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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- Prior art keywords
- aminophenol
- aniline
- described method
- ortho
- electrolysis
- Prior art date
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- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title claims 8
- 230000002194 synthesizing effect Effects 0.000 title 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 29
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 6
- 229920000642 polymer Polymers 0.000 claims abstract description 4
- 238000005868 electrolysis reaction Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 7
- 238000002484 cyclic voltammetry Methods 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- 239000008151 electrolyte solution Substances 0.000 claims description 3
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims description 3
- 238000002203 pretreatment Methods 0.000 claims description 3
- 238000010189 synthetic method Methods 0.000 claims description 3
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 2
- 239000006210 lotion Substances 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 239000001117 sulphuric acid Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 8
- 229920000767 polyaniline Polymers 0.000 abstract description 7
- 239000000243 solution Substances 0.000 abstract description 4
- 239000003929 acidic solution Substances 0.000 abstract description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 abstract 1
- 229920001577 copolymer Polymers 0.000 abstract 1
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 229910052938 sodium sulfate Inorganic materials 0.000 abstract 1
- 235000011152 sodium sulphate Nutrition 0.000 abstract 1
- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical compound NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Landscapes
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
本发明涉及一种具有导电性能的高聚物的技术领域，在铂电极组成的电解池内，将苯胺、邻氨基苯酚和硫酸进行电解，取得电解产物，再用盐酸水溶液洗涤、干燥后，得到苯胺与邻氨基苯酚共聚物，不仅具有聚苯胺的优良特性，而且它在酸性溶液中的活性也略高于聚苯胺，并且在pH为9.6的硫酸钠溶液中仍能保持很高的电化学活性，当pH从5.0上升到9.6时，它的电化学活性仅下降29%。此外，它在高的pH值下，仍有较宽的应用电位范围{-0.2～0.5V(vs，SCE)}，电导率为0.5～1.2Scm-1。The invention relates to the technical field of high polymers with conductive properties. In an electrolytic cell composed of platinum electrodes, aniline, o-aminophenol and sulfuric acid are electrolyzed to obtain electrolytic products, which are then washed with aqueous hydrochloric acid and dried to obtain aniline Copolymer with o-aminophenol not only has the excellent characteristics of polyaniline, but also has slightly higher activity in acidic solution than polyaniline, and can still maintain high electrochemical activity in sodium sulfate solution with pH 9.6, Its electrochemical activity decreased by only 29% when the pH was increased from 5.0 to 9.6. In addition, it still has a wide application potential range {-0.2-0.5V (vs, SCE)} at a high pH value, and its conductivity is 0.5-1.2Scm -1 .
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 |
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| 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 retarder |
| CN100494251C (en) * | 2006-03-02 | 2009-06-03 | 扬州大学 | Electrochemically active polyaniline at high pH and method for its preparation |
| 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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