CN102504248A - Preparation method for polyaniline - Google Patents
Preparation method for polyaniline Download PDFInfo
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- CN102504248A CN102504248A CN2011102894842A CN201110289484A CN102504248A CN 102504248 A CN102504248 A CN 102504248A CN 2011102894842 A CN2011102894842 A CN 2011102894842A CN 201110289484 A CN201110289484 A CN 201110289484A CN 102504248 A CN102504248 A CN 102504248A
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- aniline
- hydrochloric acid
- polyaniline
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Abstract
The invention discloses a preparation method for polyaniline, which belongs to the technical field of preparation of conducting high polymers. The preparation method is characterized by comprising the following steps of: pretreating aniline, distilling and purifying before use, preparing originally-doped polyaniline, and preparing a hydrochloric acid aqueous solution with the concentration of 1mol/L; dissolving 10ml of a pretreated aniline monomer in 240ml of a hydrochloric acid solution containing 15 percent of hydrochloric acid, transferring to a three-necked bottle, and uniformly stirring; weighing ammonium persulfate ((NH4)2S2O8) in the molar ratio of 1:1of the ammonium persulfate (NH4)2S2O8) to the aniline monomer, dissolving into 250ml of hydrochloric acid, slowly dropwise adding into the three-necked bottle for 1.5 hours, continuously reacting while stirring for 5 hours, stopping reacting and leaching; and repeatedly washing a filter cake with the hydrochloric acid solution containing 15 percent of hydrochloric acid and absolute ethanol repeatedly to a colorless state, and drying in vacuum at the temperature of 333K for 24 hours to obtain greenblack originally-doped polyaniline (PANI) powder.
Description
Technical field
The invention belongs to the conducting polymer preparing technical field, refer in particular to a kind of preparation method of polyaniline.
Background technology
Polyaniline (PANI) has only the history in more than 20 year as the research of conducting polymer, and in the meantime, both at home and abroad correlative study person has carried out comparatively deep research in the aspects such as structure, characteristic, synthetic, doping, modification of p-poly-phenyl amine.All good characteristics make it be considered to the conducting polymer that is hopeful in reality, to be applied most, become the research focus.Doping is the effective way of giving polyaniline conductivity, can improve 12 one magnitude through the protonic acid doping specific conductivity, and through dedoping one doping process its specific conductivity is changed in isolator semiconductor one metallic state scope.But the physics of polyaniline, chemical property depend on the character of synthetic method, condition and protonated degree and doping agent strongly.
The present invention develops a kind of preparation method of polyaniline, adopts chemical oxidization method synthetic hydrochloric acid doped polyaniline.
Summary of the invention
The objective of the invention is to develop a kind of preparation method of polyaniline, it is characterized by, prepare that polyaniline is raw materials used to do, aniline (An), ammonium persulphate (APS), hydrochloric acid, absolute ethyl alcohol all are analytical pure.The technology of preparation polyaniline is following: light is met in the pre-treatment of (1) aniline, aniline or air is prone to oxidation and is yellow, needs distillation to purify before therefore using.100g aniline is added concuss in the Erlenmeyer flask that fills the 40g Calcium Chloride Powder Anhydrous, leave standstill 24 hours to absorb moisture wherein.After water distilling apparatus mixes up, pour aniline into matrass, add the 15g zinc powder and prevent the aniline oxidation, add the 25g zeolite and prevent bumping, begin heating and regulate heating rate, 5 ℃/min of heating rate, 183～185 ℃ of Heating temperatures produce small bubbles equably.Colorless oil cut between collecting 183～185 ℃, when the vapor temperature big ups and downs, distillation finishes, and stops heating.After treating the device cooling, take out distillate, repeat above-mentioned steps, carry out second distillation.Transferring in the brown bottle, preserve at last at shady place through the aniline of second distillation.(2) preparation of former doped polyaniline, compound concentration are the aqueous hydrochloric acid of 1mol/L.Pretreated 10ml aniline monomer is dissolved in the hydrochloric acid soln of 240ml hydrochloric 15%, and is transferred to three-necked bottle, stir.Taking by weighing with the aniline monomer mol ratio is 1: 1 ammonium persulphate (NH
4)
2S
2O
8) be dissolved in the 250ml hydrochloric acid, and be transferred to tap funnel.With ammonium persulphate (NH
4)
2S
2O
8) hydrochloric acid soln slowly be added drop-wise in the three-necked bottle, that solution is become by water white transparency very soon is light green-light blue-dark blue-purplish red.Dripped 1.5 hours continued stirring reactions 5 hours, stopped reaction, suction filtration.Filter cake is cleaned to colourless with hydrochloric 15% hydrochloric acid soln, absolute ethyl alcohol successively repeatedly, and vacuum-drying promptly obtained blackish green chromogen doped polyaniline (PANI) powder in 24 hours under 333K at last.
Table 1 is seen in the influence of ammonium persulphate consumption p-poly-phenyl amine specific conductivity and productive rate.Visible by table, in each factor of reaction, the productive rate and the specific conductivity of ammonium persulphate consumption p-poly-phenyl amine have the greatest impact, and therefore keep other conditions constant earlier, inquire into proper reaction conditions and only change the ammonium persulphate consumption.Fixedly the concentration of hydrochloric acid is 1mol/L.After concentration of hydrochloric acid was fixing, along with the increase of ammonium persulphate consumption, its reaction yield obviously improved, and when the mol ratio of ammonium persulphate and aniline was 2.0, polymerization yield rate was up to 80%, after, when increasing the ammonium persulphate consumption again, polymerization yield rate descends on the contrary.The specific conductivity of product begins to increase along with the increase of ammonium persulphate consumption, and when the mol ratio of ammonium persulphate and aniline was 1.0, specific conductivity was maximum.And when the ammonium persulphate consumption was too much or very few, the specific conductivity of product all descended to some extent.
The influence of table 1 ammonium persulphate concentration p-poly-phenyl amine specific conductivity and productive rate
Differing temps is seen table 2 to the influence of aniline specific conductivity and productive rate, and visible by table, the specific conductivity of product polyaniline changes along with the different of temperature with productive rate, and aniline polymerization is thermopositive reaction, helps the carrying out of polyreaction during low temperature.Along with the continuous rising of temperature of reaction, productive rate descends, and peroxidization constantly increases, thereby causes the specific conductivity of product to descend.
The influence of table 2 differing temps p-poly-phenyl amine specific conductivity and productive rate
The mol ratio of ammonium persulphate and aniline is 1.0, temperature of reaction is 0 ℃, when the concentration of hydrochloric acid is about 1mol/L, the reaction times, the result saw table 3 to the influence of specific conductivity and productive rate.From table 3, can find out, be oxygenant with the ammonium persulphate, and the reaction times, reaction specific conductivity and productive rate all increased when changing from 1～6h.When the reaction times was 6h, specific conductivity reached peak, and continuing increases the reaction times, and specific conductivity and productive rate descend to some extent.
The influence of table 3 reaction times p-poly-phenyl amine specific conductivity and productive rate
Acid concentration in the reaction system has certain influence to the performance of the polymerization reactant of aniline, table 4 for ammonium persulphate and the mol ratio of aniline are 1.0, temperature when being 0 ℃ different concentration of hydrochloric acid to the influence of polymkeric substance.Can find out that from table 4 polymerization yield rate was not high when acid concentration was very low, the electric conductivity of products therefrom is also quite low; Rising along with concentration of hydrochloric acid; The specific conductivity and the productive rate of polyaniline all increase, and when concentration of hydrochloric acid reached 1mol/L, the specific conductivity and the productive rate of polyaniline reached peak.
The concentration of hydrochloric acid p-poly-phenyl amine specific conductivity that table 4 is different and the influence of productive rate
In sum; From raw material be easy to get, the combined factors such as specific conductivity of reaction yield, product consider that the optimised process of aniline polymerization reaction can be preferably: temperature of reaction is at 0 ℃, and the concentration of hydrochloric acid is 1mol/L; The mol ratio of ammonium persulphate and aniline is 1, reaction times 6h.The polyaniline of producing this moment not only electric conductivity is high, reaches 2.3S/cm-2.6S/cm, and productive rate is also high, reaches 55%-78.5%.
Embodiment
Prepare that polyaniline is raw materials used to do, aniline (An), ammonium persulphate (APS), hydrochloric acid, absolute ethyl alcohol all are analytical pure.The technology of preparation polyaniline is following: light is met in the pre-treatment of (1) aniline, aniline or air is prone to oxidation and is yellow, needs distillation to purify before therefore using.100g aniline is added concuss in the Erlenmeyer flask that fills the 40g Calcium Chloride Powder Anhydrous, leave standstill 24 hours to absorb moisture wherein.After water distilling apparatus mixes up, pour aniline into matrass, add the 15g zinc powder and prevent the aniline oxidation, add the 25g zeolite and prevent bumping, begin heating and regulate heating rate, 5 ℃/min of heating rate, 183～185 ℃ of Heating temperatures produce small bubbles equably.Colorless oil cut between collecting 183～185 ℃, when the vapor temperature big ups and downs, distillation finishes, and stops heating.After treating the device cooling, take out distillate, repeat above-mentioned steps, carry out second distillation.Transferring in the brown bottle, preserve at last at shady place through the aniline of second distillation.(2) preparation of former doped polyaniline, compound concentration are the aqueous hydrochloric acid of 1mol/L.Pretreated 10ml aniline monomer is dissolved in the hydrochloric acid soln of 240ml hydrochloric 15%, and is transferred to three-necked bottle, stir.Taking by weighing with the aniline monomer mol ratio is 1: 1 ammonium persulphate (NH
4)
2S
2O
8) be dissolved in the 250ml hydrochloric acid, and be transferred to tap funnel.With ammonium persulphate (NH
4)
2S
2O
8) hydrochloric acid soln slowly be added drop-wise in the three-necked bottle, that solution is become by water white transparency very soon is light green-light blue-dark blue-purplish red.Dripped 1.5 hours continued stirring reactions 5 hours, stopped reaction, suction filtration.Filter cake is cleaned to colourless with hydrochloric 15% hydrochloric acid soln, absolute ethyl alcohol successively repeatedly, and vacuum-drying promptly obtained blackish green chromogen doped polyaniline (PANI) powder in 24 hours under 333K at last.
Adopt temperature of reaction at 0 ℃, the concentration of hydrochloric acid is 1mol/L, and the mol ratio of ammonium persulphate and aniline is 1, reaction times 6h.The polyaniline of producing this moment not only electric conductivity is high, reaches 2.3S/cm-2.6S/cm, and productive rate is also high, reaches 55%-78.5%.
Claims (2)
1. the preparation method of a polyaniline is characterized by, and prepares that polyaniline is raw materials used to do, aniline, ammonium persulphate, hydrochloric acid, absolute ethyl alcohol all are analytical pure; The technology of preparation polyaniline is following: light is met in the pre-treatment of aniline, aniline or air is prone to oxidation and is yellow, needs distillation to purify before therefore using; 100g aniline is added concuss in the Erlenmeyer flask that fills the 40g Calcium Chloride Powder Anhydrous, leave standstill 24 hours to absorb moisture wherein; After water distilling apparatus mixes up, pour aniline into matrass, add the 15g zinc powder and prevent the aniline oxidation, add the 25g zeolite and prevent bumping, begin heating and regulate heating rate, 5 ℃/min of heating rate, 183～185 ℃ of Heating temperatures produce small bubbles equably; Colorless oil cut between collecting 183～185 ℃, when the vapor temperature big ups and downs, distillation finishes, and stops heating; After treating the device cooling, take out distillate, repeat above-mentioned steps, carry out second distillation; Transferring in the brown bottle, preserve at last at shady place through the aniline of second distillation; The preparation of former doped polyaniline, compound concentration are the aqueous hydrochloric acid of 1mol/L.Pretreated 10ml aniline monomer is dissolved in the hydrochloric acid soln of 240ml hydrochloric 15%, and is transferred to three-necked bottle, stir; Taking by weighing with the aniline monomer mol ratio is 1: 1 ammonium persulphate (NH
4)
2S
2O
8) be dissolved in the 250ml hydrochloric acid, and be transferred to tap funnel.With ammonium persulphate (NH
4)
2S
2O
8) hydrochloric acid soln slowly be added drop-wise in the three-necked bottle, that solution is become by water white transparency very soon is light green-light blue-dark blue-purplish red; Dripped 1.5 hours continued stirring reactions 5 hours, stopped reaction, suction filtration; Filter cake is cleaned to colourless with hydrochloric 15% hydrochloric acid soln, absolute ethyl alcohol successively repeatedly, and vacuum-drying promptly obtained blackish green chromogen doped polyaniline (PANI) powder in 24 hours under 333K at last.
2. according to the preparation method of the said a kind of polyaniline of claim 1, the optimised process of aniline polymerization reaction can be preferably: temperature of reaction is at 0 ℃, and the concentration of hydrochloric acid is 1mol/L, and the mol ratio of ammonium persulphate and aniline is 1, reaction times 6h; The polyaniline of producing this moment not only electric conductivity is high, reaches 2.3S/cm-2.6S/cm, and productive rate is also high, reaches 55%-78.5%.
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| CN 201110289484 CN102504248B (en) | 2011-09-21 | 2011-09-21 | Preparation method for polyaniline |
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| CN 201110289484 CN102504248B (en) | 2011-09-21 | 2011-09-21 | Preparation method for polyaniline |
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| CN102504248B CN102504248B (en) | 2013-09-11 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103304807A (en) * | 2013-06-08 | 2013-09-18 | 西北工业大学 | Preparation method of polyaniline/graphene/Co3O4 nanometer wave-absorbing material |
| CN106012086A (en) * | 2016-07-02 | 2016-10-12 | 苏州大学 | Graphene/polyaniline composite fiber and preparation method thereof |
| CN111116905A (en) * | 2019-12-30 | 2020-05-08 | 有研工程技术研究院有限公司 | In-situ synthesis method of conductive polyaniline with ammonia sensitivity |
| CN112592481A (en) * | 2020-12-14 | 2021-04-02 | 苏州经贸职业技术学院 | Method for modifying polyaniline polymer |
| CN112916044A (en) * | 2021-01-29 | 2021-06-08 | 蚌埠学院 | Method for catalytically synthesizing sec-butyl propionate by using sodium bisulfate doped polyaniline |
| CN113522037A (en) * | 2021-07-21 | 2021-10-22 | 江苏盈天化学有限公司 | Preparation method of pervaporation tetrahydrofuran dehydration composite membrane |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1186091A (en) * | 1996-12-25 | 1998-07-01 | 中国科学院长春应用化学研究所 | Preparation of mixed polyaniline aqueous solution and dispersant liquid |
| CN1680464A (en) * | 2004-03-22 | 2005-10-12 | 尹虎声 | Polyaniline having high electrical conductivity and producing process thereof |
| WO2007073000A1 (en) * | 2005-12-22 | 2007-06-28 | Fujifilm Corporation | Method for producing polyaniline compound |
-
2011
- 2011-09-21 CN CN 201110289484 patent/CN102504248B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1186091A (en) * | 1996-12-25 | 1998-07-01 | 中国科学院长春应用化学研究所 | Preparation of mixed polyaniline aqueous solution and dispersant liquid |
| CN1680464A (en) * | 2004-03-22 | 2005-10-12 | 尹虎声 | Polyaniline having high electrical conductivity and producing process thereof |
| WO2007073000A1 (en) * | 2005-12-22 | 2007-06-28 | Fujifilm Corporation | Method for producing polyaniline compound |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103304807A (en) * | 2013-06-08 | 2013-09-18 | 西北工业大学 | Preparation method of polyaniline/graphene/Co3O4 nanometer wave-absorbing material |
| CN106012086A (en) * | 2016-07-02 | 2016-10-12 | 苏州大学 | Graphene/polyaniline composite fiber and preparation method thereof |
| CN111116905A (en) * | 2019-12-30 | 2020-05-08 | 有研工程技术研究院有限公司 | In-situ synthesis method of conductive polyaniline with ammonia sensitivity |
| CN112592481A (en) * | 2020-12-14 | 2021-04-02 | 苏州经贸职业技术学院 | Method for modifying polyaniline polymer |
| CN112916044A (en) * | 2021-01-29 | 2021-06-08 | 蚌埠学院 | Method for catalytically synthesizing sec-butyl propionate by using sodium bisulfate doped polyaniline |
| CN113522037A (en) * | 2021-07-21 | 2021-10-22 | 江苏盈天化学有限公司 | Preparation method of pervaporation tetrahydrofuran dehydration composite membrane |
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| CN102504248B (en) | 2013-09-11 |
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