CN108492908B - A kind of preparation method of optical activity Cellulose nanocrystal body/conductive conjugated polymer composite membrane - Google Patents
A kind of preparation method of optical activity Cellulose nanocrystal body/conductive conjugated polymer composite membrane Download PDFInfo
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- 229920002678 cellulose Polymers 0.000 title claims abstract description 37
- 239000001913 cellulose Substances 0.000 title claims abstract description 37
- 239000002131 composite material Substances 0.000 title claims abstract description 33
- 230000003287 optical effect Effects 0.000 title claims abstract description 32
- 239000002159 nanocrystal Substances 0.000 title claims abstract description 27
- 239000012528 membrane Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229920000547 conjugated polymer Polymers 0.000 title claims description 20
- 238000000034 method Methods 0.000 claims abstract description 20
- 230000006698 induction Effects 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 4
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 3
- 238000003786 synthesis reaction Methods 0.000 claims abstract 2
- 229920000767 polyaniline Polymers 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000013019 agitation Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- 230000003993 interaction Effects 0.000 claims description 5
- 229920000128 polypyrrole Polymers 0.000 claims description 5
- 229920000123 polythiophene Polymers 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- 238000005903 acid hydrolysis reaction Methods 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 230000000737 periodic effect Effects 0.000 claims description 3
- 239000001117 sulphuric acid Substances 0.000 claims description 3
- 235000011149 sulphuric acid Nutrition 0.000 claims description 3
- 102000004190 Enzymes Human genes 0.000 claims description 2
- 108090000790 Enzymes Proteins 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- -1 amine compound Chemical class 0.000 claims 1
- 230000002255 enzymatic effect Effects 0.000 claims 1
- 238000002955 isolation Methods 0.000 claims 1
- 229920006389 polyphenyl polymer Polymers 0.000 claims 1
- 229920001940 conductive polymer Polymers 0.000 abstract description 23
- 239000002322 conducting polymer Substances 0.000 abstract description 18
- 239000000463 material Substances 0.000 abstract description 13
- 239000004986 Cholesteric liquid crystals (ChLC) Substances 0.000 abstract description 4
- 238000004220 aggregation Methods 0.000 abstract description 4
- 230000002776 aggregation Effects 0.000 abstract description 4
- 238000004020 luminiscence type Methods 0.000 abstract description 2
- 230000000717 retained effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 6
- 239000012071 phase Substances 0.000 description 5
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000002983 circular dichroism Methods 0.000 description 2
- 238000000502 dialysis Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 229920001197 polyacetylene Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 235000010893 Bischofia javanica Nutrition 0.000 description 1
- 240000005220 Bischofia javanica Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005557 chiral recognition Methods 0.000 description 1
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005090 crystal field Methods 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000012761 high-performance material Substances 0.000 description 1
- 229960002163 hydrogen peroxide Drugs 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical class [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 229940059939 kayexalate Drugs 0.000 description 1
- 238000002267 linear dichroism spectroscopy Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
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- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
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- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/124—Intrinsically conductive polymers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/124—Intrinsically conductive polymers
- H01B1/127—Intrinsically conductive polymers comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/124—Intrinsically conductive polymers
- H01B1/128—Intrinsically conductive polymers comprising six-membered aromatic rings in the main chain, e.g. polyanilines, polyphenylenes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/0026—Apparatus for manufacturing conducting or semi-conducting layers, e.g. deposition of metal
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Abstract
The present invention relates to the molten preparations for causing cholesteric liquid crystal, water-soluble conducting polymer and optical activity conjugated conductive composite membrane of cellulose, belong to conductive polymer composite field.The preparation of cellulose base conducting polymer composite material is used for different from traditional situ aggregation method and electrochemical process synthesis conducting polymer, here we have selected water-soluble conducting polymer, the compatibility issue of Cellulose nanocrystal body and conducting polymer is well solved, so that the molten chiral helical structure for causing cholesteric liquid crystal of cellulose is retained, and induction pattern plate is utilized it as, successfully prepare optical activity Cellulose nanocrystal body/conjugated conductive composite membrane.This material has preferable optical characteristics and electrochemical properties simultaneously, will be widely used prospect in fields such as supercapacitor, chemical biosensor, nonlinear optical material and circularly polarized luminescences.
Description
Technical field
The invention belongs to conductive polymer composite fields, are particularly exactly to be with the molten cause cholesteric liquid crystal of cellulose
Template is formed with the helical structure of sequence by the induction conducting polymer aggregation of total construction from part, to prepare optical activity conjugated conductive
Composite membrane.
Background technique
For the urgent need for meeting the Green High Performance material with Prospects of Sustainable Development, Cellulose nanocrystal body
(CNC) hot spot of material science is had become, application prospect is very wide.Cholesteric liquid crystal (N*-LCs) is cholesterine mostly
Derivative, usually chiral molecules, optical activity with higher, N*-LCs special helical structure are just derived from molecule
Chiral structure, therefore N*-LCs is also known as chiral nematic phase liquid crystal.Cholester structure is typically considered 1-D photon crystal, can be with
The light of selective reflecting specific wavelength.Cellulose can form stable CNC soliquid after sulphuric acid hydrolysis, reach certain
Critical concentration after, molten cause N*-LCs can be spontaneously formed, it is accumulated by many planes, and the rodlike CNC in plane is along long axis
Direction is arranged in parallel, and CNC long axis differently- oriented directivity is different between layers, and molecular orientation direction successively deflects between adjacent layer, shape
It is spiral.This unique helical structure is but also cellulose N*-LCs causes as a kind of splendid chiral basis material
Researcher extensive interest.
Conducting polymer is mainly the conjugated polymer of main chain pi-conjugated structure containing long-range, when by excitation in excitation state,
Can have unique light, electricity, magnetic property, with light-weight, easily molded, simple process, can large area film forming, it is environmentally protective
Feature, thus there is very tempting development prospect.In addition, this kind of material has good electric conductivity and electrochemical reversibility,
It is the ideal material for making supercapacitor.Widely used conducting polymer has polyaniline (PANI), polythiophene
(PTH), polypyrrole (PPy), polyacetylene (PA), poly (PPP) etc., biosensor, organizational project and it is organic too
The application study of positive energy battery material etc. has been achieved for important progress.
Optical activity conjugated material has both optically-active characteristic and conjugated structure, thus has the unexistent uniqueness of one-component material
Performance, to have wider potential application, including it is chiral Recognition, electrode face finish, chemical biosensor, non-linear
Optical material and circularly polarized luminescence etc..However, usual by conducting polymer prepared by situ aggregation method and electrochemical process
Without linear dichroism and circular dichroism.In order to solve this problem, Akagi etc. attempts to carry out in small molecule liquid crystal field anti-
It answers, and has successfully prepared optical activity conductive conjugated polymer.
The compatibility of presoma and basis material is the key that prepare composite material success or not, so it is total to prepare CNC/
What conjugated conductive polymer composite material first had to solve is exactly the problem of phase separation of the two.It is well known that passing through conventional method system
Standby PANI has insoluble insoluble characteristic, if only simply mixed CNC with PANI, it will what generation mutually separated
Phenomenon can not achieve the compound of the two.In addition, it is multiple to be similar to the PANI/ cellulose prepared in 106674558 A of patent CN
Condensation material is to prepare PANI by the method for in-situ polymerization in cellulose suspension, to realize PANI to the cladding of cellulose.
This method the result is that the charge of cellulose surface is shielded, and since acid doping declines system pH sharply, at this
In the case of kind, liquid crystal can not be formed at all, is only prepared for a kind of conducing composite material.Therefore, it solves CNC and conjugated conductive is poly-
Closing the compatibility of object and retaining the distinctive optical activity of N*-LCs structure is key point of the invention.
In the present invention, we innovatively prepare and have used water-soluble conducting polymer, well solved CNC with
The problem of phase separation of conducting polymer.Composite material shows periodic helical structure, in the effect of hydrogen bond and electrostatic attraction
Under, chiral transmitting is realized, to successfully prepare optical activity conjugated conductive composite membrane for the first time.
Summary of the invention
The present invention innovatively using the molten cause N*-LCs of CNC as chiral template material, is induced by the method for total assembling
Water-soluble conducting polymer aggregation is formed with the helical structure of sequence, so that it is compound successfully to have prepared optical activity conjugated conductive
Film.
The preparation method of optical activity Cellulose nanocrystal body/conductive conjugated polymer composite membrane of the present invention includes such as
Lower step:
1) the molten cause N*-LCs of CNC is prepared using sulphuric acid hydrolysis system；
2) pass through the conducting polymer (polyaniline, polypyrrole, polythiophene) of enzyme catalysis method synthesizing water-solubility；
3) according to different quality ratio (CNC/ conducting polymer), a certain amount of water-soluble conducting polymer is weighed respectively, and
It is dissolved in being configured to solution in deionized water.This has well solved conventional conductive polymer problem not soluble in water, guarantees
The total assembling of itself and CNC in aqueous phase system；
4) it is poly- that the molten cause N*-LCs of CNC prepared in a certain amount of step 1) is added dropwise to the conduction prepared in step 3)
In polymer solution, the mass fraction of CNC is adjusted to 4.0wt%.This process needs to carry out magnetic agitation, guarantees that two-phase mixtures are equal
It is even, obtain the CNC/ conductive polymer composite of different quality ratio.- SO present in water-soluble conducting polymer and CNC3 -、-
OH ,-NH and-NH2The interaction such as hydrogen bond and electrostatic attraction can be formed between equal groups, induction conducting polymer follows N*-
LCs carries out total assembling, chiral transmitting is realized, to prepare the composite material with periodic spin structure；
5) mixture obtained in 3.5g step 4) is taken to be placed in cuvette, middle standing at 16 DEG C, it is ensured that evaporation induction is altogether
Optical activity conjugated conductive film lucuriant in design can be obtained in the progress of assembling process after about 10 days.
Detailed description of the invention
Fig. 1 mass ratio is optical activity Cellulose nanocrystal body/conductive conjugated polymer composite membrane petrographic microscope of 20:1
Photo
The optical activity Cellulose nanocrystal body that Fig. 2 mass ratio is 20:1/conductive conjugated polymer composite membrane profile scanning electricity
Mirror photo.
Fig. 3 mass ratio is optical activity Cellulose nanocrystal body/conductive conjugated polymer composite membrane circular dichroism spectrogram of 20:1.
Specific embodiment
The technical characteristic that the present invention is further illustrated by the following examples, but protection scope of the present invention is not
It is confined to the following example.
Embodiment 1:
1) 10g Whatman CF11 cellulose powder is weighed in a round bottom flask, the sulfuric acid that 198mL 64w% is added is molten
Liquid, mechanic whirl-nett reaction 1h at 47 DEG C are then added 1L deionized water and terminate reaction.Stand 12h, outwell supernatant liquor, will under
Layer, which is deposited in, to be centrifuged repeatedly under 10000rpm and collects upper layer turbid solution, is subsequently placed in bag filter, dialysis treatment is carried out, to remove
Free acid extra in suspension is removed, dialysis 10 days until CNC suspension is in neutrality.Finally place it in the poly- second two of 10wt%
Concentration obtains the molten cause N*-LCs of CNC to required concentration in alcohol (PEG) solution；
2) measuring 20mL pH is 2.2 buffer solutions (0.1M citric acid and 0.2M Na2HPO4) in glass beaker, it is added
0.6mmol kayexalate (PSS) is dispersed with stirring 30min under ice bath, adds 0.6mmol aniline monomer.Stir 10h
Afterwards, 5mg ferric phosphate analogue enztme and 500 μ L hydrogenperoxide steam generators are added, react 20h under 20 DEG C of water bath conditions.Finally by preparation
PANI solution is dialysed for 24 hours in the hydrochloric acid solution that pH is 5, and to remove unreacted monomer and oligomer, 40 DEG C of vacuum drying obtain for 24 hours
Water-soluble PANI powder sample after to drying.
3) it according to CNC/PANI different mass ratioes (40:1,20:1,10:1,5:1), is weighed in a certain amount of step 2 respectively
The water-soluble PANI powder of preparation, is dissolved in being configured to PANI aqueous solution in deionized water.Large-sized PSS counter ion is inlayed
In PANI molecule interchain, the interaction of molecule interchain is reduced, moreover, undoped-SO in PSS3 -Group is water-soluble, from
And PANI is induced to dissolve, this is also the committed step for solving PANI and CNC compatibility issue；
4) it is molten that the molten cause N*-LCs of CNC prepared in a certain amount of step 1) is added dropwise to the PANI prepared in step 3)
In liquid, the mass fraction of CNC is adjusted to 4.0wt%.This process needs to carry out magnetic agitation 30min, guarantees that two-phase mixtures are uniform,
Obtain the CNC/PANI compound of different quality ratio (100:1~5:1).Hydrogen bond is formed by between two-phase substance group and electrostatic draws
The interactions such as power induction water solubility PANI follows N*-LCs to carry out total assembling, realizes chiral transmitting, so that preparing has week
The composite material of phase property helical structure；
5) CNC/PANI mixture obtained in 3.5g step 4) is taken to be placed in cuvette, middle standing at 16 DEG C is naturally dry
It is dry, it is ensured that evaporation induce altogether assembling process progress, can be obtained after about 10 days optical activity Cellulose nanocrystal body lucuriant in design/
Conductive conjugated polymer composite membrane.
Embodiment 2:
The present embodiment is same as Example 1, the difference is that conducting polymer used is different, can also be water-soluble
Polypyrrole, polythiophene etc..
Embodiment 3:
The present embodiment is same as Example 1, the difference is that the preparation molten cause N*-LCs of CNC is to utilize TEMPO oxidizing process,
Referring to Chinese patent: the preparation method in CN 106317423A.
Embodiment 4:
The present embodiment is same as Example 1, the difference is that it is molten water-soluble PANI powder can be dispersed directly into CNC
It causes in N*-LCs.
Embodiment 5:
The present embodiment is same as Example 1, the difference is that the pH range of mix suspending liquid system can be in step 4)
It is 3~11, Optimal pH is between 6~8.
Embodiment 6:
The present embodiment is same as Example 1, the difference is that in step 4) the magnetic agitation time can 20~
Within the scope of 120min.
Embodiment 7:
The present embodiment is same as Example 1, the difference is that magnetic agitation can be changed to using ultrasound carefully in step 4)
Born of the same parents' pulverizer carries out high-power ultrasonic dispersion.
Embodiment 8:
The present embodiment is same as Example 1, the difference is that can be replaced using vacuum filtration membrane formation process in step 5)
Solvent evaporation method prepares optical activity Cellulose nanocrystal body/conductive conjugated polymer composite membrane.
Embodiment 9:
The present embodiment is same as Example 1, the difference is that the dwell temperature in step 5) can be 10~50 DEG C, most
Good temperature is within the scope of 10 DEG C~30 DEG C.
Claims (10)
1. a kind of preparation method of optical activity Cellulose nanocrystal body/conductive conjugated polymer composite membrane, feature includes following
Step:
The molten cause N*-LCs of CNC is prepared using sulphuric acid hydrolysis, it is large-sized by Enzyme catalyzed synthesis water-soluble conducting polyaniline
PSS counter ion is embedded in PANI molecule interchain, reduces the interaction of molecule interchain, moreover, undoped-SO in PSS3 -Base
Group is water-soluble, so that PANI be induced to dissolve, this is also the key point for solving PANI and CNC compatibility issue, is added dropwise dropwise
Into the aqueous solution of different water solubility PANI contents, magnetic agitation mixes them thoroughly uniformly to be mixed the molten cause N*-LCs of CNC
Suspension system, hydrogen bond is formed by between two-phase substance group and electrostatic attraction interaction induction water solubility PANI follows N*-
LCs carries out total assembling, chiral transmitting is realized, to prepare Cellulose nanocrystal body/polyphenyl with periodic spin structure
CNC/PANI compound is placed in cuvette by amine compound, is spontaneously dried, it is ensured that it can complete evaporation induction and assemble altogether
Optical activity conjugated conductive composite membrane can be obtained in journey after 10 days.
2. the preparation method of optical activity Cellulose nanocrystal body/conductive conjugated polymer composite membrane according to claim 1,
It is characterized in that, the water-soluble conducting polyaniline replaces with polypyrrole, polythiophene.
3. the preparation method of optical activity Cellulose nanocrystal body/conductive conjugated polymer composite membrane according to claim 1,
It is characterized in that, the molten cause N*-LCs of the CNC also utilizes TEMPO oxidizing process, enzymatic isolation method preparation.
4. the preparation method of optical activity Cellulose nanocrystal body/conductive conjugated polymer composite membrane according to claim 1,
It is characterized in that, the pH range of the mix suspending liquid system is 3~11.
5. the preparation method of optical activity Cellulose nanocrystal body/conductive conjugated polymer composite membrane according to claim 1,
It is characterized in that, the Cellulose nanocrystal body length range is tens nanometers to several microns, diameter is 5~30nm.
6. the preparation method of optical activity Cellulose nanocrystal body/conductive conjugated polymer composite membrane according to claim 1,
It is characterized in that, Cellulose nanocrystal body/Polyaniline mass ratio is within the scope of 100:1~5:1.
7. the preparation method of optical activity Cellulose nanocrystal body/conductive conjugated polymer composite membrane according to claim 1,
It is characterized in that, the Cellulose nanocrystal constitution in the Cellulose nanocrystal body/Polyaniline as induction pattern plate
Measuring fraction range is 3.0~10.0wt%, and concentration is within the scope of 3.0~6.0wt%.
8. the preparation method of optical activity Cellulose nanocrystal body/conductive conjugated polymer composite membrane according to claim 1,
It is characterized in that, the time of the magnetic agitation is within the scope of 20~120min.
9. the preparation method of optical activity Cellulose nanocrystal body/conductive conjugated polymer composite membrane according to claim 1,
It is characterized in that, Cellulose nanocrystal body/Polyaniline Zeta potential will be between -60~-30mv.
10. the preparation side of optical activity Cellulose nanocrystal body/conductive conjugated polymer composite membrane according to claim 1
Method, which is characterized in that the temperature of the natural drying is 10 DEG C~50 DEG C.
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| CN102295786A (en) * | 2011-06-13 | 2011-12-28 | 青岛科技大学 | Nano cellulose crystal / polyaniline composite material, preparation method and product thereof |
| CN106146836A (en) * | 2015-04-17 | 2016-11-23 | 天津工业大学 | A kind of preparation method of conducting polymer/regenerated celulose fibre composite |
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| CN102906165B (en) * | 2010-05-12 | 2016-05-25 | 多伦多大学董事局 | Produce the method for conducting polymer and cellulose nano-complex |
| KR20170036558A (en) * | 2015-09-24 | 2017-04-03 | 삼성전자주식회사 | Conductive composites and compositions for producing the same and production methods thereof |
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2018
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102295786A (en) * | 2011-06-13 | 2011-12-28 | 青岛科技大学 | Nano cellulose crystal / polyaniline composite material, preparation method and product thereof |
| CN106146836A (en) * | 2015-04-17 | 2016-11-23 | 天津工业大学 | A kind of preparation method of conducting polymer/regenerated celulose fibre composite |
Non-Patent Citations (2)
| Title |
|---|
| 导电聚合物/纤维素纳米晶复合材料的制备与性能;吴谦;《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》;20151215;第B020-24页 |
| 聚苯胺微/纳米结构及其应用;朱英 等;《高分子通报》;20111015;第15-29页 |
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