CN1733820A - Preparation method of composite acids doped with conductive polyaniline - Google Patents
Preparation method of composite acids doped with conductive polyaniline Download PDFInfo
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- CN1733820A CN1733820A CN 200510057245 CN200510057245A CN1733820A CN 1733820 A CN1733820 A CN 1733820A CN 200510057245 CN200510057245 CN 200510057245 CN 200510057245 A CN200510057245 A CN 200510057245A CN 1733820 A CN1733820 A CN 1733820A
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- electrically conductive
- composite
- conductive polyaniline
- acids doped
- composite acids
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Abstract
The preparation method for conductive polyaniline with doped-composite acid is characterized in that, adding the aniline monomer, dopant, solvent, oxidant, and acidic solution into reactor to mix rapidly and form emulsion; controlling strictly the reaction condition; then, adding demulsifying agent, clearing, filtering, baking, and grinding to solid powder; adjusting the composite proportion between sulfosalicylic acid and type of other assist doped acid to control effectively the conductivity. This product can be used in antistatic material, EM shielding material and electronic element package.
Description
Technical field
The present invention relates to a kind of composite acids doped method for preparing electrically conductive polyaniline.
Background technology
In recent years, with development of electronic technology, developed the electronic material of many novelties.Particularly, obtained the technological innovation of attracting attention relating to high-performance organic materials field.Even only aspect electro-conductive material, oneself develops by some mineral acids or macromole function protonic acid as doping agent, the conducting polymer materials that the mode of mix electron conjugated polymkeric substance such as polyacetylene, Polythiophene, polypyrrole and polyaniline etc. makes.And polyaniline is the conducting polymer that has practicability to wish most.It has excellent chemical property and chemical stability, unique doping and dedoping mechanism, and raw materials for production are easy to get, simple synthetic method, at the energy, opto-electronic device, information, transmitter, molecular wire and molecular device, and extensive, tempting application prospect is all arranged on electromagnetic shielding, anti-corrosion of metal and the stealthy technique, caused people's extensive concern.
Polyaniline is because conjugated backbone structure and the indissoluble infusibility has limited its practical application at some special occasions improves the workability of polyaniline, and particularly solubility just seems extremely important.The selection of doping agent and doping way is to influence polyaniline conductivity and deliquescent important factor, therefore is one of hot fields of polyaniline research.
Chinese patent CN1583830A, a kind of method of utilizing the direct synthesized polyaniline solution of aniline monomer is disclosed, use Witco 1298 Soft Acid, dinonyl naphthalene sulfuric acid, dodecyl sulphate, dodecyl sodium sulfonate, stearic acid, oleic acid or their sodium salt, sylvite as doping agent, described solution comprises organic solvent and doped polyaniline, and prepared is polyaniline solutions but not emulsion.
Chinese patent CN1294154A, a kind of electrically conductive aqueous latex of polyphnenylamine is disclosed, its doping agent is selected from Witco 1298 Soft Acid, dinonyl naphthalene sulfuric acid, dodecyl sulphate, dodecyl sodium sulfonate, stearic acid, oleic acid or their sodium salt, sylvite equally, described latex comprises water, doped polyaniline and polymer and disperses auxiliary agent, has obtained a kind of polyaniline latex with highly stable water.
What above patent was all used in actual mechanical process is that single doping agent mixes to aniline monomer, make doping agent and use such as organic acids such as Witco 1298 Soft Acids, all to use the preparation of emulsion splitter p-poly-phenyl amine to make subsequent disposal, make subsequent technique become complicated.
The specific conductivity of polyaniline in eigenstate is very low, is electrical insulating property.After with protonic acid p-poly-phenyl amino-group doping, specific conductivity can reach 5～10S/cm, can realize the transformation from the isolator to the conductor, is the effective way of giving polyaniline conductivity.The fusing point and the boiling point of organic macromolecule sulfonic acid are higher, are better than mineral acid aspect environmental stability, and it had both contained non-polar group, polar functionalities again, and not only specific conductivity is higher to make doped polyaniline, and the solvability in solvent improves.
Chinese patent CN1325382A disclose a kind of with Phenylsulfonic acid and derivative thereof as dopant acid, prepare the method for electrically conductive polyaniline, its dopant acid molecule is described as having following constitutional features:
The doping agent that can be used as electron conjugated polymkeric substance, and, have high conductivity and good thermotolerance with the conducting polymer materials that this compound doped conjugated polymers is made, can be used as the electro-conductive material of the negative electrode in the solid electrolytic capacitor.But this dopant acid complicated process of preparation, and cost is higher.
Summary of the invention
The purpose of this invention is to provide the method that a kind of cost is low, technology simple, conductivity prepares electrically conductive polyaniline preferably.
Technical scheme of the present invention is to adopt a kind of composite acids doped preparation electrically conductive polyaniline, and provide a kind of novel doping agent, described doping agent is made up of main doping agent and auxiliary dopant, the maximum characteristics of this doping agent are that main doping agent selects sulphosalicylic acid (SSA) for use, and its molecule has following constitutional features:
The step of composite acids doped preparation electrically conductive polyaniline is as follows:
1) takes by weighing a certain amount of doping agent and dissolve in the distilled water, pour reaction unit into and be stirred to dissolving fully;
2) slowly drip aniline monomer, the mass ratio of aniline monomer and doping agent is 1: 4, high-speed stirring;
3) stir 30min after, slowly drip assistant for emulsifying agent, become transparent or semitransparent and have blue light to glow up to whole emulsion system, the generation that indicate microemulsion this moment;
4) drip the oxidizing agent solution that has prepared, the mol ratio of its oxygenant consumption and aniline monomer is 1: 1, and the dropping time is 30min;
5) at a certain temperature, reacted ten hours, solution need not breakdown of emulsion, and directly suction filtration places the polyaniline filter cake in the baking oven, in 50～60 ℃ of bakings 24 hours, grind into powder.
Also can cancellation step 3 in the above-mentioned steps), promptly prepare electrically conductive polyaniline with emulsion method.
Above-mentioned steps 2) relate to a kind of aniline monomer in and have following molecular formula:
In the formula, R
1, R
2, R
3R
4, R
5Be respectively-H ,-CH
3,-N0
2,-F ,-Cl ,-OCH
3,-G
2H
5,-Br and/or-I.
Above-mentioned steps 1) relate to a kind of composite mixed dose in, doping agent is divided into main doping agent and auxiliary dopant.Main doping agent is that sulphosalicylic acid (SSA) has following molecular formula:
Content is 70～100% in doping agent.Auxiliary dopant is Sodium dodecylbenzene sulfonate (SDBS).
Above-mentioned steps 3) relate to a kind of assistant for emulsifying agent in, this assistant for emulsifying agent is a propyl carbinol.
Above-mentioned steps 4) relate to a kind of oxygenant in, this oxygenant is an ammonium persulphate.
Above-mentioned steps 5) relating to temperature of reaction is 0～60 ℃.
The size of polyaniline specific conductivity and doping agent, solvent, oxygenant and acidic solution all have relation, but wherein doping agent plays decisive influence for the specific conductivity of polyaniline, so by the proportioning that changes dopant species, dopant component content, doping agent and aniline monomer is the specific conductivity size of may command polyaniline, this be characteristics of the present invention it.
Polyaniline emulsion provided by the invention and powder can be applicable to aspects such as antistatic material, electromagnetic shielding material, sensitive components, smart window, secondary cell, stealth material and anticorrosion material, microelectronics packing and electronic package material.
Embodiment
Below in conjunction with embodiment the present invention is further described, the specific conductivity among the following embodiment is to adopt the four point probe method to record.
Embodiment 1
Take by weighing the 8g sulphosalicylic acid with beaker and dissolve in the 100ml distilled water, be stirred to dissolving fully.Solution is poured in the 250ml three-necked bottle, slowly dripped 2g aniline, high-speed stirring.Drip the ammonium peroxide solution that has prepared after stirring 30min, the dropping time is 30min.Under 15 ℃, reacted ten hours, suction filtration places the polyaniline filter cake in the baking oven, and baking is 24 hours in about 50 ℃, grind into powder.Recording this polyaniline powder specific conductivity with four electrode conductance rate instrument is 11S/cm.
Embodiment 2
Keep doping agent and aniline monomer mass ratio constant, changing dopant component is sulphosalicylic acid and Sodium dodecylbenzene sulfonate codoped, and changing sulphosalicylic acid component in compound doping agent is 87.5%, and other condition is identical with embodiment 1.Recording this polyaniline powder specific conductivity is 8.3S/cm.
Embodiment 3
Take by weighing the 5.6g sulphosalicylic acid and the 2.4g Sodium dodecylbenzene sulfonate dissolves in the 100ml distilled water with beaker, be stirred to dissolving fully.Solution is poured in the 250ml three-necked bottle, slowly dripped 2g aniline, high-speed stirring.Slowly dripping butanol solution to whole emulsion system after 30 minutes becomes transparent.Drip the ammonium peroxide solution that has prepared then, the dropping time is 30min.Under 15 ℃, reacted ten hours, suction filtration places the polyaniline filter cake in the baking oven, and baking is 24 hours in about 50 ℃, grind into powder.Recording this polyaniline powder specific conductivity is 5.8S/cm.
Embodiment 4,5
Change temperature of reaction and be respectively 0 ℃ and 60 ℃, other condition is identical with embodiment 1.Record this polyaniline powder specific conductivity and be respectively 9S/cm and 9.7S/cm.
Comparative Examples
The commodity polyaniline of selling in the market by the production of Changchun applied chemistry institute is tested its specific conductivity with identical method, and compare, the results are shown in Table 1 with the specific conductivity that adopts the prepared sample of the inventive method
Table 1
| Embodiment 12345 Comparative Examples |
| Specific conductivity 11 8.3 5.8 9 9.7 0.4 (Scm -1) |
By above embodiment and table 1 as can be seen, adopt that the composite acids doped method for preparing electrically conductive polyaniline described in the invention not only is easy to produce, subsequent disposal is simple, and and in the market commodity polyaniline compare, aspect electroconductibility, increase significantly.
Claims (7)
1, a kind of composite acids doped method for preparing electrically conductive polyaniline is characterized in that step is as follows:
1) takes by weighing a certain amount of composite acids doped dose and dissolve in the distilled water, pour reaction unit into and be stirred to dissolving fully;
2) slowly drip aniline monomer, the mass ratio of aniline monomer and doping agent is 1: 4, high-speed stirring;
3) stir 30min after, slowly drip assistant for emulsifying agent, become transparent or semitransparent and have blue light to glow up to whole emulsion system, the generation that indicate microemulsion this moment;
4) drip the oxidizing agent solution that has prepared, the mol ratio of its oxygenant consumption and aniline monomer is 1: 1, and the dropping time is 30min;
5) at a certain temperature, reacted ten hours, solution need not breakdown of emulsion, and directly suction filtration places the polyaniline filter cake in the baking oven, in 50～60 ℃ of bakings 24 hours, grind into powder.
2, the composite acids doped method for preparing electrically conductive polyaniline according to claim 1 is characterized in that step 2) in aniline monomer have following molecular formula:
In the formula, R1, R2, R3, R4, R5 be respectively-H ,-CH
3,-NO
2,-F ,-Cl ,-OCH
3,-C
2H
5,-Br and/or-I.
3, the composite acids doped method for preparing electrically conductive polyaniline according to claim 1, it is characterized in that described in the step 1) that composite acids doped dose also is emulsifying agent, wherein composite acids doped dose is divided into main doping agent and auxiliary dopant, and main doping agent is sulphosalicylic acid (SSA), and its molecular formula is as follows:
Main doping agent content in composite acids doped dose is 70～100%, and auxiliary dopant is Sodium dodecylbenzene sulfonate (SDBS), and content is 0～30% in doping agent.
4, the composite acids doped method for preparing electrically conductive polyaniline according to claim 1 is characterized in that assistant for emulsifying agent described in the step 3) is a propyl carbinol.
5, the composite acids doped method for preparing electrically conductive polyaniline according to claim 1 is characterized in that oxygenant described in the step 4) is an ammonium persulphate.
6, the composite acids doped method for preparing electrically conductive polyaniline according to claim 1 is characterized in that temperature of reaction is 0～60 ℃ in the step 5).
7, the composite acids doped method for preparing electrically conductive polyaniline according to claim 1 is characterized in that cancellation step 3), promptly adopt emulsion method to prepare electrically conductive polyaniline.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2005100572459A CN100487023C (en) | 2005-08-26 | 2005-08-26 | Preparation method of composite acids doped with conductive polyaniline |
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|---|---|---|---|
| CNB2005100572459A CN100487023C (en) | 2005-08-26 | 2005-08-26 | Preparation method of composite acids doped with conductive polyaniline |
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|---|---|
| CN1733820A true CN1733820A (en) | 2006-02-15 |
| CN100487023C CN100487023C (en) | 2009-05-13 |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102276830A (en) * | 2011-07-05 | 2011-12-14 | 绍兴贝斯美化工有限公司 | Preparation of doped poly(2,3-dimethylaniline) and application in anticorrosive coating thereof |
| CN102391644A (en) * | 2011-09-08 | 2012-03-28 | 北京化工大学 | Preparation method of polyimide antistatic material |
| CN102702516A (en) * | 2012-05-28 | 2012-10-03 | 东华大学 | Method for preparing polyaniline through multielement doping |
| CN103172875A (en) * | 2013-04-18 | 2013-06-26 | 哈尔滨工业大学 | Preparation method of doped polyaniline nano particles |
| CN105949459A (en) * | 2016-05-19 | 2016-09-21 | 合肥师范学院 | Meshed polyaniline nanosheet and preparation method thereof |
| CN106835707A (en) * | 2017-01-11 | 2017-06-13 | 东莞市佳乾新材料科技有限公司 | A kind of stainless steel fibre based on bamboo fibre doped polyaniline and preparation method thereof |
| CN109216564A (en) * | 2018-07-25 | 2019-01-15 | 安徽理工大学 | A kind of polyaniline photosensor chip and preparation method thereof |
| CN113522037A (en) * | 2021-07-21 | 2021-10-22 | 江苏盈天化学有限公司 | Preparation method of pervaporation tetrahydrofuran dehydration composite membrane |
-
2005
- 2005-08-26 CN CNB2005100572459A patent/CN100487023C/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102276830A (en) * | 2011-07-05 | 2011-12-14 | 绍兴贝斯美化工有限公司 | Preparation of doped poly(2,3-dimethylaniline) and application in anticorrosive coating thereof |
| CN102391644A (en) * | 2011-09-08 | 2012-03-28 | 北京化工大学 | Preparation method of polyimide antistatic material |
| CN102391644B (en) * | 2011-09-08 | 2013-01-23 | 北京化工大学 | Preparation method of polyimide antistatic material |
| CN102702516A (en) * | 2012-05-28 | 2012-10-03 | 东华大学 | Method for preparing polyaniline through multielement doping |
| CN102702516B (en) * | 2012-05-28 | 2014-02-26 | 东华大学 | Method for preparing polyaniline through multielement doping |
| CN103172875A (en) * | 2013-04-18 | 2013-06-26 | 哈尔滨工业大学 | Preparation method of doped polyaniline nano particles |
| CN103172875B (en) * | 2013-04-18 | 2014-12-03 | 哈尔滨工业大学 | Preparation method of doped polyaniline nano particles |
| CN105949459A (en) * | 2016-05-19 | 2016-09-21 | 合肥师范学院 | Meshed polyaniline nanosheet and preparation method thereof |
| CN105949459B (en) * | 2016-05-19 | 2019-02-19 | 合肥师范学院 | A kind of netted polyaniline nano piece and preparation method thereof |
| CN106835707A (en) * | 2017-01-11 | 2017-06-13 | 东莞市佳乾新材料科技有限公司 | A kind of stainless steel fibre based on bamboo fibre doped polyaniline and preparation method thereof |
| CN109216564A (en) * | 2018-07-25 | 2019-01-15 | 安徽理工大学 | A kind of polyaniline photosensor chip and preparation method thereof |
| CN113522037A (en) * | 2021-07-21 | 2021-10-22 | 江苏盈天化学有限公司 | Preparation method of pervaporation tetrahydrofuran dehydration composite membrane |
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|---|---|
| CN100487023C (en) | 2009-05-13 |
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