CN1709941A - Method for preparing nano polyaniline - Google Patents
Method for preparing nano polyaniline Download PDFInfo
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- CN1709941A CN1709941A CN 200510057011 CN200510057011A CN1709941A CN 1709941 A CN1709941 A CN 1709941A CN 200510057011 CN200510057011 CN 200510057011 CN 200510057011 A CN200510057011 A CN 200510057011A CN 1709941 A CN1709941 A CN 1709941A
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Abstract
The invention relates to the preparation of nano-polyaniline. It makes sodium dodecylbnzene sulfonate and hydrochloric acid as compound emulsifier, n-butanol (NBA) as emulsifier, ammonium persulphate (APS) as oxidant, through micro-emulsion polymerizing reaction, by emulsion breaking, washing, drying to synthesize nano-polyaniline powder. The method remarkably reduces the dosage of emulsifier, and can recycle to circulating use, so it greatly reduces the preparation cost, and makes the industrializing production of nano-polyaniline become possible. The purity of synthesized nano-polyaniline of the method can get to over 99%, the conductivity can get to 7.5 S/cm, its solubility in N-methyl-2-pyrrolidone can get to 99%, and 95% of its particles' size can be under 10 nm.
Description
Technical field
The present invention relates to the preparation method of nano polyaniline, be mainly used in corrosion-resistant field.
Background technology
In numerous conducting polymers, polyaniline is because monomer is easy to get, structure variation, unique mechanism of doping effect, good environmental stability and technology application prospect widely, and causes scientist's concern.But characteristics such as the indissoluble of polyaniline, infusibility, poor in processability have limited polyaniline and have been difficult to realize suitability for industrialized production, therefore, and synthetic specific conductivity height, the focus that solvability is good, polyaniline that particle diameter is little becomes current research.At present, the method for synthesizing nano polyaniline mainly contains dispersion copolymerization method, pulse potentiostatic method and microemulsion method.Dispersion copolymerization method is too high to the requirement of stablizer, if the solvability of stablizer in dispersion medium is very poor, then is difficult to obtain nanoparticle; The pulse potentiostatic method be difficult to realize large-scale production, and cost is higher; The microemulsion method prefered method that conveniently becomes synthesizing nano polyaniline simple to operate, synthetic.
The people such as Song Genping of Yangzhou normal university adopt the two-phase system of SDBS/ aniline/water/three component O/W type microemulsions and monomer coexistence, with the monomer is the micro-emulsion polymerization that monomer source carries out aniline, the particle diameter of the polyaniline of gained is 3nm, and is evenly distributed, and has higher specific conductivity.The Zhu new life of University Of Suzhou waits in the human BA microemulsion that (propyl carbinol)/aniline/water// SDBS formed and has carried out polyreaction, has also synthesized Nano particles of polyaniline, and particle diameter is about 20nm.
What Song Genping adopted is the positive microemulsion method, and what Zhu new life adopted is reverse microemulsion process, though method is slightly variant, has all obtained the nano polyaniline particle.But they have used a large amount of emulsifying agents in microemulsion method synthetic, and its quality approximately is 4.5 times of aniline monomer, thus give product washing, purify and brought very big difficulty, and be difficult to realize industrialized production.
Summary of the invention
The objective of the invention is to reduce the consumption of emulsifying agent, reduce preparation cost, make microemulsion method synthesizing nano polyaniline suitability for industrialized production become possibility in order to solve the deficiency of microemulsion method synthesizing nano polyaniline.
The technical scheme of microemulsion method synthesizing nano polyaniline involved in the present invention is as follows:
1) preparation microemulsion: take by weighing an amount of Sodium dodecylbenzene sulfonate, be made into mass percent concentration and be 1%～1.25% the aqueous solution, with the pH value of hydrochloric acid conditioning solution, making the pH value is 0～0.5, stirs 0.5～1h, slowly drip aniline monomer, the add-on of aniline monomer is 3～4 times of Sodium dodecylbenzene sulfonate, continues to stir 0.5～1h, slowly drips propyl carbinol again, the add-on of propyl carbinol is 2.5～3 times of Sodium dodecylbenzene sulfonate, forms the microemulsion of clear;
2) configuration ammonium persulfate aqueous solution: take by weighing an amount of ammonium persulphate, the amount that makes ammonium persulphate is 2.5～2.8 times of aniline, is made into mass percent concentration then and is 8%～10% the aqueous solution;
3) micro-emulsion polymerization reaction: stir above-mentioned microemulsion 30～40min, drip the Ammonium Persulfate 98.5 aqueous solution that configures, in 20～60min, drip off, reaction 4～8h;
4) separate dry: above-mentioned reaction solution to going in the beaker, add with the isopyknic acetone of reaction solution and carry out breakdown of emulsion, suction filtration behind 6～12h, be that 0～3 hydrochloric acid soln washs to the filtrate clear with the pH value again, then behind vacuum-drying 6～12h, use ball mill grinding a few hours again, can obtain the nano polyaniline powder.
Institute of the present invention synthetic nano polyaniline has following advantage: 1) purity of polyaniline can reach more than 99% than higher.Because the emulsifying agent that uses in this scheme is few, aniline monomer is many, makes that separating purification is easy to many.2) specific conductivity is higher, can reach 7.5S/cm.Because in this building-up reactions, the compound emulsifying agent of employing can produce Cl
-And C
12H
25PhSO
3 -Two kinds to negatively charged ion and protonated polyaniline molecule chain the competition binding interactions take place, thereby have improved the specific conductivity of product.3) solvability is good.This programme synthetic polyaniline 0.1g, the dissolution rate in the 20mlN-methyl-2-pyrrolidone can reach 99%.4) the synthetic particle diameter is little.The atomic force microscope test result finds that 95% particle diameter is about 10nm.5) with low cost.In the present invention, filtrate is recycled, and the rate of recovery has reached 85%, and in scheme, the emulsifying agent of use also seldom so saved cost greatly, makes the industrialization of polyaniline become possibility.
Description of drawings
Fig. 1 process flow sheet
The atomic force microscope picture of Fig. 2 sample A
The atomic force microscope picture of Fig. 3 sample B
Embodiment
Introduce the specific embodiments of method for preparing polyaniline involved in the present invention below, its technical process as shown in Figure 1.
Embodiment 1:
1) preparation microemulsion: take by weighing the 2.5g Sodium dodecylbenzene sulfonate, be made into mass percent concentration and be 1.25% the aqueous solution, pH value with hydrochloric acid conditioning solution, making the pH value is 0, stir 0.5～1h, slowly drip the 10g aniline monomer, continue to stir 0.5～1h, slowly drip the 6.25g propyl carbinol again, form the microemulsion of clear;
2) configuration ammonium persulfate aqueous solution: take by weighing the 28g ammonium persulphate, be made into mass percent concentration and be 10% the aqueous solution;
3) micro-emulsion polymerization reaction: stir above-mentioned microemulsion 30～40min, drip the Ammonium Persulfate 98.5 aqueous solution that configures, in 20～60min, drip off, reaction 4～8h;
4) separate dry: above-mentioned reaction solution to going in the beaker, add with the isopyknic acetone of reaction solution and carry out breakdown of emulsion, suction filtration behind 6～12h, be that 0 hydrochloric acid soln washs to the filtrate clear with the pH value again, then behind vacuum-drying 6～12h, use ball mill grinding a few hours again, obtained polyaniline powder, be designated as sample A, Fig. 2 is the atomic force microscope picture of sample A, as can be seen from the figure, particle diameter be 2.5～7nm account for 86%, particle diameter be 7～12nm account for 9%, particle diameter be 12～30nm only account for 5%.
Embodiment 2:
1) preparation microemulsion: take by weighing the 2.5g Sodium dodecylbenzene sulfonate, be made into mass percent concentration and be 1% the aqueous solution, pH value with hydrochloric acid conditioning solution, making the pH value is 0.5, stir 0.5～1h, slowly drip the 7.5g aniline monomer, continue to stir 0.5～1h, slowly drip the 7.5g propyl carbinol again, form the microemulsion of clear;
2) configuration ammonium persulfate aqueous solution: take by weighing the 18.75g ammonium persulphate, be made into mass percent concentration and be 8% the aqueous solution;
3) micro-emulsion polymerization reaction: stir above-mentioned microemulsion 30～40min, drip the Ammonium Persulfate 98.5 aqueous solution that configures, in 20～60min, drip off, reaction 4～8h;
4) separate dry: above-mentioned reaction solution to going in the beaker, add with the isopyknic acetone of reaction solution and carry out breakdown of emulsion, suction filtration behind 6～12h, be that 3 hydrochloric acid soln washs to the filtrate clear with the pH value again, then behind vacuum-drying 6～12h, use ball mill grinding a few hours again, obtained polyaniline powder, be designated as sample B.Fig. 3 is the atomic force microscope picture of sample B, as can be seen from the figure, particle diameter be 2.5～7nm account for 83%, particle diameter be 7～12nm account for 12%, particle diameter be 12～30nm only account for 5%.
Claims (1)
1, a kind of method for preparing nano polyaniline is characterized in that:
1) preparation microemulsion: take by weighing an amount of Sodium dodecylbenzene sulfonate, be made into mass percent concentration and be 1%～1.25% the aqueous solution, with the pH value of hydrochloric acid conditioning solution, making the pH value is 0～0.5, stirs 0.5～1h, slowly drip aniline monomer, the add-on of aniline monomer is 3～4 times of Sodium dodecylbenzene sulfonate, continues to stir 0.5～1h, slowly drips propyl carbinol again, the add-on of propyl carbinol is 2.5～3 times of Sodium dodecylbenzene sulfonate, forms the microemulsion of clear;
2) configuration ammonium persulfate aqueous solution: take by weighing an amount of ammonium persulphate, the amount that makes ammonium persulphate is 2.5～2.8 times of aniline, is made into mass percent concentration then and is 8%～10% the aqueous solution;
3) micro-emulsion polymerization reaction: stir above-mentioned microemulsion 30～40min, drip the Ammonium Persulfate 98.5 aqueous solution that configures, in 20～60min, drip off, reaction 4～8h;
4) separate dry: above-mentioned reaction solution to going in the beaker, add with the isopyknic acetone of reaction solution and carry out breakdown of emulsion, suction filtration behind 6～12h, be that 0～3 hydrochloric acid soln washs to the filtrate clear with the pH value again, then behind vacuum-drying 6～12h, use ball mill grinding a few hours again, can obtain the nano polyaniline powder.
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100526367C (en) * | 2007-08-28 | 2009-08-12 | 厦门大学 | Method for preparing polyaniline nano thread |
| CN101225165B (en) * | 2008-01-31 | 2010-07-21 | 上海交通大学 | Ball-milling force chemical synthesis method of polyaniline |
| CN101125895B (en) * | 2007-07-16 | 2010-09-15 | 南开大学 | Full-methylated cyclodextrinaniline nano supermolecule conducting polymer and its preparation method and use |
| CN101186750B (en) * | 2007-11-16 | 2010-09-15 | 辽宁大学 | Method for preparing polyaniline/MCM-48 mesoporous molecular screen composition |
| CN102702516A (en) * | 2012-05-28 | 2012-10-03 | 东华大学 | Method for preparing polyaniline through multielement doping |
| CN102050947B (en) * | 2009-11-10 | 2013-05-15 | 黑龙江大学 | Emulsion polymer of polyaniline nanofiber and preparation method thereof |
| CN103450474A (en) * | 2013-08-23 | 2013-12-18 | 苏州利材高分子科技材料有限公司 | Method of preparing nano material by utilizing micro-emulsion method |
| CN104264267A (en) * | 2014-09-12 | 2015-01-07 | 广西师范大学 | Porous polyaniline-doped nano fiber material with three-dimensional structure as well as preparation method and application of porous polyaniline-doped nano fiber material |
| CN105218807A (en) * | 2015-09-17 | 2016-01-06 | 南京理工大学 | Ferrite composite material that nano polyaniline is coated and preparation method thereof |
| CN105949459A (en) * | 2016-05-19 | 2016-09-21 | 合肥师范学院 | Meshed polyaniline nanosheet and preparation method thereof |
| CN105999267A (en) * | 2016-07-05 | 2016-10-12 | 天津大学 | Molybdenum disulfide nanodot/polyaniline nano hybrid and preparation method and application thereof |
| CN106119908A (en) * | 2016-08-16 | 2016-11-16 | 王世群 | A kind of scaffold nano-particles reinforcement electroplate liquid |
| CN106400090A (en) * | 2016-06-03 | 2017-02-15 | 安徽长青电子机械（集团）有限公司 | Scaffolding antistatic composite electroplate liquid |
| CN113025194A (en) * | 2021-03-03 | 2021-06-25 | 杭州米土新材料科技有限公司 | Preparation method, cleaning method and using method of transparent conductive composite film for glass surface of photovoltaic panel |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3813362A1 (en) * | 1988-04-21 | 1989-11-02 | Bayer Ag | ELECTRICALLY CONDUCTIVE POLYHETEROAROMATS AND A METHOD FOR THEIR PRODUCTION |
| KR100627470B1 (en) * | 2001-09-05 | 2006-09-22 | 주식회사 포스코 | Preparing method for soluble microemulsion polymer of polyaniline-co-oanthranilic acid, the microemulsion polymer prepared thereby and steel or metal products having the same |
| KR100437222B1 (en) * | 2001-11-02 | 2004-07-02 | 주식회사 동운인터내셔널 | Preparation of polypyrrole nanoparticles using low temperature microemulsion polymerization |
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Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101125895B (en) * | 2007-07-16 | 2010-09-15 | 南开大学 | Full-methylated cyclodextrinaniline nano supermolecule conducting polymer and its preparation method and use |
| CN100526367C (en) * | 2007-08-28 | 2009-08-12 | 厦门大学 | Method for preparing polyaniline nano thread |
| CN101186750B (en) * | 2007-11-16 | 2010-09-15 | 辽宁大学 | Method for preparing polyaniline/MCM-48 mesoporous molecular screen composition |
| CN101225165B (en) * | 2008-01-31 | 2010-07-21 | 上海交通大学 | Ball-milling force chemical synthesis method of polyaniline |
| CN102050947B (en) * | 2009-11-10 | 2013-05-15 | 黑龙江大学 | Emulsion polymer of polyaniline nanofiber and preparation method thereof |
| CN102702516A (en) * | 2012-05-28 | 2012-10-03 | 东华大学 | Method for preparing polyaniline through multielement doping |
| CN102702516B (en) * | 2012-05-28 | 2014-02-26 | 东华大学 | Method for preparing polyaniline through multielement doping |
| CN103450474B (en) * | 2013-08-23 | 2016-06-08 | 苏州利材高分子科技材料有限公司 | A kind of method utilizing Preparing Nano-Materials in Microemulsions |
| CN103450474A (en) * | 2013-08-23 | 2013-12-18 | 苏州利材高分子科技材料有限公司 | Method of preparing nano material by utilizing micro-emulsion method |
| CN104264267A (en) * | 2014-09-12 | 2015-01-07 | 广西师范大学 | Porous polyaniline-doped nano fiber material with three-dimensional structure as well as preparation method and application of porous polyaniline-doped nano fiber material |
| CN105218807A (en) * | 2015-09-17 | 2016-01-06 | 南京理工大学 | Ferrite composite material that nano polyaniline is coated and preparation method thereof |
| CN105949459A (en) * | 2016-05-19 | 2016-09-21 | 合肥师范学院 | Meshed polyaniline nanosheet and preparation method thereof |
| CN105949459B (en) * | 2016-05-19 | 2019-02-19 | 合肥师范学院 | A kind of netted polyaniline nano piece and preparation method thereof |
| CN106400090A (en) * | 2016-06-03 | 2017-02-15 | 安徽长青电子机械（集团）有限公司 | Scaffolding antistatic composite electroplate liquid |
| CN105999267A (en) * | 2016-07-05 | 2016-10-12 | 天津大学 | Molybdenum disulfide nanodot/polyaniline nano hybrid and preparation method and application thereof |
| CN105999267B (en) * | 2016-07-05 | 2019-12-13 | 天津大学 | Molybdenum disulfide nanodot/polyaniline nano hybrid and preparation method and application thereof |
| CN106119908A (en) * | 2016-08-16 | 2016-11-16 | 王世群 | A kind of scaffold nano-particles reinforcement electroplate liquid |
| CN113025194A (en) * | 2021-03-03 | 2021-06-25 | 杭州米土新材料科技有限公司 | Preparation method, cleaning method and using method of transparent conductive composite film for glass surface of photovoltaic panel |
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