CN105837817A - Polyaniline nanometer fiber film preparation method - Google Patents
Polyaniline nanometer fiber film preparation method Download PDFInfo
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- CN105837817A CN105837817A CN201610188754.3A CN201610188754A CN105837817A CN 105837817 A CN105837817 A CN 105837817A CN 201610188754 A CN201610188754 A CN 201610188754A CN 105837817 A CN105837817 A CN 105837817A
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- 229920000767 polyaniline Polymers 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000000835 fiber Substances 0.000 title abstract description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000002131 composite material Substances 0.000 claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 39
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N EtOH Substances CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000843 powder Substances 0.000 claims abstract description 16
- JPVGJILDANOJDX-UHFFFAOYSA-N C(Cl)(Cl)(Cl)Cl.NC1=CC=CC=C1 Chemical compound C(Cl)(Cl)(Cl)Cl.NC1=CC=CC=C1 JPVGJILDANOJDX-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 238000000926 separation method Methods 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 9
- -1 persulfuric acid Ammonium salt Chemical class 0.000 claims description 46
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 38
- 229920000265 Polyparaphenylene Polymers 0.000 claims description 37
- 150000001412 amines Chemical class 0.000 claims description 37
- 239000002121 nanofiber Substances 0.000 claims description 35
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 28
- 239000010409 thin film Substances 0.000 claims description 23
- 239000000376 reactant Substances 0.000 claims description 21
- 239000007787 solid Substances 0.000 claims description 21
- 238000004140 cleaning Methods 0.000 claims description 20
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 19
- 239000011260 aqueous acid Substances 0.000 claims description 17
- JHJUUEHSAZXEEO-UHFFFAOYSA-M sodium;4-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=C(S([O-])(=O)=O)C=C1 JHJUUEHSAZXEEO-UHFFFAOYSA-M 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 238000005119 centrifugation Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 230000007480 spreading Effects 0.000 claims description 7
- 238000003892 spreading Methods 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 238000012695 Interfacial polymerization Methods 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 32
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000012544 monitoring process Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 abstract 6
- 239000007864 aqueous solution Substances 0.000 abstract 4
- ADHFGLVXSIGCIG-UHFFFAOYSA-N diazanium sulfate hydrochloride Chemical compound [NH4+].[NH4+].Cl.[O-]S([O-])(=O)=O ADHFGLVXSIGCIG-UHFFFAOYSA-N 0.000 abstract 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 abstract 1
- 239000000047 product Substances 0.000 description 22
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 16
- 229910021529 ammonia Inorganic materials 0.000 description 14
- 238000001514 detection method Methods 0.000 description 6
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 5
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 5
- 235000011130 ammonium sulphate Nutrition 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 150000003863 ammonium salts Chemical class 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 4
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001548 drop coating Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000006855 networking Effects 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000004153 renaturation Methods 0.000 description 1
- 210000001533 respiratory mucosa Anatomy 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/026—Wholly aromatic polyamines
- C08G73/0266—Polyanilines or derivatives thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/02—Polyamines
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Polymers & Plastics (AREA)
- Nanotechnology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Organic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Artificial Filaments (AREA)
Abstract
The invention discloses a polyaniline nanometer fiber film preparation method. The preparation method comprises transferring an ammonium sulfate-hydrochloric acid aqueous solution to the surface of an aniline-carbon tetrachloride solution so that the solutions undergo a reaction to produce a reaction solution, collecting an invisible green reaction solution in the upper layer of the reaction solution, orderly carrying out solid-liquid separation, washing and drying to obtain composite polyaniline powder, preparing a composite polyaniline-ethanol aqueous solution from the composite polyaniline powder and an ethanol aqueous solution, slowly and dropwisely adding the composite polyaniline-ethanol aqueous solution into water to obtain composite polyaniline spread on the water surface and dropwisely adding a sodium dodecyl benzene sulfonate solution into water to obtain a fluffy netty desired product composed of nanometer fibers, wherein film thickness is greater than or equal to 0.8 microns and a nanometer fiber composed of polyaniline and hydrochloric acid has the diameter of 50-100nm. The polyaniline nanometer fiber film has even quality and a large specific surface area, is suitable for large scale and green eco-friendly production and can be widely used for monitoring an ammonia gas concentration of an ambient atmosphere.
Description
Technical field
The present invention relates to the preparation method of a kind of fiber membrane, the preparation method of a kind of polyaniline nano fiber thin film.
Background technology
Ammonia (NH3) be widely present in the living environment of nature and people, as technical azotification reaction can generate substantial amounts of ammonia
Gas, the filler of concrete can discharge ammonia, kitichen and toilet and also can discharge generation ammonia when high temperature.Ammonia gas toxicity is relatively
By force, having strong stink, suck a small amount of ammonia, can stimulate respiratory mucosa and the eyes of people, substantial amounts of suction can be tight
Heavily damage respiratory tract and the eyes of people, even result in death.Therefore, quickly identification, on-line tracing detection and the prison to ammonia
Survey and just seem particularly significant.In the recent period, the sensor that people are more excellent in order to obtain the detection performance to ammonia, it is made that various exerting
Power, such as entitled " Polyaniline Nanofiber Gas Sensors:Examination of Response Mechanisms ",
NANO LETTERS, 2004, Vol.4, No.3,491-496 (" polyaniline nano fiber gas sensor: Response Mechanism is surveyed
Examination ", " nanometer bulletin ", volume 4 the 3rd phase page 491～496 in 2004) article.The ammonia mentioned in this article passes
Sensor is film like, and it is made up of the polyaniline nano fiber networking of the hydrochloric acid that adulterates；Preparation method uses interfacial polymerization and drips
Coating, concretely comprises the following steps and first uses interfacial polymerization to obtain the aqueous phase dissolved with hydrochloric acid and oxidant, the oil phase dissolved with aniline monomer
To doped hydrochloride state polyaniline nano fiber, then doped hydrochloride state polyaniline nano fiber is dissolved in hexafluoroisopropanol (HFIP)
Or after in N-Methyl pyrrolidone (NMP), its solution uses the filter membrane of 0.2 μm carry out sucking filtration, obtains filtrate, afterwards,
Filtrate is dripped and is dried after in electrode basement, it is thus achieved that product.Though this product can as detection ammonia sensor, so itself and
Preparation method all also exists weak point, and first, the nanometer fiber net constituting product is uneven, causes between product difference relatively
Greatly, so that the performance of its detection ammonia is difficult to keep consistent；Secondly, the preparation method of drop coating can not ensure product qualities
Concordance, be only applicable to again the making of small lot, also need to use poisonous organic solvent.
Summary of the invention
The technical problem to be solved in the present invention is for overcoming weak point of the prior art, it is provided that a kind of uniform quality, be suitable to rule
The preparation method of the polyaniline nano fiber thin film that modelling and environmental protection produce.
For solving the technical problem of the present invention, the technical scheme used is: the preparation method bag of polyaniline nano fiber thin film
Including interfacial polymerization, particularly key step is as follows,
Step 1, first according to the ratio that mol ratio is 0.8:1～50:180 of Ammonium persulfate., hydrochloric acid and water, prepares persulfuric acid
Ammonium salt aqueous acid, the volume ratio according still further to the aniline carbon tetrachloride solution of Ammonium persulfate. aqueous hydrochloric acid solution and 0.32mol/L is
The ratio of 1:0.8～1.2, after Ammonium persulfate. aqueous hydrochloric acid solution is transferred to the surface of aniline carbon tetrachloride solution, be placed in 20～
React at least 20h at 30 DEG C, obtain reactant liquor；
Step 2, after first collecting the blackish green reactant liquor on reactant liquor upper strata, carries out solid-liquid separation successively, washs and be dried it
Process, obtain composite polyphenylene amine powder, according still further to composite polyphenylene amine powder and the weight of the ethanol water of 40～60vol%
Ratio is the ratio of 1.8～2.2:1, prepares composite polyphenylene amine ethanol water；
Step 3, is 1 according to the weight ratio of composite polyphenylene amine ethanol water and the dodecylbenzene sodium sulfonate solution of 2g/L:
The ratio of 4.8～5.2, is first slowly dropped into composite polyphenylene amine ethanol water in water, obtains spreading in the composite polyphenylene of the water surface
Amine, then in water, drip dodecylbenzene sodium sulfonate solution, prepare polyaniline nano fiber thin film；
Described polyaniline nano fiber thin film is made up of fluffy network-like nanofiber, wherein, and thickness >=0.8 μm of thin film,
Nanofiber is made up of polyaniline and hydrochloric acid, and they are a diameter of 50～100nm years old.
Further improvement as the preparation method of polyaniline nano fiber thin film:
Preferably, during preparation Ammonium persulfate. aqueous hydrochloric acid solution, it is carried out the hydrotropy solution of ultrasonic 30min.
Preferably, solid-liquid separation is processed as centrifugation, and its rotating speed is 2000～6000r/min, the time is 2～6min.
Preferably, carrying out washing treatment is to use deionized water, ethanol and acetone that the solids of isolated is carried out 10 times successively
Alternately cleaning, separating solids during cleaning is centrifugation.
Preferably, dried is that the solids after cleaning is placed at 40～50 DEG C vacuum drying 20h.
Provide the benefit that relative to prior art:
One, uses scanning electron microscope, infrared spectrometer and X-ray diffractometer to characterize prepared purpose product respectively,
From its result, purpose product is film like, and it is made up of fluffy network-like nanofiber；Wherein, the thickness of thin film >=
0.8 μm, nanofiber is made up of polyaniline and hydrochloric acid, and they are a diameter of 50～100nm years old.This it is made up of polyaniline and hydrochloric acid
Nanofiber be assembled into uniform fluffy network-like purpose product, both due to nanofiber, there is bigger specific surface area,
Not only make the difference between purpose product be suppressed because nanofiber is assembled into uniform fluffy network-like again, also make nanometer
The advantage of pulp freeness is fully played.
Its two, using prepared purpose product as gas sensor, through ammonia being carried out the surveys of the repeatedly many batches under variable concentrations
Examination, as the concentration as little as 20ppm of tested ammonia, remain to effectively detect it, and its detection concordance and weight
Renaturation multiple spot on purpose product and any point are the best.
Its three, preparation method is simple, science, effectively.Not only prepare the purpose product polyaniline nano of uniform quality
Fiber membrane；Also make it have bigger specific surface area, thus correspondingly improve the sensitivity of detection ammonia；More have
Be suitable to scale and the feature of environmental protection production；The particularly method of self-assembled film ensure that purpose product internal microstructure
Concordance, for guaranteeing that the quality of purpose product is laid a good foundation；And then make purpose product be extremely easy to be widely used in environment
Monitoring to ammonia concentration in air.
Accompanying drawing explanation
Fig. 1 is to one of result that the purpose product that preparation method is prepared uses scanning electron microscope (SEM) to characterize.SEM schemes
As demonstrating that purpose product is film like, it is made up of fluffy network-like nanofiber.
Fig. 2 is to one of result that prepared purpose product use FTIR spectrum (FTIR) instrument characterizes.FTIR
Spectrogram shows that purpose product has the molecular structure of polyaniline.
Fig. 3 is to one of result that prepared purpose product use X-ray diffraction (XRD) instrument characterizes.XRD spectra is demonstrate,proved
Real purpose product is made up of polyaniline and hydrochloric acid.
Fig. 4 is to be placed in room temperature by prepared purpose product, to its carry out air-sensitive test under different ammonia concentration result it
One.
Detailed description of the invention
Below in conjunction with the accompanying drawings the optimal way of the present invention is described in further detail.
First buy from market or prepare voluntarily:
Ammonium persulfate.；Hydrochloric acid；Water；Aniline；Carbon tetrachloride；Ethanol；Dodecylbenzene sodium sulfonate.
Then,
Embodiment 1
Concretely comprising the following steps of preparation:
Step 1, first according to the ratio that mol ratio is 0.8:1:180 of Ammonium persulfate., hydrochloric acid and water, prepares persulfuric acid ammonium salt
Aqueous acid；Wherein, during preparation Ammonium persulfate. aqueous hydrochloric acid solution, it is carried out the hydrotropy solution of ultrasonic 30min.According still further to mistake
The ratio that volume ratio is 1:0.8 of the aniline carbon tetrachloride solution of ammonium sulfate aqueous acid and 0.32mol/L, by persulfuric acid
After ammonium salt aqueous acid is transferred to the surface of aniline carbon tetrachloride solution, it is placed at 20 DEG C reaction 24h, obtains reactant liquor.
Step 2, after first collecting the blackish green reactant liquor on reactant liquor upper strata, carries out solid-liquid separation successively, washs and be dried it
Process；Wherein, solid-liquid separation is processed as centrifugation, and its rotating speed is 2000r/min, the time is 6min, carrying out washing treatment
For the alternately cleaning using deionized water, ethanol and acetone that the solids of isolated carries out 10 times successively, separate during cleaning
Solids is centrifugation, and dried is that the solids after cleaning is placed at 40 DEG C vacuum drying 20h, obtains compound poly-
Aniline powder.According still further to the ratio that weight ratio is 1.8:1 of the ethanol water of composite polyphenylene amine powder and 40vol%, join
Composite polyphenylene amine ethanol water processed.
Step 3, is 1 according to the weight ratio of composite polyphenylene amine ethanol water and the dodecylbenzene sodium sulfonate solution of 2g/L:
The ratio of 4.8, is first slowly dropped into composite polyphenylene amine ethanol water in water, obtains spreading in the composite polyphenylene amine of the water surface,
In water, drip dodecylbenzene sodium sulfonate solution again, prepare and be similar to shown in Fig. 1, and such as the curve in Fig. 2 and Fig. 3
Shown polyaniline nano fiber thin film.
Embodiment 2
Concretely comprising the following steps of preparation:
Step 1, first according to the ratio that mol ratio is 0.8:13:180 of Ammonium persulfate., hydrochloric acid and water, prepares persulfuric acid ammonium salt
Aqueous acid；Wherein, during preparation Ammonium persulfate. aqueous hydrochloric acid solution, it is carried out the hydrotropy solution of ultrasonic 30min.According still further to mistake
The ratio that volume ratio is 1:0.9 of the aniline carbon tetrachloride solution of ammonium sulfate aqueous acid and 0.32mol/L, by persulfuric acid
After ammonium salt aqueous acid is transferred to the surface of aniline carbon tetrachloride solution, it is placed at 23 DEG C reaction 23h, obtains reactant liquor.
Step 2, after first collecting the blackish green reactant liquor on reactant liquor upper strata, carries out solid-liquid separation successively, washs and be dried it
Process；Wherein, solid-liquid separation is processed as centrifugation, and its rotating speed is 3000r/min, the time is 5min, carrying out washing treatment
For the alternately cleaning using deionized water, ethanol and acetone that the solids of isolated carries out 10 times successively, separate during cleaning
Solids is centrifugation, and dried is that the solids after cleaning is placed at 43 DEG C vacuum drying 20h, obtains compound poly-
Aniline powder.According still further to the ratio that weight ratio is 1.9:1 of the ethanol water of composite polyphenylene amine powder and 45vol%, join
Composite polyphenylene amine ethanol water processed.
Step 3, is 1 according to the weight ratio of composite polyphenylene amine ethanol water and the dodecylbenzene sodium sulfonate solution of 2g/L:
The ratio of 4.9, is first slowly dropped into composite polyphenylene amine ethanol water in water, obtains spreading in the composite polyphenylene amine of the water surface,
In water, drip dodecylbenzene sodium sulfonate solution again, prepare and be similar to shown in Fig. 1, and such as the curve in Fig. 2 and Fig. 3
Shown polyaniline nano fiber thin film.
Embodiment 3
Concretely comprising the following steps of preparation:
Step 1, first according to the ratio that mol ratio is 0.8:25:180 of Ammonium persulfate., hydrochloric acid and water, prepares persulfuric acid ammonium salt
Aqueous acid；Wherein, during preparation Ammonium persulfate. aqueous hydrochloric acid solution, it is carried out the hydrotropy solution of ultrasonic 30min.According still further to mistake
The ratio that volume ratio is 1:1 of the aniline carbon tetrachloride solution of ammonium sulfate aqueous acid and 0.32mol/L, by Ammonium persulfate.
After aqueous hydrochloric acid solution is transferred to the surface of aniline carbon tetrachloride solution, it is placed at 25 DEG C reaction 22h, obtains reactant liquor.
Step 2, after first collecting the blackish green reactant liquor on reactant liquor upper strata, carries out solid-liquid separation successively, washs and be dried it
Process；Wherein, solid-liquid separation is processed as centrifugation, and its rotating speed is 4000r/min, the time is 4min, carrying out washing treatment
For the alternately cleaning using deionized water, ethanol and acetone that the solids of isolated carries out 10 times successively, separate during cleaning
Solids is centrifugation, and dried is that the solids after cleaning is placed at 45 DEG C vacuum drying 20h, obtains compound poly-
Aniline powder.According still further to the ratio that weight ratio is 2:1 of the ethanol water of composite polyphenylene amine powder and 50vol%, preparation
Composite polyphenylene amine ethanol water.
Step 3, is 1:5 according to the weight ratio of composite polyphenylene amine ethanol water and the dodecylbenzene sodium sulfonate solution of 2g/L
Ratio, first composite polyphenylene amine ethanol water is slowly dropped in water, obtains spreading in the composite polyphenylene amine of the water surface, then to
Water drips dodecylbenzene sodium sulfonate solution, prepares as it is shown in figure 1, and poly-as shown in the curve in Fig. 2 and Fig. 3
Aniline nano-fiber thin film.
Embodiment 4
Concretely comprising the following steps of preparation:
Step 1, first according to the ratio that mol ratio is 0.8:38:180 of Ammonium persulfate., hydrochloric acid and water, prepares persulfuric acid ammonium salt
Aqueous acid；Wherein, during preparation Ammonium persulfate. aqueous hydrochloric acid solution, it is carried out the hydrotropy solution of ultrasonic 30min.According still further to mistake
The ratio that volume ratio is 1:1.1 of the aniline carbon tetrachloride solution of ammonium sulfate aqueous acid and 0.32mol/L, by persulfuric acid
After ammonium salt aqueous acid is transferred to the surface of aniline carbon tetrachloride solution, it is placed at 28 DEG C reaction 21h, obtains reactant liquor.
Step 2, after first collecting the blackish green reactant liquor on reactant liquor upper strata, carries out solid-liquid separation successively, washs and be dried it
Process；Wherein, solid-liquid separation is processed as centrifugation, and its rotating speed is 5000r/min, the time is 3min, carrying out washing treatment
For the alternately cleaning using deionized water, ethanol and acetone that the solids of isolated carries out 10 times successively, separate during cleaning
Solids is centrifugation, and dried is that the solids after cleaning is placed at 48 DEG C vacuum drying 20h, obtains compound poly-
Aniline powder.According still further to the ratio that weight ratio is 2.1:1 of the ethanol water of composite polyphenylene amine powder and 55vol%, join
Composite polyphenylene amine ethanol water processed.
Step 3, is 1 according to the weight ratio of composite polyphenylene amine ethanol water and the dodecylbenzene sodium sulfonate solution of 2g/L:
The ratio of 5.1, is first slowly dropped into composite polyphenylene amine ethanol water in water, obtains spreading in the composite polyphenylene amine of the water surface,
In water, drip dodecylbenzene sodium sulfonate solution again, prepare and be similar to shown in Fig. 1, and such as the curve in Fig. 2 and Fig. 3
Shown polyaniline nano fiber thin film.
Embodiment 5
Concretely comprising the following steps of preparation:
Step 1, first according to the ratio that mol ratio is 0.8:50:180 of Ammonium persulfate., hydrochloric acid and water, prepares persulfuric acid ammonium salt
Aqueous acid；Wherein, during preparation Ammonium persulfate. aqueous hydrochloric acid solution, it is carried out the hydrotropy solution of ultrasonic 30min.According still further to mistake
The ratio that volume ratio is 1:1.2 of the aniline carbon tetrachloride solution of ammonium sulfate aqueous acid and 0.32mol/L, by persulfuric acid
After ammonium salt aqueous acid is transferred to the surface of aniline carbon tetrachloride solution, it is placed at 30 DEG C reaction 20h, obtains reactant liquor.
Step 2, after first collecting the blackish green reactant liquor on reactant liquor upper strata, carries out solid-liquid separation successively, washs and be dried it
Process；Wherein, solid-liquid separation is processed as centrifugation, and its rotating speed is 6000r/min, the time is 2min, carrying out washing treatment
For the alternately cleaning using deionized water, ethanol and acetone that the solids of isolated carries out 10 times successively, separate during cleaning
Solids is centrifugation, and dried is that the solids after cleaning is placed at 50 DEG C vacuum drying 20h, obtains compound poly-
Aniline powder.According still further to the ratio that weight ratio is 2.2:1 of the ethanol water of composite polyphenylene amine powder and 60vol%, join
Composite polyphenylene amine ethanol water processed.
Step 3, is 1 according to the weight ratio of composite polyphenylene amine ethanol water and the dodecylbenzene sodium sulfonate solution of 2g/L:
The ratio of 5.2, is first slowly dropped into composite polyphenylene amine ethanol water in water, obtains spreading in the composite polyphenylene amine of the water surface,
In water, drip dodecylbenzene sodium sulfonate solution again, prepare and be similar to shown in Fig. 1, and such as the curve in Fig. 2 and Fig. 3
Shown polyaniline nano fiber thin film.
Obviously, those skilled in the art can carry out various changing to the preparation method of the polyaniline nano fiber thin film of the present invention
Move with modification without departing from the spirit and scope of the present invention.So, if these amendments and modification to the present invention belong to this
Within the scope of bright claim and equivalent technologies thereof, then the present invention is also intended to comprise these change and modification.
Claims (5)
1. a preparation method for polyaniline nano fiber thin film, including interfacial polymerization, it is characterised in that key step is as follows:
Step 1, first according to the ratio that mol ratio is 0.8:1～50:180 of Ammonium persulfate., hydrochloric acid and water, prepares persulfuric acid
Ammonium salt aqueous acid, the volume ratio according still further to the aniline carbon tetrachloride solution of Ammonium persulfate. aqueous hydrochloric acid solution and 0.32mol/L is
The ratio of 1:0.8～1.2, after Ammonium persulfate. aqueous hydrochloric acid solution is transferred to the surface of aniline carbon tetrachloride solution, be placed in 20～
React at least 20h at 30 DEG C, obtain reactant liquor；
Step 2, after first collecting the blackish green reactant liquor on reactant liquor upper strata, carries out solid-liquid separation successively, washs and be dried it
Process, obtain composite polyphenylene amine powder, according still further to composite polyphenylene amine powder and the weight of the ethanol water of 40～60vol%
Ratio is the ratio of 1.8～2.2:1, prepares composite polyphenylene amine ethanol water；
Step 3, is 1 according to the weight ratio of composite polyphenylene amine ethanol water and the dodecylbenzene sodium sulfonate solution of 2g/L:
The ratio of 4.8～5.2, is first slowly dropped into composite polyphenylene amine ethanol water in water, obtains spreading in the composite polyphenylene of the water surface
Amine, then in water, drip dodecylbenzene sodium sulfonate solution, prepare polyaniline nano fiber thin film；
Described polyaniline nano fiber thin film is made up of fluffy network-like nanofiber, wherein, and thickness >=0.8 μm of thin film,
Nanofiber is made up of polyaniline and hydrochloric acid, and they are a diameter of 50～100nm years old.
The preparation method of polyaniline nano fiber thin film the most according to claim 1, is characterized in that preparing persulfuric acid ammonium salt
During aqueous acid, it is carried out the hydrotropy solution of ultrasonic 30min.
The preparation method of polyaniline nano fiber thin film the most according to claim 1, is characterized in that solid-liquid separation is processed as
Centrifugation, its rotating speed is 2000～6000r/min, the time is 2～6min.
The preparation method of polyaniline nano fiber thin film the most according to claim 3, is characterized in that carrying out washing treatment is successively
The alternately cleaning using deionized water, ethanol and acetone that the solids of isolated carries out 10 times, separates solids during cleaning
For centrifugation.
The preparation method of polyaniline nano fiber thin film the most according to claim 4, is characterized in that dried is by clearly
Solids after washing is placed at 40～50 DEG C vacuum drying 20h.
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| CN108342079A (en) * | 2018-04-04 | 2018-07-31 | 温州市赢创新材料技术有限公司 | A kind of multifilament layer/polyaniline conductive film and preparation method thereof |
| CN111440351A (en) * | 2020-03-13 | 2020-07-24 | 辽宁大学 | 3D supermolecule self-assembly conductive biomass aerogel, preparation method thereof and application thereof in super capacitor |
| CN116116392A (en) * | 2022-11-23 | 2023-05-16 | 安徽理工大学 | Polyaniline nanofiber, preparation method and application thereof, and method for exploring iodine ore |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108342079A (en) * | 2018-04-04 | 2018-07-31 | 温州市赢创新材料技术有限公司 | A kind of multifilament layer/polyaniline conductive film and preparation method thereof |
| CN111440351A (en) * | 2020-03-13 | 2020-07-24 | 辽宁大学 | 3D supermolecule self-assembly conductive biomass aerogel, preparation method thereof and application thereof in super capacitor |
| CN111440351B (en) * | 2020-03-13 | 2023-09-15 | 辽宁大学 | 3D supermolecule self-assembled conductive biomass aerogel, preparation method thereof and application thereof in super capacitor |
| CN116116392A (en) * | 2022-11-23 | 2023-05-16 | 安徽理工大学 | Polyaniline nanofiber, preparation method and application thereof, and method for exploring iodine ore |
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