CN101265339A - Method for preparing formable conducting polyaniline composite material - Google Patents
Method for preparing formable conducting polyaniline composite material Download PDFInfo
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- CN101265339A CN101265339A CNA2007101884851A CN200710188485A CN101265339A CN 101265339 A CN101265339 A CN 101265339A CN A2007101884851 A CNA2007101884851 A CN A2007101884851A CN 200710188485 A CN200710188485 A CN 200710188485A CN 101265339 A CN101265339 A CN 101265339A
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- mmt
- ctab
- aniline
- formable
- polyaniline composite
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Abstract
The invention provides a method for preparing a moulded conductive polyaniline composite material. The method is characterized in that in the water solution system of sulfamic acid, PE, as a base material, initiates polymerization of aniline monomers between organic soil CTAB2-Ni1-MMT layers of a two-step intercalation layer so that a polymerisate PANI/CTAB2-Ni1-MMT uniformly deposit on the surface of the base material PE, thus forming a dense film and preparing the moulded conductive polyaniline composite material.
Description
Technical field
The present invention relates to the polyaniline composite material preparation method.
Background technology
In many conductive conjugated polymers, polyaniline is cheap and easy to get because of its raw material, preparation is simple and convenient, excellent chemical property and chemical stability are considered to the conductive polymers that is hopeful to be applied in practice most, thereby become the research focus.Yet,, limited its widespread use technically because electrically conductive polyaniline is insoluble not molten.At present only realized limited application in minority fields such as antistatic, battery shielding and secondary cells.Become this urgent, the most attracting research direction in field with the applied basic research that is applied as target.Can prepare soluble conductive polyaniline mixture by the function protonic acid doping, improve the solubility and the processibility of electrically conductive polyaniline, obtain composite polyphenylene amine electro-conductive material with general polymer material recombination energy.This class composite polyphenylene amine electro-conductive material has that electroconductibility is adjustable on a large scale, mechanical property better, easily machine-shaping and can be made into characteristics such as transparent material, thereby caused that various countries' researcher competitively studies.
Preparation polyaniline/polymeric thing electro-conductive material mainly contains solution blended process, mechanical melt-blending process, emulsion dispersion and " scene " adsorpting polymerization method at present, wherein " scene " adsorpting polymerization method is that base materials such as fiber, textiles, plastics are immersed in the acidic aqueous solution mixture of the ammonium persulphate of new preparation and aniline, make aniline oxidative polymerization take place on the surface of base material, polyaniline equably " deposition " at substrate surface, form good dense film, to make electro-conductive material.
Thionamic acid is a kind of industrial chemicals, is inorganic solid acid (NH
2SO
3H), the rhombic system plate crystal, colourless, odorless, soluble in water, and stability is very high, non-volatile, and fusing point is about 205 ℃, and decomposition temperature is 209 ℃, can decompose fully to generate SO under 260 ℃
2, SO
3, N
2With products such as water, very low to metal protection.Thionamic acid is a kind of middle strong acid, ionization fully in water.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of formable conducting polyaniline composite material,
The present invention is a base material with PE under the thionamic acid water solution system, causes the organophilic clay CTAB of aniline monomer at secondary intercalation
2-Ni
1The polymerization of-MMT interlayer makes polymerisate PANI/CTAB
2-Ni
1-MMT is deposited on base material PE surface equably, forms dense film, makes formable conducting polyaniline composite material.
The present invention adopts " scene " adsorpting polymerization method, a kind of thionamic acid doped conductive polyaniline PANI/CTAB that obtains
2-Ni
1-MMT/PE matrix material, has good chemical stability, electroconductibility is adjustable on a large scale, mechanical property better, easily machine-shaping and can be made into transparent material, and simple synthetic method, raw material sources are extensive, cheap, can take into account performances such as mechanics, electricity, optics, demonstrate the advantage of many uniquenesses, have than application prospects in fields such as antistatic, electromagnetic shielding, electrode materials and antifouling protective systems.
CTAB is the english abbreviation of cetyl trimethylammonium bromide, and PANI is the english abbreviation of polyaniline, and the poly english abbreviation of PE, MMT are the english abbreviations of polynite, and Na-MMT is the sodium polynite.
Embodiment
The present invention is a kind of preparation method of formable conducting polyaniline composite material, under the thionamic acid water solution system, is base material with PE, causes the organophilic clay CTAB of aniline monomer at secondary intercalation
2-Ni
1The polymerization of-MMT interlayer makes polymerisate PANI/CTAB
2-Ni
1-MMT is deposited on base material PE surface equably, forms dense film, to make formable conducting polyaniline composite material.
Organophilic clay CTAB
2-Ni
1-MMT weight is PANI/CTAB
2-Ni
15～40% of-MMT, PANI/CTAB
2-Ni
1The weight of-MMT is PANI/CTAB
2-Ni
11～35% of-MMT/PE matrix material, the weight of PE are PANI/CTAB
2-Ni
135～99% of-MMT/PE matrix material.
Preparation method's of the present invention step is as follows:
(1) thionamic acid is dissolved in the distilled water, makes mass concentration and be 4～16% solution;
(2) in above-mentioned solution, add aniline monomer, organophilic clay CTAB
2-Ni
1-MMT, PE, wherein the weight ratio of aniline add-on and thionamic acid is 1: 50～1: 3, organophilic clay CTAB
2-Ni
1The weight of-MMT is 5～40% of aniline, the weight ratio of PE and aniline 50: 1～3: 1, stir, time remaining 6 hours, slowly drip the oxidized form initiator, the weight ratio of oxidized form initiator and aniline is 0.5: 1～3.5: 1, under 0～40 ℃ temperature, and high-speed stirring solution, carry out polymerization, time remaining 2～8 hours leaves standstill after the reaction, filters, wash with water 2～4 times, and use acetone drip washing, and dry under vacuum environment, obtain being uniformly coated with the particle of the formable conducting polyaniline composite material of blackish green powder.
Above-described oxidized form initiator is an ammonium persulphate, perhaps is potassium bichromate, perhaps is Potassium Iodate.
Be more specifically embodiment of the present invention below:
Embodiment 1
A certain amount of thionamic acid is dissolved in the distilled water, is made into mass concentration and is 4% solution; Add aniline then, organophilic clay CTAB
2-Ni
1-MMT, PE, wherein the weight ratio of the add-on of aniline and thionamic acid is 1: 50; The weight of organophilic clay is 5% of aniline; The weight ratio of PE and aniline is 50: 1, adds aniline, organophilic clay CTAB
2-Ni
1Behind-MMT, the PE, stir, form intercalation, time remaining 6 hours slowly drips the oxidized form initiator ammonium persulfate, and the weight ratio of ammonium persulphate and aniline is 1: 1; Under 0 ℃ temperature, high-speed stirring is carried out polymerization, time remaining 2 hours, leave standstill after the reaction, filter, wash with water 2～4 times, and use acetone drip washing, and dry under vacuum environment, obtain being uniformly coated with the particle of the formable conducting polyaniline composite material of blackish green powder.
Embodiment 2
A certain amount of thionamic acid is dissolved in the distilled water, is made into mass concentration and is 15% solution; Add aniline then, organophilic clay CTAB
2-Ni
1-MMT, PE, wherein the weight ratio of the add-on of aniline and thionamic acid is 1: 3; The weight of organophilic clay is 40% of aniline; The weight ratio of PE and aniline is 3: 1, adds aniline, organophilic clay CTAB
2-Ni
1Behind-MMT, the PE, stir, form intercalation, time remaining 6 hours slowly drips the oxidized form initiator ammonium persulfate, and the weight ratio of ammonium persulphate and aniline is 3.5: 1; Under 40 ℃ temperature, high-speed stirring is carried out polymerization, time remaining 8 hours; Leave standstill after the reaction, filter, wash 2～4 times with water, and use acetone drip washing, drying under vacuum environment obtains being uniformly coated with the particle of the formable conducting polyaniline composite material of blackish green powder.
Embodiment 3
A certain amount of thionamic acid is dissolved in the distilled water, is made into mass concentration and is 13% solution; Add aniline then, organophilic clay CTAB
2-Ni
1-MMT, PE, wherein the weight ratio of the add-on of aniline and thionamic acid is 1: 5; The weight of organophilic clay is 20% of aniline; The weight ratio of PE and aniline is 5: 1, adds aniline, organophilic clay CTAB
2-Ni
1Behind-MMT, the PE, stir, form intercalation, time remaining 6 hours slowly drips the oxidized form initiator ammonium persulfate, and the mass ratio of ammonium persulphate and aniline is 1.7: 1; Under 20 ℃ temperature, high-speed stirring is carried out polymerization, time remaining 6 hours; Leave standstill after the reaction, filter, wash 2～4 times with water, and use acetone drip washing, drying under vacuum environment obtains being uniformly coated with the particle of the formable conducting polyaniline composite material of blackish green powder.
Embodiment 4
A certain amount of thionamic acid is dissolved in the distilled water, is made into mass concentration and is 13% solution; Add aniline then, organophilic clay CTAB
2-Ni
1-MMT, PE, wherein the weight ratio of the add-on of aniline and thionamic acid is 1: 3; The weight of organophilic clay is 20% of aniline; The weight ratio of PE and aniline is 3: 1, adds aniline, organophilic clay CTAB
2-Ni
1Behind-MMT, the PE, stir, form intercalation, time remaining 6 hours slowly drips the oxidized form initiator ammonium persulfate, and the weight ratio of ammonium persulphate and aniline is 1.7: 1; Under 20 ℃ temperature, high-speed stirring is carried out polymerization, time remaining 6 hours; Leave standstill after the reaction, filter, wash 2～4 times with water, and use acetone drip washing, drying under vacuum environment obtains being uniformly coated with the particle of the formable conducting polyaniline composite material of blackish green powder.
Embodiment 5
A certain amount of thionamic acid is dissolved in the distilled water, is made into mass concentration and is 13% solution; Add aniline then, organophilic clay CTAB
2-Ni
1-MMT, PE, wherein the weight ratio of the add-on of aniline and thionamic acid is 1: 5; The weight of organophilic clay is 20% of aniline; The weight ratio of PE and aniline is 5: 1, adds aniline, organophilic clay CTAB
2-Ni
1Behind-MMT, the PE, stir, form intercalation, time remaining 6 hours slowly drips oxidized form initiator potassium bichromate, and the weight ratio of potassium bichromate and aniline is 1: 1; Under 20 ℃ temperature, high-speed stirring is carried out polymerization, time remaining 6 hours; Leave standstill after the reaction, filter, wash 2～4 times with water, and use acetone drip washing, drying under vacuum environment obtains being uniformly coated with the particle of the formable conducting polyaniline composite material of blackish green powder.
Embodiment 6
A certain amount of thionamic acid is dissolved in the distilled water, is made into mass concentration and is 13% solution; Add aniline then, organophilic clay CTAB
2-Ni
1-MMT, PE, wherein the weight ratio of the add-on of aniline and thionamic acid is 1: 5; The weight of organophilic clay is 20% of aniline; The weight ratio of PE and aniline is 5: 1, adds aniline, organophilic clay CTAB
2-Ni
1Behind-MMT, the PE, stir, form intercalation, time remaining 6 hours slowly drips oxidized form initiator Potassium Iodate, and the weight ratio of Potassium Iodate and aniline is 1: 1; Under 20 ℃ temperature, high-speed stirring is carried out polymerization, time remaining 6 hours; Leave standstill after the reaction, filter, wash 2～4 times with water, and use acetone drip washing, drying under vacuum environment obtains being uniformly coated with the particle of the formable conducting polyaniline composite material of blackish green powder.
Claims (4)
1, the preparation method of formable conducting polyaniline composite material is characterized in that under the thionamic acid water solution system, is base material with PE, causes the organophilic clay CTAB of aniline monomer at secondary intercalation
2-Ni
1The polymerization of-MMT interlayer makes polymerisate PANI/CTAB
2-Ni
1-MMT is deposited on base material PE surface equably, forms dense film, makes formable conducting polyaniline composite material.
2, the preparation method of formable conducting polyaniline composite material according to claim 1 is characterized in that organophilic clay CTAB
2-Ni
1-MMT weight is PANI/CTAB
2-Ni
15～40% of-MMT matrix material, PANI/CTAB
2-Ni
1The weight of-MMT is PANI/CTAB
2-Ni
11～35% of-MMT/PE matrix material, the weight of PE are PANI/CTAB
2-Ni
135～99% of-MMT/PE matrix material.
3, the preparation method of formable conducting polyaniline composite material according to claim 1, its preparation process is as follows:
(1) thionamic acid is dissolved in the distilled water, makes mass concentration and be 4～16% solution;
(2) in above-mentioned solution, add aniline monomer, organophilic clay CTAB
2-Ni
1-MMT, PE, wherein the weight ratio of aniline add-on and thionamic acid is 1: 50～1: 3, organophilic clay CTAB
2-Ni
1The weight of-MMT is 5～40% of aniline, and the mass ratio of PE and aniline 50: 1～3: 1 adds aniline monomer, organophilic clay CTAB
2-Ni
1Behind-MMT, the PE, stir time remaining 6 hours, slowly drip the oxidized form initiator, the weight ratio of oxidized form initiator and aniline is 0.5: 1～3.5: 1, under 0～40 ℃ temperature, high-speed stirring solution, carry out polymerization, time remaining 2～8 hours leaves standstill after the reaction, filter, wash with water 2～4 times, dry under vacuum environment, obtain being uniformly coated with the particle of the formable conducting polyaniline composite material of blackish green powder.
4, according to claim 1, or the preparation method of 3 described formable conducting polyaniline composite materials, it is characterized in that the oxidized form initiator is an ammonium persulphate, perhaps be potassium bichromate, perhaps be Potassium Iodate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007101884851A CN101265339A (en) | 2007-11-16 | 2007-11-16 | Method for preparing formable conducting polyaniline composite material |
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|---|---|---|---|
| CNA2007101884851A CN101265339A (en) | 2007-11-16 | 2007-11-16 | Method for preparing formable conducting polyaniline composite material |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107820382A (en) * | 2017-09-14 | 2018-03-20 | 天津工业大学 | A kind of method for preparing ultralight electromagnetic shielding composite material |
| CN112625591A (en) * | 2020-10-20 | 2021-04-09 | 兰州理工大学 | High-stability multifunctional conductive super-hydrophobic anticorrosive coating, preparation method and application |
| CN113750822A (en) * | 2021-09-28 | 2021-12-07 | 太原理工大学 | Preparation method and application of mixed matrix composite membrane based on polyaniline intercalation modified acid activated montmorillonite |
-
2007
- 2007-11-16 CN CNA2007101884851A patent/CN101265339A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107820382A (en) * | 2017-09-14 | 2018-03-20 | 天津工业大学 | A kind of method for preparing ultralight electromagnetic shielding composite material |
| CN112625591A (en) * | 2020-10-20 | 2021-04-09 | 兰州理工大学 | High-stability multifunctional conductive super-hydrophobic anticorrosive coating, preparation method and application |
| CN113750822A (en) * | 2021-09-28 | 2021-12-07 | 太原理工大学 | Preparation method and application of mixed matrix composite membrane based on polyaniline intercalation modified acid activated montmorillonite |
| CN113750822B (en) * | 2021-09-28 | 2023-06-30 | 太原理工大学 | Preparation method and application of mixed matrix composite membrane based on polyaniline intercalation modified acid-activated montmorillonite |
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Open date: 20080917 |