CN102604084B - Method for preparing water-soluble conducting polyaniline - Google Patents
Method for preparing water-soluble conducting polyaniline Download PDFInfo
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- CN102604084B CN102604084B CN2012100103009A CN201210010300A CN102604084B CN 102604084 B CN102604084 B CN 102604084B CN 2012100103009 A CN2012100103009 A CN 2012100103009A CN 201210010300 A CN201210010300 A CN 201210010300A CN 102604084 B CN102604084 B CN 102604084B
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Abstract
The invention discloses a method for preparing water-soluble conducting polyaniline by applying efficient catalysis of hemoglobin in a dodecylbenzene sulfonic acid (DBSA) micellar system. The method comprises the following steps of: dissolving DBSA into a buffer solution and adding a phenylamine monomer to stir, wherein the pH value range of the buffer solution is 1-3, and the mole ratio of phenylamine to DBSA is 1: (0.1-10); adding hemoglobin, uniformly stirring, then dropping a hydrogen dioxide solution and stirring to react for 8-48h; and demulsifying and taking precipitate. The hemoglobin is used as a catalyst so that the advantages of low price, mild reaction condition, good catalytic effect and high yield are achieved; and pollutants are prevented from being discharged so as to be beneficial to environment protection.
Description
Technical field
The present invention relates to chemistry and biochemical field, be specially a kind of method of utilizing oxyphorase efficient catalytic in DBSA (Witco 1298 Soft Acid) micella to prepare water-soluble conducting polyaniline.
Background technology
Since the polyacetylene of the iodine of discovery doping first in 1977 had the characteristic of metal, conductive polymers had been subject to extensive concern.And the polyaniline in conduction high polymer (PANI) gets most of the attention in current research because structure is various, mechanism of doping effect is unique, stability high-tech application prospect is extensive etc.Light, electricity, magnetic property as electrically conductive polyaniline can be used for preparing transparency electrode, photodiode, printed circuit board (PCB), also can be used for electromagnetic shielding, microwave joining, antistatic material; Conducting polyaniline amino-group doping-dedoping performance can be applicable to prepare gas separation membrane, sensor, support of the catalyst etc.Based on the vital role of electrically conductive polyaniline, its synthetic method also receives much concern.
The method of traditional synthesized polyaniline has two large classes: chemosynthesis and electrochemical synthesis.But these two kinds of methods all exist because peroxidation causes the more problem of the by product synthesized, and the polyaniline chain rigidity is very strong, all insoluble in general solvent, make the workability of product poor, have limited its industrial application.These traditional synthetic methods are all used strong oxidizer such as ammonium persulphate for causing reagent in addition, easily cause the pollution of environment, and may be present in the product polyaniline product purity is descended.Biological catalyst reaches the specificity to the substrate height because have the catalytic efficiency of height, and the polymerization process of its catalysis is gentle, environmental protection, product easily separates, and seldom, thereby biocatalysis more and more gets more and more people's extensive concerning in the synthetic field of superpolymer by product.
Biological catalyst such as horseradish peroxidase are to come from natural green resource, and aromatics is had to high selectivity, thereby have extensively been applied in polyaniline synthetic.The method of template direction polymerization has substantially all been adopted in the reaction that current applying biological catalysis prepares electrically conductive polyaniline, that is: in the formed emulsion system of polyanion template or the formed micella of tensio-active agent, carry out.The electrically conductive polyaniline that uses micellar system to prepare, exist with soluble status in micella, illustrate that its water-soluble and non-micellar system is compared to have obtained large increase, thereby also greatly improved the processing characteristics of polyaniline.
But by the method for biocatalysis, prepare the problem that also there are two aspects in water-soluble conducting polyaniline at present: the one, biological catalyst such as horseradish peroxidase price comparison costliness, cost is high; Use on the other hand the yield of the preparation-obtained electrically conductive polyaniline of method of biocatalysis mostly lower.For these problems, we have carried out the research that oxyphorase catalysis prepares water-soluble conducting polyaniline.Oxyphorase is the reduced hematin centered by iron porphyrin extensively existed in the higher organism body, its reaction mechanism and horseradish peroxidase are very similar, and cheap (price only have horseradish peroxidase 1/200), therefore carry out the research that oxyphorase catalysis prepares water-soluble conducting polyaniline and have great importance.
Summary of the invention
The purpose of this invention is to provide a kind of method of using oxyphorase efficient catalytic in DBSA micellar system to prepare water-soluble conducting polyaniline.
The object of the present invention is achieved like this:
Adopt oxyphorase as catalyzer, to prepare the method for water-soluble conducting polyaniline, comprise the following steps:
(1) Witco 1298 Soft Acid (DBSA) is dissolved in damping fluid, adds aniline monomer to stir;
The mol ratio of aniline and Witco 1298 Soft Acid is 1: 0.1～10, be preferably 1: 0.5～and 2;
(2) add oxyphorase, the rear dropping superoxol that stirs, stirring reaction 8～48 hours;
The amount ratio of aniline and oxyphorase and hydrogen peroxide is 1mmol: 1～500mg: 0.05～10mmol, is preferably 1mmol: 5～50mg: 0.1～2mmol.
(3) breakdown of emulsion, get precipitation.
By resulting washing of precipitate drying, namely obtain water-soluble conducting polyaniline.
The pH value scope of described buffered soln is 1～3, and damping fluid is citric acid-disodium bicarbonate damping fluid;
The amount ratio of Witco 1298 Soft Acid, aniline monomer, hydrogen peroxide and oxyphorase is 1mol: 0.1～10mol: 0.1～10mol: 1～200g, is preferably 1mol: 0.4～2.5mol: 0.4～2mol: 2～100g.
In reaction system, the concentration of DBSA is 5～100mmol/L, is preferably 5～40mmoL/L;
In reaction system, the concentration of aniline is 5～100mmol/L, is preferably 10～30mmoL/L;
In reaction system, the concentration of oxyphorase is 0.1～50g/L, is preferably 0.1～1g/L;
In reaction system, the concentration of hydrogen peroxide is 10～200mmol/L, is preferably 10～20mmol/L.
Beneficial effect of the present invention and advantage be, the present invention adopts oxyphorase to prepare water-soluble conducting polyaniline as catalyzer, and this catalyzer is cheap, reaction conditions is gentle, excellent catalytic effect.The yield of electrically conductive polyaniline can be up to 126.9% in an embodiment.And product has well water-soluble, greatly improved its processing characteristics.Adopt present method to prepare in the electrically conductive polyaniline process, replaced the strong oxidizer ammonium persulphate in the chemical method with hydrogen peroxide, avoided pollutant emission, be conducive to protection of the environment, therefore have certain industrial application exploitation and be worth.
Embodiment
Embodiment 1
The citric acid of preparation pH=2.0-disodium hydrogen phosphate buffer solution 10mL, take 0.1mmol DBSA and be dissolved in above-mentioned buffered soln; After magnetic agitation, add aniline monomer 0.1mmol; Take the bovine hemoglobin (Hb) of 1mg with after 100 μ l distilled waters dissolvings, adding in system; The superoxol 1mL that by concentration is again 120mmol/L is added dropwise in reaction system.Stirring reaction adds isopyknic acetone to carry out breakdown of emulsion, termination reaction after 48 hours.After product precipitation, carry out centrifugal collection, dry after electrically conductive polyaniline the analysis yield be 126.9%.
Embodiment 2
The citric acid of preparation pH=2.0-disodium hydrogen phosphate buffer solution 10mL, take 0.3mmol DBSA and be dissolved in above-mentioned buffered soln, after magnetic agitation, adds aniline monomer 0.2mmol.Take the bovine hemoglobin (Hb) of 1mg with after 100 μ l distilled waters dissolvings, adding in system.The superoxol 1mL that is 140mmol/L by concentration is added dropwise in reaction system.Stirring reaction adds isopyknic acetone to carry out breakdown of emulsion, termination reaction after 8 hours.After product precipitation, carry out centrifugal collection, dry after electrically conductive polyaniline the analysis yield be 45.7%.
Embodiment 3
The citric acid of preparation pH=2.5-disodium hydrogen phosphate buffer solution 10mL, take DBSA0.3mmol and be dissolved in above-mentioned buffered soln, after magnetic agitation, adds aniline monomer 0.15mmol.Take the bovine hemoglobin (Hb) of 2mg with after 100 μ l distilled waters dissolvings, adding in system.The superoxol 1mL that is 120mmol/L by concentration is added dropwise in reaction system.Stirring reaction adds isopyknic acetone to carry out breakdown of emulsion, termination reaction after 48 hours.After product precipitation, carry out centrifugal collection, dry after electrically conductive polyaniline the analysis yield be 77.4%.
Embodiment 4
The citric acid of preparation pH=3-disodium hydrogen phosphate buffer solution 10mL, take DBSA0.2mmol and be dissolved in above-mentioned buffered soln, after magnetic agitation, adds aniline monomer 0.15mmol.Take the bovine hemoglobin (Hb) of 1mg with after 100 μ l distilled waters dissolvings, adding in system.The superoxol 1mL that is 160mmol/L by concentration is added dropwise in reaction system.Stirring reaction adds isopyknic acetone to carry out breakdown of emulsion, termination reaction after 48 hours.After product precipitation, carry out centrifugal collection, dry after electrically conductive polyaniline the analysis yield be 49.3%.
Embodiment 5
The citric acid of preparation pH=1-disodium hydrogen phosphate buffer solution 10mL, take DBSA0.1mmol and be dissolved in above-mentioned buffered soln, after magnetic agitation, adds aniline monomer 0.2mmol.Take the bovine hemoglobin (Hb) of 10mg with after 100 μ l distilled waters dissolvings, adding in system.The superoxol 1mL that is 200mmol/L by concentration is added dropwise in reaction system.Stirring reaction adds isopyknic acetone to carry out breakdown of emulsion, termination reaction after 24 hours.After product precipitation, carry out centrifugal collection, dry after electrically conductive polyaniline the analysis yield be 81.7%.
Above said content is the basic explanation under conceiving for the present invention only, and, according to any equivalent transformation that technical scheme of the present invention is done, all should belong to protection scope of the present invention.
Claims (1)
1. prepare the method for water-soluble conducting polyaniline, it is characterized in that, comprise the following steps:
(1) Witco 1298 Soft Acid is dissolved in damping fluid, adds aniline monomer to stir; The pH value scope of described buffered soln is 1～3; The mol ratio of aniline and Witco 1298 Soft Acid is 1:0.1～10;
(2) add oxyphorase, the rear dropping superoxol that stirs, stirring reaction 8～48 hours;
The amount ratio of Witco 1298 Soft Acid, aniline, hydrogen peroxide and oxyphorase is 1mol:0.4～2.5mol:0.4～2mol:2～100g;
In reaction system, Witco 1298 Soft Acid concentration is 10～50mmol/L, and concentration of aniline is 5～30mmol/L, and hemoglobin concentration is 0.1～1g/L, and concentration of hydrogen peroxide is 10～20mmol/L;
Described buffered soln is citric acid-Sodium phosphate dibasic damping fluid, and described oxyphorase is bovine hemoglobin;
(3) breakdown of emulsion, get precipitation.
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| CN102786686B (en) * | 2012-08-24 | 2014-04-23 | 上海师范大学 | Method for preparing high-conductivity polyaniline by means of biological catalysis in reverse micelles |
| CN103292685B (en) * | 2013-06-09 | 2015-09-23 | 青岛大学 | A kind of preparation method of bending-type flexible and transparent strain transducer |
| CN103613756B (en) * | 2013-11-08 | 2016-07-06 | 上海师范大学 | A kind of protein induced method preparing chiral polyaniline |
| CN105561953A (en) * | 2016-01-29 | 2016-05-11 | 南京理工大学 | Compound adsorbent PANI-CMC and application thereof to dye wastewater treatment |
| CN105561952A (en) * | 2016-01-29 | 2016-05-11 | 南京理工大学 | Multifunctional material PANI-CMC-Fe3O4 and application of multifunctional material PANI-CMC-Fe3O4 to treatment of printing and dyeing wastewater |
| CN105622935B (en) * | 2016-03-30 | 2018-08-07 | 常州工程职业技术学院 | A kind of synthetic method of solubility substituted aniline polymer |
| CN107325282B (en) * | 2017-01-13 | 2019-04-16 | 北京林业大学 | A kind of material for promotion biomethanation performance in Anaerobic wastewater treatment |
| CN108384000B (en) * | 2018-03-10 | 2022-01-07 | 山东赫达股份有限公司 | Preparation method of water-soluble polyaniline with biocompatibility |
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