CN107268182B - To the nano micro crystal cellulose nano-fiber composite film and preparation method thereof of humidity sensitive - Google Patents
To the nano micro crystal cellulose nano-fiber composite film and preparation method thereof of humidity sensitive Download PDFInfo
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- CN107268182B CN107268182B CN201710350816.0A CN201710350816A CN107268182B CN 107268182 B CN107268182 B CN 107268182B CN 201710350816 A CN201710350816 A CN 201710350816A CN 107268182 B CN107268182 B CN 107268182B
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
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- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2201/00—Cellulose-based fibres, e.g. vegetable fibres
- D10B2201/01—Natural vegetable fibres
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- D10B2201/00—Cellulose-based fibres, e.g. vegetable fibres
- D10B2201/01—Natural vegetable fibres
- D10B2201/02—Cotton
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- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2201/00—Cellulose-based fibres, e.g. vegetable fibres
- D10B2201/20—Cellulose-derived artificial fibres
- D10B2201/22—Cellulose-derived artificial fibres made from cellulose solutions
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- D10B2321/00—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D10B2321/06—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polymers of unsaturated alcohols, e.g. polyvinyl alcohol, or of their acetals or ketals
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- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
- D10B2331/02—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyamides
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- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
- D10B2331/04—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyesters, e.g. polyethylene terephthalate [PET]
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
- D10B2331/10—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyurethanes
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- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2401/00—Physical properties
- D10B2401/02—Moisture-responsive characteristics
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Abstract
The present invention relates to humidity sensor material field more particularly to the nano micro crystal cellulose nano-fiber composite films and preparation method thereof of a kind of pair of humidity sensitive.To the preparation method of the nano micro crystal cellulose nano-fiber composite film of humidity sensitive, include the following steps, nano micro crystal cellulose suspension is made in acid hydrolyzed cellulose first, then nano micro crystal cellulose suspension and thermoplastic polymer nanofiber fibrous suspension are coated on substrate surface after mixing, dry rear substrate surface forms film layer, removes substrate up to the nano micro crystal cellulose nano-fiber composite film to humidity sensitive.The nano micro crystal cellulose nano-fiber composite film has the characteristics that humidity quick response and fast quick-recovery.
Description
Technical field
The present invention relates to the nano micro crystal celluloses in humidity sensor material field more particularly to a kind of pair of humidity sensitive to receive
Rice composite fiber membrane and preparation method thereof.
Background technique
Cellulose is a kind of from a wealth of sources, nontoxic natural macromolecular material, except common timber, cotton, crudefiber crop
In addition, the microorganisms such as algae, which also separate, obtains cellulose, and it is basic structural unit that cellulose, which is by D- glucopyranosyl, is led to
Cross the linear polymeric of 1,4 glucosides key connection of β-composition.Common acid-hydrolysis method, alkaline process, biologic enzymolysis method, mechanical-physical processing
The means such as method handle cellulose, can remove the noncrystalline domain in cellulosic structure to which crystalline nanofibers element be prepared.
Crystalline nanofibers element has high specific surface area, large specific surface area, crystallinity as a kind of emerging functional polymer material
The properties such as height, good biocompatibility.In addition, crystalline nanofibers element surface exposes great amount of hydroxy group, reducing end under neutral hydroxyl etc.
Active group, hydrophily are preferable.
It has been reported that responsive polymer such as polyacrylamide, n-isopropyl acrylamide, photoresponse resin etc. and nanometer
The compound obtained responsive gel material of microcrystalline cellulose, swelling/shrinkage phenomenon, which occurs, after external condition change leads to gel face
Color changes.These are all based on nano micro crystal cellulose suspension and are self-assembly of cholesteric liquid crystal structure, screw pitch
The color that changes will change, i.e., has the polymer of responsiveness to external conditions such as light, heat, humidity by another
Variation reach color response purpose.Yu Ping Zhang etc. reports that nano micro crystal cellulose film has vapor in the literature
There is certain absorbability, its color changes a lot after water suction, can be as the response sensor to air humidity.It is similar
, 103,529,085 103,512,927 102,826,761 103217458 A, CN 104569074 of A, CN of B, CN of B, CN of CN
A, patents ZnO, FeO such as 102435636 A of CN3、TiO2、CoTiO3、BaTiO3, multi-walled carbon nanotube, graphene, polypyrrole
Equal materials are added in fiber or film as humidity responsiveness material makes it have humidity responding ability, still, so far,
There is not yet report of the composite membrane of nano micro crystal cellulose and nanofiber as humidity sensitive responsor.Based on nano microcrystalline fibre
Dimension element preparation fexible film composite material it is less, it is typically compound with resin film, nylon film, and response performance compared with
Difference is only capable of judging by the faint variation of color, seriously limits its practical application.And preparation step is cumbersome, required raw material
It is more expensive, influence its industrialization degree.
Summary of the invention
In order to solve the above problem, the object of the present invention is to provide the nanometer of a kind of pair of humidity quick response and fast quick-recovery is micro-
Crystalline cellulose nano-fiber composite film and preparation method thereof.
To achieve the above object, the technical solution designed by the present invention are as follows:
To the preparation method of the nano micro crystal cellulose nano-fiber composite film of humidity sensitive, include the following steps, first
Nano micro crystal cellulose suspension is made in acid hydrolyzed cellulose, then by nano micro crystal cellulose suspension and thermoplastic polymer
Nanofiber suspension is coated on substrate surface after mixing, and dry rear substrate surface forms film layer, removes substrate to obtain the final product
Nano micro crystal cellulose nano-fiber composite film.
Completing the preferable technical solution of the present invention is: to the nano micro crystal cellulose nano-fiber composite film of humidity sensitive
Preparation method includes the following steps:
1) it prepares nano micro crystal cellulose suspension: cellulose being added in acid solution anti-to cellulose progress sour water solution
It answers, after completion of the reaction, obtained nano micro crystal cellulose suspension will be diluted with water after reaction solution washes clean；
2) it prepares thermoplastic polymer nanofiber fibrous suspension: thermoplastic polymer nanofiber fiber is added to mixed solvent
In, nanofiber is broken up using homogenizer, obtains finely dispersed thermoplastic polymer nanofiber fibrous suspension；
3) it prepares nano micro crystal cellulose nano-fiber composite film: nano micro crystal cellulose suspension is polymerize with thermoplasticity
Object nanofiber suspension is uniformly dispersed, and mixing suspension is obtained, then mixing suspension is coated on substrate, under natural conditions
It air-dries, substrate of tearing obtains nano micro crystal cellulose nano-fiber composite film.
Further, in the step 1), cellulose is cotton, wood pulp or sisal hemp；The acid solution is 60~70wt%
Sulfuric acid solution, the mass ratio of the cellulose and acid solution is 1:8~9, and the temperature of acid hydrolytic reaction is 45~55 DEG C, the time
Process for 30~50min, the washing is that pure water is used after being first centrifuged reaction solution, then dialyse with pure water straight
Until pH stablizes, the mass percentage concentration of the nano micro crystal cellulose suspension is 0.5%~5%.
Further, in the step 2), thermoplastic polymer nanofiber fiber is polyvinyl alcohol-ethylene copolymer (PVA-
Co-PE) nanofiber, polyamide (PA) nanofiber, polyethylene terephthalate (PET) nanofiber or polyurethane
(PU) nanofiber, the mass percentage concentration of the thermoplastic nanofibers fibrous suspension are 0.8%~3%, the mixed solvent
For alcohol-water mixture, and the mass ratio of alcohol and water is 7:3~5:5, and the alcohol is normal propyl alcohol, isopropanol, n-butanol or the tert-butyl alcohol
One of.
Further, in the step 3), nano micro crystal cellulose suspension and thermoplastic polymer nanofiber fiber suspension
The mass ratio of liquid is that 0.05:1~1:1, the nano micro crystal cellulose suspension and nanofiber suspension are carried out using ultrasound
Dispersion；The substrate is one of PET cloth, PP fusion spray cloth, nonwoven polypropylene fabric or PP non-woven fabrics.
To the nano micro crystal cellulose nano-fiber composite film of humidity sensitive, by the above nano micro crystal cellulose nanofiber
The preparation method of composite membrane is prepared and obtains.The nano micro crystal cellulose nano-fiber composite film is hanged by nano micro crystal cellulose
Supernatant liquid and thermoplastic polymer nanofiber fibrous suspension are coated in one layer of composite membrane that substrate surface is formed after being blended.
To the application of the nano micro crystal cellulose nano-fiber composite film of humidity sensitive in terms of flexible humidity sensor.System
Standby flexible humidity sensor is to be placed in the sensitive membrane using the nano micro crystal cellulose nano-fiber composite film as sensitive membrane
It in gas shielded shell, is placed in sample to be tested, the bending state by observing sensitive membrane can quickly judge the variation of humidity.
Wherein, preparation method referenced patent the CN 105148996A, CN 104014196 of thermoplastic polymer nanofiber fiber
The preparation method recorded in 103884695 A of B, CN.Melted using two kinds of mutual exclusive polymer of thermodynamics in twin-screw
Abundant melt blending in extruder squeezes out, and the polymer melt of blending is in extruder and spinning head by shearing force and stretching
The effect of compound force field and elongation strain, form bundles of nanofibers, finally, removal matrix polymer, obtains thermoplastic polymer
Nanofiber.For preparing polyvinyl alcohol-ethylene copolymer nanofiber, preparation method is: polyvinyl alcohol-ethylene is copolymerized
Object (PVA-co-PE) is blended with acetylbutyrylcellulose (CAB), squeezes out through twin-screw melt extruder, recycles acetone removal
CAB is up to polyvinyl alcohol-ethylene copolymer nanofiber.
Nano micro crystal cellulose nano-fiber composite film produced by the present invention is able to achieve is to the principle of humidity response: fiber
It is basic structural unit that element, which is by D- glucopyranosyl, passes through β-Isosorbide-5-Nitrae glucosides key connection composition linear polymeric.It is common
The means such as acid-hydrolysis method, alkaline process, biologic enzymolysis method, mechanical-physical processing method handle cellulose, can remove in cellulosic structure
Noncrystalline domain to which crystalline nanofibers element be prepared, crystalline nanofibers element is as the emerging functional polymer material of one kind
Material has the properties such as high specific surface area, large specific surface area, crystallinity height, good biocompatibility.Due to nano micro crystal cellulose
There is hydroxyl abundant, hydrophily is fabulous, hydroxyl after humidity becomes larger when composite membrane side, on hydrone and nano micro crystal cellulose
Hydrogenbond is generated, volume becomes larger, thus the curving for driving entire composite nano-fiber membrane big to humidity, according to curved
Angle can correspond to the size for calculating humidity.
The present invention has the advantages that
1, due to highly brittle after pure nano micro crystal cellulose film forming, flexibility is poor, therefore nano micro crystal cellulose is hanged
Supernatant liquid is mixed with thermoplastic nanofibers fibrous suspension, after film is made, the flexibility with thermoplastic fibre and have receive
The humidity response performance of rice microcrystalline cellulose.
2, since nano micro crystal cellulose and thermoplastic nanofibers fiber are all Nano grades, the film formed after blending is nanometer
Tunica fibrosa, surface have certain hole, and specific surface area is bigger, more sensitive to the variation of humidity.
3, nano micro crystal cellulose nano-fiber composite film produced by the present invention is generated when slight change occurs for humidity
Deformation, it is big to the sensitivity interval of humidity, it is 5%RH-98%RH；And the response time is short, the reaction time is respectively less than 2s, and restores
Speed is very fast, and most fast resume speed is up to 2s.
4, compared to materials such as traditional multi-walled carbon nanotube, graphene, polypyrroles as humidity responsiveness material, this hair
It is bright to obtain nano micro crystal cellulose using acid hydrolyzed cellulose, using nano micro crystal cellulose as humidity responsiveness material, at
This is cheaper, and manufacture craft is simpler, and it is more environmentally-friendly to obtain this humidity responsiveness material.
Detailed description of the invention
Fig. 1 is that embodiment 1 obtains amplifying 2000 times to the nano micro crystal cellulose nano-fiber composite film of humidity sensitive
Electron-microscope scanning figure；
Fig. 2 is that embodiment 1 obtains amplifying 10000 times to the nano micro crystal cellulose nano-fiber composite film of humidity sensitive
Electron-microscope scanning figure；
Fig. 3 be embodiment 1 obtain to response time of the nano micro crystal cellulose nano-fiber composite film of humidity sensitive and
Recovery time.Humidity stimulation is given in figure in 0-1s, removes humidity stimulation after 1s；
Fig. 4 is 20 times that embodiment 2 responds the nano micro crystal cellulose nano-fiber composite film of humidity sensitive to humidity
Cycle performance；
When Fig. 5 is that embodiment 2 does not respond the nano micro crystal cellulose nano-fiber composite film of humidity sensitive to humidity,
Formation state figure；
When Fig. 6 is that embodiment 2 responds the nano micro crystal cellulose nano-fiber composite film of humidity sensitive to humidity, volume
Bent state diagram.
Specific embodiment
For a better understanding of the invention, invention is described in detail below with reference to drawings and concrete examples.
Embodiment 1
To the preparation method of the nano micro crystal cellulose nano-fiber composite film of humidity sensitive, specifically comprise the following steps:
1) it prepares nano micro crystal cellulose suspension: cotton being added in the sulfuric acid solution of 60wt%, acid is carried out to cotton
The mass ratio of hydrolysis, cotton and acid solution is 1:8, and the temperature of acid hydrolytic reaction is 45 DEG C, and time 30min has reacted
Bi Hou uses pure water after being first centrifuged reaction solution, then carry out dialysis until pH stablizes with pure water, be finally diluted with water
The nano micro crystal cellulose suspension that mass percentage concentration is 0.5% is made；
2) thermoplastic polymer nanofiber fibrous suspension is prepared: by polyvinyl alcohol-ethylene copolymer (PVA-co-PE) nanometer
Fiber is added in alcohol-water mixture, and alcohol-water mixture is the mixed liquor of normal propyl alcohol and water, and the mass ratio of alcohol and water is 7:3,
Nanofiber is broken up using homogenizer, obtains finely dispersed thermoplastic polymer nanofiber fibrous suspension, thermoplastic nanofibers
The mass percentage concentration of fibrous suspension is 0.8%；
3) prepare nano micro crystal cellulose nano-fiber composite film: in mass ratio, by nano micro crystal cellulose suspension with
Thermoplastic polymer nanofiber fibrous suspension is uniformly dispersed for 0.05:1, obtains mixing suspension, then mixing suspension is coated
On PET cloth, air-dried under natural conditions, substrate of tearing obtains compound to the nano micro crystal cellulose nanofiber of humidity sensitive
Film.
Such as Fig. 1, the nano micro crystal cellulose nano-fiber composite film that the present embodiment 1 obtains amplifies 2000 times of electron-microscope scanning
Figure, such as Fig. 2, the nano micro crystal cellulose nano-fiber composite film that the present embodiment 1 obtains amplify 10000 times of electron-microscope scanning figure.
The nano micro crystal cellulose nano-fiber composite film that the present embodiment 1 obtains is carried out in the environment that humidity is 80%
Test, as shown in connection with fig. 3, response time 1s, maximum bending angle is 185 °, recovery time 2.5s.Fig. 3 illustrates that this is received
The response speed and resume speed of rice microcrystalline cellulose nano-fiber composite film are all than very fast.
Embodiment 2
To the preparation method of the nano micro crystal cellulose nano-fiber composite film of humidity sensitive, specifically comprise the following steps:
1) it prepares nano micro crystal cellulose suspension: wood pulp being added in the sulfuric acid solution of 65wt%, acid is carried out to wood pulp
The mass ratio of hydrolysis, wood pulp and acid solution is 1:8.75, and the temperature of acid hydrolytic reaction is 50 DEG C, time 40min, reaction
After, pure water is used after being first centrifuged reaction solution, then carries out dialysis until pH stablizes with pure water, finally plus water is dilute
Release the nano micro crystal cellulose suspension that obtained mass percentage concentration is 2%；
2) it prepares thermoplastic polymer nanofiber fibrous suspension: polyamide (PA) nanofiber is added to alcohol-water mixture
In, alcohol-water mixture is the mixed liquor of isopropanol and water, and the mass ratio of alcohol and water is 6:4, using homogenizer by nanofiber
It breaks up, obtains finely dispersed thermoplastic polymer nanofiber fibrous suspension；The quality percentage of thermoplastic nanofibers fibrous suspension
Concentration is 1%；
3) prepare nano micro crystal cellulose nano-fiber composite film: in mass ratio, by nano micro crystal cellulose suspension with
Thermoplastic polymer nanofiber fibrous suspension is uniformly dispersed for 0.8:1, obtains mixing suspension, then mixing suspension is coated in
On PP fusion spray cloth, air-dried under natural conditions, substrate of tearing obtains compound to the nano micro crystal cellulose nanofiber of humidity sensitive
Film.
The nano micro crystal cellulose nano-fiber composite film that the present embodiment obtains is tried in the environment that humidity is 60%
It tests, response time 0.8s, maximum bending angle is 215 °, recovery time 4s.
As shown in connection with fig. 4, reach maximum after humidity stimulation is given when nano micro crystal cellulose nano-fiber composite film is smooth
Bending angle or reach remove humidity stimulation after maximum angle after nano-fiber composite film restore smooth, be defined as one and follow
Ring.Fig. 4 explanation still keeps preferable responding ability by 20 circulations, the nano micro crystal cellulose nano-fiber composite film.
In conjunction with shown in Fig. 5 and Fig. 6, when not responded to humidity, nano micro crystal cellulose nano-fiber composite film formation state
Figure is as shown in Figure 5；The nano micro crystal cellulose nano-fiber composite film is contacted with hand, it is therefore intended that is received to nano micro crystal cellulose
Humidity stimulation is given in the upper surface of rice composite fiber membrane, and rolled state figure is as shown in Figure 6.
Embodiment 3
To the preparation method of the nano micro crystal cellulose nano-fiber composite film of humidity sensitive, specifically comprise the following steps:
1) it prepares nano micro crystal cellulose suspension: sisal hemp being added in the sulfuric acid solution of 70wt%, acid is carried out to sisal hemp
The mass ratio of hydrolysis, sisal hemp and acid solution is 1:9, and the temperature of acid hydrolytic reaction is 55 DEG C, and time 50min has reacted
Bi Hou uses pure water after being first centrifuged reaction solution, then carry out dialysis until pH stablizes with pure water, be finally diluted with water
The nano micro crystal cellulose suspension that mass percentage concentration is 3% is made；
2) thermoplastic polymer nanofiber fibrous suspension is prepared: by polyethylene terephthalate (PET) nanofiber
It is added in alcohol-water mixture, alcohol-water mixture is the mixed liquor of n-butanol and water, and the mass ratio of alcohol and water is 5:5, is used
Homogenizer breaks up nanofiber, obtains finely dispersed thermoplastic polymer nanofiber fibrous suspension；Thermoplastic nanofibers fiber
The mass percentage concentration of suspension is 3%；
3) prepare nano micro crystal cellulose nano-fiber composite film: in mass ratio, by nano micro crystal cellulose suspension with
Thermoplastic polymer nanofiber fibrous suspension is uniformly dispersed for 0.2:1, obtains mixing suspension, then mixing suspension is coated in
It in nonwoven polypropylene fabric, is air-dried under natural conditions, substrate of tearing obtains multiple to the nano micro crystal cellulose nanofiber of humidity sensitive
Close film.
The nano micro crystal cellulose nano-fiber composite film that the present embodiment obtains is tried in the environment that humidity is 70%
It tests, response time 1.6s, maximum bending angle is 205 °, recovery time 12s.
Embodiment 4
To the preparation method of the nano micro crystal cellulose nano-fiber composite film of humidity sensitive, specifically comprise the following steps:
1) it prepares nano micro crystal cellulose suspension: sisal hemp being added in the sulfuric acid solution of 70wt%, acid is carried out to sisal hemp
The mass ratio of hydrolysis, sisal hemp and acid solution is 1:8.75, and the temperature of acid hydrolytic reaction is 50 DEG C, time 50min, reaction
After, pure water is used after being first centrifuged reaction solution, then carries out dialysis until pH stablizes with pure water, finally plus water is dilute
Release the nano micro crystal cellulose suspension that obtained mass percentage concentration is 5%；
2) it prepares thermoplastic polymer nanofiber fibrous suspension: polyurethane (PU) nanofiber is added to alcohol-water mixture
In, alcohol-water mixture is the mixed liquor of the tert-butyl alcohol and water, and the mass ratio of alcohol and water is 5:5, using homogenizer by nanofiber
It breaks up, obtains finely dispersed thermoplastic polymer nanofiber fibrous suspension；The quality percentage of thermoplastic nanofibers fibrous suspension
Concentration is 3%；
3) prepare nano micro crystal cellulose nano-fiber composite film: in mass ratio, by nano micro crystal cellulose suspension with
Thermoplastic polymer nanofiber fibrous suspension is uniformly dispersed for 0.6:1, obtains mixing suspension, then mixing suspension is coated in
On PP non-woven fabrics, air-dried under natural conditions, substrate of tearing obtains compound to the nano micro crystal cellulose nanofiber of humidity sensitive
Film.
The nano micro crystal cellulose nano-fiber composite film that the present embodiment obtains is tried in the environment that humidity is 30%
It tests, response time 1.5s, maximum bending angle is 195 °, recovery time 4s.
Embodiment 5
To the preparation method of the nano micro crystal cellulose nano-fiber composite film of humidity sensitive, specifically comprise the following steps:
1) it prepares nano micro crystal cellulose suspension: wood pulp being added in the sulfuric acid solution of 70wt%, acid is carried out to wood pulp
The mass ratio of hydrolysis, wood pulp and acid solution is 1:8.75, and the temperature of acid hydrolytic reaction is 50 DEG C, time 40min, reaction
After, pure water is used after being first centrifuged reaction solution, then carries out dialysis until pH stablizes with pure water, finally plus water is dilute
Release the nano micro crystal cellulose suspension that obtained mass percentage concentration is 4%；
2) thermoplastic polymer nanofiber fibrous suspension is prepared: by polyvinyl alcohol-ethylene copolymer (PVA-co-PE) nanometer
Fiber is added in alcohol-water mixture, and alcohol-water mixture is the mixed liquor of the tert-butyl alcohol and water, and the mass ratio of alcohol and water is 5:5,
Nanofiber is broken up using homogenizer, obtains finely dispersed thermoplastic polymer nanofiber fibrous suspension；Thermoplastic nanofibers
The mass percentage concentration of fibrous suspension is 2%；
3) prepare nano micro crystal cellulose nano-fiber composite film: in mass ratio, by nano micro crystal cellulose suspension with
Thermoplastic polymer nanofiber fibrous suspension is uniformly dispersed for 1:1, obtains mixing suspension, then mixing suspension is coated in
On PET cloth, air-dried under natural conditions, substrate of tearing obtains the nano micro crystal cellulose nano-fiber composite film to humidity sensitive.
The nano micro crystal cellulose nano-fiber composite film that the present embodiment obtains is tried in the environment that humidity is 20%
It tests, response time 0.6s, maximum bending angle is 210 °, recovery time 2s.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
Limitations on the scope of the patent of the present invention therefore cannot be interpreted as.It should be pointed out that for those of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to guarantor of the invention
Protect range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (6)
1. the preparation method of the nano micro crystal cellulose nano-fiber composite film of a kind of pair of humidity sensitive, it is characterised in that: including
Nano micro crystal cellulose suspension is made in following steps, first acid hydrolyzed cellulose, then by nano micro crystal cellulose suspension
It is coated on substrate surface after mixing with thermoplastic polymer nanofiber fibrous suspension, dry rear substrate surface forms film
Layer removes substrate up to nano micro crystal cellulose nano-fiber composite film；Specifically comprise the following steps:
1) it prepares nano micro crystal cellulose suspension: cellulose being added in acid solution, acid hydrolytic reaction is carried out to cellulose,
After completion of the reaction, obtained nano micro crystal cellulose suspension will be diluted with water after reaction solution washes clean；
2) it prepares thermoplastic polymer nanofiber fibrous suspension: thermoplastic polymer nanofiber fiber is added in the mixed solvent,
Nanofiber is broken up using homogenizer, obtains finely dispersed thermoplastic polymer nanofiber fibrous suspension；
3) it prepares nano micro crystal cellulose nano-fiber composite film: nano micro crystal cellulose suspension is received with thermoplastic polymer
Rice fibrous suspension is uniformly dispersed, and obtains mixing suspension, then mixing suspension is coated on substrate, natural conditions leeward
Dry, substrate of tearing obtains nano micro crystal cellulose nano-fiber composite film.
2. according to claim 1 to the preparation method of the nano micro crystal cellulose nano-fiber composite film of humidity sensitive,
Be characterized in that: in the step 1), cellulose is cotton, wood pulp or sisal hemp；The acid solution is that the sulfuric acid of 60~70wt% is molten
The mass ratio of liquid, the cellulose and acid solution is 1:8~9, and the temperature of acid hydrolytic reaction is 45~55 DEG C, the time is 30~
The process of 50min, the washing are that pure water is used after being first centrifuged reaction solution, then carry out dialysis with pure water until pH is steady
It is set to only, the mass percentage concentration of the nano micro crystal cellulose suspension is 0.5%~5%.
3. according to claim 1 to the preparation method of the nano micro crystal cellulose nano-fiber composite film of humidity sensitive,
Be characterized in that: in the step 2), thermoplastic polymer nanofiber fiber is polyvinyl alcohol-ethylene copolymer nanofiber, polyamides
Amine nanofiber, polyethylene terephthalate nanofiber or polyurethane nanofiber, the thermoplastic nanofibers fiber are outstanding
The mass percentage concentration of supernatant liquid is 0.8%-3%, and the mixed solvent is alcohol-water mixture, and the mass ratio of alcohol and water is 7:3
~5:5, the alcohol are one of normal propyl alcohol, isopropanol, n-butanol or tert-butyl alcohol.
4. according to claim 1 to the preparation method of the nano micro crystal cellulose nano-fiber composite film of humidity sensitive,
It is characterized in that: in the step 3), the quality of nano micro crystal cellulose suspension and thermoplastic polymer nanofiber fibrous suspension
Than for 0.05:1~1:1, the nano micro crystal cellulose suspension is dispersed with nanofiber suspension using ultrasound；It is described
Substrate is one of PET cloth, PP fusion spray cloth, nonwoven polypropylene fabric or PP non-woven fabrics.
5. the nano micro crystal cellulose nano-fiber composite film of a kind of pair of humidity sensitive, it is characterised in that: it is by claim 1
The preparation method of nano micro crystal cellulose nano-fiber composite film described in any one of~4 is prepared and obtains.
6. a kind of as claimed in claim 5 pass the nano micro crystal cellulose nano-fiber composite film of humidity sensitive in flexible humidity
Application in terms of sensor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710350816.0A CN107268182B (en) | 2017-05-18 | 2017-05-18 | To the nano micro crystal cellulose nano-fiber composite film and preparation method thereof of humidity sensitive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201710350816.0A CN107268182B (en) | 2017-05-18 | 2017-05-18 | To the nano micro crystal cellulose nano-fiber composite film and preparation method thereof of humidity sensitive |
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| TWI680288B (en) * | 2018-11-12 | 2019-12-21 | 國立交通大學 | A device for extracting water droplet from ambient air |
| CN109719817B (en) * | 2019-02-25 | 2021-02-26 | 山东农业大学 | Preparation method of moisture stimulus response type wood driver |
| US11421041B2 (en) | 2020-10-15 | 2022-08-23 | Jiangnan University | Multi-response cellulose nanocrystals-composite film and preparation method thereof |
| CN112266502B (en) * | 2020-10-15 | 2021-09-28 | 江南大学 | Multi-response nano-cellulose composite membrane and preparation method thereof |
| CN112121650B (en) * | 2020-10-15 | 2022-07-08 | 武汉纺织大学 | Nano-fiber chitosan membrane and preparation method thereof |
| CN112834576B (en) * | 2021-02-05 | 2023-02-03 | 武汉纺织大学 | Fiber-based humidity sensor based on moisture absorption variable resistance and preparation method thereof |
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