CN100545193C - The chemical oxidation synthesis method of electric conductive high polymer-aniline and metal aminophenol copolymer - Google Patents
The chemical oxidation synthesis method of electric conductive high polymer-aniline and metal aminophenol copolymer Download PDFInfo
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- CN100545193C CN100545193C CNB2006100864004A CN200610086400A CN100545193C CN 100545193 C CN100545193 C CN 100545193C CN B2006100864004 A CNB2006100864004 A CN B2006100864004A CN 200610086400 A CN200610086400 A CN 200610086400A CN 100545193 C CN100545193 C CN 100545193C
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- aniline
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- multipolymer
- metal
- high polymer
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Abstract
The chemical oxidation synthesis method of conduction high polymer-aniline and metal aminophenol copolymer, relate to a kind of synthesis technical field with superpolymer of conductivity, aniline and Metha Amino Phenon are generated multipolymer by the ammonium persulphate oxidation simultaneously in strongly acidic solution, be reflected under stirring and the normal temperature and carried out 8～12 hours, then with after the aqueous hydrochloric acid washing of resultant with pH=3,70～90 ℃ of following vacuum-dryings, get described conductive copolymer.Good characteristic with polyaniline, and in the metabisulfite solution of strong acid and pH 1.0 to 11.0, still can keep very high electrochemical activity.When pH 4.0 rises to 11.0, the electrochemical activity of multipolymer only descends 47.0%.Multipolymer is in the pH of above-mentioned solution scope, and its potential range used is-0.2～0.80V (vs.SCE).The specific conductivity of multipolymer is 1.5～2.5S.cm
-1, and less the pH value that depends on.
Description
Technical field
The present invention relates to a kind of technical field with superpolymer of conductivity.
Background technology
In conducting polymer, polyaniline is the most attractive.This is because polyaniline has the color of higher specific conductivity, redox reversible, film can be changed rapidly with current potential, and it is highly stable in the aqueous solution and air.These character are suitable for the application with aspects such as store battery, electrocatalysis, electrochromism and opto-electronic conversion.In addition, synthetic convenience of polyaniline and cost are low.But above-mentioned these character all are subjected to the influence of pH value, thereby have limited its application to a certain extent, and this is that its specific conductivity also becomes very low because when pH＞4, polyaniline has almost completely lost its electrochemical activity.So the pH characteristic of polyaniline is the character of control polyaniline and a key factor of application.(application number: 2006100377056), this multipolymer has well electroactive in wide pH and potential range the electrochemical synthesis of aniline and metal aminophenol copolymer, can be used as the cathode material of store battery applying for a patent.
According to the infrared spectra of electric conductive high polymer-aniline and metal aminophenol copolymer poly (aniline-co-m-aminophenol),
1The characteristic of H NMR (nucleus magnetic resonance) and cyclic voltammogram, the molecular structural formula of going back ortho states and oxidation state of the present invention is respectively:
Ortho states also:
Oxidation state:
In the formula, A-is
Doping negatively charged ion SO4
2Or Cl.
X-diffraction and scanning electron microscope experimental result confirm that the unit of the Metha Amino Phenon in the polymer chain is relevant with the Metha Amino Phenon concentration in the reaction solution with the unitary ratio of aniline.
Summary of the invention
The object of the invention is the another kind of synthetic method of invention electric conductive high polymer-aniline and metal aminophenol copolymer, to satisfy application requiring, so that produce multipolymer in enormous quantities.
The present invention aniline and Metha Amino Phenon in strongly acidic solution are generated multipolymer by the ammonium persulphate oxidation simultaneously, be reflected under stirring and the normal temperature and carried out 8～12 hours, with after the aqueous hydrochloric acid washing of resultant with pH=3,, get above-mentioned conductive copolymer then 70～90 ℃ of following vacuum-dryings.
Purpose of the present invention is with synthetic aniline of chemical oxidization method and metal aminophenol copolymer, and its electrical property comprises that specific conductivity and electrochemical activity are better than electrochemical method synthetic.Multipolymer not only has the good characteristic of polyaniline, and still can keep very high electrochemical activity in the metabisulfite solution of strong acid and pH 1.0 to 11.0.When pH 4.0 rises to 11.0, the electrochemical activity of multipolymer only descends 47.0%.Multipolymer is in the pH of above-mentioned solution scope, and its potential range used is-0.2～0.80V (vs.SCE).The specific conductivity of multipolymer is 1.5～2.5Scm
-1, and less the pH value that depends on.
Because aniline is easily oxidized in air, considers the influence of the purity of aniline to copolyreaction and product, before reaction, aniline is kept under 4 ℃ of environment standby through underpressure distillation.
Described strongly acidic solution is sulfuric acid or hydrochloric acid.
Aniline concentration is 0.25～0.40moldm in reaction mixture
-3, Metha Amino Phenon concentration be 0.008～0.016moldm
-3, ammonium persulphate concentration be 0.3～0.6moldm
-3, sulfuric acid concentration is 1.8～3.0moldm
-3
Preferred version is: aniline concentration is 0.34moldm
-3, Metha Amino Phenon concentration be 0.012moldm
-3, ammonium persulphate concentration be 0.47moldm
-3, sulfuric acid concentration is 2.0moldm
-3
Can in reaction mixture, aniline concentration be 0.25～0.40moldm also
-3, Metha Amino Phenon concentration be 0.008～0.016moldm
-3, ammonium persulphate concentration be 0.3～0.6moldm
-3, concentration of hydrochloric acid is 2.5～6.0moldm
-3
Preferred version is: aniline concentration is 0.34moldm
-3, Metha Amino Phenon concentration be 0.012moldm
-3, ammonium persulphate concentration be 0.47moldm
-3, concentration of hydrochloric acid is 4.0moldm
-3
Specific embodiment
1, raw material
Aniline, Metha Amino Phenon, ammonium persulphate and sulfuric acid or hydrochloric acid
Aniline is kept in 4 ℃ of refrigerators standby after underpressure distillation, and used distilled water is redistilled water.
2, solution allocation
(a) configuration 25ml contains 0.94moldm
-3Ammonium persulphate and 2moldm
-3Aqueous sulfuric acid.
(b) configuration 25ml contains 0.68moldm
-3Aniline, 0.024moldm
-3Metha Amino Phenon and 2moldm
-3Aqueous sulfuric acid.
Aniline and Metha Amino Phenon are joined in sulfuric acid or the aqueous hydrochloric acid, be stirred to homogeneous phase, and to make aniline concentration be 0.34moldm with magnetic stirrer
-3, Metha Amino Phenon concentration is 0.012moldm
-3, sulfuric acid or concentration of hydrochloric acid are respectively 2.0moldm
-3And 4.0moldm
-3.
3, chemical method prepares aniline and metal aminophenol copolymer
25ml solution (a) in the above-mentioned steps 2 joined in the solution (b) (finished in 5 minutes), stir, reacted 12 hours, resultant is a multipolymer.
4, filter, wash
Common filter paper is put in the B, and the mixed solution with reactant joins suction strainer in the B again, and the aqueous hydrochloric acid with pH=3 washs repeatedly, and till filtrate was colourless, filter cake was multipolymer.
5, drying
70～90 ℃ of following vacuum-dryings, getting final product is the multipolymer of aniline and Metha Amino Phenon with the filter cake in the above-mentioned steps 4.
6, measured the molecular weight of copolymer that is soluble in the N-N-methyl-2-2-pyrrolidone N-with osmometry, its molecular weight is 2.99 * 10
4± 600, its molecular weight is slightly larger than the molecular weight of the multipolymer of electrochemical synthesis, and (application number: the 2006100377056) number of repeat unit in structural formula (x), the same present being difficult to polyaniline accurately determined.
7, the specific conductivity of multipolymer is at 1.5～2.5Scm
-1, after in the multipolymer immersion distilled water 15 hours, its specific conductivity still is 0.47Scm
-1
Claims (4)
1, the chemical oxidation synthesis method of electric conductive high polymer-aniline and metal aminophenol copolymer, aniline and Metha Amino Phenon are generated multipolymer by the ammonium persulphate oxidation simultaneously in strongly acidic solution, it is characterized in that, be reflected under stirring and the normal temperature and carried out 8～12 hours, then with after the aqueous hydrochloric acid washing of resultant with pH=3,70～90 ℃ of following vacuum-dryings, get described conductive copolymer; Described strongly acidic solution is sulfuric acid or hydrochloric acid soln; Aniline concentration is 0.25～0.40moldm in reaction mixture
-3, Metha Amino Phenon concentration be 0.008～0.016moldm
-3, ammonium persulphate concentration be 0.3～0.6moldm
-3, sulfuric acid concentration is 1.8～3.0moldm
-3Or concentration of hydrochloric acid is 2.5～6.0moldm
-3
2, according to the chemical oxidation synthesis method of described electric conductive high polymer-aniline of claim 1 and metal aminophenol copolymer, it is characterized in that aniline before use through underpressure distillation, be kept under 4 ℃ of environment standby.
3,, it is characterized in that aniline concentration is 0.34moldm in reaction mixture according to the chemical oxidation synthesis method of described electric conductive high polymer-aniline of claim 1 and metal aminophenol copolymer
-3, Metha Amino Phenon concentration be 0.012moldm
-3, ammonium persulphate concentration be 0.47moldm
-3, sulfuric acid concentration is 2.0moldm
-3
4,, it is characterized in that aniline concentration is 0.34moldm in reaction mixture according to the chemical oxidation synthesis method of described electric conductive high polymer-aniline of claim 1 and metal aminophenol copolymer
-3, Metha Amino Phenon concentration be 0.012moldm
-3, ammonium persulphate concentration be 0.47moldm
-3, concentration of hydrochloric acid is 4.0moldm
-3
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100864004A CN100545193C (en) | 2006-07-14 | 2006-07-14 | The chemical oxidation synthesis method of electric conductive high polymer-aniline and metal aminophenol copolymer |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100864004A CN100545193C (en) | 2006-07-14 | 2006-07-14 | The chemical oxidation synthesis method of electric conductive high polymer-aniline and metal aminophenol copolymer |
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|---|---|
| CN1903913A CN1903913A (en) | 2007-01-31 |
| CN100545193C true CN100545193C (en) | 2009-09-30 |
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| CNB2006100864004A Expired - Fee Related CN100545193C (en) | 2006-07-14 | 2006-07-14 | The chemical oxidation synthesis method of electric conductive high polymer-aniline and metal aminophenol copolymer |
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| CN104001483B (en) * | 2014-05-15 | 2016-02-24 | 昆明理工大学 | Antibiotic macromolecular material of a kind of absorption and its preparation method and application |
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Granted publication date: 20090930 Termination date: 20120714 |