Agent is volatilized, and obtains chiral nematic nano-cellulose-redox graphene laminated film that thickness is 15 μm.
It can be calculated, the mass content of redox graphene is the 10% (matter of redox graphene in laminated film
Measure quality/laminated film quality of content=redox graphene).
Gained laminated film is observed using SEM, gained SEM spectrum is as shown in Figure 1；According to Fig. 1
As can be seen that gained laminated film has obvious chiral nematic structure.
Embodiment 2
Weigh 30g cotton fibers to add in 100mL round-bottomed flasks, add the 150ml concentrated sulfuric acid (H2SO4), control speed of agitator
For 1000rpm, in 70 DEG C of stirred in water bath 3 hours, nano-cellulose suspension is obtained；Gained nano-cellulose suspension is used
Distilled water water dilution (distilled water volume is 10 times of the volume of the concentrated sulfuric acid used), stops hydrolysis, and standing sedimentation 15h, will be clear
Clear top layer liquid is poured out, and remaining turbidity screen is centrifuged into 3~5 times, and (centrifugal rotational speed is 5000rpm, and the single spin time is
9min), until suspension pH value 3, last time is centrifuged to the nano-cellulose suspension obtained and is placed in dialysis membrane (retention molecule
Amount is 12000) interior, is dialysed 8 days with distilled water, until reaching that suspension pH value is 7.0, the gained suspension that then will dialyse is 100
It is 3% that mass concentration is concentrated into DEG C baking oven, obtains chiral nematic nano-cellulose liquid crystal phase material.
0.5g graphene oxides are weighed, deionized water 10ml, ultrasonic vibration 30min (ultrasonic power is 500W) is added, obtains
To graphene oxide suspension (mass concentration is 5%), graphene oxide suspension is put into three-necked flask, 1.0g tea is added
Polyphenol, 1.5h (speed of agitator is 800rpm) is stirred under 100 DEG C of water bath conditions, the reaction containing redox graphene is obtained
Liquid；Distilled water 10ml is added to the reaction solution containing redox graphene, supernatant liquor is outwelled after standing 5h, will be remaining muddy
The turbid leafing heart 3 times (centrifugal rotational speed is 4000rpm, and the single spin time is 8min), until centrifuging to pH value 7.0, is reduced
Graphene oxide suspension；It is 20% that redox graphene suspension is concentrated into mass concentration at 105 DEG C.
Chiral nematic structure nano cellulose solution crystalline phase material 6g, ultrasonic vibration 10min (ultrasonic power is 300W) are weighed,
Weigh redox graphene suspension 0.1g to add in the chiral nematic structure nano cellulose solution after ultrasound, in 800rpm
Magnetic agitation under the conditions of stir 2h, obtain mixture, pour the mixture into polystyrene square box, make at ambient temperature molten
Agent is volatilized, and obtains chiral nematic nano-cellulose-redox graphene laminated film that thickness is 20 μm.
It can be calculated, the mass content of redox graphene is the 10% (matter of redox graphene in laminated film
Measure quality/laminated film quality of content=redox graphene).
Embodiment 3
Change the consumption of redox graphene suspension, other preparation process be the same as Examples 1 prepare reduction-oxidation respectively
Graphene mass content is 0,1%, 2%, 2.5%, 4%, 6%, 8%, 10% chiral nematic nano-cellulose-reduction-oxidation
Graphene composite film.
Translucency of the gained laminated film under air, room temperature condition is observed, acquired results are as shown in Figure 2；Root
According to Fig. 2 as can be seen that when graphene addition is different, laminated film embodies different translucency.
Acquired results are as shown in Figure 3 to be detected to the electric conductivity of gained laminated film；According to Fig. 3 as can be seen that with
The increase of redox graphene content, the electric conductivity of gained laminated film gradually increases, and reduction-oxidation in laminated film
When the content of graphene is 10%, the electrical conductivity of film can reach more than 0.8sm, can with excellent electric conductivity
It is widely used in conductive material.
Gained redox graphene content is carried out for 4% spectrum change of the laminated film under different relative humidity
Detection, acquired results are as shown in Figure 4；According to Fig. 4 as can be seen that with the increase of relative humidity, the reflection wavelength of laminated film
Gradually red shift, when relative humidity is 11%, the reflection wavelength of laminated film is 412nm, and relative humidity is 85%, the reflection of film
Red shift of wavelength is to 565nm, and illustrating the laminated film of the present invention has Unordered system, can apply to wet sensitive and indicates in material.
It is former the invention provides a kind of preparation method of chiral nematic nano-cellulose-redox graphene laminated film
Material environmental protection is easy to get, and method is simple, and by chiral nematic nano-cellulose liquid crystal phase material and redox graphene water slurry
Convection drying film forming after mixing, will not produce destruction to the chiral nematic structure of nano-cellulose.The THIN COMPOSITE that the present invention is provided
Film remains the chiral nematic structure of nano-cellulose, with excellent optical property and electric conductivity.
As seen from the above embodiment, it is only the preferred embodiment of the present invention that the present invention is described above, it is noted that for
For those skilled in the art, under the premise without departing from the principles of the invention, can also make it is some improvement and
Retouching, these improvements and modifications also should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of chiral nematic nano-cellulose-redox graphene laminated film, comprises the following steps：
Fiber and sulfuric acid are mixed reaction is hydrolyzed, obtain nano-cellulose suspension；
The nano-cellulose suspension is centrifuged, dialysed and concentrated successively, chiral nematic nano-cellulose liquid crystal is obtained
Phase material；
The chiral nematic nano-cellulose liquid crystal phase material and redox graphene water slurry are mixed, drying and forming-film is obtained
To chiral nematic nano-cellulose-redox graphene laminated film.
2. preparation method according to claim 1, it is characterised in that the mass concentration of the sulfuric acid is 90~98%；
The quality of the fiber and the volume ratio of sulfuric acid are 10~30g：100~200ml.
3. preparation method according to claim 1, it is characterised in that the temperature of the hydrolysis is 30~70 DEG C；Water
The time of solution reaction is 1~3h.
4. preparation method according to claim 1, it is characterised in that the endpoint pH of the dialysis is 6.5~7.5；
The concentration is specially that the mass concentration of nano-cellulose suspension is concentrated into 2~5%.
5. preparation method according to claim 1, it is characterised in that the quality of the redox graphene water slurry
Concentration is 10~20%；
The mass ratio of the chiral nematic nano-cellulose liquid crystal phase material and redox graphene water slurry is 1~5：1
~5.
6. preparation method according to claim 1, it is characterised in that the preparation of the redox graphene water slurry
Method comprises the following steps：
Graphene oxide and reducing agent are subjected to reduction reaction in water, the reaction solution containing redox graphene is obtained；
It is 6.5~7.5 that the reaction solution containing redox graphene, which is centrifuged to pH value, obtains redox graphene water
Suspension.
7. preparation method according to claim 6, it is characterised in that the reducing agent is vitamin C and/or Tea Polyphenols；
The mass ratio of the graphene oxide and reducing agent is 0.1~0.5：0.3~1.
8. chiral nematic nano-cellulose-redox graphene prepared by preparation method described in claim 1~7 any one
Laminated film.
9. chiral nematic nano-cellulose-redox graphene laminated film described in claim 8 is in conductive material
Using.
10. chiral nematic nano-cellulose-redox graphene laminated film described in claim 8 indicates material in wet sensitive
In application.
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| CN110527145A (en) * | 2019-07-15 | 2019-12-03 | 华南理工大学 | Nanocrystalline/chiral azobenzene composite membrane of a kind of bacteria cellulose and preparation method thereof |
| CN112778579A (en) * | 2020-12-31 | 2021-05-11 | 安徽农业大学 | Hemicellulose-based conductive composite film and preparation method thereof |
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