CN1730510A - Water-soluble high temperature-resistant polyaniline conducting material and its preparation method - Google Patents
Water-soluble high temperature-resistant polyaniline conducting material and its preparation method Download PDFInfo
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- CN1730510A CN1730510A CN 200510102994 CN200510102994A CN1730510A CN 1730510 A CN1730510 A CN 1730510A CN 200510102994 CN200510102994 CN 200510102994 CN 200510102994 A CN200510102994 A CN 200510102994A CN 1730510 A CN1730510 A CN 1730510A
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Abstract
The invention relates to water-soluble poly amino benzenes high temperature resisting conductive material and method for preparation, wherein the material is prepared from p-phenylene diamine 54-216 parts, monomer propenoic acid 35-71 parts, horseradish peroxidase 0.05-3 parts as raw material, p-phenylene diamine and propenoic acid as monomers, deionized water as solvent, horse radish peroxidase HRP as catalyst, H2O2 as oxidation agent through copolymerization, acetone deposition and vacuum drying 48 hours at 50 deg C.
Description
Technical field
The present invention relates to a kind of water miscible polyaniline compound material and preparation method thereof, particularly a kind of water-soluble high temperature-resistant polyaniline conducting material and preparation method thereof.
Background technology
The middle and later periods seventies 20th century, discovery polyacetylene films such as Shirakawa mix up by I2 steam and can make its electric conductivity improve 11 orders of magnitude, and this discovery has promoted the conducting polymer subject development based on conjugated polymer rapidly.Polyaniline was developed as conducting polymer by Mac Diarmid etc. again in 1984.For other conjugated polymer, its synthesis material is easy to get, method is simple, having higher electricity leads and workability, has good environmental stability simultaneously, make it become the focus of present conducting polymer research, and become of greatest concern and have most using value one of three big conducting polymer kinds (polyaniline, Polythiophene and polypyrrole).
Because the strong rigidity of polyaniline chain and the strong interaction of interchain make its most of water insoluble and most organic solvents, this has just limited to the structural characterization to it, the research of structure-performance relation, limited its widespread use technically, thereby the solubility problem of solution polyaniline has become the focus that various countries are competitively studied.
The investigator has carried out big quantity research to water-soluble poly aniline both at home and abroad.United States Patent (USP) 420621 (application number) has been applied for a kind of method that sulfonic acid medium prepares water-soluble conducting polyaniline of introducing; United States Patent (USP) 424421 (application number) has been applied for a kind of preparation method with polyaniline of magnetic and electrical property; United States Patent (USP) 872560 (application number) has been applied for the method for the mixture of the water miscible electrically conductive polyaniline of chemosynthesis; Chinese patent publication number 1415645 has been applied for carrying out the method that hot doping prepares the soluble conductive polyaniline a kind of polyaniline in eigenstate and macromole function protonic acid are formed in the mixed solvent at water and solubility promoter; Chinese patent publication number 1410474 has been applied for the preparation method of polyaniline-polyacrylic acid hydrogel.Polyaniline in the above patent all is that chemical process prepares, and generally only has water-soluble and two kinds of features of electroconductibility, and does not have resistant to elevated temperatures feature.
Summary of the invention
The object of the invention is to overcome the defective of prior art and a kind of have water-soluble, electroconductibility and resistant to elevated temperatures water-soluble high temperature-resistant polyaniline conducting material is provided.
Another object of the present invention is to provide a kind of method for preparing water-soluble high temperature-resistant polyaniline conducting material.
Purpose of the present invention can be achieved through the following technical solutions, and described water-soluble high temperature-resistant polyaniline conducting material is that the raw material reaction by the following weight ratio forms:
54～216 parts of Ursol D;
35～71 parts in monomer vinylformic acid;
0.05～3 part of horseradish peroxidase.
The preparation method of described water-soluble high temperature-resistant polyaniline conducting material is as follows:
1, Sodium phosphate dibasic and the SODIUM PHOSPHATE, MONOBASIC mixed solution with pH=7 fully dissolves 0.05～3 part of horseradish peroxidase as damping fluid, makes horseradish peroxidase solution;
2, be that 54～216 parts of Ursol D are dissolved in the deionized water with weight, and fully stirring make its dissolving, adds 35～71 parts of monomer vinylformic acid then, stirs;
3, the above-mentioned horseradish peroxidase solution that makes is added the above-mentioned liquid that stirs, drip weight concentration then in batches and be 0.3%～0.03% superoxol, added 1 time in per 20～35 minutes, 0.2～1 part/time, add altogether 4～6 times, the inflated with nitrogen protection was reacted 20～30 hours;
4, products therefrom is directly joined in the acetone soln, precipitation, washing, 48 ℃～80 ℃ vacuum-drying 45～52 hours promptly makes product of the present invention.
The present invention has following advantage:
1, the preparation of this material is to be catalyzer with the biological enzyme, removes the dried up solvent that is, reaction is the solution polymerization of homogeneous, avoided initiators such as Sodium Persulfate commonly used, organic solvents such as dioxane have reduced environmental pollution, and significantly reduce the enzyme amount, reduced cost.
2, the polyaniline compound electro-conductive material of the present invention preparation is simultaneously soluble in water, and is dissolved in the stronger organic solvent of other polarity, and has certain electroactively, and specific conductivity is 10-5S/cm.
3, this material has good thermostability, and second-order transition temperature is up to 410.4 ℃, residue 66.2% when quality still remains between 81.5%, 600 ℃-900 ℃ weightless 3.2%, 1198 ℃ when being heated to 900 ℃.
Description of drawings
Fig. 1 is the cyclic voltammogram of polyaniline compound material water solution of the present invention.
Fig. 2 is the thermogravimetric comparison diagram of polyaniline compound material of the present invention and polyaniline in eigenstate material, and wherein A is a polyaniline compound material of the present invention, and B is the polyaniline in eigenstate material.
Embodiment
Embodiment 1
Take by weighing Ursol D 0.108 gram, fully dissolving in 8 ml deionized water adds vinylformic acid 0.071 gram, mixes; 2 milligrams of horseradish peroxidase are dissolved in Sodium phosphate dibasic and the SODIUM PHOSPHATE, MONOBASIC blended buffered soln of pH=7 fully, join then in the above-mentioned mixed solution; Splash into weight ratio 0.3%H after thorough mixing is even
2O
2Solution, each 0.4 milligram, added 1 time in per 20 minutes, add altogether 6 times; After hydrogen peroxide adds, continue reaction 20 hours, the inflated with nitrogen protection; Then, product and reaction solution joined in the acetone soln precipitate, obtain the powdery substance of black; Repeatedly wash with acetone again, remove the polymkeric substance of unreacted monomer and part small molecular weight; 48 ℃ of vacuum-drying 52 hours promptly obtains product of the present invention.
Embodiment 2
Take by weighing Ursol D 0.108 gram, fully dissolving in 8 ml deionized water adds vinylformic acid 0.036 gram, mixes; 120 milligrams of horseradish peroxidase are dissolved in Sodium phosphate dibasic and the SODIUM PHOSPHATE, MONOBASIC blended buffered soln of pH=7 fully, join then in the above-mentioned mixed solution; Splash into weight ratio 0.03%H after thorough mixing is even
2O
2Solution, each 2 milligrams, added 1 time in per 35 minutes, add altogether 4 times; After hydrogen peroxide adds, continue reaction 30 hours, the inflated with nitrogen protection; Then, product and reaction solution joined in the acetone soln precipitate, obtain the powdery substance of black, repeatedly wash with acetone again, remove the polymkeric substance of unreacted monomer and part small molecular weight; 80 ℃ of vacuum-drying 45 hours promptly obtains product of the present invention.
Embodiment 3
Take by weighing Ursol D 0.108 gram, fully dissolving in 8 ml deionized water adds vinylformic acid 0.018 gram, mixes.60 milligrams of horseradish peroxidase are dissolved in Sodium phosphate dibasic and the SODIUM PHOSPHATE, MONOBASIC blended buffered soln of pH=7 fully, join then in the above-mentioned mixed solution.Splash into weight ratio 0.15%H after thorough mixing is even
2O
2Solution, each 1 milligram, added 1 time in per 30 minutes, add altogether 5 times.After hydrogen peroxide adds, continue reaction 25 hours, the inflated with nitrogen protection.Then, product and reaction solution joined in the acetone soln precipitate, obtain the powdery substance of black, repeatedly wash with acetone again, remove the polymkeric substance of unreacted monomer and part small molecular weight.60 ℃ of vacuum-drying 50 hours promptly obtains product of the present invention.
Embodiment 4
Take by weighing Ursol D 0.1080 gram, fully dissolving in 8 ml deionized water adds vinylformic acid 0.142 gram, mixes.10 milligrams of horseradish peroxidase are dissolved in Sodium phosphate dibasic and the SODIUM PHOSPHATE, MONOBASIC blended buffered soln of pH=7 fully, join then in the above-mentioned mixed solution.Splash into weight ratio 0.08%H after thorough mixing is even
2O
2Solution, each 1.5 milligrams, added 1 time in per 27 minutes, add altogether 5 times.After hydrogen peroxide adds, continue reaction 28 hours, the inflated with nitrogen protection.Then, product and reaction solution joined in the acetone soln precipitate, obtain the powdery substance of black, repeatedly wash with acetone again, remove the polymkeric substance of unreacted monomer and part small molecular weight.50 ℃ of vacuum-drying 50 hours promptly obtains product of the present invention.
By ultraviolet (UV), infrared spectra (FT-IR), cyclic voltammetric (CV), photoelectron spectrum (XPS), thermogravimetric-differential thermal analysis (TG/DTA), scanning electron microscope (SEM) detection means is tested its conjugated degree, characteristic group, electroactive and thermostability etc.; The result shows: cyclic voltammetric has shown that this water-soluble poly phenyl amines material has electroactive preferably; Photoelectron spectrum shows=N-,-N-,-N
+The existence of-three kinds of structures; Thermogravimetric-differential thermal analysis shows that its second-order transition temperature is 410.4 ℃, mass excess 81.5% during 84.7%, 900 ℃ of mass excess when being heated to 600 ℃, and residue 66.2% when being heated to 1198 ℃, as seen this material has goodish resistance to elevated temperatures.
Claims (2)
1. water-soluble high temperature-resistant polyaniline conducting material preparation method is characterized in that the preparation method is as follows:
1) fully dissolves 0.05～3 part of horseradish peroxidase with the Sodium phosphate dibasic of pH=7 and the buffered soln of SODIUM PHOSPHATE, MONOBASIC preparation, make horseradish peroxidase solution;
2) be that 54～216 parts of Ursol D are dissolved in the deionized water with weight, and fully stirring make its dissolving, adds 35～71 parts of monomer vinylformic acid then, stirs;
3) the above-mentioned horseradish peroxidase solution that makes is added the above-mentioned liquid that stirs, drip weight concentration then in batches and be 0.3%～0.03% superoxol, added 1 time in per 20～35 minutes, 0.2～1 part/time, add altogether 4～6 times, the inflated with nitrogen protection was reacted 20～30 hours;
4) products therefrom is directly joined in the acetone soln, precipitation, washing, 48 ℃～80 ℃ vacuum-drying 45～52 hours, both product of the present invention.
2, the prepared product of a kind of preparation method of water-soluble high temperature-resistant polyaniline conducting material according to claim 1 is characterized in that, it is that raw material reaction by the following weight ratio forms:
54～216 parts of Ursol D;
35～71 parts in monomer vinylformic acid;
0.05～3 part of horseradish peroxidase.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101220150B (en) * | 2008-01-29 | 2010-06-02 | 同济大学 | Copolymer of m-phenylenediamine and sulfonation m-phenylenediamine, and method for producing the same |
| CN101812176A (en) * | 2010-04-13 | 2010-08-25 | 无锡中美亿芯生物科技有限公司 | Conductive polyaniline with bioactivity, preparation thereof and use thereof |
| CN102604084A (en) * | 2012-01-13 | 2012-07-25 | 上海师范大学 | Method for preparing water-soluble conducting polyaniline |
| CN103848987A (en) * | 2012-11-30 | 2014-06-11 | 南京理工大学 | High-crystallinity polyaniline and preparation method thereof |
| CN105418930A (en) * | 2014-09-23 | 2016-03-23 | 中国石油化工股份有限公司 | Preparation method of water-soluble polyaniline |
| CN104277218B (en) * | 2014-10-20 | 2016-07-13 | 青岛科技大学 | A kind of method that nano black selenium Mimetic Peroxidase catalyzes and synthesizes water-soluble conducting polymer |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5324453A (en) * | 1992-08-07 | 1994-06-28 | Neste Oy | Electrically conducting polyaniline: method for emulsion polymerization |
| EP0582919B2 (en) * | 1992-08-11 | 2006-02-15 | Fortum Oil and Gas Oy | Conducting plastics material and a method for its preparation |
| TW278096B (en) * | 1992-09-24 | 1996-06-11 | Dsm Nv | |
| CN1056163C (en) * | 1997-01-30 | 2000-09-06 | 中国科学院长春应用化学研究所 | Prepn. of ultra-low molecular polyphenyl amine |
| JP4658436B2 (en) * | 2000-04-04 | 2011-03-23 | パニポル オイ | Method and apparatus for producing polyaniline |
-
2005
- 2005-09-16 CN CNB2005101029949A patent/CN100448916C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101220150B (en) * | 2008-01-29 | 2010-06-02 | 同济大学 | Copolymer of m-phenylenediamine and sulfonation m-phenylenediamine, and method for producing the same |
| CN101812176A (en) * | 2010-04-13 | 2010-08-25 | 无锡中美亿芯生物科技有限公司 | Conductive polyaniline with bioactivity, preparation thereof and use thereof |
| CN102604084A (en) * | 2012-01-13 | 2012-07-25 | 上海师范大学 | Method for preparing water-soluble conducting polyaniline |
| CN103848987A (en) * | 2012-11-30 | 2014-06-11 | 南京理工大学 | High-crystallinity polyaniline and preparation method thereof |
| CN103848987B (en) * | 2012-11-30 | 2016-08-03 | 南京理工大学 | High crystalline polyaniline and preparation method thereof |
| CN105418930A (en) * | 2014-09-23 | 2016-03-23 | 中国石油化工股份有限公司 | Preparation method of water-soluble polyaniline |
| CN105418930B (en) * | 2014-09-23 | 2018-02-02 | 中国石油化工股份有限公司 | A kind of preparation method of water-soluble polyaniline |
| CN104277218B (en) * | 2014-10-20 | 2016-07-13 | 青岛科技大学 | A kind of method that nano black selenium Mimetic Peroxidase catalyzes and synthesizes water-soluble conducting polymer |
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| CN100448916C (en) | 2009-01-07 |
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