CN1631939A - Process for preparing doped conductive polyaniline - Google Patents
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- CN1631939A CN1631939A CN 200410061063 CN200410061063A CN1631939A CN 1631939 A CN1631939 A CN 1631939A CN 200410061063 CN200410061063 CN 200410061063 CN 200410061063 A CN200410061063 A CN 200410061063A CN 1631939 A CN1631939 A CN 1631939A
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Abstract
The keypoint of synthesizing mixed conducting polyanion by chemical oxidation is the separation of oxidant remained and polyanion. The invention uses 4 as catalyzer and hydrogen peroxide as oxidant, in water system or water phase/organic phase system, prepares the mixed conducting polyanion dirctly. When the reaction is finished, use iodide as breakingdown catalyzer of the remained hydrogen peroxide, then clear away water and substance of low molecular by azeotropic distillation method method, acquiring the product. The invention is benefit for the development of large-scaled-industrialized production and safety and azeotropic distillation method the environment.
Description
Technical Field
The invention relates to a preparation method of doped conductive polyaniline.
Background
The conductive polyaniline can be prepared by electrochemical oxidation or chemical oxidation in an acidic aqueous or organic solvent. The chemical oxidation method is particularly important because it is easy for large-scale industrial production. Typical oxidizing agents used in chemical oxidation processes are persulfates, periodates, perchlorates, chromates and dichromate permanganates, organic peroxides and hydroperoxides, such as ammonium persulfate, potassium dichromate, benzoyl peroxide and hydrogen peroxide (U.S. patent: RE37, 370). The effect of aniline polymerization on product conductivity and yield was investigated by Pron et al using different oxidants and different aniline/oxidant ratios (a. Pron, f. genend, c. mernardo, m. nichtschein, synth. metals, 24(1988)193) and it was believed that the type of oxidant does not have a significant effect on aniline polymerization in aqueous systems and that most oxidants give similar reaction results.
Therefore, in view of the serious environmental pollution caused by heavy metal ions of chromium and manganese and the danger of using organic peroxides, ammonium persulfate is mostly used in the preparation of polyaniline by the chemical oxidation method (s.p. arms, j.f. miller, synth. metals, 22(1988) 385). However, when a doped polyaniline is produced using an inorganic acid such as hydrochloric acid or sulfuric acid or an organic acid such as alkylbenzenesulfonic acid, it is difficult to separate ammonium persulfate and its decomposition product ammonium sulfate remaining in the reaction system from the particulate polyaniline by a common filtration method, and it is difficult to obtain a purified polyaniline.
The inherent conductivity of doped polyaniline is affected by the content of various inorganic and organic electrolytes often mixed in polyaniline and polyaniline composites, and the free electrolytes are easy to run off from the surface of the polyaniline or the polyaniline composites, so that the conductivity of the material is greatly reduced.
Hydrogen peroxide is the most suitable oxidizing agent in view of economy, safety, environmental compatibility, and the like of polyaniline synthesis. Compared with organic peroxide, an industrial aqueous hydrogen peroxide solution with a concentration of about 30% does not have a risk of explosive explosion, and only water is generated as a by-product of hydrogen peroxide, so that the purified polyaniline can be obtained by removing only water or an organic solvent in an aqueous system or an aqueous/organic 2-phase system.
However, hydrogen peroxide has a weak oxidizing ability at low or room temperature. Thus, D.K. moon et al used H2O2/FeSO4/H2SO4Systems (D.K. moon, K.Osakata, T.Maruyama, T.Yamamoto, Makromol.chem., 193(1992)1723), Z.Sun et al used H2O2/FeCl2the/HCl system (z.su, y.geng, j.li,x.king, f.wang, synth. metals, 84(1997)99) directly synthesized doped polyaniline in aqueous systems. But even under laboratory conditions, in hydrogen peroxideAddition of catalytic amounts of Fe2+Ions are also easy to cause severe decomposition of hydrogen peroxide, so that the yield of polyaniline is reduced, and industrial production is difficult to realize.
Disclosure of Invention
The invention aims to provide a manufacturing technology for directly synthesizing doped conductive polyaniline by using a chemical oxidation method. The key of the industrial manufacturing technology for directly synthesizing doped conductive polyaniline by a chemical oxidation method is the separation of residual oxidant and decomposition products thereof from particulate polyaniline.
The invention successfully solves the problem in the aspects of economy, safety and environmental harmony, namely: a process for preparing doped electrically conductive polyaniline directly from tungstic peroxide as homogeneous catalyst and hydrogen peroxide as oxidant in aqueous or aqueous/organic phase 2-phase system. In the method for preparing doped conductive polyaniline of the invention, after the reaction of polyaniline generation is finished, iodide such as iodine, iodic acid and potassium iodide is used as a decomposition catalyst of hydrogen peroxide to remove residual hydrogen peroxide in a reaction system. A method for purifying doped conductive polyaniline, which comprises decomposing residual hydrogen peroxide in a reaction system, and then removing water and low-molecular substances in the reaction system by azeotropic distillation with water/organic solvent.
The following is a detailed description of the present invention.
1. Preparation of tungstic acid peroxide
Wang Qianghui et al have synthesized stable 2, 2, 6, 6-tetramethylpiperidine nitroxide free radical compounds (open/jar 2001-19674 and open/jar 2003-55347) using tungstic acid peroxide as a homogeneous catalyst and hydrogen peroxide as an oxidant. The invention successfully prepares the doped conductive polyaniline by using the method under mild and smooth reaction conditions.
The powdered tungstic acid is not dissolved in water and low-concentration hydrogen peroxide (generally less than 10 wt%), but the tungstic acid peroxide dissolved in water and low-concentration hydrogen peroxide aqueous solution can be generated only by selecting proper reaction temperature and reacting the tungstic acid with the amount of the catalyst and the hydrogen peroxide aqueous solution with the concentration of 10-70 wt%. Therefore, compared with a heterogeneous catalyst of tungstic acid powder, tungstic peroxide used as a homogeneous catalyst can greatly increase the oxidation capacity of hydrogen peroxide in the process of synthesizing polyaniline.
The method for preparing the tungstic acid peroxide is very simple and convenient, namely, the tungstic acid powder is slowly added into hydrogen peroxide with the concentrationof 10-70 wt% under stirring, and the hydrogen peroxide aqueous solution containing the tungstic acid peroxide can be generated by continuous stirring. It is believed that the reaction of tungstic acid peroxide formation is shown in formula (1):
the temperature for preparing the tungstic acid peroxide is generally in the range of 0-50 ℃. When the temperature is lower than 0 ℃, the tungstic acid can not be fully converted into the tungstic peroxide, and when the temperature is higher than 50 ℃, the hydrogen peroxide is easily decomposed, which is not beneficial to the generation of the tungstic peroxide. The time required for generating the tungstic acid peroxide is different according to different reaction temperatures, and generally, the tungstic acid and the hydrogen peroxide are mixed and then react for about 5-40 min to generate a light yellow transparent liquid, and the reaction is visible to be finished. When the tungstic acid peroxide is prepared, the mol ratio of the tungstic acid to the hydrogen peroxide is generally more than 1: 5mol ratio calculated according to the active ingredients of the hydrogen peroxide, and if the tungstic acid peroxide reacts within the range of 1: 10-1000 mol ratio, the tungstic acid peroxide is more favorably generated. When the amount of hydrogen peroxide is less than this range, the tungstic acid is not sufficiently converted into tungstic peroxide, and when it is more than this range, the formation of tungstic peroxide is not substantially adversely affected. Generally, the tungstic peroxide generated does not need to be separated from aqueous hydrogen peroxide, and the aqueous hydrogen peroxide containing the tungstic peroxide can be directly added into a polyaniline generation reaction system.
2. Synthesis of doped polyaniline
The invention uses tungstic acid peroxide as homogeneous catalyst and hydrogen peroxide as oxidant to directly synthesize doped conductive polyaniline in water system or water phase/organic phase 2 phase system. When a doped conductive polyaniline is directly synthesized using an inorganic acid such as hydrochloric acid or sulfuric acid, the reaction is generally performed in an aqueous system, and when a doped conductive polyaniline is directly synthesized using an organic acid such as a long-chain alkylbenzenesulfonic acid, the polyaniline-forming reaction can be completed in an aqueous system or in an aqueous phase/organic phase 2 phase.
In the aqueous phase/organic phase 2 phase system, the organic phase is an organic substance substantially insoluble in water, and generally can be selected from organic solvents such as chloroform, carbon tetrachloride, benzene, toluene and xylene. The invention has the main characteristics that: after the reaction is finished, water, organic solvent and low molecular substances in the reaction system are removed by using an azeotropic distillation method, so that the aim of refining the doped conductive polyaniline is fulfilled. Therefore, it is preferable to select a nonpolar organic solvent such as benzene, toluene and xylene which can form an azeotrope with water. The reaction of the present invention is not particularly limited in comparison with the water/organic phase 2. In order to smoothly carry out the reaction, the ratio of the aqueous phase to the organic phase is generally 1: 1 to 4.
In the polyaniline generation reaction of the invention, the mol ratio of aniline to hydrogen peroxide is generally 1.0: 1.1-4.0, and the most suitable ratio is in the range of 1.0: 1.2-3.0. The amount of hydrogen peroxide used outside this range may decrease the yield of polyaniline or increase the cost of raw materials.
In the synthesis reaction of doped polyaniline,the ratio of aniline to tungstic peroxide is generally 1.0 (mol): 1.5(mmol) -5.0 (mmol), and when the addition amount of tungstic peroxide is less than this range, aniline cannot be fully converted into polyaniline even if the reaction is carried out for a long time, so that the yield is greatly reduced. When the amount is more than this range, the catalyst for producing polyaniline is not significant, and the cost of raw materials is increased.
The reaction temperature for synthesizing polyaniline is generally in the range of 5-40 ℃. When the reaction temperature is lower than 5 ℃, the reaction can be completed for a long time, and when the reaction temperature is higher than 40 ℃, byproducts are easily generated, and the conductivity of the polyaniline is reduced.
The reaction time is not particularly limited, the reaction time generally varies according to the addition amounts of tungstic acid peroxide and hydrogen peroxide and the reaction temperature, generally ranges from 12 hours to 24 hours, when the reaction system is turned into dark green or black, the reaction is considered to be nearly finished, and after sampling and filtering, the content of residual aniline in filtrate is measured by a gas chromatograph, so that the reaction rate of the aniline is determined.
3. Decomposition reaction of residual hydrogen peroxide
After the synthesis of the doped conductive polyaniline is finished, the residual hydrogen peroxide in the reaction system must be completely decomposed by using a catalyst. Otherwise, hydrogen peroxide remaining in the doped conductive polyaniline is easily decomposed to generate OH radicals according to formula (2) under the influence of the environment, thereby accelerating the aging of the organic polymer material.
In addition, if the residual hydrogen peroxide in the reaction system is not removed, explosion accidents are likely to occur when the polyaniline powder and the organic solvent are concentrated and dried.
The catalyst for decomposing hydrogen peroxide is generally a heavy metal oxide such as water-insoluble manganese dioxide, tweezers trioxide, or a heavy metal ion such as iron, cobalt, tweezers, or copper. However, the use of these heavy metal substances as a catalyst for decomposing residual hydrogen peroxide causes environmental pollution problems such as wastewater treatment. When residual hydrogen peroxide is decomposed by using alkaline substances such as sodium carbonate, the chemical structure of doped polyaniline is destroyed.
The present invention uses iodides such as iodine, iodic acid and potassium iodide as a catalyst for decomposing residual hydrogen peroxide. As shown in the formulas (3) and (4), potassium iodide is used as a redox catalyst to decompose residual hydrogen peroxide in a reaction system.
Under acidic condition, hydrogen peroxide reacts with potassium iodide to generate I2And I is2Self-regeneration of oxidation-reduction to IO3 -And 5I-，IO3 -And 5I-But also react with hydrogen peroxide until all hydrogen peroxide is consumed, and the generated iodine compound in the amount of the catalyst can be easily removed from the reaction system.
The usage amount of the catalyst for decomposing the residual hydrogen peroxide in thereaction system is 0.05-0.1 percent of the usage amount of the aniline.
Detailed description of the preferred embodiments
The present invention will be described in more detail below, but the scope of the claims of the present invention is not limited to the examples. Raw materials
1. Aniline
Analytical purity, Bodi chemical Co., Ltd, Tianjin
2. Hydrogen peroxide (30 wt%)
Analytical pure, Shanghai chemical reagents of Chinese medicine (group)
3. Tungstic acid
Analytical pure, Shanghai chemical reagent second factory of China
4. P-methyl benzene sulfonic acid
Chemical reagent factory for analytical purity, Shanghai high and new
5. Dodecyl benzene sulfonic acid
Industrial grade, Nanjing alkylbenzene works
6.2M hydrochloric acid aqueous solution (laboratory self-made)
7.2M aqueous sulfuric acid (laboratory self-prepared)
8. Potassium iodide
Analytical pure, Tianjin chemical reagent Co., Ltd
9. Toluene (technical grade)
Example 1:
adding 14g of hydrogen peroxide (30 percent) into a 50ml glass beaker, adding 45mg of tungstic acid into the glass beaker under magnetic stirring, heating the mixture to 40 ℃, reacting the tungstic acid with the hydrogen peroxide for 15min, dissolving the mixture into light yellow transparent liquid, and cooling the light yellow transparent liquid toroom temperature (18 ℃) for later use after the reaction is finished.
After 19g (0.1mol) of p-toluenesulfonic acid, 200ml of water, 9.3g (0.1mol) of aniline and the above-mentioned tungstic acid peroxide-hydrogen peroxide aqueous solution were charged into a 500ml 3-neck glass reaction flask equipped with a stirrer and a condenser, the reaction was stirred at 18 ℃ for 16 hours, and when the reaction system became dark green, the reaction was completed. Adding 50mg potassium iodide, and heating at 70 deg.C for 30min to remove residual hydrogen peroxide. And confirming that the content of the hydrogen peroxide in the system is less than 10ppm by using a hydrogen peroxide detection test paper.
80ml of toluene was added to the reaction system, and after removing water by azeotropic distillation at a temperature of 90 to 120 ℃, the mixture was dried under reduced pressure at 85 ℃ for 8 hours to obtain doped conductive polyaniline fine particles-1 of example 1.
Example 2:
after 33g (0.1mol) of p-dodecylbenzenesulfonic acid, 100ml of water, 100ml of toluene, 9.3g (0.1mol) of aniline and the aqueous solution containing tungstic acid peroxide and hydrogen peroxide described in example 1 were charged into a 500ml 3-neck glass reaction flask equipped with a stirrer and a condenser, the reaction was stirred at 18 ℃ for 16 hours, and the reaction system was blackish green. 93mg of potassium iodide was added and the mixture was heated at 70 ℃ for 30min to remove residual hydrogen peroxide. And confirming that the content of the hydrogen peroxide in the system is less than 10ppm by using a hydrogen peroxide detection test paper.
The reaction system was subjected to azeotropic distillation at a temperature of 90 to 120 ℃ to remove water, and then dried under reduced pressure at 85 ℃ for 8 hours to obtain doped conductive polyaniline fine particles-2 of example 2.
Example 3:
by the preparation method described in example 1, 19g of toluenesulfonic acid was replaced with 50ml of 2M hydrochloric acid, and doped conductive polyaniline fine particle-3 of example 3 was obtained.
Example 4:
by the preparation method described in example 1, 19g of toluenesulfonic acid was replaced with 50ml of 2M sulfuric acid, and doped conductive polyaniline fine particles-4 of example 4 were obtained.
Example 5:
using the preparation method described in example 1, the addition amount of tungstic acid was reduced from 45mg to 37.5g and the polyaniline-forming reaction time was prolonged to 24 hours in the preparation of tungstic peroxide, to obtain doped conductive polyaniline fine particles-5 of example 5.
Example 6:
when tungstic acid peroxide was prepared by the method described in example 2, the amount of hydrogen peroxide was increased from 14g to 34g, and doped conductive polyaniline fine particles-6 of example 6 were obtained.
Comparative example 1:
19g (0.1mol) of p-toluenesulfonic acid, 200ml of water, 9.3g (0.1mol) of aniline, and an aqueous solution (30 wt%) of hydrogen peroxide were charged into a 500ml 3-neck glass reaction flask equipped with a stirrer and a condenser, and then stirred at 18 ℃ for 16 hours to complete the reaction. The aniline concentration in the reaction system was measured by gas chromatography, and it was confirmed that only 6 wt% of aniline was converted into polyaniline.
Comparative example 2:
19g (0.1mol) of p-toluenesulfonic acid, 200ml of water, 9.3g (0.1mol) of aniline, and an aqueous solution (30 wt%) of hydrogen peroxide were charged into a 500ml 3-neck glass reaction flask equipped with a stirrer and a condenser, and then stirred at 18 ℃ for 16 hours to complete the reaction. The aniline concentration in the reaction system was measured by gas chromatography, and it was confirmed that only 23 wt% of aniline was converted into polyaniline.
The reaction rate of aniline measured by gas chromatography and the conductivity measured by a four-probe conductivity meter are shown in Table 1.
Effects of the invention
The invention uses tungstic acid peroxide as homogeneous catalyst and hydrogen peroxide as oxidant of aniline, uses iodide as decomposition catalyst of residual hydrogen peroxide, and finally uses azeotropic distillation method to remove water and low molecular substance. The reaction rate of the aniline reaches more than 90 percent, and the conductivity of the obtained doped polyaniline is 10-2S/cm range.
Table 1.
| Example (b) | No. | Reaction Rate of Aniline (□) | Conductivity sigma (S/cm) |
| Examples | 1 | 94 | 5.8×10-2 |
| 2 | 93 | 4.2×10-2 | |
| 3 | 98 | 9.7×10-2 | |
| 4 | 96 | 8.5×10-2 | |
| 5 | 91 | 6.5×10-2 | |
| 6 | 100 | 7.1×10-2 | |
| Comparative example | 1 | 6 | Failure to measure |
| 2 | 23 | Failure to measure |
Claims (2)
1. A method for preparing doped conductive polyaniline is characterized in that tungstic peroxide is used as a homogeneous catalyst and hydrogen peroxide is used as an oxidant, and the doped conductive polyaniline is directly prepared in a water system or a water phase/organic phase 2 phase system; after the polyaniline generation reaction is finished, iodide such as iodine, iodic acid, potassium iodide and the like is used as a decomposition catalyst of hydrogen peroxide to remove residual hydrogen peroxide in a reaction system; after the residual hydrogen peroxide in the reaction system is decomposed, removing water and low molecular substances in the reaction system by using a water/organic solvent azeotropic distillation method, wherein the ratio of aniline to tungstic acid peroxide is generally 1.0(mol) to 1.5(mmol) to 5.0(mmol), the reaction temperature is 5-40 ℃, the reaction time is generally 12-24 hours, the reaction is considered to be nearly finished when the system is converted into dark green or black, and the usage amount of the catalyst for decomposing the residual hydrogen peroxide in the reaction system is more than 0.05-0.1 percent of the usage amount of aniline.
2. The method for producing a doped conductive polyaniline according to claim 1, wherein when a doped conductive polyaniline is directly synthesized using an inorganic acid such as hydrochloric acid or sulfuric acid, the reaction is generally performed in an aqueous system; when an organic acid such as a long-chain alkylbenzenesulfonic acid is used, the polyaniline-forming reaction can be completed in an aqueous system or in an aqueous/organic phase 2 phase, wherein: in the aqueous phase/organic phase 2 phase system, the organic phase is an organic substance which is substantially insoluble in water, and generally can be selected from organic solvents such as trichloromethane, carbon tetrachloride, benzene, toluene, xylene and the like, and the mol ratio of the aqueous phase/the organic phase is 1: 1-4.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100363445C (en) * | 2005-09-29 | 2008-01-23 | 武汉理工大学 | Phosphoric acid doped polyphenylamine phosphate priming paint and preparing process thereof |
| CN101376712B (en) * | 2008-09-12 | 2011-03-30 | 江苏工业学院 | Method for improving conductive heat stability of polyaniline/inorganic nano conductive composite material |
| CN112480858A (en) * | 2020-11-20 | 2021-03-12 | 山东北方现代化学工业有限公司 | High-strength conductive single-component silane modified polyurethane sealant with electromagnetic shielding performance and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1062877C (en) * | 1995-07-27 | 2001-03-07 | 中国科学院长春应用化学研究所 | Method for preparing soluble aniline and derivatives with various molecular wt. |
| CN1056165C (en) * | 1996-12-25 | 2000-09-06 | 中国科学院长春应用化学研究所 | Preparation of mixed polyaniline aqueous solution and dispersant liquid |
| US6630567B1 (en) * | 2002-03-13 | 2003-10-07 | Council Of Scientific And Industrial Research | Process for the preparation of polyaniline salt |
| CN1189502C (en) * | 2002-11-14 | 2005-02-16 | 华东理工大学 | Method for preparing fusible conductive polyaniline |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100363445C (en) * | 2005-09-29 | 2008-01-23 | 武汉理工大学 | Phosphoric acid doped polyphenylamine phosphate priming paint and preparing process thereof |
| CN101376712B (en) * | 2008-09-12 | 2011-03-30 | 江苏工业学院 | Method for improving conductive heat stability of polyaniline/inorganic nano conductive composite material |
| CN112480858A (en) * | 2020-11-20 | 2021-03-12 | 山东北方现代化学工业有限公司 | High-strength conductive single-component silane modified polyurethane sealant with electromagnetic shielding performance and preparation method thereof |
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