CN100408633C - Method of re-doping preparing high electric polyaniline under magnetic field - Google Patents
Method of re-doping preparing high electric polyaniline under magnetic field Download PDFInfo
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- CN100408633C CN100408633C CNB2006100951553A CN200610095155A CN100408633C CN 100408633 C CN100408633 C CN 100408633C CN B2006100951553 A CNB2006100951553 A CN B2006100951553A CN 200610095155 A CN200610095155 A CN 200610095155A CN 100408633 C CN100408633 C CN 100408633C
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Abstract
The present invention is process of preparing high conductivity polyaniline through doping intrinsic polyaniline under the action of magnetic field. Magnetic field is introduced into the intrinsic polyaniline doping process, and conductive polyaniline is prepared through a process of dope-eliminating dope and doping in magnetic field. The feasibility of the present invention is verified with sulfosalicylic acid. The test on the conductivity and dissolvability on the product shows that the conductivity and the dissolvability of the polyaniline re-doped in magnetic field are obviously raised.
Description
Technical field
The present invention relates generally to the method by re-doping preparing high electric polyaniline under the action of a magnetic field.
Background technology
Polyaniline all has been subjected to people at home and abroad and has paid attention to greatly because monomer is cheap, synthesize advantages such as easy, that environmental stability is good.It all is with a wide range of applications aspect many in anticorrosion, anti-electrostatic, stealth material, electrochromism, biological chemistry etc.
Magnetic field material synthetic with preparation process in application caused people's concern widely, and carried out a large amount of exploitative experiments and theoretical investigation.As far back as 1971, professor Lao Le of Brown Univ USA just pointed out, is in the reaction system in the magnetic field, and the spin of the not sharing electron of reactant will be affected, thereby had influenced the entropy of system, influenced the process of chemical reaction.Soviet Union scientist has confirmed this viewpoint soon by observing.Comprise that numerous chemists of China have done the research of a large amount of relevant influence of magnetic field chemical reactions, have obtained sure conclusion.
The viewpoint of influence of magnetic field chemical reaction can be accepted by most of people.Maret etc. reported in 1985 that relevant polymkeric substance was orientated the research of behavior in high-intensity magnetic field, and Mogi and Goto etc. also reported the research report of relevant high-intensity magnetic field p-poly-phenyl amine compound influence respectively.They are primarily aimed at the research of high-intensity magnetic field to the orientation behavior of the influence of electrochemical process precipitation polyaniline film and the polyaniline compound that high-intensity magnetic field to side chain is the liquid crystal group, do not investigate polyaniline orientation behavior during polymerization under high-intensity magnetic field.
By the magnetic field macromolecular method of synthetic polymer fast and effeciently, once classified as science major issue in 1986 by U.S. scientific circles.In recent years, along with to further deep research of electrically conductive polyaniline, some scholar is under the high-intensity magnetic field, and preliminary research has been done in polyaniline and doping behavior thereof, found that its structure of polyaniline and the performance that polymerization under the magnetic field environment generates and does not add magnetic field and the polyaniline that generates has very big difference.
The Dalian University of Technology section beautiful equality people write in " influence of strong magnetic field action p-poly-phenyl amine granule-morphology and electrical property " literary composition: the grain pattern of polyaniline, shape characteristic and and the electrical property of its formation matrix material after obtaining polyaniline and observe abundant polymerization with chemical oxidation solution situ aggregation method under the effect of 10T high-intensity magnetic field.Experiment showed, that polyaniline in eigenstate mixes under high-intensity magnetic field again obtains the spherical particle of 20～30nm, and its composite material resistance rate but reduces by 1 order of magnitude.Think this mainly due to the orientation effect of high-intensity magnetic field p-poly-phenyl amine crystal grain and high-intensity magnetic field to due to the influence of polymerization doping process.
Yangzhou University is by to containing 0.5mol/dm Dysprosium trichloride (DyCl
3) aniline solution to apply different magnetic field forces (be Polyaniline/DyCl
3Under/Bp the environment) mix and contain DyCl
3Polyaniline, the result shows that there is orientation effect in the polymkeric substance in the magnetic field, dysprosium ion (Dy
3+) and magnetic field have synergistic effect; The size of polymer conductivity and magnetic field force big or small closely related.Compare Polyaniline/DyCl with the product that the PAN-HCl environment that does not add magnetic field generates down
3The product that/Bp environment generates down has higher degree of crystallinity.
Xiamen University is by rare earth doped positively charged ion in magnetic field environment, study under the magnetic field environment with this, rare-earth cation p-poly-phenyl amine method for making and Effect on Performance found that: rare-earth cation can increase the polymerization rate of polyaniline greatly, its response capacity big or small as follows: Tb
3+＞Nd
3+＞Ce
3+When parallel the action of a magnetic field in electrode surface, and magnetic field force is when equaling 0.5T, the polymerization rate maximum, in certain magnetic field range, speed of reaction increases with the increase of magnetic flux simultaneously.0.7T the specific conductivity of the polyaniline film of following generation is 115.4Scm
-1, bigger than the specific conductivity of the polyaniline film that under the environment that does not have magnetic field and rare-earth cation, generates.
Be to improve the electroconductibility of polyaniline, the measure of taking usually is exactly that polyaniline to dedoping mixes again.
As: Institutes Of Technology Of Nanjing's academic dissertation " chemosynthesis of polyaniline and performance characterization thereof " literary grace has carried out mixing research with solution method and mechanical milling method to polyaniline in eigenstate respectively with doping-dedoping-adulterated again technological line again.
South China Science ﹠ Engineering University's journal has been reported people such as Zhou Zhentao " Polyaniline Doped, remove and mix and the research of a doping and structure and performance again " literary composition, and this article has mainly been studied doped polyaniline and except that difference and the rule of doped polyaniline at structure and aspect of performance.
Chinese patent CN200410061063.4, a kind of preparation method of the attitude electrically conductive polyaniline that mixes is disclosed, it is characterized in that using tungstic add peroxide as homogeneous phase catalyst and hydrogen peroxide as oxygenant, direct preparation doping attitude electrically conductive polyaniline in water system or water/organic phase 2 phase systems.
About under magnetic field environment, passing through the method for re-doping preparing high electric polyaniline, up to the present do not see the patent and the bibliographical information of related fields as yet, based on above research background, the invention is characterized under magnetic field environment polyaniline in eigenstate is mixed again, preparation high conductivity polyaniline.
Summary of the invention
Purpose of the present invention is passed through re-doping preparing high electric polyaniline exactly under magnetic field environment.
Technical scheme of the present invention is under magnetic field environment the polyaniline in eigenstate powder to be mixed again, and concrete steps are as follows:
1) doped polyaniline is put into 25wt% ammoniacal liquor, its ratio is 1g/50ml, carries out suction filtration after at room temperature stirring 24h, is about 7 with deionized water repetitive scrubbing to filtrate pH value simultaneously;
2) product places 65 ℃ of down dry 6～12h of vacuum drying oven, obtains polyaniline in eigenstate;
3) be that 0.2～3mol/l doping agent is put into reactor with 100ml concentration, add 2g polyaniline in eigenstate powder again, then reactor is put into magnetic field, stir under the room temperature;
4) stir about 8h, the gained polyaniline is filtered and use the deionized water repetitive scrubbing, dry 6～12h in 65 ℃ vacuum drying oven obtains adulterated polyaniline powder at last again then.
The present invention introduces magnetic field in the doping process again of polyaniline in eigenstate.Adopt that dedoping---adulterated again method makes electrically conductive polyaniline in the magnetic field environment, proved under the action of a magnetic field that by test the specific conductivity of doped polyaniline and solubleness all increase again, its method is simple, and effect is obvious.
Embodiment
Be example with the sulphosalicylic acid below, in conjunction with the embodiments the present invention be further described.But embodiment does not constitute limitation of the scope of the invention.Among the embodiment, specific conductivity is tested with four point probe, and deliquescent test is carried out in dimethylbenzene.
Embodiment
It is 25% ammoniacal liquor that the 2g polyaniline powder is put into the 100ml mass concentration, carries out suction filtration after stirring 24h under the room temperature, and uses the deionized water repetitive scrubbing, till washings pH value is approximately at 7 o'clock.Filter cake is put into 65 ℃ of down dry 6～12h of baking oven, obtain the polyaniline in eigenstate powder.Take by weighing this polyaniline in eigenstate powder of 2g and put into reactor, adding 100ml concentration again is the sulphosalicylic acid solution of 1mol/L, then reactor is placed magnetic field, at room temperature stirs about 6h.The gained polyaniline is filtered and with the deionized water repetitive scrubbing, put into 65 ℃ the dry 6～12h of vacuum drying oven again, obtains adulterated polyaniline powder at last again.
Constant and do not have under the situation in magnetic field and repeat above-mentioned experiment in other conditions, obtain not having the powder of doped polyaniline again of the action of a magnetic field.Respectively said two products is carried out specific conductivity and solvability test, the relatively quality of its correlated performance.Experimental data sees Table 1.
Table 1 adds magnetic and does not add polyaniline performance under the action of a magnetic field
More above-mentioned test result, as can be seen, p-poly-phenyl amine mixes again under magnetic field environment, and its specific conductivity and solvability are all than adulterated again polyaniline height under the no the action of a magnetic field.
Claims (2)
1. method at re-doping preparing high electric polyaniline under magnetic field is characterized in that step is as follows:
1) doped polyaniline is put into 25wt% ammoniacal liquor, its ratio is 1g/50ml, carries out suction filtration after at room temperature stirring 24h, is 7 with deionized water repetitive scrubbing to filtrate pH value simultaneously;
2) above-mentioned product is placed vacuum drying oven,, obtain polyaniline in eigenstate at 65 ℃ of down dry 6～12h;
3) be that 0.2～3mol/l doping agent is put into reactor with 100ml concentration, add 2g polyaniline in eigenstate powder again, then reactor is put into magnetic field, stir under the room temperature;
4) stir 8h, the gained polyaniline is filtered, use the deionized water repetitive scrubbing, dry 6～12h in 65 ℃ vacuum drying oven obtains adulterated polyaniline powder at last again then.
2. the method at re-doping preparing high electric polyaniline under magnetic field according to claim 1 is characterized in that: wherein doping agent is wherein a kind of of Witco 1298 Soft Acid, camphorsulfonic acid, sulphosalicylic acid, p-methyl benzenesulfonic acid, hydrochloric acid, sulfuric acid, phosphoric acid, iodine or wherein several in the step 3); Involved magnetic field is permanent-magnetic field or electromagnetic field.
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| CN100408633C true CN100408633C (en) | 2008-08-06 |
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| CN103819667B (en) * | 2014-03-07 | 2017-01-18 | 青岛科技大学 | Method for preparing secondarily-doped polyaniline nanofiber material through total liquid phase method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09208675A (en) * | 1996-01-30 | 1997-08-12 | Ricoh Co Ltd | Organic conductor and its production |
| CN1733821A (en) * | 2005-08-26 | 2006-02-15 | 重庆大学 | Preparation method of high conductivity polyaniline in magnetic field |
| CN1814653A (en) * | 2006-03-03 | 2006-08-09 | 扬州大学 | Method for synthesizing polyaniline nano particles |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09208675A (en) * | 1996-01-30 | 1997-08-12 | Ricoh Co Ltd | Organic conductor and its production |
| CN1733821A (en) * | 2005-08-26 | 2006-02-15 | 重庆大学 | Preparation method of high conductivity polyaniline in magnetic field |
| CN1814653A (en) * | 2006-03-03 | 2006-08-09 | 扬州大学 | Method for synthesizing polyaniline nano particles |
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