CN1995096A - Polyaniline nano fiber and its preparing process - Google Patents
Polyaniline nano fiber and its preparing process Download PDFInfo
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- CN1995096A CN1995096A CN 200610170914 CN200610170914A CN1995096A CN 1995096 A CN1995096 A CN 1995096A CN 200610170914 CN200610170914 CN 200610170914 CN 200610170914 A CN200610170914 A CN 200610170914A CN 1995096 A CN1995096 A CN 1995096A
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Abstract
The invention discloses a polyaniline nanometer fiber and making method, which comprises the following steps: blending inorganic solution of vanadic anhydride and inorganic acid solution of phenylamine with molar rate at 1 1-14 completely; controlling the molar density of inorganic acid at 0.1-2mol/L; reacting at 0-5 deg. c for 1-24h; obtaining the polymer product; centrifuging; washing; drying to obtain the product.
Description
Technical field
The present invention relates to a kind of method for preparing polyaniline nano fiber, relating in particular to a kind of is the method that the chemical oxidising polymerisation of oxygenant prepares polyaniline nano fiber with the vanadic acid.The invention further relates to polyaniline nano fiber with method for preparing.
Background technology
Polyaniline is a kind of conductive polymers with conjugated double bond.Owing to have the simple non-oxide reduction doping character of mixing/separate, polyaniline is very unique in numerous conductive polymerss.Through after simple acid/alkali doping treatment, its electric conductivity can be from original σ＜10
-10S/cm (isolator) brings up to σ＞1S/cm (conductor).The traditional chemistry or the polyaniline of electrochemical preparation be spheroidal particle normally.The one dimension polyaniline nano fiber has the advantage of organic conductor and low-dimensional nano structure simultaneously, has become one of focus of people's research in recent years.It all has potential to use at aspects such as polymer lead, chemical sensor and excitor, biosensor, rechargeable battery, shielding material, absorbing material, luminous and microelectronic devices.At present, the chemical oxidising polymerisation oxygenant for preparing polyaniline nano fiber mainly contains ammonium persulphate, hydrochloro-auric acid and iron trichloride etc.So far do not see the method report that adopts vanadic acid to prepare the one dimension polyaniline nano fiber as oxygenant.Nano material is meant to have the material of one dimension size less than 100nm in the three-dimensional space at least.Can be divided three classes by dimension: zero dimension; One dimension; Two dimension.Wherein, one dimension is meant has bidimensional to be in nanoscale in the space, as nanofiber, nanometer rod, nanotube etc.It is template, tensio-active agent guidance, interfacial polymerization etc. that the preparation method of polyaniline nano fiber mainly relies on porous polymer and pellumina.Yet obtain purified polyaniline nano fiber, these methods often relate to the aftertreatment technology that template, tensio-active agent and organic solvent are removed, and not only pollute the environment, and destroy the pattern of polyaniline nano fiber easily.
Summary of the invention
Aftertreatment problem at the complexity of bringing because of template, tensio-active agent and organic solvent removal etc. that exists in the preparation of present polyaniline nano fiber, the present invention proposes a kind of is the method that the chemical oxidising polymerisation of oxygenant prepares polyaniline nano fiber with the vanadic acid, this method does not relate to any template, tensio-active agent and organic solvent in preparation process, technology is simple, the polyaniline nano fiber pattern is controlled easily, is easy to produce in batches.
For achieving the above object, the present invention has adopted following technical proposals.
The invention discloses a kind of method for preparing polyaniline nano fiber, comprise the following order step:
Is 1: 1～1: 4 thorough mixing with Vanadium Pentoxide in FLAKES inorganic acid aqueous solution and aniline inorganic acid aqueous solution by Vanadium Pentoxide in FLAKES and aniline mol ratio, the volumetric molar concentration of control mineral acid is 0.1-2mol/L, in temperature is 0-5 ℃ of reaction 1～24 hour, obtains polymerisate; Polymerisate is after centrifugation and washing, and drying obtains polyaniline nano fiber.
The present invention further discloses a kind of polyaniline nano fiber, the method processing through comprising the following order step obtains:
Is 1: 1～1: 4 thorough mixing with Vanadium Pentoxide in FLAKES inorganic acid aqueous solution and aniline inorganic acid aqueous solution by Vanadium Pentoxide in FLAKES and aniline mol ratio, the volumetric molar concentration of control mineral acid is 0.1-2mol/L, in temperature is 0-5 ℃ of reaction 1～24 hour, obtains polymerisate; Polymerisate is after centrifugation and washing, and drying obtains polyaniline nano fiber.
Described mineral acid is one or more in hydrochloric acid, sulfuric acid, phosphoric acid, the fluoroboric acid.The present invention also can adopt other mineral acids that the acid concentration of mixing solutions is adjusted.
Described Vanadium Pentoxide in FLAKES inorganic acid aqueous solution and aniline inorganic acid aqueous solution adopt the deionized water preparation.
Polymerisate is after centrifugation, and water and alcohol flushing promptly obtain the product polyaniline nano fiber for several times after the drying at room temperature.
The size of polyaniline nano fiber of the present invention is confirmed by scanning electronic microscope (SEM).The molecular structure of polyaniline of the present invention is confirmed by Fourier infrared spectrum (FTIR).
In the technique scheme, Vanadium Pentoxide in FLAKES is dissolved in dopant acid (mineral acid) solution of different concns, along with the raising of dopant acid concentration can generate the vanadic acid of different polymerization degree, and can behind chemical oxidising polymerisation, obtain the polyaniline nano fiber of different-shape and diameter.Wherein when configuration Vanadium Pentoxide in FLAKES inorganic acid aqueous solution and aniline inorganic acid aqueous solution, adjust the volumetric molar concentration of the acid of Vanadium Pentoxide in FLAKES inorganic acid aqueous solution and aniline inorganic acid aqueous solution usually, so that with after the aniline inorganic acid aqueous solution mixes, the volumetric molar concentration of control mineral acid is 0.1-2mol/L at the Vanadium Pentoxide in FLAKES inorganic acid aqueous solution.Can certainly add mineral acid at the Vanadium Pentoxide in FLAKES inorganic acid aqueous solution with after the aniline inorganic acid aqueous solution mixes, the volumetric molar concentration of adjusting mixing solutions is to 0.1-2mol/L.
Polyaniline nano fiber pattern of the present invention is controlled easily, and its surface variation can be regulated and control to smooth from nanometer rod, nanoparticle.This method technology is simple, does not relate to the use of any template, tensio-active agent and organic solvent in the preparation process, is easy to produce in batches.
Description of drawings
Fig. 1 is the SEM photo by the polyaniline nano fiber of the inventive method preparation.
Fig. 2 for by the inventive method preparation the FTIR spectrogram of polyaniline.
Fig. 3 is the SEM photo by the polyaniline nano fiber of the inventive method preparation.
Embodiment
Embodiment 1:
A kind of to be oxygenant with the vanadic acid prepare the method for polyaniline nano fiber by chemical oxidising polymerisation, comprises the following order step:
(1) be 1: 1 thorough mixing with Vanadium Pentoxide in FLAKES aqueous hydrochloric acid and aniline salt aqueous acid according to Vanadium Pentoxide in FLAKES, aniline mol ratio, and control mixing solutions hydrochloric acid volumetric molar concentration is 0.1-0.5mol/L,, obtains polymerisate 0-3 ℃ of reaction 1～10 hour;
(2) with above-mentioned reaction product after centrifugation, respectively after water and the washing with alcohol three times, then, product at room temperature dry 24 hours, is obtained cyan polyaniline nano fiber.
Embodiment 2:
A kind of to be oxygenant with the vanadic acid prepare the method for polyaniline nano fiber by chemical oxidising polymerisation, comprises the following order step:
(1) be 1: 2 thorough mixing with Vanadium Pentoxide in FLAKES fluoborate aqueous solution and aniline salt aqueous acid according to Vanadium Pentoxide in FLAKES, aniline mol ratio, and control mixing solutions hydrochloric acid volumetric molar concentration is 0.5-2mol/L, the back obtains polymerisate 3-5 ℃ of reaction 8～18 hours;
(2) with above-mentioned reaction product after centrifugation, wash removal impurity with water, after at room temperature dry 24 hours, obtain cyan polyaniline nano fiber.
Embodiment 3:
A kind of to be oxygenant with the vanadic acid prepare the method for polyaniline nano fiber by chemical oxidising polymerisation, comprises the following order step:
(1) be 1: 4 thorough mixing with Vanadium Pentoxide in FLAKES aqueous hydrochloric acid and aniline phosphate aqueous solution according to Vanadium Pentoxide in FLAKES, aniline mol ratio, and control mixing solutions hydrochloric acid volumetric molar concentration is 0.5-2mol/L,, obtains polymerisate 0-5 ℃ of reaction 10～24 hours;
(2) with above-mentioned reaction product after centrifugation, water and washing with alcohol are removed impurity, after at room temperature dry 24 hours, obtain cyan polyaniline nano fiber.
Embodiment 4:
A kind of to be oxygenant with the vanadic acid prepare the method for polyaniline nano fiber by chemical oxidising polymerisation, comprises the following order step:
(1) be 1: 3 thorough mixing with Vanadium Pentoxide in FLAKES aqueous hydrochloric acid and aniline salt aqueous acid according to Vanadium Pentoxide in FLAKES, aniline mol ratio, and control mixing solutions hydrochloric acid volumetric molar concentration is 1.5-2mol/L, the back obtains polymerisate 2-5 ℃ of reaction 12～24 hours;
(2) with above-mentioned reaction product after centrifugation, at room temperature dry after water and washing with alcohol are removed impurity, obtain cyan polyaniline nano fiber.
Embodiment 5:
A kind of to be oxygenant with the vanadic acid prepare the method for polyaniline nano fiber by chemical oxidising polymerisation, comprises the following order step:
(1) be 1: 3.5 thorough mixing with Vanadium Pentoxide in FLAKES aqueous sulfuric acid and aniline salt aqueous acid according to Vanadium Pentoxide in FLAKES, aniline mol ratio, and control mixing solutions hydrochloric acid volumetric molar concentration is 1.5-2mol/L,, obtains polymerisate 0-3 ℃ of reaction 10～24 hours;
(2) with above-mentioned reaction product after centrifugation, wash with water and remove impurity, at room temperature after the drying, obtain polyaniline nano fiber.
Embodiment 6:
A kind of polyaniline nano fiber, the method processing through comprising the following order step obtains:
(1) be 1: 3.5 thorough mixing with Vanadium Pentoxide in FLAKES aqueous hydrochloric acid and aniline aqueous sulfuric acid according to Vanadium Pentoxide in FLAKES, aniline mol ratio, and control mixing solutions acid volumetric molar concentration is 1.5-2mol/L,, obtains polymerisate 2-3 ℃ of reaction 1～10 hour;
(2) with above-mentioned reaction product after centrifugation, wash with water and remove impurity, at room temperature after the drying, obtain polyaniline nano fiber.
Embodiment 7:
A kind of polyaniline nano fiber, the method processing through comprising the following order step obtains:
(1) be 1: 3 thorough mixing with Vanadium Pentoxide in FLAKES phosphate aqueous solution and aniline aqueous sulfuric acid according to Vanadium Pentoxide in FLAKES, aniline mol ratio, and control mixing solutions acid volumetric molar concentration is 0.1-1mol/L,, obtains polymerisate 2-3 ℃ of reaction 5～15 hours;
(2) with above-mentioned reaction product after centrifugation, wash with water and remove impurity, at room temperature after the drying, obtain polyaniline nano fiber.
Embodiment 8:
A kind of polyaniline nano fiber, the method processing through comprising the following order step obtains:
(1) be 1: 1.5 thorough mixing with Vanadium Pentoxide in FLAKES phosphate aqueous solution and aniline fluoborate aqueous solution according to Vanadium Pentoxide in FLAKES, aniline mol ratio, and control mixing solutions acid volumetric molar concentration is 0.5-1.5mol/L, 3-5 ℃ of reaction 16～24 hours, obtain polymerisate;
(2) with above-mentioned reaction product after centrifugation, water and washing with alcohol are removed impurity, at room temperature after the drying, obtain polyaniline nano fiber.
Embodiment 9:
A kind of polyaniline nano fiber, the method processing through comprising the following order step obtains:
(1) be 1: 3 thorough mixing with Vanadium Pentoxide in FLAKES phosphate aqueous solution and aniline fluoborate aqueous solution according to Vanadium Pentoxide in FLAKES, aniline mol ratio, control mixing solutions acid volumetric molar concentration is 0.5-1.5mol/L, 0-3 ℃ of reaction 15～20 hours, obtains polymerisate;
(2) with above-mentioned reaction product after centrifugation, water and washing with alcohol are removed impurity, at room temperature after the drying, obtain polyaniline nano fiber.
According to the method that above-mentioned embodiment adopts, can prepare polyaniline nano fiber as Fig. 1, pattern shown in Figure 3, collection of illustrative plates shown in Figure 2.
Wherein the polyaniline nano fiber diameter is 40-100nm among Fig. 1, and length can reach tens microns.
1633cm in Fig. 2 spectrogram
-1And 1465cm
-1Absorption peak be respectively the characteristic peak of quinone ring and phenyl ring C=C stretching vibration in the polyaniline molecule chain.
The diameter of polyaniline nano fiber is 150-300nm among Fig. 3, and surface topography is that the diameter of radial arrangement is the polyaniline nano-rod of 10-20nm.
Claims (8)
1, a kind of preparation method of polyaniline nano fiber comprises the following order step:
Is 1: 1～1: 4 thorough mixing with Vanadium Pentoxide in FLAKES inorganic acid aqueous solution and aniline inorganic acid aqueous solution by Vanadium Pentoxide in FLAKES and aniline mol ratio, and the volumetric molar concentration of control mineral acid is 0.1-2mol/L, temperature 0-5 ℃ of reaction 1～24 hour, obtains polymerisate; Polymerisate is after centrifugation and washing, and drying obtains polyaniline nano fiber.
2, require the preparation method of described polyaniline nano fiber according to right 1, it is characterized in that: described mineral acid is one or more in hydrochloric acid, sulfuric acid, phosphoric acid, the fluoroboric acid.
3, the preparation method of polyaniline nano fiber according to claim 1 is characterized in that, described Vanadium Pentoxide in FLAKES inorganic acid aqueous solution and aniline inorganic acid aqueous solution adopt the deionized water preparation.
4, the preparation method of polyaniline nano fiber according to claim 1 is characterized in that: polymerisate is after centrifugation, and water and alcohol flushing promptly obtain the product polyaniline fiber for several times after the drying at room temperature.
5, a kind of polyaniline nano fiber, the method processing through comprising the following order step obtains:
Is 1: 1～1: 4 thorough mixing with Vanadium Pentoxide in FLAKES inorganic acid aqueous solution and aniline inorganic acid aqueous solution by Vanadium Pentoxide in FLAKES and aniline mol ratio, the volumetric molar concentration of control mineral acid is 0.1-2mol/L, controlled temperature 0-5 ℃ was reacted 1～24 hour, and obtained polymerisate; Polymerisate is after centrifugation and washing, and drying obtains polyaniline nano fiber.
6, require described polyaniline nano fiber according to right 5, it is characterized in that: described mineral acid is one or more in hydrochloric acid, sulfuric acid, phosphoric acid, the fluoroboric acid.
7, require described polyaniline nano fiber according to right 5, it is characterized in that, described Vanadium Pentoxide in FLAKES inorganic acid aqueous solution and aniline inorganic acid aqueous solution adopt the deionized water preparation.
8, require described polyaniline nano fiber according to right 5, it is characterized in that: polymerisate is after centrifugation, and water and alcohol flushing promptly obtain the product polyaniline fiber for several times after the drying at room temperature.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101942090A (en) * | 2010-09-10 | 2011-01-12 | 太原理工大学 | Preparation method of nano-fiber poly-aniline |
| CN102952268A (en) * | 2012-10-29 | 2013-03-06 | 太原理工大学 | Single cis-conformation polyaniline conducting polymer material and preparation method thereof |
| CN104818542A (en) * | 2015-04-13 | 2015-08-05 | 昆明理工大学 | Preparation method of polyaniline and derivative nanofiber |
| CN108624044A (en) * | 2018-06-08 | 2018-10-09 | 广州建翎电子技术有限公司 | A kind of new-energy automobile charging pile socket nanometer conductive material |
| CN110003467A (en) * | 2019-03-14 | 2019-07-12 | 中山大学 | A kind of preparation method of overlength polypyrrole nanofibers |
| CN113024805A (en) * | 2020-11-25 | 2021-06-25 | 重庆大学 | Method for preparing polyaniline film in large area |
Families Citing this family (1)
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| CN109879267B (en) * | 2019-03-14 | 2021-01-26 | 中山大学 | Preparation method of nano porous carbon material |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1040898C (en) * | 1993-08-25 | 1998-11-25 | 沈陆海 | Method for making polyaniline conductive dacron fibre |
| US7074887B2 (en) * | 2002-12-17 | 2006-07-11 | The Regents Of The University Of California | Chemical synthesis of chiral conducting polymers |
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2006
- 2006-12-25 CN CNB2006101709148A patent/CN100412110C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101942090A (en) * | 2010-09-10 | 2011-01-12 | 太原理工大学 | Preparation method of nano-fiber poly-aniline |
| CN102952268A (en) * | 2012-10-29 | 2013-03-06 | 太原理工大学 | Single cis-conformation polyaniline conducting polymer material and preparation method thereof |
| CN104818542A (en) * | 2015-04-13 | 2015-08-05 | 昆明理工大学 | Preparation method of polyaniline and derivative nanofiber |
| CN108624044A (en) * | 2018-06-08 | 2018-10-09 | 广州建翎电子技术有限公司 | A kind of new-energy automobile charging pile socket nanometer conductive material |
| CN110003467A (en) * | 2019-03-14 | 2019-07-12 | 中山大学 | A kind of preparation method of overlength polypyrrole nanofibers |
| CN110003467B (en) * | 2019-03-14 | 2021-05-25 | 中山大学 | Preparation method of ultralong polypyrrole nano-fibers |
| CN113024805A (en) * | 2020-11-25 | 2021-06-25 | 重庆大学 | Method for preparing polyaniline film in large area |
| CN113024805B (en) * | 2020-11-25 | 2022-07-01 | 重庆大学 | Method for preparing polyaniline film in large area |
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Assignee: Zibo Dongda Medical Rubber & Plastic Co., Ltd. Assignor: Qingdao University of Science & Technology Contract record no.: 2010370000232 Denomination of invention: Polyaniline nano fiber and its preparing process Granted publication date: 20080820 License type: Exclusive License Open date: 20070711 Record date: 20100512 |
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