JP2008075039A - Preparation of electrically conductive polyaniline complex - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for preparing a polyaniline complex having high electrical conductivity in a short reaction time. <P>SOLUTION: The method for preparing a polyaniline complex comprises polymerizing aniline or an aniline derivative in a two-phase polymerization solvent composed of an organic solvent substantially immiscible with water and water or an aqueous solution in the presence of component (a): a compound having a sulfonic acid group and component (b): a surface active agent. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a method for producing a polyaniline complex that is soluble in an organic solvent and exhibits high conductivity, and a polyaniline composition.

Polyaniline is known as a conductive material that is thermally stable and stable even in air, and is expected to be applied to capacitors, batteries, sensors, electroluminescent materials, antistatic materials, and the like.
Polyaniline has a problem that in the state of emeraldine salt exhibiting conductivity, the solubility in a solvent is extremely low, and the workability in forming a film or sheet or forming a conductive film is very low. Thus, a method for stably and efficiently producing polyaniline having excellent conductivity and solubility has been sought.

As a method for solving both the problems of high conductivity and solubility, Non-Patent Document 1 discloses that dodecylbenzene sulfonic acid and dibutyl naphthalene sulfonic acid are present in a water-acetone mixed solvent to contain aniline. A method is described in which polyaniline soluble in chloroform, tetrahydrofuran and m-cresol is obtained by polymerization with ammonium sulfate.
However, the conductivity of the obtained polyaniline was as low as 1.8 S / cm. Further, there is no disclosure or suggestion about a combination of a surfactant having a sulfone group and another surfactant.

Non-Patent Document 2 discloses poly (ethylene glycol) -block poly (propylene glycol) -block (polyethylene glycol) as a nonionic surfactant in aniline dissolved in chloroform without using a protonic acid. A method is described in which a copolymer-containing aqueous solution-containing aqueous solution is added to make an emulsion, and an ammonium persulfate aqueous solution is dropped to obtain a polymer.
However, the obtained polyaniline was insoluble in the polymerization solvent, and the conductivity was as low as about 1.0 × 10 ⁻² S / cm. Moreover, there is no disclosure about adding a compound having a sulfone group to the polymerization reaction system.

Patent Document 1 discloses a complex (emeraldine salt) soluble in an organic solvent by adding a protonic acid having a sulfone group when aniline is polymerized in a two-layer system of an organic layer and an aqueous layer. A polyaniline composition is disclosed that exhibits high conductivity and excellent solubility by being prepared and further adding a compound having a phenolic hydroxyl group.
However, a long polymerization time is required to obtain a high conductivity, and the conductivity when the reaction time is shortened is not necessarily high. Furthermore, this document neither discloses nor suggests a method for polymerizing aniline using a protonic acid having a sulfone group and a surfactant in combination.

Further, Patent Document 2 discloses polyaniline exhibiting high conductivity. However, in order to obtain polyaniline exhibiting high conductivity, the polymerized polyaniline must be dedoped and then mixed with an acid again, and the production method has not been simple. Also in this document, there is no disclosure or suggestion about a polymerization method of aniline using a protonic acid having a sulfone group and a surfactant in combination.
International Publication No. 2005/052058 Pamphlet JP 2005-272840 A European Polymer Journal 36 (2000) 2201 Journal of Macromolecular Science, Part A: Pure and Applied Chemistry, 42: 891 (2005).

  In view of the above problems, an object of the present invention is to provide a method for producing a polyaniline complex having high conductivity in a short reaction time.

  In order to achieve the above object, as a result of intensive research conducted by the present inventors, a stable emulsified state can be obtained by adding a compound having a sulfone group and other surfactant during the polymerization of aniline. The present inventors have found that a polyaniline complex having high conductivity can be stably obtained in a short reaction time.

According to the present invention, the following method for producing a polyaniline complex and the like are provided.
1. An aniline or an aniline derivative is polymerized in the presence of the following components (a) and (b) in a two-phase polymerization solvent consisting of an organic solvent substantially immiscible with water and water or an aqueous solution. A method for producing a polyaniline complex.
(A) Compound having a sulfone group (b) Surfactant 2. The method for producing a polyaniline complex according to 1, wherein the surfactant (b) is a phosphoric acid anionic surfactant.
3. 2. The method for producing a polyaniline complex according to 1, wherein the (b) surfactant is a nonionic surfactant.
4). The method for producing a polyaniline complex according to any one of 1 to 3, wherein the compound (a) having a sulfone group is a sulfosuccinic acid derivative.
5. A polyaniline complex obtained by the production method according to any one of 1 to 4 and containing the surfactant (b).
6). 6. A polyaniline composition comprising the polyaniline complex according to 5 above and a compound having a phenolic hydroxyl group.
7). 7. A conductive molded body obtained from the polyaniline composition as described in 6 above.

  According to the present invention, a polyaniline complex having both high conductivity and good solubility can be stably produced in a short polymerization time.

In the method for producing the polyaniline complex of the present invention, the polymerization solvent is a two-phase system composed of an organic solvent that is substantially immiscible with water and water or an aqueous solution. Among them, the monomer aniline or aniline derivative is prepared. The polymerization is carried out in the presence of the following components (a) and (b).
(A) Compound having sulfone group (b) Surfactant

  In the production method of the present invention, (a) a sulfone group-containing compound and (b) a surfactant are used in combination, so that the reaction system forms a stable emulsion state and the reaction rate is improved.

(A) The sulfone group-containing compound has a function as a dopant in the polyaniline complex. The sulfone group-containing compound has a function of reducing the size of the droplet (organic layer) at the time of polymerization, but the size of the droplet cannot be sufficiently reduced only by this compound. Therefore, as a result, in order to obtain a polyaniline complex having a high conductivity, it is necessary to lengthen the polymerization time.
Therefore, in the present invention, by using the surfactant (b) in combination, the droplets are sufficiently small, and even when the polymerization time is shortened, a polyaniline complex having a high conductivity can be obtained.

  Examples of organic solvents that are substantially immiscible with water include hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, cumene, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, trichloroethane, tetrachloroethane, and the like. Listed are ester solvents such as halogen solvents and ethyl acetate. Toluene, xylene, and chloroform are preferable from the viewpoint of excellent solubility of the produced polyaniline complex.

As the aqueous solution, an acidic aqueous solution can be used.
The volume ratio of the polymerization solvent in the reaction system is preferably such that the amount of water or aqueous solution is larger than that of the organic solvent. This facilitates the removal of the polymerization reaction heat and reduces side reactions.

  As the aniline or aniline derivative which is a monomer, an aniline derivative which is unsubstituted or substituted with a methyl group, an ethyl group, a hexyl group, a methoxy group, an ethoxy group, a hexyloxy group or the like can be used. Unsubstituted aniline is preferred because it is readily available.

  (A) As a compound which has a sulfone group, alkylbenzenesulfonic acid, polyoxyethylene alkyl ether sulfate, naphthalenesulfonic acid formalin condensate, alkylsulfosuccinate, etc. are mentioned. Alkylsulfosuccinate is preferable.

Preferred examples of the sulfone group-containing compound include an organic protonic acid represented by the following formula (I) or a salt thereof (hereinafter referred to as organic protonic acid (I) or a salt thereof).
M (YARn) m (I)
This compound is preferable because of its high acidity and easy doping. This improves the conductivity and solubility of the protonated polyaniline.

In formula (I), M is a hydrogen atom or an organic or inorganic free radical. Examples of the organic free radical include a pyridinium group, an imidazolium group, and an anilinium group. Examples of the inorganic free radical include sodium, lithium, potassium, cerium, and ammonium.
Y is a —SO ₃ ^— group.

  A is a hydrocarbon group which may contain a substituent, for example, a linear or branched alkyl or alkenyl group having 1 to 24 carbon atoms, a substituent such as cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, menthyl and the like. Including optionally substituted cycloalkyl groups, dicyclohexyl groups such as bicyclohexyl, norbornyl, adamantyl or the like or polycycloalkyl groups, phenyl, tosyl, thiophenyl, pyrrolinyl, pyridinyl, furanyl and the like An aryl group containing an aromatic ring, naphthyl, anthracenyl, fluorenyl, 1,2,3,4-tetrahydronaphthyl, indanyl, quinolinyl, indonyl, etc., may be condensed diaryl group or polyaryl group, alkylaryl group, etc. Is mentioned.

R is each independently —R ¹ , —OR ¹ , —COR ¹ , —COOR ¹ , —CO (COR ¹ ), or —CO (COOR ¹ ). Here, R ¹ is a hydrocarbon group that may contain a substituent having 4 or more carbon atoms, a silyl group, an alkylsilyl group, or a — (R ² O) x—R ³ group, — (OSiR ³ ₂ ) x—. OR ³ (R ² is an alkylene group, R ³ is a hydrocarbon group which may be the same or different, and x is an integer of 1 or more). Examples of when R ¹ is a hydrocarbon group include linear or branched butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, pentadecyl, eicosanyl, etc. Can be mentioned.
n is an integer of 2 or more, and m is the valence of M.

As the compound represented by the formula (I), dialkylbenzenesulfonic acid, dialkylnaphthalene sulfonic acid, sulfophthalic acid ester, and a compound represented by the following formula (II) can be preferably used from the viewpoint of easy doping.
M (YCR ⁴ (CR ⁵ ₂ COOR ⁶ ) COOR ⁷ ) _p (II)
In the above formula (II), M is a hydrogen atom or an organic or inorganic free radical as in the case of the formula (I). Examples of the organic free radical include a pyridinium group, an imidazolium group, and an anilinium group. Examples of the inorganic free radical include sodium, lithium, potassium, cerium, and ammonium.
Y is a —SO ₃ ^— group.

R ⁴ and R ⁵ are each independently a hydrogen atom, a hydrocarbon group or an R ⁸ ₃ Si— group (wherein R ⁸ is a hydrocarbon group, and three R ⁸ may be the same or different). ). Examples of the hydrocarbon group when R ⁴ and R ⁵ are hydrocarbon groups include a linear or branched alkyl group having 1 to 24 carbon atoms, an aryl group containing an aromatic ring, and an alkylaryl group. The hydrocarbon group when R ⁸ is a hydrocarbon group is the same as in the case of R ⁴ and R ⁵ .

R ⁶ and R ⁷ are each independently a hydrocarbon group or — (R ⁹ O) _q —R ¹⁰ group [wherein R ⁹ is a hydrocarbon group or a silylene group, and R ¹⁰ is a hydrogen atom or a hydrocarbon, A group or R ¹¹ ₃ Si— (R ¹¹ is a hydrocarbon group, three R ¹¹ may be the same or different), and q is an integer of 1 or more. Examples of the hydrocarbon group when R ⁶ and R ⁷ are hydrocarbon groups include a linear or branched alkyl group having 1 to 24 carbon atoms, an aryl group containing an aromatic ring, and an alkylaryl group. Among these, those having 4 or more carbon atoms are preferable from the viewpoint of obtaining a polyaniline complex that is easily dissolved in an organic solvent immiscible with water. Specific examples of the hydrocarbon group when R ⁶ and R ⁷ are hydrocarbon groups include a linear or branched butyl group, pentyl group, hexyl group, octyl group, decyl group and the like.

In R ⁶ and R ⁷ , when R ⁹ is a hydrocarbon group, the hydrocarbon group includes a linear or branched alkylene group having 1 to 24 carbon atoms, an arylene group containing an aromatic ring, an alkylarylene group, an aryl An alkylene group and the like; The hydrocarbon group in R ⁶ and R ⁷ when R ¹⁰ and R ¹¹ are hydrocarbon groups is the same as in the case of R ⁴ and R ⁵ , and q is 1 to 10. preferable.

（式中、Ｙは−ＳＯ_３基である） Specific examples of the case where R ⁶ and R ⁷ are — (R ⁹ O) _q —R ¹⁰ groups include groups represented by the following formulas.

Wherein Y is a —SO ₃ group.

  p is the valence of M.

The organic protonic acid (II) or a salt thereof is more preferably a sulfosuccinic acid derivative represented by the following formula (III) (hereinafter referred to as sulfosuccinic acid derivative (III)) from the viewpoint of conductivity and solubility.
M (O ₃ SCH (CH ₂ COOR ¹² ) COOR ¹³ ) _m (III)
In the above formula (III), M and m are the same as in the above formula (I).

R ¹² and R ¹³ are each independently a hydrocarbon group or — (R ¹⁴ O) _r —R ¹⁵ group [wherein R ¹⁴ is a hydrocarbon group or a silylene group, and R ¹⁵ is a hydrogen atom or a hydrocarbon, A group or an R ¹⁶ ₃ Si— group (wherein R ¹⁶ is a hydrocarbon group, three R ¹⁶ may be the same or different), and r is an integer of 1 or more].

The hydrocarbon group when R ¹² and R ¹³ are hydrocarbon groups is the same as R ⁶ and R ⁷ .

In R ¹² and R ¹³ , the hydrocarbon group in the case where R ¹⁴ is a hydrocarbon group is the same as R ⁹ described above. In R ¹² and R ¹³ , the hydrocarbon group in the case where R ¹⁵ and R ¹⁶ are hydrocarbon groups is the same as R ⁴ and R ⁵ described above.

  r is preferably from 1 to 10.

Specific examples in the case where R ¹² and R ¹³ are — (R ¹⁴ O) _r —R ¹⁵ groups are the same as those for — (R ⁹ O) _q —R ¹⁰ in R ⁶ and R ⁷ .

In the case where R ¹² and R ¹³ are hydrocarbon groups, the hydrocarbon group is the same as R ⁶ and R ⁷ and is a butyl group from the viewpoint of obtaining a polyaniline complex that is easily dissolved in an organic solvent immiscible with water. Hexyl group, 2-ethylhexyl group, decyl group and the like are preferable.

  The organic protonic acid or a salt thereof has a function of protonating polyaniline and exists as a dopant (counter anion) in the polyaniline complex.

(B) Examples of surfactants include anionic surfactants such as fatty acids, disproportionated rosin soaps, higher alcohol esters, polyoxyethylene alkyl ether phosphoric acid, alkenyl succinic acid, sarcosinate, and salts thereof, Nonionic surfactants such as polyoxyethylene alkyl ether, polypropylene glycol polyethylene glycol ether, polyoxyethylene glycerol borate fatty acid ester, cationic surfactants such as alkyldimethylbenzylammonium salt and alkyltrimethylammonium salt, alkylbetaine type, alkyl Examples include amphoteric surfactants such as amide betaine type, amino acid type, and amine oxide type.
In addition, you may use the general surfactant which consists of a compound containing the sulfone group of (a) mentioned above, or a compound which has a sulfone group as surfactant. In this case, in the production method of the present invention, two or more “compounds containing a sulfone group” are used.

  Preferable examples include anionic surfactants and nonionic (nonionic) surfactants. Of the anionic surfactants, those based on phosphoric acid are preferred. The surfactant may be used alone or in combination of two or more.

In the present invention, it is preferable to use a catalyst (oxidant) during the polymerization.
Examples of the oxidizing agent include persulfuric acid or a salt thereof, chromic acid or a salt thereof, perchloric acid or a salt thereof, iodic acid, permanganic acid or a salt thereof, and the like. For reasons such as stability and ease of handling, persulfates such as ammonium persulfate are preferred.

Next, the polymerization method will be described.
Into the reaction vessel, the above-described organic solvent, water or aqueous solution, monomer, sulfone group-containing compound (a), and surfactant (b) are added, and polymerization is performed by adding a catalyst (oxidant) while stirring. Make it progress.
The charged concentration of the monomer is usually 1 to 100 g / l, preferably 5 to 50 g / l.
As addition amount of a sulfone group containing compound (a), 0.1-0.5 equivalent (molar ratio) is preferable with respect to monomer amount, and about 0.2-0.4 equivalent (molar ratio) is especially preferable.
The addition amount of the surfactant (b) is preferably about 0.05 to 0.2 equivalent (molar ratio) of the sulfone group-containing compound (a).

The reaction can be carried out in the range from −20 ° C. to around room temperature. Preferably it is 5 degrees C or less. In addition, it is not preferable to polymerize at a temperature near room temperature or higher, for example, a temperature exceeding 30 ° C., because side reactions proceed.
The polymerization time is about 2 to 20 hours, but is completed in a short time of about 2 to 10 hours.

  It is also effective to stir the system in advance before adding the oxidizing agent. In this case, the reaction system exhibits a milky white milky state. The stirring time at this time is about 5 minutes to 8 hours, and preferably about 30 minutes to 2 hours.

After the stirring is stopped, the contents are transferred to a separatory funnel, the aqueous solution layer and the organic solvent layer are allowed to stand and separated, and the organic layer is washed with ion-exchanged water or aqueous hydrochloric acid after separation to recover the polyaniline complex solution. it can.
From this polyaniline complex solution, for example, a volatile matter is distilled off under reduced pressure to obtain a dry solid polyaniline complex.
This polyaniline complex has a high conductivity. Further, the production method of the present invention has good reproducibility, and even when a polyaniline complex is produced repeatedly, a polyaniline complex having a high conductivity can be produced stably.

The polyaniline composition of the present invention contains a polyaniline complex produced by the above-described method of the present invention and a compound having a phenolic hydroxyl group. In the composition of the present invention, the compound having a phenolic hydroxyl group functions as a dopant.
Examples of the compound having a phenolic hydroxyl group include phenol, o-, m-, p-cresol, o-, m-, p-ethylphenol, o-, m-, p-propylphenol, o-, m-, p. -Substituted phenols such as chlorophenol, naphthols such as 1-naphthol and 2-naphthol, polyhydric phenols such as catechol and resorcinol, and polynuclear phenols such as biphenol and bisphenol A.

  For example, the composition can be prepared by referring to the method described in WO2005 / 052058. Specifically, a conductive polyaniline composition solution can be obtained by blending a phenolic compound into a solution in which the polyaniline complex is dissolved.

The ratio of the polyaniline complex in an organic solvent such as toluene is usually 900 g / L or less, preferably in the range of 0.01 to 300 g / L, depending on the type of organic solvent.
The molar concentration of the phenolic compound in the entire polyaniline composition is preferably in the range of 0.01 mol / L to 5 mol / L. In this range, particularly excellent conductivity can be obtained. In particular, the range is preferably from 0.2 mol / L to 2 mol / L.
In addition, you may add another resin material, an inorganic material, a hardening | curing agent, a plasticizer, etc. to the polyaniline composition of this invention according to the objective.

By drying the polyaniline composition of the present invention and removing the organic solvent, a conductive molded body can be obtained.
For example, a conductive film can be manufactured by applying to a substrate such as glass, a resin film, or a sheet having a desired shape and removing the organic solvent.

  As a method for applying the composition of the present invention to a substrate, known general methods such as a casting method, a spray method, a dip coating method, a doctor blade method, a barcode method, a spin coating method, a screen printing, a gravure printing method, etc. The method can be used.

  In order to remove the water-immiscible organic solvent, the organic solvent may be volatilized by heating. As a method for volatilizing the water-immiscible organic solvent, for example, heating is performed at a temperature of 250 ° C. or less, preferably 50 to 200 ° C. under an air stream, and further, heating is performed under reduced pressure as necessary. The heating temperature and the heating time are not particularly limited and may be appropriately selected according to the material used.

  Moreover, it can also be set as the self-supporting molded object which does not have a base material. In the case of forming a self-supporting molded article, a molded article having a desired mechanical strength can be obtained by adding the above-described other resin material to the composition of the present invention.

When the molded product of the present invention is a film or a film, the thickness is usually 1 mm or less, preferably 10 nm to 50 μm. A film having a thickness in this range is advantageous in that it does not easily crack during film formation and has uniform electrical characteristics.
In addition, as an example of a molded body other than a film or a film, a thread, a pellet, or the like can be given.

Example 1
In a separable flask with a volume of 500 ml, 1.8 g (4 mmol) of AOT (aerosol OT, sodium dioctylsulfosuccinate, manufactured by Wako Pure Chemical Industries, Ltd.) as component (a), and aniline purified under reduced pressure and stored under nitrogen 50 ml of a toluene solution in which 1.8 g (20 mmol) was dissolved was added.
Surfacter FP-120 (manufactured by Toho Chemical Industry Co., Ltd., phosphate anionic surfactant) 0.33 g (0.1 equivalent of AOT: molar ratio) was added to this as the component (b) surfactant. It was.
Further, 150 ml of a 1N aqueous HCl solution was poured, and the mixture was set in a constant temperature bath set at 5 ° C. and stirred for 30 minutes with a mechanical stirrer. To this, a solution obtained by adding 2.7 g (12 mmol) of ammonium persulfate (oxidant) to 50 ml of 1N HCl aqueous solution was dropped from a dropping funnel over 2 hours. After completion of the dropwise addition, the mixture was further stirred at the same temperature for 8 hours (total reaction time 10 hours).
After the stirring was stopped, the contents were transferred to a separatory funnel, and the aqueous layer and the toluene layer were allowed to stand and be separated. After separation, the organic layer was washed twice with 50 ml of ion-exchanged water and once with 50 ml of 1N HCl aqueous solution to obtain a polyaniline complex solution.

When a volatile matter was distilled off from a toluene solution of the polyaniline complex under reduced pressure, a dark blue dry solid was obtained. This solid was dissolved again in toluene and suction filtered with 5B filter paper. After removing the insoluble matter with the filter paper of No. 2, the volatile matter was distilled off from the toluene-soluble fraction under reduced pressure, and the toluene solution was adjusted so that the solid content concentration was 5 wt / v%.
4 ml of this solution was placed in a 20 ml sample bottle, 400 μl of m-cresol was added, and the mixture was stirred for 30 minutes in a 30 ° C. water bath to obtain a polyaniline composition solution.
This solution was cast on a glass plate and dried at 80 ° C. for 30 minutes to form a film. As a result, a self-supporting film having a thickness of 15 μm was obtained. It was 260 S / cm when the intrinsic conductivity of this film | membrane was measured by the four terminal method (measuring instrument: Loresta GP, Mitsubishi Chemical make).
Moreover, when 0.04 g of this film was added 4.5 ml of nitric acid and 0.5 ml of perchloric acid, it was decomposed and diluted with a microwave pretreatment device, and phosphorus was quantified by inductively coupled plasma (ICP) emission analysis. .17% found to be contained. Since no other compound containing phosphorus is added to the reaction system, this phosphorus is considered to be derived from the component (b).

Comparative Example 1
A polyaniline composite was produced in the same manner as in Example 1 except that the surfactant (b) was not added, and a polyaniline composition was formed and evaluated.
As a result, the intrinsic conductivity of the obtained film was 62 S / cm, which was inferior to that of Example 1.

Example 2
A 500 ml separable flask was charged with 50 ml of a toluene solution of 1.8 g (4 mmol) of AOT and 1.8 g (20 mmol) of aniline, Surfmer FP-120, 0.33 g. 150 ml of 1N HCl aqueous solution was poured into this, set in a constant temperature bath set at 5 ° C., and stirred for 30 minutes.
Thereafter, 50 ml of a 1N HCl aqueous solution containing 2.7 g (12 mmol) of ammonium persulfate was dropped from the dropping funnel over 2 hours, and further stirred at the same temperature for 4 hours (total reaction time 6 hours).
After the stirring was stopped, the contents were transferred to a separatory funnel and treated in the same manner as in Example 1 to obtain a polyaniline complex solution. Thereafter, a polyaniline composition was produced in the same manner as in Example 1, and a film was formed. It was 218 S / cm when the electrical conductivity of the obtained film | membrane was measured.
This indicates that a polyaniline composition having high conductivity can be obtained even when the total reaction time is about 6 hours.

Example 3
A polyaniline complex was prepared in the same manner as in Example 2 except that 50 ml of 1N HCl aqueous solution containing ammonium persulfate was dropped from the dropping funnel over 2 hours and stirred at the same temperature for 2 hours (total reaction time 4 hours). The polyaniline composition was produced and evaluated.
As a result, the intrinsic conductivity of the obtained film was 193 S / cm. In the present invention, it was shown that a highly conductive polyaniline composition can be obtained in a short polymerization time of 4 hours.

Comparative Example 2
A polyaniline complex and a composition were prepared in the same manner as in Comparative Example 1 except that the stirring time after the dropping of the HCl aqueous solution containing ammonium persulfate was 2 hours (total reaction time 4 hours).
Although an attempt was made to form a film of the obtained polyaniline composition solution, the film became viscous and a film capable of measuring conductivity could not be obtained.
Thus, when the surfactant which is the component (b) is not added, it is presumed that polyaniline having a molecular weight high enough to form a film is not produced in a polymerization time of about 4 hours.

Example 4
A polyaniline complex was produced in the same manner as in Example 1 except that the reaction vessel volume was 1 L, and the amount of solvent and the amount of reagents were all doubled from Example 1, and the polyaniline composition was formed into a film and evaluated. did.
As a result, the intrinsic conductivity of the obtained film was 251 S / cm. As described above, it was confirmed that a polyaniline composition exhibiting substantially the same conductivity could be produced even when scaled up twice. Even if scaled up, polyaniline with equivalent performance is expected to be obtained.

Example 5
A polyaniline composite was prepared in the same manner as in Example 1 except that the amount of AOT was 2.7 g (6 mmol), 0.33 g of Surfer FP-120 was added, and the mixture was stirred for 30 minutes in advance. A product was formed and evaluated. As a result, the intrinsic conductivity of the obtained film was 402 S / cm.

Example 6
(B) Instead of Surfer FP-120, 0.8 g (sulfosuccinic acid surfactant, manufactured by Toho Chemical Industry Co., Ltd.) 0.8 g (0.1 equivalent of AOT) was used instead of Surfer FP-120, A polyaniline composite was produced in the same manner as in Example 1, and a polyaniline composition was formed into a film and evaluated.
As a result, the intrinsic conductivity of the obtained film was 170 S / cm.

Example 7
(B) Instead of Surfmer FP-120, Phosphanol RD-510Y (manufactured by Toho Chemical Industry Co., Ltd., phosphate ester type surfactant) 0.18 g (0.1 equivalent of AOT) was used. Otherwise, a polyaniline composite was produced in the same manner as in Example 1, and a polyaniline composition was formed into a film and evaluated.
As a result, the intrinsic conductivity of the obtained film was 223 S / cm.

Example 8
(B) Instead of Surfer FP-120, 0.18 g (0.84 equivalent of AOT) of Peganol TH-8 (manufactured by Toho Chemical Co., Ltd., polyoxyethylene alkyl ether type nonionic surfactant) A polyaniline complex was produced in the same manner as in Example 1 except that it was used, and a polyaniline composition was formed into a film and evaluated.
As a result, the intrinsic conductivity of the obtained film was 223 S / cm.

Example 9
(B) Instead of Surfer FP-120, 0.32 g (0.11 equivalent of AOT) of Peganol L-12S (manufactured by Toho Chemical Co., Ltd., polyoxyethylene alkyl ether type nonionic surfactant) A polyaniline complex was produced in the same manner as in Example 1 except that it was used, and a polyaniline composition was formed into a film and evaluated.
As a result, the intrinsic conductivity of the obtained film was 98 S / cm.

Example 10
(B) Instead of Surfer FP-120, 0.14 g (0.1 equivalent of AOT) of sorbone S-20 (manufactured by Toho Chemical Co., Ltd., sorbitan fatty acid ester type nonionic surfactant) was used. Otherwise, a polyaniline composite was produced in the same manner as in Example 1, and a polyaniline composition was formed into a film and evaluated.
As a result, the intrinsic conductivity of the obtained film was 157 S / cm.

Example 11
(B) Instead of Surfmer FP-120, 0.5 g of sorbon T-20 (manufactured by Toho Chemical Co., Ltd., polyoxyethylene sorbitan fatty acid ester nonionic surfactant) (0.1 equivalent of AOT) A polyaniline composite was produced in the same manner as in Example 1 except that was used, and a polyaniline composition was formed into a film and evaluated.
As a result, the intrinsic conductivity of the obtained film was 121 S / cm.

  The polyaniline composite obtained by the production method of the present invention is used in the fields of power electronics and optoelectronics, particularly for electrostatic and antistatic materials, transparent electrodes and conductive film materials, electroluminescent element materials, circuit materials, and capacitor dielectrics. -It can be used for electrolytes, electrode materials for solar cells and secondary batteries, fuel cell separator materials, and the like.

Claims (7)

An aniline or an aniline derivative is polymerized in the presence of the following components (a) and (b) in a two-phase polymerization solvent consisting of an organic solvent substantially immiscible with water and water or an aqueous solution. A method for producing a polyaniline complex.
(A) Compound having sulfone group (b) Surfactant   The method for producing a polyaniline complex according to claim 1, wherein the surfactant (b) is a phosphoric acid anionic surfactant.   The method for producing a polyaniline complex according to claim 1, wherein the surfactant (b) is a nonionic surfactant.   The method for producing a polyaniline complex according to any one of claims 1 to 3, wherein the compound (a) having a sulfone group is a sulfosuccinic acid derivative.   A polyaniline complex obtained by the production method according to claim 1 and containing the surfactant (b).   A polyaniline composition comprising the polyaniline complex according to claim 5 and a compound having a phenolic hydroxyl group.   The electroconductive molded object obtained from the polyaniline composition of Claim 6.