CN1235945C - Conductive high polymer-aminobenzene and o-aminophenol copalymer and synthesizing method thereof - Google Patents
Conductive high polymer-aminobenzene and o-aminophenol copalymer and synthesizing method thereof Download PDFInfo
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- CN1235945C CN1235945C CN 03127257 CN03127257A CN1235945C CN 1235945 C CN1235945 C CN 1235945C CN 03127257 CN03127257 CN 03127257 CN 03127257 A CN03127257 A CN 03127257A CN 1235945 C CN1235945 C CN 1235945C
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- aminophenol
- ortho
- described method
- aniline
- electrolysis
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Abstract
The present invention relates to the technical field of a high polymer having electric conducting performance. Phenylamine, ortho-aminophenol and sulphuric acid are electrolyzed in an electrolytic cell composed of platinum electrodes to obtain an electrolytic product; a copolymer of the phenylamine and the ortho-aminophenol is obtained after the electrolytic product is washed with a water solution of hydrochloric acid and dried. The copolymer has the superior characteristics of polyaniline and the activity slightly higher than that of the polyaniline in an acidic solution; very high electrochemical activity of the copolymer can still be maintained in a sodium sulfate solution having a pH value of 9.6, and the electrochemical activity of the copolymer is only lowered 29% when the pH value rises from 5.0 to 9.6. Additionally, the copolymer still has a wide applied electrical potential range of {-0.2 to 0.5V(vs, SCE)} under the condition of a high pH value, and the electric conductivity is from 0.5 to 1.2 S/cm.
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 high 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 applicable to the application of aspects such as store battery, electrocatalysis, electrochromism and opto-electronic conversion.But its electric conductivity, energy density, catalytic activity, electrochromism and energy transformation are influenced by pH all, and this has limited its application to a certain extent.This is because in pH＞4 o'clock, and polyaniline has almost lost its electrochemical activity, and specific conductivity also becomes very low.
Summary of the invention
The object of the invention is to invent under the condition of a kind of pH＞4, still has the novel conductive superpolymer of high electrochemical activity and electroconductibility.
The present invention goes back ortho states and the oxidation state molecular structural formula is respectively:
The present invention not only has the good characteristic of polyaniline, and its activity in acidic solution is also a little more than polyaniline, and in pH is 9.6 metabisulfite solution, still can keep very high electrochemical activity, when pH when 5.0 rise to 9.6, its electrochemical activity only descends 29%.In addition, it still has the application potential range { 0.2～0.5V (vs.SCE) } of broad under high pH value, and the specific conductivity of multipolymer is 0.5～1.2Scm
-1
Another object of the present invention is to provide the synthetic method of the novel conductive superpolymer with high conductivity.
In the electrolyzer that platinum electrode is formed, aniline, Ortho-Aminophenol and sulfuric acid are carried out electrolysis, obtain electrolysate, after the aqueous hydrochloric acid washing with pH=3, dry under 60～75 ℃ of vacuum again, obtain above-mentioned conduction high polymer.
Platinum electrode uses the washing lotion of being made up of potassium bichromate and sulfuric acid to carry out pre-treatment earlier before the electrolysis of the present invention.
Because aniline is easily oxidized in air, for improving electrolytic validity, aniline of the present invention through underpressure distillation, is kept under 4 ℃ of environment standby before electrolysis.
The concentration of aniline is 0.1～0.3moldm in the electrolytic solution of the present invention
-3, the concentration of Ortho-Aminophenol is 0.005～0.015mol dm
-3, vitriolic concentration is 0.4～1.2moldm
-3
Specific embodiment
1, raw material:
Aniline, Ortho-Aminophenol, sulfuric acid.
Aniline is kept in 4 ℃ of refrigerators standby after underpressure distillation.
2, preparation electrolytic solution:
Aniline and Ortho-Aminophenol are joined in the aqueous sulfuric acid, be stirred to homogeneous phase, and to make aniline concentration be 0.1～0.3moldm with magnetic stirrer
-3, anthranilic acid concentration is 0.005～0.015moldm
-3, sulfuric acid concentration is 0.4～1.2moldm
-3
3, electrolyzer is prepared:
Electrolyzer adopts three-electrode system, is made of two platinized platinums and a saturated calomel electrode (SCE) reference electrode.
Two platinized platinums carry out pre-treatment through potassium bichromate and vitriolic mixing solutions before electrolysis.
4, electrolytic synthesis:
The solution of preparation is joined in the ionogen, carry out electrolysis with cyclic voltammetry.The scanning control of Electric potentials is at-0.2～1.1V (vs.SCE).The rate-controlling of electric potential scanning is at 30～180mVs
-1
5, washing:
(1) solids of separating out on the platinum electrode surface is taken off, use 0.05mol dm
-3Sulphuric acid soln washs, until the hydrolysis of removing unreacted aniline and Ortho-Aminophenol fully and preventing multipolymer.
(2) aqueous hydrochloric acid with pH=3 carries out secondary washing, sulfate radical-free in filtrate.
6, drying:
The solid matter that obtains in the above-mentioned steps 5 is dry in 60～75 ℃ of vacuum, obtain multipolymer.
Claims (9)
1, conduction high polymer---aniline and Ortho-Aminophenol multipolymer is characterized in that it goes back ortho states and the oxidation state molecular structural formula is respectively:
2, the described conduction high polymer of claim 1---the synthetic method of aniline and Ortho-Aminophenol multipolymer, it is characterized in that, in the electrolyzer that three electrodes are formed, aniline, Ortho-Aminophenol and sulfuric acid are carried out electrolysis, on platinum electrode, obtain electrolysate, after the aqueous hydrochloric acid washing with pH=3, dry under 60～75 ℃ of vacuum again, obtain above-mentioned conduction high polymer.
3,, it is characterized in that platinum electrode uses the washing lotion of being made up of potassium bichromate and sulfuric acid to carry out pre-treatment earlier before the electrolysis according to the described method of claim 2.
4, according to the described method of claim 2, it is characterized in that described electrolyzer is a three-electrode system, form by two platinized platinums and a saturated calomel electrode reference electrode.
5, according to the described method of claim 2, it is characterized in that aniline before electrolysis through underpressure distillation, be kept under 4 ℃ of environment standby.
6, according to the described method of claim 2, the concentration that it is characterized in that aniline in the electrolytic solution is 0.1～0.3moldm
-3, the concentration of Ortho-Aminophenol is 0.005～0.015moldm
-3, vitriolic concentration is 0.4～1.2moldm
-3
7, according to the described method of claim 2, it is characterized in that described electrolysis under normal temperature, normal pressure, adopt cyclic voltammetry to carry out electrolysis.
8, according to the described method of claim 7, it is characterized in that the scanning potential voltage of cyclic voltammetry is-0.2～1.1V, scanning current potential speed is 30～180mVs
-1
9,, it is characterized in that electrolytic resultant before washing with aqueous hydrochloric acid, uses 0.05moldm earlier according to the described method of claim 2
-3Sulphuric acid soln washs.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03127257 CN1235945C (en) | 2003-09-28 | 2003-09-28 | Conductive high polymer-aminobenzene and o-aminophenol copalymer and synthesizing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03127257 CN1235945C (en) | 2003-09-28 | 2003-09-28 | Conductive high polymer-aminobenzene and o-aminophenol copalymer and synthesizing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1528803A CN1528803A (en) | 2004-09-15 |
| CN1235945C true CN1235945C (en) | 2006-01-11 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 03127257 Expired - Fee Related CN1235945C (en) | 2003-09-28 | 2003-09-28 | Conductive high polymer-aminobenzene and o-aminophenol copalymer and synthesizing method thereof |
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| CN (1) | CN1235945C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100413910C (en) * | 2005-04-28 | 2008-08-27 | 财团法人工业技术研究院 | Aniline polymerization delayed-action activator |
| CN100494251C (en) * | 2006-03-02 | 2009-06-03 | 扬州大学 | Polyaniline with electrochemical activity under high-pH value and preparing method |
| CN102352515A (en) * | 2011-07-08 | 2012-02-15 | 北京化工大学 | Method for protecting coating to realize zero discharge of waste water by using polymer prepared by phenol waste water |
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| CN1528803A (en) | 2004-09-15 |
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