CN100395280C - Method for preparing self-dispersion nano-level conducting polyaniline - Google Patents
Method for preparing self-dispersion nano-level conducting polyaniline Download PDFInfo
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- CN100395280C CN100395280C CNB2006100269051A CN200610026905A CN100395280C CN 100395280 C CN100395280 C CN 100395280C CN B2006100269051 A CNB2006100269051 A CN B2006100269051A CN 200610026905 A CN200610026905 A CN 200610026905A CN 100395280 C CN100395280 C CN 100395280C
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Abstract
The present invention relates to a preparation method for electric conduction polyaniline, which has the main preparation step that electric conduction polyaniline is formed by the oxidative polymerization of aniline monomer. The present invention is characterized in that cyclodextrin is added in the process of oxidative polymerization, and the mol ratio of the aniline monomer to the cyclodextrin is 1: (0.1 to 1.2). The preparation method of the present invention is simple and is easy to operate, and the electric conduction polyaniline does not need any dispersing agents so that the electric conduction polyaniline is stably dispersed in water media (an automatic dispersion type). The processing performance of the electric conduction polyaniline is improved, and thereby, the application scope of the electric conduction polyaniline is widened. The present invention has the advantage of environmental protection in the preparation and use process.
Description
Technical field
The present invention relates to a kind of preparation method of electrically conductive polyaniline.
Background technology
Conducting polymer is one of representative the most outstanding in the numerous functional polymers that grow up mid-term in 20th century, because therefore the physicochemical property that conducting polymer has a series of uniquenesses can be widely used in exploitation multifunctional material and device.
For other conducting polymer, polyaniline has raw material and is easy to get, synthesizes easy and good advantages such as environmental stability, thereby becomes one of focus of conducting polymer research field.Electrically conductive polyaniline is to be raw material with the aniline monomer, makes by chemistry or electrochemical method oxypolymerization in acidic aqueous solution.Yet the electrically conductive polyaniline by existing chemistry or electrochemical method oxypolymerization preparation all is that indissoluble is separated and difficult fused the processing characteristics extreme difference.
Numerous results of study show, can improve processing characteristics (P.Ghosh, S.K.Siddhanta, S.R.Haque, A.Chakrabarit, Synth.Met.2001,123,83 of electrically conductive polyaniline by the doping organic acid; A.J.Dominis, G.M.Spinks, L.A.P.Kane-Maguire, G.G.Wallace, Synth.Met.2002,129,165; A.A.Athawale, M.V.Kulkarni, V.V.Chabukswar, Materials Chemistry and Physics 2002,73,106; S.Shreepathi, R.Holze, Chem.Mater.2005,17,4078).Although through organic acid doped electrically conductive polyaniline can be dissolved in the compatible organic solvent of these acid in, solved the processability problems of electrically conductive polyaniline to a certain extent; But in preparation and application process, use lot of organic acids and organic solvent can cause serious environmental pollution and increase to administer the difficulty and the cost of environment.
Some scientific workers also find, also can reach and improve the deliquescent purpose of electrically conductive polyaniline (X.G.Li by polymerization single polymerization monomer being carried out modification (promptly being polymerization single polymerization monomer or aniline and other monomer copolymerization with the anils); M.R.Huang; W.Duan; Y.L.Yang.Chem Rev, 2002,102,2925; W.J.Bae, K.H.Kim, Y.H.Park, W.H.Jo, Chem.Commun.2003,2768; S.H.Lee, D.H.Lee, L.Lee, C.W.Lee, Adv.Funct.Mater.2005,14,1495), however this method is a cost with the electroconductibility of sacrificing electrically conductive polyaniline often.
Recently, people such as D.Li find behind the electrically conductive polyaniline nano fiber purifying, by strictness control (best pH=2.6) pH value, increase the electrically conductive polyaniline nano fiber colloid aqueous solution (D.Li that interparticle electrostatic repulsion forces also can prepare does not need additionally to add dispersion agent, R.B.Kaner, Chem.Commun.2005,3286.).Although this up-to-date achievement in research provides a new way that solves the electrically conductive polyaniline processing problems on nanometer level, but realize the pH value control of strict intimate harshness and the preparation and the purifying of a large amount of electrically conductive polyaniline nano fibers, still quite difficult at present.
In addition, directly make the emulsion of electrically conductive polyaniline, also the processability problems of " solution " electrically conductive polyaniline to a certain extent by letex polymerization.But using can for usually the electrically conductive polyaniline emulsion, tensio-active agent that adds or water miscible macromolecule stabilizer bring adverse influence in emulsion polymerization process, and the depositing and transport and also be subjected to certain restriction of emulsion.
Given this, this area presses for a kind of simple and prepared electrically conductive polyaniline and has the preparation method of the electrically conductive polyaniline of excellent machinability.
Summary of the invention
The objective of the invention is to, a kind of preparation method of simple self-dispersion nano-level conducting polyaniline is provided.
Cyclodextrin (cyclodextrin) be by cyclomaltodextrin glucanotransferase act on that starch produces a group with α-1, the cyclic oligomer saccharide compound that the 4-glycosidic link is formed by connecting.Common have alpha-cylodextrin, beta-cyclodextrin and a γ-Huan Hujing, they be respectively by 6,7 and 8 D-glucopyranose units with α-1, " awl tube " shape molecule of 4-glycosidic link be combined into.Because cyclodextrin has hydrophilic outside frame and hydrophobic inner chamber, thereby cyclodextrin is a representative host molecule, it can form inclusion compounds with all kinds of objects, thereby improves the solvability of guest molecule and reactive behavior and without any need for other chemically modified.The present invention has utilized this characteristic of cyclodextrin just, the inclusion compound that adopts cyclodextrin and acid radical anion or hydration acid radical anion has made the self-dispersion nano-level conducting polyaniline that does not need can be implemented in by any dispersion agent again stable dispersion in the water medium as doping agent and surface-modifying agent by traditional chemical oxidative polymerization method.
The said method for preparing electrically conductive polyaniline of the present invention, its key step is: made through oxypolymerization by aniline monomer, it is characterized in that, add cyclodextrin in the oxypolymerization process, the mol ratio of aniline monomer and cyclodextrin is 1: (0.1～1.2).
The present invention recommends to use beta-cyclodextrin, alpha-cylodextrin or γ-Huan Hujing, and employed cyclodextrin is commercially available product.
The present invention has following advantage:
(1) the simple and prepared electrically conductive polyaniline of preparation method does not need can be implemented in stable dispersion (self-dispersion type) in the water medium by any dispersion agent again, thereby improved the range of application that the electrically conductive polyaniline processing characteristics has been widened electrically conductive polyaniline, and preparation and more environmental protection of use.
(2) the prepared electrically conductive polyaniline of the present invention can with many general water-soluble high-molecular material blend, and be coated with or the method for evaporating is prepared the different conductive polymer film of performance by casting, also can be used as the water-borne coatings that the filler preparation has anti-static function.
Description of drawings
Fig. 1 is for adopting the Electronic Speculum figure of the obtained electrically conductive polyaniline of embodiment 1 method
Fig. 2 is for adopting the dispersion state (leave standstill at least 24 hour) of the obtained electrically conductive polyaniline of embodiment 1 method under condition of different pH
Wherein: the dispersion state when a bottle is pH=2, the dispersion state when the b bottle is pH=3, the dispersion state when the c bottle is pH=4.
Embodiment
The said method for preparing electrically conductive polyaniline of the present invention, it comprises the steps:
(1) be that 1M～2M mineral acid (preferred hydrochloric acid or sulfuric acid) aqueous solution places reactor with aniline monomer and concentration, in this reactor, add ammonium persulfate aqueous solution (oxygenant), under 10 ℃～30 ℃ conditions, stirred 10～30 minutes, add cyclodextrin (beta-cyclodextrin, alpha-cylodextrin or γ-Huan Hujing), the mol ratio of aniline monomer and cyclodextrin is 1: (0.1～1.2), under 10 ℃～30 ℃ conditions, stirred 24～36 hours again.
(2) the undissolved cyclodextrin of filtering, add remaining ammonium persulfate aqueous solution (oxygenant) again, under 10 ℃～30 ℃ conditions, continue oxypolymerization 5～8 hours, filtration, filter cake after washing and vacuum-drying (the vacuum-drying optimum condition is: temperature is 50 ℃, and the time is 24 hours) promptly get target compound;
Among the present invention, the mol ratio of oxygenant and aniline monomer is controlled at 1: (0.5～1.5).
The invention will be further described below by embodiment, and its purpose only is better to understand content of the present invention and unrestricted protection scope of the present invention:
Embodiment 1
Get the distilled aniline of 1.0ml and put into the there-necked flask that contains 20ml 2MHCl solution; add 1.0ml 0.8M ammonium persulfate aqueous solution; stirred 20 minutes under 20 ℃ of conditions, add 3.0g beta-cyclodextrin (Shanghai chemical reagents corporation of Chinese Medicine group), 20 ℃ are stirred placement 24 hours down.Filter undissolved beta-cyclodextrin, add the ammonium persulfate aqueous solution of residue 9.0ml 0.8M in batches, under 20 ℃ and agitation condition, continue oxypolymerization 5 hours, filter, the vacuum-drying 24 hours under 50 ℃ of conditions of washing back, obtain the light green pressed powder.The diameter of fibrous electrically conductive polyaniline is less than 100nm, and specific conductivity is 8.7S/cm, and need can not be dispersed in once more in the water medium by means of any dispersion agent, places no obvious sedimentation demixing phenomenon about three weeks under this dispersion system room temperature.
Embodiment 2
Get the distilled aniline of 1.0ml and put into the there-necked flask that contains 20ml 1.5MHCl solution, the ammonium persulfate aqueous solution that adds 1.0ml 0.8M, stirred 20 minutes under 20 ℃ of conditions, add 10g alpha-cylodextrin (Aldrich Co.), 20 ℃ are stirred placement 24 hours down.Filter undissolved alpha-cylodextrin, add the ammonium persulfate aqueous solution of residue 9.0ml 0.8M in batches, under 20 ℃ and agitation condition, continue oxypolymerization 7 hours, filter, the vacuum-drying 24 hours under 50 ℃ of conditions of washing back, obtain the light green pressed powder.The diameter of fibrous electrically conductive polyaniline is less than 100nm, and specific conductivity is 5.3S/cm, and need can not be dispersed in once more in the water medium by means of any dispersion agent, places no obvious sedimentation demixing phenomenon about three weeks under this dispersion system room temperature.
Embodiment 3
Get the distilled aniline of 1.0ml and put into the there-necked flask that contains 20ml 1MHCl solution, adding 1.0ml 0.8M ammonium persulfate aqueous solution stirred 20 minutes under 25 ℃ of conditions, added the 3.0g beta-cyclodextrin, and 25 ℃ are stirred placement 36 hours down.Filter undissolved beta-cyclodextrin, add the ammonium persulfate aqueous solution of residue 9.0ml 0.8M in batches, under 25 ℃ and agitation condition, continue oxypolymerization 8 hours, filter, the vacuum-drying 24 hours under 50 ℃ of conditions of washing back, obtain the light green pressed powder.The diameter of fibrous electrically conductive polyaniline is less than 100nm, and specific conductivity is 2.7S/cm, and need can not be dispersed in once more in the water medium by means of any dispersion agent, places no obvious sedimentation demixing phenomenon about three weeks under this dispersion system room temperature.
Embodiment 4
Get the distilled aniline of 1.0ml and put into the there-necked flask that contains 20ml 2MHCl solution, adding 1.0ml 0.8M ammonium persulfate aqueous solution stirred 10 minutes under 18 ℃ of conditions, added the 3.0g beta-cyclodextrin, and 18 ℃ are stirred placement 24 hours down.Filter undissolved beta-cyclodextrin, add the ammonium persulfate aqueous solution of residue 9.0ml 0.8M in batches, under 18 ℃ and agitation condition, continue oxypolymerization 5 hours, filter, the vacuum-drying 24 hours under 50 ℃ of conditions of washing back, obtain the light green pressed powder.The diameter of fibrous electrically conductive polyaniline is less than 100nm, and specific conductivity is 8.1S/cm, and need can not be dispersed in once more in the water medium by means of any dispersion agent, places no obvious sedimentation demixing phenomenon about three weeks under this dispersion system room temperature.
Embodiment 5
Get the distilled aniline of 1.0ml and put into the there-necked flask that contains 20ml 1.5MHCl solution, adding 1.0ml 0.8M ammonium persulfate aqueous solution stirred 30 minutes under 25 ℃ of conditions, added the 3.0g beta-cyclodextrin, and 25 ℃ are stirred placement 24 hours down.Filter undissolved beta-cyclodextrin, add the ammonium persulfate aqueous solution of residue 9.0ml 0.8M in batches, under 25 ℃ and agitation condition, continue oxypolymerization 5 hours, filter, the vacuum-drying 24 hours under 50 ℃ of conditions of washing back, obtain the light green pressed powder.The diameter of fibrous electrically conductive polyaniline is less than 100nm, and specific conductivity is 7.0S/cm, and need can not be dispersed in once more in the water medium by means of any dispersion agent, places no obvious sedimentation demixing phenomenon about three weeks under this dispersion system room temperature.
Embodiment 6
Get the distilled aniline of 1.0ml and put into the there-necked flask that contains 20ml 2MHCl solution, add 1.0ml 0.80M ammonium persulphate aqueous oxidizing agent solution, stirred 20 minutes under 18 ℃ of conditions, add 15g γ-Huan Hujing (Sigma Co.), 18 ℃ are stirred placement 24 hours down.Filter undissolved γ-Huan Hujing, the ammonium persulphate aqueous oxidizing agent solution that in batches adds residue 9.0ml 0.8M, under 18 ℃ and agitation condition, continue oxypolymerization 8 hours, filter, vacuum-drying 24 hours under the back 50 ℃ of conditions of washing, obtain the light green pressed powder.The diameter of fibrous electrically conductive polyaniline is less than 100nm, and specific conductivity is 4.3S/cm, and need can not be dispersed in once more in the water medium by means of any dispersion agent, places no obvious sedimentation demixing phenomenon about three weeks under this dispersion system room temperature.
Embodiment 7
Get the distilled aniline of 1.0ml and put into the there-necked flask that contains 20ml 1.5MHCl solution, adding 1.5ml 0.5M ammonium persulfate aqueous solution stirred 10 minutes under 20 ℃ of conditions, added the 3.0g beta-cyclodextrin, and 20 ℃ are stirred placement 24 hours down.Filter undissolved beta-cyclodextrin, the ammonium persulphate aqueous oxidizing agent solution that in batches adds residue 8.5ml 0.5M, under 20 ℃ and agitation condition, continue oxypolymerization 8 hours, filter, the vacuum-drying 24 hours under 50 ℃ of conditions of washing back, obtain the light green pressed powder.The diameter of fibrous electrically conductive polyaniline is less than 100nm, and specific conductivity is 6.5S/cm, and need can not be dispersed in once more in the water medium by means of any dispersion agent, places no obvious sedimentation demixing phenomenon about three weeks under this dispersion system room temperature.
Embodiment 8
Get the distilled aniline of 1.0ml and put into the there-necked flask that contains 20ml 1MHCl solution, adding 0.5ml 1.5M ammonium persulfate aqueous solution stirred 20 minutes under 23 ℃ of conditions, added the 3.0g beta-cyclodextrin, and 23 ℃ are stirred placement 30 hours down.Filter undissolved beta-cyclodextrin, add the ammonium persulfate aqueous solution of residue 9.5ml 1.5M in batches, under 23 ℃ and agitation condition, continued oxidation poly-5 hours, filter, the vacuum-drying 24 hours under 50 ℃ of conditions of washing back, obtain the light green pressed powder.The diameter of fibrous electrically conductive polyaniline is less than 100nm, and specific conductivity is 3.9S/cm, and need can not be dispersed in once more in the water medium by means of any dispersion agent, places no obvious sedimentation demixing phenomenon about three weeks under this dispersion system room temperature.
Embodiment 9
Get the distilled aniline of 1.0ml and put into the there-necked flask that contains 20ml 1.5MHCl solution, adding 1.5ml 0.5M ammonium persulfate aqueous solution stirred 10 minutes under 25 ℃ of conditions, added the 5.5g beta-cyclodextrin, and 25 ℃ are stirred placement 28 hours down.Filter undissolved beta-cyclodextrin, add the ammonium persulfate aqueous solution of residue 8.5ml 0.5M in batches, under 25 ℃ and agitation condition, continue oxypolymerization 8 hours, filter, the vacuum-drying 24 hours under 50 ℃ of conditions of washing back, obtain the light green pressed powder.The diameter of fibrous electrically conductive polyaniline is less than 100nm, and specific conductivity is 7.9S/cm, and need can not be dispersed in once more in the water medium by means of any dispersion agent, places no obvious sedimentation demixing phenomenon about three weeks under this dispersion system room temperature.
Embodiment 10
Get the distilled aniline of 1.0ml and put into the there-necked flask that contains 20ml 1.5MHCl solution, the ammonium persulfate aqueous solution of adding 1.5ml 0.5M stirred 10 minutes under 20 ℃ of conditions, added the 1.1g beta-cyclodextrin, and 20 ℃ are stirred placement 24 hours down.Filter undissolved beta-cyclodextrin, add the ammonium persulfate aqueous solution of residue 8.5ml 0.5M in batches, under 20 ℃ and agitation condition, continue oxypolymerization 8 hours, filter, the vacuum-drying 24 hours under 50 ℃ of conditions of washing back, obtain the light green pressed powder.The diameter of fibrous electrically conductive polyaniline is less than 100nm, and specific conductivity is 5.1S/cm, and need can not be dispersed in once more in the water medium by means of any dispersion agent, places no obvious sedimentation demixing phenomenon about three weeks under this dispersion system room temperature.
Embodiment 11
Getting the distilled aniline of 1.0ml puts into and contains 20ml 2MH
2SO
4In the there-necked flask of solution, the ammonium persulfate aqueous solution of adding 1.5ml 0.5M stirred 20 minutes under 20 ℃ of conditions, added the 3.0g beta-cyclodextrin, and 20 ℃ are stirred placement 24 hours down.Filter undissolved beta-cyclodextrin, add the ammonium persulfate aqueous solution of residue 8.5ml 0.5M in batches, under 20 ℃ and agitation condition, continue oxypolymerization 8 hours, filter, the vacuum-drying 24 hours under 50 ℃ of conditions of washing back, obtain the light green pressed powder.The diameter of fibrous electrically conductive polyaniline is less than 100nm, and specific conductivity is 6.1S/cm, and need can not be dispersed in once more in the water medium by means of any dispersion agent, places no obvious sedimentation demixing phenomenon about three weeks under this dispersion system room temperature.
Embodiment 12
Get the distilled aniline of 2.0ml and put into the there-necked flask that contains 20ml 2MHCl solution, the ammonium persulphate aqueous oxidizing agent solution of adding 0.1ml 2.0M stirred 20 minutes under 20 ℃ of conditions, added the 2.3g beta-cyclodextrin, and 20 ℃ are stirred placement 24 hours down.Filter undissolved beta-cyclodextrin, add residue 9.9ml 2.0M ammonium persulphate aqueous oxidizing agent solution in batches, under 20 ℃ and agitation condition, continue oxypolymerization 5 hours, filter, the vacuum-drying 24 hours under 50 ℃ of conditions of washing back, obtain the light green pressed powder.The diameter of fibrous electrically conductive polyaniline is less than 100nm, and specific conductivity is 8.6S/cm, and need can not be dispersed in once more in the water medium by means of any dispersion agent, places no obvious sedimentation demixing phenomenon about three weeks under this dispersion system room temperature.
Claims (6)
1. method for preparing electrically conductive polyaniline, its key step is: made through oxypolymerization by aniline monomer, it is characterized in that, add cyclodextrin in the oxypolymerization process, the mol ratio of aniline monomer and cyclodextrin is 1: (0.1～1.2).
2. preparation method as claimed in claim 1 is characterized in that, wherein said cyclodextrin is beta-cyclodextrin, alpha-cylodextrin or γ-Huan Hujing.
3. preparation method as claimed in claim 1 is characterized in that, wherein used oxygenant is an ammonium persulfate aqueous solution in the oxypolymerization, and the mol ratio of oxygenant and aniline monomer is 1: (0.5～1.5).
4. as any described preparation method in the claim 1～3, it is characterized in that said preparation method comprises the steps:
(1) be that 1M～2M inorganic acid aqueous solution places reactor with aniline monomer and concentration, in this reactor, add ammonium persulfate aqueous solution, under 10～30 ℃ of conditions, stirred 10～30 minutes, add beta-cyclodextrin, alpha-cylodextrin or γ-Huan Hujing, aniline monomer is 1 with the mol ratio of the cyclodextrin that is added: (0.1～1.2), and under 10～30 ℃ of conditions, stir again and placed 24～36 hours.
(2) the undissolved cyclodextrin that adds of filtering adds remaining ammonium persulfate aqueous solution again, continues oxypolymerization 5～8 hours under 10～30 ℃ of conditions, and filtration, filter cake promptly get target compound after washing and vacuum-drying.
5. the preparation method described in claim 4 is characterized in that, wherein said mineral acid is hydrochloric acid or sulfuric acid.
6. the preparation method described in claim 4 is characterized in that, wherein vacuum drying temperature is 50 ℃, and the vacuum drying time is 24 hours.
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| 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 |
| CN103242524B (en) * | 2013-05-16 | 2015-06-03 | 东华大学 | Method of preparing polyaniline nanotube by utilizing cyclodextrin as template |
| CN103409840B (en) * | 2013-07-15 | 2016-08-10 | 东华大学 | A kind of method preparing polyaniline nano fiber for template with cyclodextrin |
| CN103467740B (en) * | 2013-09-09 | 2015-12-23 | 东华大学 | Take beta-cyclodextrin as the method for the controlled polyaniline nanotube in Template preparation aperture |
| CN108440777B (en) * | 2018-03-19 | 2021-02-12 | 河北中烯科技有限公司 | Graphene water-based electrothermal film and preparation method thereof |
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| CN1294154A (en) * | 1999-10-26 | 2001-05-09 | 北京燕山石油化工公司研究院 | Electrically conductive aqueous latex of polyphnenylamine and its preparing process and application |
| CN1150225C (en) * | 1999-06-04 | 2004-05-19 | 罗姆和哈斯公司 | Process for preparing intrinsic conductive copolymer and copolymer composition thereby |
| US6805816B1 (en) * | 1999-05-20 | 2004-10-19 | Bayer Aktiengesellschaft | Method of producing π-conjugated polymers |
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| US6805816B1 (en) * | 1999-05-20 | 2004-10-19 | Bayer Aktiengesellschaft | Method of producing π-conjugated polymers |
| CN1150225C (en) * | 1999-06-04 | 2004-05-19 | 罗姆和哈斯公司 | Process for preparing intrinsic conductive copolymer and copolymer composition thereby |
| CN1294154A (en) * | 1999-10-26 | 2001-05-09 | 北京燕山石油化工公司研究院 | Electrically conductive aqueous latex of polyphnenylamine and its preparing process and application |
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