JP2909848B2 - Method for producing polyaniline derivative - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for manufacturing a swellable polyaniline derived material with an organic solvent.

[0002]

2. Description of the Related Art In recent years, polyaniline has been used as a new electronic material and conductive material as a battery electrode material, an antistatic material,
Application to a wide range of fields, such as electromagnetic wave shielding materials, photoelectric conversion elements, optical memories, functional elements such as various sensors, display elements, various hybrid materials, transparent conductors, various terminal devices, etc., is being studied.

By the way, polyaniline generally has a highly developed π-conjugated system, so that the main chain of the polymer is rigid, the interaction between molecular chains is strong, and there are many strong hydrogen bonds between molecular chains. Since it is present, it is insoluble in most organic solvents and does not melt even by heating, so it has poor moldability and has a major drawback that it cannot be cast or coated. For this purpose, for example, fibers of a polymer material,
An aniline monomer is impregnated into a substrate having a desired shape such as a porous body, and the aniline monomer is brought into contact with an appropriate polymerization catalyst, or is polymerized by electrolytic oxidation to form a conductive composite material, or An aniline monomer is polymerized in the presence of a thermoplastic polymer powder to obtain a similar composite material.

[0004] On the other hand, polyaniline soluble only in N-methyl-2-pyrrolidone has been synthesized by devising a polymerization catalyst and a reaction temperature (M. Abe et a).
l. : J. Chem. Soc. Chem. C
ommun. , 1989, 1736). However,
This polyaniline was hardly dissolved in other general-purpose organic solvents, and its application range was limited.

On the other hand, many gel-like polymer compounds have been known for a long time, and processing techniques such as gel stretching have been developed for processing fibers, films and the like of the polymer compound. As for polyaniline, those capable of gelling have been proposed. For example, by reducing the above-mentioned soluble polyaniline with hydrazine, an intermolecular cross-link by hydrogen bond is formed, and polyaniline capable of gelling is formed. It is known to obtain derivatives (O. Oka
et al. : J. Jpn. J. Appl.
Phys. , 29 (1990) L679). However, in this method, it is difficult to control the degree of crosslinking of the polyaniline derivative, and there is a problem in workability. Furthermore, it is possible to crosslink with various polyfunctional polycarboxylic acids or isocyanates to obtain a polyaniline derivative that can be gelled, but as the degree of crosslinking increases,
There is a problem that the conductivity is reduced.

[0006]

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems in the prior art. An object of the present invention is to swell in an organic solvent, there can be processed to provide a manufacturing methods polyaniline derivative drop is less conductive.

[0007]

The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that the above problems can be solved by reacting polyaniline with hydrazine. Reached.

The polyaniline derivative swellable with an organic solvent according to the present invention is represented by the following general formula (I):

Embedded image

(Where m ≧ 0, n ≧ 1, m + n = 20 to
5000), a number average molecular weight of 2,000 to 50
A solution prepared by dissolving an aniphosphorylated polymer of 0000 in an amide-based solvent is heated to 80 ° C. or higher, and then treated with hydrazine in an amide-based solvent at 0.35 times or more the weight of the aniphosphorylated polymer. Which has a structure in which the main chain of the aniphosphorylated polymer is partially crosslinked, the gel fraction measured with N-methyl-2-pyrrolidone is 50% or more, It has a volume swelling ratio of 1.2 to 500 in methyl-2-pyrrolidone. The volume swelling means the ratio of the swelling volume to the dry volume of the polyaniline derivative, and serves as an index of the degree of crosslinking.

The polyaniline derivative swellable with an organic solvent of the present invention is produced as follows. That is, an aniphosphorylated polymer obtained by oxidatively polymerizing aniline at a low temperature, for example, at a temperature in the range of −20 to 50 ° C. using ammonium persulfate or the like as an oxidizing agent,
Converted to soluble polyaniline by treating with ammonia,
The number average molecular weight represented by the general formula (I) is from 2,000 to 2,000.
A soluble aniphosphorylated polymer having a number average molecular weight in terms of polystyrene of 500,000 [measured by GPC (N-methyl-2-pyrrolidone solvent)] is obtained. The obtained soluble aniphosphorylated polymer is soluble in N-methyl-2-pyrrolidone or N, N-dimethylacetamide, but is almost insoluble in other general-purpose organic solvents such as chloroform and tetrahydrofuran. It is.

Next, the soluble aniphosphorylated polymer is dissolved in an amide-based solvent to prepare a solution having a concentration of 5 to 50% by weight, and the solution is heated to 80 ° C. or higher, preferably 80 to 1%.
The amide-based solvent is completely or partially evaporated at a temperature in the range of 80 ° C. in air, in an inert gas such as nitrogen or argon, or under reduced pressure to synthesize a crosslinked polyaniline derivative. This crosslinked polyaniline derivative is unnecessary for most solvents, including amide solvents,
Also, it hardly swells. Next, the polyaniline derivative obtained as described above is immersed in an amide-based solvent containing hydrazine in a weight ratio of 0.35 or more, and
The reduction reaction is carried out for at least one hour. At this time, the concentration of hydrazine in the amide solvent is preferably in the range of 1 to 50% by weight. By this immersion treatment, a crosslinked polyaniline derivative which can swell with an organic solvent and has a small decrease in electric conductivity can be obtained.

The amide solvents used in the present invention include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, 1,3-dimethyl-
2-imidazolidinone and the like can be used.

The polyaniline derivative of the present invention produced as described above may be an amide solvent such as N-methyl-2-pyrrolidone or N, N-dimethylacetamide, or a halogenated hydrocarbon solvent such as chloroform, dichloroethane or dichloromethane. Swellable with a polar solvent such as dimethylsulfoxide and the like, and a self-supporting film or fiber can be produced from the obtained gel. Further, if a film-like crosslinked polyaniline derivative is produced from a soluble polyaniline and then treated with hydrazine as described above, it is possible to produce a gel-like film that can be stretched into a desired shape. .

Further, a formed product such as a film or fiber and a gel can be obtained by doping with a dopant having an acceptor property to have a high conductivity of 10 ⁻³ to 10 S / cm.

The dopant used here is not particularly limited, and any dopant can be used as long as it is used as a dopant when doping an aniline-based conductive polymer. Specific examples include iodine, bromine, chlorine, halogen compounds such as iodine trichloride, sulfuric acid, hydrochloric acid, nitric acid, perchloric acid, protic acids such as borofluoric acid, various salts of the above protic acids, aluminum trichloride, Various compounds such as Lewis acids such as iron trichloride, molybdenum chloride, antimony chloride and arsenic pentafluoride, and organic acids such as acetic acid, trifluoroacetic acid, benzenesulfonic acid and p-toluenesulfonic acid can be mentioned.

The method of doping these compounds is not particularly limited, and any known method can be used. In general, the gel obtained by swelling the polyaniline derivative or the molded product thereof may be brought into contact with the dopant compound, and the gelation can be performed in a gas phase or a liquid phase. Alternatively, a method of electrochemically doping in a solution of the above-described protonic acid or a salt thereof can also be used.

[0017]

The present invention will be described below with reference to examples. Example 1 4.1 g of aniline and 21.9 g of concentrated hydrochloric acid were dissolved in water to obtain 1
Make up to 00 ml and cool to -5 ° C. Concentrated hydrochloric acid 21.9 g,
Dissolve 6.28 g of ammonium persulfate in water and add 100 m
The solution was also cooled to -5 ° C and slowly added dropwise to the previous aniline solution, and stirring was continued at -5 ° C for 4 hours. The thus obtained number average molecular weight of 12,000 (GP
The aniphosphorylated polymer measured in a C, N-methyl-2-pyrrolidone solvent and having a number average molecular weight in terms of polystyrene; n + m = 120) was sufficiently washed with water, and further dedoped with ammonia water.

1 g of the soluble aniphosphorylated polymer thus obtained was completely dissolved in 30 ml of N-methyl-2-pyrrolidone, and this solution was heated at 100 ° C. for 5 hours in a nitrogen stream to completely remove N-methyl-2-pyrrolidone. -Methyl-2-pyrrolidone was evaporated to give 1 g of massive copper colored crosslinked polyaniline derivative. This polyaniline derivative did not change for more than one month in N-methyl-2-pyrrolidone. The crosslinked polyaniline derivative was immersed in 20 ml of N-methyl-2-pyrrolidone containing 1 g of hydrazine for 10 hours. The polyaniline derivative of the present invention was obtained as a light brown gel-like substance. This was dried overnight under reduced pressure to obtain a blue polyaniline derivative. The gelation ratio of this polyaniline derivative was 97%, and the degree of volume swelling with respect to N-methyl-2-pyrrolidone was 5.5. Also,
When the infrared absorption spectrum of this polyaniline derivative was examined, 1600, 1500, 1300, 11
An absorption pattern unique to polyaniline was observed at 70 and 820 cm ⁻¹ , confirming that the main chain had a polyaniline structure.

When 1 g of the obtained polyaniline derivative was immersed in 10 ml of N-methyl-2-pyrrolidone and stirred at room temperature, it gelled, and a film could be formed by spinning or drawing. This film was immersed in a 20% hydrochloric acid aqueous solution for 24 hours to dope, dried, and then measured for electrical conductivity.
It was confirmed to be 1.5 S / cm. Also, instead of N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, pyridine, chloroform, dichloroethane, dichloromethane,
Similar gelation was possible even when an organic solvent such as tetrahydrofuran was used.

Example 2 1 g of the soluble aniphosphorylated polymer used in Example 1 was
Dissolved in 10 ml of -methyl-2-pyrrolidone, cast on a Teflon plate, and heated at 80 ° C in air to completely remove the solvent to obtain a brown crosslinked film of a polyaniline derivative. 1g of this film
Was immersed in 30 ml of N-methyl-2-pyrrolidone containing 0.5 g of hydrazine and reacted for 20 hours. As a result, the polyaniline derivative of the present invention was obtained as a thin brown gel-like film. When this was dried, a blue polyaniline derivative film was obtained. The gelation rate of this polyaniline derivative was 95%, and N-methyl-
The volume swelling ratio for 2-pyrrolidone was 7.1.
Further, the infrared absorption spectrum of this polyaniline derivative was examined.
00, 1500, 1300, 1170, 820 cm
^-1 , an absorption pattern unique to polyaniline was observed, and it was confirmed that the main chain had a polyaniline structure.

The above gel-like film is stretched,
It could be deformed to a desired shape, and after stretching or deformation, it could be dried to a blue film.
This film was immersed in a 20% aqueous hydrochloric acid solution for 24 hours to perform a dope treatment, dried, and then measured for electrical conductivity. As a result, it was confirmed that the value was 1.5 S / cm. Furthermore, a blue polyaniline derivative film obtained by drying the gel-like film once is N-methyl-2-pyrrolidone, N,
With an organic solvent such as N-dimethylacetamide, N, N-dimethylformamide, pyridine, chloroform, dichloroethane, dichloromethane, tetrahydrofuran, etc.
Gelation was possible again and processing was possible.

Example 3 A polyaniline derivative of the present invention was obtained in the same manner as in Example 1, except that the amount of hydrazine was changed to 10 g and the reaction was carried out for 5 hours. The gelation ratio of this polyaniline derivative was 93%, and the degree of volume swelling with respect to N-methyl-2-pyrrolidone was 12.1. Further, the infrared absorption spectrum of this polyaniline derivative was examined. As in the case of Example 1, 1600, 15
At 00, 1300, 1170, and 820 cm ⁻¹ , absorption patterns unique to polyaniline were observed, and it was confirmed that the main chain had a polyaniline structure.

When 1 g of the obtained polyaniline derivative was immersed in 10 ml of N-methyl-2-pyrrolidone and stirred at room temperature, it gelled, and a film could be formed by spinning or drawing. This film was immersed in a 20% aqueous hydrochloric acid solution for 24 hours to perform a dope treatment, dried, and then measured for electrical conductivity. As a result, it was confirmed that the value was 1.5 S / cm. Also, instead of N-methyl-2-pyrrolidone, N, N-
Gelation was also possible using an organic solvent such as dimethylacetamide, N, N-dimethylformamide, pyridine, chloroform, dichloroethane, dichloromethane, tetrahydrofuran and the like.

[0024]

The polyaniline derivative produced by the method of the present invention can be gelled with various organic solvents,
It can be processed by gel stretching, spinning, or other molding techniques.
In addition, since high conductivity is obtained by doping, it is very useful for various uses as an electronic material or a conductive material.

Claims (1)

(57) [Claims] 1. A compound represented by the following general formula (I) (Wherein m ≧ 0, n ≧ 1, m + n = 20 to 5000), a solution prepared by dissolving an aniphosphorylated polymer having a number average molecular weight of 2,000 to 500,000 in an amide-based solvent is
After heating to 0 ℃ or higher, characterized in that treatment with 0.35 times the hydrazine relative to the weight of the aniline oxidative polymer in amide solvent, the backbone of the aniline oxidative polymer partially crosslinked The gel fraction measured by N-methyl-2-pyrrolidone is 50% or more, and the volume swelling in N-methyl-2-pyrrolidone is 1.2 to 500.
Production of swellable polyaniline derivatives der Ru organic solvent
How .