CN101338031A - Process for preparing large length-diameter ratio polyaniline nano-line - Google Patents
Process for preparing large length-diameter ratio polyaniline nano-line Download PDFInfo
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- CN101338031A CN101338031A CNA2008100555758A CN200810055575A CN101338031A CN 101338031 A CN101338031 A CN 101338031A CN A2008100555758 A CNA2008100555758 A CN A2008100555758A CN 200810055575 A CN200810055575 A CN 200810055575A CN 101338031 A CN101338031 A CN 101338031A
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Abstract
A preparation method for polyaniline nano-wires with big aspect ratio is as folloes: aniline monomers dissolve in an organic solvent to be made into an aniline organic phase with 0.08 to 0.32mol/L concentration; weak oxidants dissolve in hydrochloric acid to be made into a water phase with 0.08 to 0.32mol/L concentration; by the molar ratio of aniline: weak oxidants =1:0.25 to1, the high intensity organic phase or the water phase is firstly added in a reactor under the temperature of 0 DEG C to the room temperature, and then is added with the low intensity water phase or the organic phase to react for 15 to 35 hours to obtain a solid product; the solid product is washed to neutrality, and is dried in vacuum for 15 to 20 hours under the temperature of 60 to 70 DEG C. The preparation method has the advantages of simple process and equipment, low energy consumption and big aspect ration of the obtained polyaniline nano-wires.
Description
Technical field
The invention belongs to a kind of synthetic method of conductive polymer nanometer structure, relate in particular to a kind of method of in interfacial, using weak oxidant oxypolymerization to prepare the big polyaniline nano-line of length-to-diameter ratio.
Background technology
Polyaniline is as a member special in the conductive polymers family, characteristics such as easily synthetic with it, that stability is higher and unique doping/dedoping mechanism and receiving much concern have obtained widespread use in many fields such as transmitter, battery, anti-corrosion of metal, electromagnetic shielding and catalysis.Polyaniline nano-line is except that the physicochemical property with organic conductive polymkeric substance excellence, also have size and the dimensionality effect of one dimension Nano structure in aspect uniquenesses such as electric transmission behavior, optical characteristics and mechanics mechanical propertys, recent two decades becomes the emphasis of research fields such as photochemistry, electrochemistry and relevant nano-device.But because stronger interaction force makes polyaniline nano-line be easy to be agglomerated into particle between the flexibility of polyaniline molecule itself and one dimension Nano structure, and then influence its character and application.
Developed at present the method that some prepare polyaniline nano-line: electrochemical process [Angew.Chem.Int.Ed.Vol.41,3665, (2002)], electrical spinning method [Synth.Met.Vol.114,109, (2000)], interfacial polymerization [J.Am.Chem.Soc.Vol.125,314, (2003)], template [Science Vol.266,1961, (1994)], surfactant method [Macromolecules Vol.37,2683, (2004); Chem.Commun.Vol.20,2360, (2004)], the auxiliary polymerization [J.Am.Chem.Soc, Vol.126,2278, (2004)] of oligopolymer etc.In these methods, electrical spinning method apparatus and process complexity, energy consumption is big, and template and surfactant method need be introduced template or tensio-active agent in advance, and subsequent disposal is more loaded down with trivial details.Interfacial polymerization neither uses template also not introduce tensio-active agent, and need not complex apparatus and technology, and energy consumption is low, and the reaction conditions gentleness is a kind of simple and effective method for preparing polyaniline nano-line.But used in the method oxygenant (ammonium persulphate) oxidisability strong (redox potential height), prepared is poly-
The aniline nano line can be agglomerated into thicker nano wire of diameter even particle along with the increase in reaction times, and the character and the potential application of p-poly-phenyl amine nano wire have caused influence.
Summary of the invention:
The purpose of this invention is to provide a kind of polyaniline nano-line that can effectively suppress and reunite the method for the polyaniline nano-line that the preparation length-to-diameter ratio is big.
Preparation method of the present invention is as follows:
(1) aniline monomer being dissolved in the volumetric molar concentration that is made into aniline in the organic solvent is the organic phase of 0.08-0.32mol/L;
(2) weak oxidant is dissolved in 0.5-1.5M hydrochloric acid and makes the water that volumetric molar concentration is 0.08-0.32mol/L;
(3) mol ratio by material is an aniline: weak oxidant=1: 0.25-1, under 0 ℃-room temperature, organic phase and water are pressed its density size, in reactor, add big organic phase or the water of density earlier, add little water of density or organic phase then, react after 15-35 hour, filtration obtains solid product, with solid product washing to neutral, 60 ℃-70 ℃ vacuum-drying 15-20 hour.
Weak oxidant comprises the low oxygenants of redox potential such as hydrogen peroxide, iron trichloride, cupric chloride or copper sulfate as mentioned above; Organic solvent comprises methylene dichloride, trichloromethane, tetracol phenixin, dithiocarbonic anhydride, normal hexane, hexanaphthene, benzene, toluene or dichlorobenzene etc.
The present invention has following advantage:
(1) raw materials such as used aniline, oxygenant and solvent are cheap and easy to get, need not pre-treatment, help reducing cost.
(2) the synthesis process flow process is simple, and is easy and simple to handle, and influence factor is few, is convenient to control, favorable reproducibility.
(3) can be in room temperature or more synthetic under the low temperature, the reaction conditions gentleness, and energy consumption is low.
(4) Zhi Bei polyaniline nano-line length-to-diameter ratio is big, and can keep its pattern in a long time and do not reunite.
(5) do not need additionally to introduce catalyzer.
(6) be convenient to mass-producing and prepare polyaniline nano-line in a large number.
Embodiment
Embodiment 1
Under the room temperature, get 1.4585ml aniline and be dissolved in 50ml methylene dichloride adding reactor, getting 0.4086ml hydrogen peroxide (massfraction 30%) again is dissolved in the 50ml 1M hydrochloric acid soln, add reactor, form two-phase reaction system, reacted 20 hours, filter the solid of collecting aqueous phase, to neutral, 60 ℃ of dryings were collected after 20 hours in vacuum drying oven with deionized water wash.The pattern of observation sample under transmission electron microscope (TEM), diameter Distribution 20-30nm, length 2-3 μ m, length-to-diameter ratio reaches 100-150.
Embodiment 2
Measure 0.8172ml hydrogen peroxide (massfraction 30%) and be dissolved in 50ml 0.5M hydrochloric acid soln, add reactor, reactor places the container that mixture of ice and water is housed; Measure 0.7293ml aniline again and be dissolved in the 50ml normal hexane, and after the mixture of ice and water cooling, add reactor, form two-phase reaction system, reacted 30 hours.Filter the solid of collecting aqueous phase, to neutral, 60 ℃ of dryings were collected after 20 hours in vacuum drying oven with deionized water wash.The pattern of observation sample under transmission electron microscope (TEM), diameter Distribution 15-25nm, length 2-3 μ m, length-to-diameter ratio reaches 130-200.
Embodiment 3
Under the room temperature, measure 0.7293ml aniline and be dissolved in 50ml tetracol phenixin adding reactor, take by weighing 0.6489g iron(ic) chloride again and be dissolved in 50ml 1M hydrochloric acid soln, add reactor, form two-phase reaction system.Reacted 25 hours, and filtered the solid of collecting aqueous phase, to neutral, 65 ℃ of dryings were collected after 18 hours in vacuum drying oven with deionized water wash.The pattern of observation sample under transmission electron microscope (TEM), diameter Distribution 20-30nm, about length 3 μ m, length-to-diameter ratio reaches 100-150.
Embodiment 4
Under the room temperature, take by weighing 0.6489g iron(ic) chloride and be dissolved in 50ml 1.2M hydrochloric acid soln, add reactor, measure 0.3646ml aniline again and be dissolved in the 50ml hexanaphthene, join in the reactor, form two-phase reaction system.Reacted 25 hours, and filtered the solid of collecting aqueous phase, to neutral, 65 ℃ of dryings were collected after 18 hours in vacuum drying oven with deionized water wash.The pattern of observation sample under transmission electron microscope (TEM), diameter Distribution 18-30nm, length 2-3 μ m, length-to-diameter ratio reaches more than 100.
Embodiment 5
Take by weighing the 0.6819g cupric chloride and be dissolved in 50ml 0.8M hydrochloric acid soln, add reactor, reactor is placed in the mixture of ice and water; Measure 1.4585ml aniline again and be dissolved in 50ml benzene, add reactor, form two-phase reaction system with mixture of ice and water cooling back.Reacted 30 hours, and filter to collect the solid of aqueous phase, to neutral, in vacuum drying oven, collect after dry 12-20 hour for 70 ℃ with deionized water wash.The pattern of observation sample under transmission electron microscope (TEM), diameter Distribution 15-20nm, length 2-3 μ m, length-to-diameter ratio reaches as high as 200.
Embodiment 6
Measure 0.7293ml aniline and be dissolved in 50ml dithiocarbonic anhydride, add reactor, reactor is placed in the mixture of ice and water; Getting 0.4086ml hydrogen peroxide (massfraction 30%) again is dissolved in the 50ml 1.5M hydrochloric acid soln, add in the reactor with mixture of ice and water cooling back, form two-phase reaction system, reacted 28 hours, filter the solid of collecting aqueous phase, to neutral, 60 ℃ of dryings were collected in 20 hours in vacuum drying oven with deionized water wash.The pattern of observation sample under transmission electron microscope (TEM), diameter Distribution 20-25nm, length 2-3 μ m, length-to-diameter ratio is about 150.
Embodiment 7
Under the room temperature, measure 1.4585ml aniline and be dissolved in 50ml dichlorobenzene adding reactor; Get 1.6344ml hydrogen peroxide (massfraction 30%) again and be dissolved in 50ml 1M hydrochloric acid soln, add reactor, form two-phase reaction system.Reacted 15 hours, and filtered the solid of collecting aqueous phase, to neutral, 60 ℃ of dryings were collected after 20 hours in vacuum drying oven with deionized water wash.The pattern of observation sample under transmission electron microscope (TEM), diameter Distribution 25-35nm, length 2-3 μ m, length-to-diameter ratio can reach about 100.
Embodiment 8
Measure 1.4585ml aniline and be dissolved in 50ml trichloromethane adding reactor; Take by weighing 2.5956g iron(ic) chloride again and be dissolved in 50ml 1M hydrochloric acid soln, add reactor, form two-phase reaction system.Reaction is 25 hours under the room temperature, filters the solid of collecting aqueous phase, and to neutral, 70 ℃ of dryings were collected after 15 hours in vacuum drying oven with deionized water wash.The pattern of observation sample under transmission electron microscope (TEM), diameter Distribution 18-35nm, length 2-3 μ m, length-to-diameter ratio can reach about 100.
Embodiment 9
Under the room temperature, measure 1.4585ml aniline and be dissolved in 50ml tetracol phenixin adding reactor; Take by weighing the 2.7276g cupric chloride again and be dissolved in 50ml 1.2M hydrochloric acid soln, add reactor, form two-phase reaction system.Reacted 30 hours, and filtered the solid of collecting aqueous phase, to neutral, 70 ℃ of dryings were collected after 15 hours in vacuum drying oven with deionized water wash.The pattern of observation sample under transmission electron microscope (TEM), diameter Distribution 15-25nm, length 2-3 μ m, length-to-diameter ratio can reach about 150.
Embodiment 10
Take by weighing 1.2800g copper sulfate and be dissolved in 50ml 1M hydrochloric acid soln, add reactor, reactor is placed in the mixture of ice and water; Measure 0.7293ml aniline again and be dissolved in 50ml toluene, add in the reactor, form two-phase reaction system with mixture of ice and water cooling back, reacted 32 hours, filter the solid of collecting aqueous phase, to neutral, 70 ℃ of dryings were collected after 15 hours in vacuum drying oven with deionized water wash.The pattern of observation sample under transmission electron microscope (TEM), diameter Distribution 28-40nm, length 2-3 μ m, length-to-diameter ratio can reach about 100.
Embodiment 11
Take by weighing the 1.3638g cupric chloride and be dissolved in 50ml 0.8M hydrochloric acid soln, add reactor, reactor is placed in the mixture of ice and water; Measure 1.4585ml aniline again and be dissolved in 50ml benzene,, form two-phase reaction system with joining in the reactor after the mixture of ice and water cooling, reacted 35 hours, filter the solid of collecting aqueous phase, to neutral, 70 ℃ of dryings were collected after 15 hours in vacuum drying oven with deionized water wash.The pattern of observation sample under transmission electron microscope (TEM), diameter Distribution 15-30nm, length 2-3 μ m, length-to-diameter ratio can reach about 150.
Claims (3)
1, a kind of method for preparing the big polyaniline nano-line of length-to-diameter ratio is characterized in that comprising the steps:
(1) aniline monomer being dissolved in the volumetric molar concentration that is made into aniline in the organic solvent is the organic phase of 0.08-0.32mol/L;
(2) weak oxidant is dissolved in 0.5-1.5M hydrochloric acid and makes the water that volumetric molar concentration is 0.08-0.32mol/L;
(3) mol ratio by material is an aniline: weak oxidant=1: 0.25-1, under 0 ℃-room temperature, organic phase and water are pressed its density size, in reactor, add big organic phase or the water of density earlier, add little water of density or organic phase then, react after 15-35 hour, filtration obtains solid product, with solid product washing to neutral, 60 ℃-70 ℃ vacuum-drying 15-20 hour.
2, a kind of method for preparing the big polyaniline nano-line of length-to-diameter ratio as claimed in claim 1 is characterized in that described weak oxidant is hydrogen peroxide, iron trichloride, cupric chloride or copper sulfate.
3, a kind of method for preparing the big polyaniline nano-line of length-to-diameter ratio as claimed in claim 1 is characterized in that described organic solvent is methylene dichloride, trichloromethane, tetracol phenixin, dithiocarbonic anhydride, normal hexane, hexanaphthene, benzene, toluene or dichlorobenzene.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102532892A (en) * | 2012-01-20 | 2012-07-04 | 北京师范大学 | Conductive polymer film and preparation method thereof |
| CN103539943A (en) * | 2013-11-06 | 2014-01-29 | 中国科学院长春应用化学研究所 | Preparation method of polyaniline |
| CN105061732A (en) * | 2015-09-28 | 2015-11-18 | 吉林大学 | Tellurium-containing electric-conducting high-polymer composite nanowire and preparation method thereof |
| CN110684194A (en) * | 2019-10-14 | 2020-01-14 | 东华大学 | Polyaniline nano-belt and preparation method thereof |
-
2008
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102532892A (en) * | 2012-01-20 | 2012-07-04 | 北京师范大学 | Conductive polymer film and preparation method thereof |
| CN102532892B (en) * | 2012-01-20 | 2013-07-24 | 北京师范大学 | Conductive polymer film and preparation method thereof |
| CN103539943A (en) * | 2013-11-06 | 2014-01-29 | 中国科学院长春应用化学研究所 | Preparation method of polyaniline |
| CN103539943B (en) * | 2013-11-06 | 2016-01-20 | 中国科学院长春应用化学研究所 | A kind of preparation method of polyaniline |
| CN105061732A (en) * | 2015-09-28 | 2015-11-18 | 吉林大学 | Tellurium-containing electric-conducting high-polymer composite nanowire and preparation method thereof |
| CN110684194A (en) * | 2019-10-14 | 2020-01-14 | 东华大学 | Polyaniline nano-belt and preparation method thereof |
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| CN101338031B (en) | 2010-09-22 |
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