JPH07100736B2 - Polyaniline derivative and method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a comb-shaped polyaniline derivative which is soluble in an organic solvent and gives a flexible and free-standing film, and a method for producing the same.

[0002]

2. Description of the Related Art Recently, polyaniline is a new electronic material,
As a conductive material, it is used in a wide range of fields such as battery electrode materials, antistatic materials, 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. The application of is being considered.

However, in general, polyaniline has a π
Since the conjugated system is highly developed, the polymer main chain is rigid and the interactions between the molecular chains are strong, and since many strong hydrogen bonds exist between the molecular chains, it is insoluble in most organic solvents. In addition, since it does not melt even when heated, it has poor moldability and has a major drawback that it cannot be processed into a film.

For that purpose, for example, a base material having a desired shape such as a polymer material fiber or a porous material is impregnated with a monomer,
This monomer is polymerized by contact with an appropriate polymerization catalyst or by electrolytic oxidation to form a conductive composite material,
Alternatively, the same composite material was obtained by polymerizing the monomers in the presence of the thermoplastic polymer powder.

On the other hand, polyaniline soluble only in N-methyl-2-pyrrolidone has been synthesized by devising the polymerization catalyst and reaction temperature (M.Abe et al .; J. Chem. Soc., Che.
m.Commun., 1989, 1736). However, this polyaniline was hardly dissolved in other general-purpose organic solvents, and its application range was limited. In addition, polyaniline derivatives soluble in organic solvents have been synthesized by using various aniline derivatives, but it has not been possible to provide a film having sufficient flexibility.

[0006]

SUMMARY OF THE INVENTION The present invention is intended to solve the above problems in the prior art. That is, an object of the present invention is to provide a polyaniline derivative which is soluble in an organic solvent and gives a flexible and self-supporting film, and a method for producing the same.

[0007]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventor has reacted polyaniline with a polybutadiene-acrylonitrile copolymer having a carboxyl group or a haloformyl group at one end, It was found that a polyaniline derivative having a branched structure, soluble in an organic solvent and giving a flexible and self-supporting film can be obtained, and completed the present invention.

The present invention has the following formula (I)

[Chemical 6] [Wherein, m is an integer of 0 or more, n is an integer of 2 or more] and the following formula (II)

[Chemical 7] [In the formula, k is an integer of 1 to 2500, and X is the following structural formula (II
A polybutadiene-acrylonitrile copolymer structure represented by I),

[Chemical 8] x = 1 to 10, y = 1 to 10, y / (x + y) = 0.0
1-0.5, z = 5-15, and the terminal Z is 2-butenyl or hydrogen. ] The structural unit represented by
/ (K + n) = 0 to 100, k + m + n = 10 to 500
The polyaniline derivative is characterized in that 0, k / (k + 2m + n) = 0.0001 to 0.5.

The polyaniline derivative of the present invention is manufactured as follows. That is, using aniline at a low temperature, for example, -20 to 50, using ammonium persulfate as an oxidizing agent.
The polyaniline obtained by oxidative polymerization at a temperature in the range of ° C is first treated with ammonia to obtain a soluble polyaniline. Then, this is treated with an excess of hydrazine to give the following general formula (IV)

[Chemical 9] [In the formula, p is an integer of 10 to 5000] Number average molecular weight 2000 to 500000 [GPC (N-methyl-
2-pyrrolidone solvent) to obtain reduced polyaniline having a polystyrene equivalent number average molecular weight]. The hydrazine treatment is carried out by dispersing soluble polyaniline in water, adding hydrazine in an equivalent amount or more, preferably 3 times or more, to the nitrogen atom in polyaniline under a nitrogen atmosphere for 24 hours or more,
It is performed by stirring at 0 to 30 ° C.

The reduced polyaniline obtained is soluble in N-methyl-2-pyrrolidone or N, N-dimethylacetamide, but almost insoluble in other general-purpose organic solvents such as chloroform and tetrahydrofuran.

A polybutadiene-acrylonitrile copolymer having a carboxyl group at one end is dissolved in pyridine, and an equivalent amount or more of N,
N′-disubstituted carbodiimides were added while cooling to −10 to 10 ° C., stirring was continued at that temperature for 1 to 4 hours, then the amide solution of reduced polyaniline was added, and the temperature was slowly returned to room temperature. Continue stirring for 1-24 hours. The reaction mixture is poured into dilute hydrochloric acid and the polymer formed is precipitated. Since this polymer is doped with hydrochloric acid, the polyaniline derivative of the present invention can be produced by dedoping with aqueous ammonia.

Alternatively, a polybutadiene-acrylonitrile copolymer having a haloformyl group at one end is dissolved in chloroform and slowly added dropwise to an amide solution of reduced polyaniline, and stirring is continued at room temperature for 1 to 24 hours. The reaction mixture is poured into dilute hydrochloric acid and the polymer formed is precipitated. Since this polymer is doped with hydrochloric acid, the polyaniline derivative of the present invention can be produced by dedoping with aqueous ammonia.

K + in the formula of the polyaniline derivative of the present invention
It is known that the value of 2m + n is not different from that of the starting material polymer (reduced polyaniline), and is equal to the value of p of reduced polyaniline. Further, the ratio of m to k + n in the formula of the polyaniline derivative of the present invention can be controlled by oxidizing (increasing m) or reducing (increasing k + n) the product after the completion of the grafting reaction. The oxidation or reduction method is
It is possible to bring the product into contact with an oxidizing agent or a reducing agent, or to carry out electrochemical redox. The ratio of m to k + n can be determined from the intensity ratio of the peak derived from the quinoid structure and the peak derived from the benzenoid using ¹³ C-NMR. The polyaniline derivative of the present invention is also characterized in that it is a comb-type polymer having a main chain represented by the above formula (I) and a side chain represented by the above formula (II) having a regular length. Is.

As the amide solvent, N-methyl-2-
Pyrrolidone, N, N-dimethylazetamide, N, N-
Dimethylformamide, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidinone and the like can be used.

As the polymer compound having a carboxyl group at one terminal used in the present invention, one represented by the general formula (V) HOOC-X (V) [wherein X has the above-mentioned meaning] is used. . The polymer compound represented by the general formula (V) is Go
The trade name Hycar CTBN marketed by odrich is applicable to the present invention.

The polymer compound having a haloformyl group at one end used in the present invention is represented by the general formula (VI) YOC-X (VI) [wherein X has the above meaning and Y is chlorine or bromine. ] What is represented by is used. The polymer compound having a haloformyl group at one end is a carboxylic acid of the general formula (V) or an ester of the carboxylic acid (methyl,
It can be easily derived from esters of lower alcohols such as ethyl) or salts of carboxylic acids thereof (alkali metal salts, ammonium salts, etc.).

From the carboxylic acid,
An inorganic halogen compound such as phosphoryl chloride, thionyl chloride, phosphorus pentachloride or phosphorus trichloride is added in an equivalent amount or more and reacted in an inert solvent such as benzene to give a polymer compound having a haloformyl group at one end used in the present invention. Obtainable. In this case, zinc chloride, pyridine, iodine, triethylamine or the like may be added as a catalyst. Alternatively, for said carboxylic acid, acid halides such as benzoyl chloride, phthalic acid chloride, oxalic acid chloride, α, α-dihalogeno ethers, halogenated alkylamines, triphenylphosphine / carbon tetrachloride, pyro It can be obtained by reacting an organic halide such as catealkyl phosphotrichloride, diethylhalophosphochloride, triphenylhalophosphobromide and the like in an inert solvent such as benzene and chlorobenzene.

From the carboxylic acid ester, a polymer compound having a haloformyl group at one end used in the present invention is obtained by using a triphenylhalophosphohalide or a complex thereof with boron fluoride for the carboxylic acid ester. be able to. From the carboxylate, a dicarboxylic acid salt, a phosphoryl chloride, an inorganic halogen compound such as phosphorus pentachloride or a complex of thionyl chloride and dimethylformamide is used to obtain a polymer compound having a haloformyl group at one end used in the present invention. Obtainable. Other than these, there is no problem as long as it is a reaction capable of converting a carboxyl group to a haloformyl group, and a polymer compound having a haloformyl group at one end used in the present invention can be obtained.

The N, N'-disubstituted carbodiimides used in the present invention are compounds represented by the following structural formula (VII) R'-N = C = NR "(VII) ′ And R ″ may be the same or different and, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group,
Alkyl group such as 3-dimethylaminopropyl group, cyclic alkyl group such as cyclohexyl group, phenyl group, p-tolyl group, m-tolyl group, p-N, N-dimethylaminophenyl group, p-chlorophenyl group, p Examples thereof include aryl groups such as -nitrophenyl group and p-cyanophenyl group. Specifically, diethylcarbodiimide, diisopropylcarbodiimide, dicyclocarbodiimide, diphenylcarbodiimide, di-p-tolylcarbodiimide,
1-ethyl-3- (3-dimethylaminopropyl) carbodiimide and the like can be mentioned.

The nitrogen atom imparted to the branch of the formula (II) is preferably in the range of 0.01 to 50% on average of the nitrogen atom of polyaniline. When the ratio of nitrogen atoms given to the branch of the general formula (1I) is higher than 50%, there is a problem that the conductivity is drastically lowered. On the other hand, if it is lower than 0.01%, there is a problem that sufficient solubility cannot be obtained and sufficient flexibility is not obtained.

The polyaniline derivative of the present invention produced as described above is an amide solvent such as N-methyl-2-pyrrolidone or N, N-dimethylacetamide, a halogenated hydrocarbon solvent such as chloroform, dichloroethane or dichloromethane. It is soluble in ether solvents such as and tetrahydrofuran, amine solvents such as pyridine, and polar solvents such as dimethylsulfoxide. From this solution it is possible to produce free-standing films and fibers. Further, the processed products such as the film and the fiber can be doped with an acceptor dopant so as to have a concentration of 10 ^-3 ~.
It exhibits a high conductivity of 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 in doping the 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 acid such as borofluoric acid, various salts of the protic acid, aluminum trichloride, Examples thereof include 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.

The method for doping these compounds is not particularly limited, and any known method can be used. Generally, the derivative of polyaniline, or a molded product thereof and the dopant compound may be brought into contact with each other, and the process can be carried out in a gas phase or a liquid phase. Alternatively, a method of electrochemically doping in the solution of the above-mentioned protonic acid or its salt can be used.

[0024]

EXAMPLES 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 prepare 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 to 100 ml
This solution was also cooled to −10 ° C., slowly added dropwise to the above aniline solution, and stirring was continued at −10 ° C. for 6 hours. Thus, the number average molecular weight is 12000 (measured in GPC, N-methyl-2-pyrrolidone solvent, polystyrene equivalent number average molecular weight, 2m + n = 130, m / n = 0.5)
Of polyaniline was obtained. After thoroughly washing this with water,
Further, dedoping treatment was performed with aqueous ammonia. The soluble polyaniline thus obtained was dispersed in 200 ml of water,
50 ml of hydrazine was added under a nitrogen atmosphere, stirring was continued at room temperature for 24 hours, filtered and dried to obtain an off-white reduced polyaniline. 1 g of the obtained reduced polyaniline (number average molecular weight 12000, p = 130) was N 2 under a nitrogen stream.
-Completely dissolved in 30 ml of methyl-2-pyrrolidone.

On the other hand, Hyc which is a polybutadiene-acrylonitrile copolymer having a carboxyl group at one end
ar CTBN (molecular weight ≈ 3600, y / (x + y) =
0.17, made by Goodrich) 1.97 g 30 m
Dissolve in 1 pyridine and cool to 0 ° C. Add 0.2266 g of dicyclohexylcarbodiimide, and for 1 hour, 0
Continue stirring at ° C. The reduced polyaniline solution was added thereto, and the reaction was continued for 6 hours while gradually returning to room temperature.
This solution was poured into 1 liter of diluted hydrochloric acid while stirring,
The precipitate was filtered off, exposed to ammonia vapor and washed with water to remove hydrogen halide, and dried to obtain 2.78 g of the polyaniline derivative of the present invention. When the infrared absorption spectrum was measured, it was found to be 1645c due to the structure of (II) above.
m ^-1 (C = O expansion / contraction), 2236 cm ^-1 (CN expansion / contraction), 2
Absorption of 850 to 2950 cm ^-1 (aliphatic C-H stretch) was observed. Furthermore, 1600, 1500, 1300, 1
An absorption pattern peculiar to polyaniline (I) was observed at 170 and 820 cm ^−1, and it was confirmed that the main chain had a polyaniline structure.

From the reaction yield, the number of nitrogen atoms given to the branch of formula (II) was about 9% of the nitrogen atoms of polyaniline. It was k + 2m + n = 130. Also, ¹³ C-NM
Intensity of peak (chemical shift 138 ppm / TMS) derived from quinoid structure of R spectrum and peak derived from benzenoid structure (chemical shift 122 ppm / TMS)
From the intensity ratio of m / (k + n) = 0.42.

1 g of the obtained polyaniline derivative was put in 5 g of N-methyl-2-pyrrolidone and dissolved at room temperature, and a very flexible film was obtained by casting.
Further, when this film was dipped in a 20% sulfuric acid aqueous solution for 24 hours and was doped and dried, the conductivity was 0.1 S / cm. Further, instead of N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, pyridine, chloroform, dichloroethane,
Similar processing was possible using an organic solvent such as dichloromethane or tetrahydrofuran.

Example 2 Hycar, which is a polybutadiene-acrylonitrile copolymer having a carboxyl group at one end in Example 1, was used.
CTBN (molecular weight ≈ 3600, y / (x + y) = 0.1
0.20 g (manufactured by Goodrich) and 0.0452 g of dicyclohexylcarbodiimide were used to obtain 1.15 g of the polyaniline derivative of the present invention by the same procedure as described below.
When the infrared absorption spectrum was measured, it was found to be 1645 cm ⁻¹ (C═O stretching) due to the above-mentioned structure (II), 223
6 cm ^-1 (cn stretch), absorption of 2850~2950cm ^-1 (aliphatic C-H stretching) was observed. Furthermore, 160
An absorption pattern peculiar to polyaniline (I) was observed at ⁰ , 1500, 1300, 1170, and 820 cm ^−1, and it was confirmed that the main chain had a polyaniline structure.

From the reaction yield, the number of nitrogen atoms given to the branch of formula (II) was about 0.8% of the nitrogen atoms of polyaniline. It was k + 2m + n = 130. Also, ¹³ C-N
Intensity of peak derived from quinoid structure (chemical shift 138 ppm / TMS) and peak derived from benzenoid structure of MR spectrum (chemical shift 122 ppm / TM)
From the intensity ratio of S), m / (k + n) = 0.49.

1 g of the obtained polyaniline derivative was added to 5 g of N-methyl-2-pyrrolidone and dissolved at room temperature, and a very flexible film was obtained by casting.
Further, when this film was dipped in a 20% sulfuric acid aqueous solution for 24 hours and was doped and dried, the conductivity was 0.1 S / cm. Further, instead of N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, pyridine, chloroform, dichloroethane,
Similar processing was possible using an organic solvent such as dichloromethane or tetrahydrofuran.

Example 3 Hycar, which is a polybutadiene-acrylonitrile copolymer having a carboxyl group at one end in Example 1, was used.
CTBN (molecular weight ≈ 3600, y / (x + y) = 0.1
7.93 g, manufactured by Goodrich Co., Ltd., and 0.878 g of dicyclohexylcarbodiimide were used to obtain 6.85 g of the polyaniline derivative of the present invention in the same procedure as described below. When the infrared absorption spectrum was measured, it was found to be 1645 cm ⁻¹ (C═O stretching) due to the structure of (II) above, 2236
cm ^-1 (CN stretching), the absorption of 2850~2950cm ^-1 (aliphatic C-H stretching) was observed. Furthermore, 1600,
Absorption patterns peculiar to polyaniline (I) were observed at 1500, 1300, 1170, and 820 cm ^−1, and it was confirmed that the main chain had a polyaniline structure.

From the reaction yield, the number of nitrogen atoms given to the branch of formula (II) was about 13% of the nitrogen atoms of polyaniline. It was k + 2m + n = 130. Also, ¹³ C-NM
Intensity of peak (chemical shift 138 ppm / TMS) derived from quinoid structure of R spectrum and peak derived from benzenoid structure (chemical shift 122 ppm / TMS)
From the intensity ratio of m / (k + n) = 0.38.

1 g of the obtained polyaniline derivative was added to 5 g of N-methyl-2-pyrrolidone and dissolved at room temperature, and a very flexible film was obtained by casting.
Further, when this film was dipped in a 20% sulfuric acid aqueous solution for 24 hours and was doped and dried, the conductivity was 0.01 S / cm. Further, instead of N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, pyridine, chloroform, dichloroethane,
Similar processing was possible using an organic solvent such as dichloromethane or tetrahydrofuran.

Example 4 Hycar CTBN (molecular weight≈3600, y / (x + y) = 0.17, Good, which is a polybutadiene-acrylonitrile copolymer having a carboxyl group at one end
(manufactured by Rich Co.) 1.97 g is dissolved in 20 ml of dehydrated benzene, 0.28 g of oxalyl chloride is added and the temperature is 70 ° C.
And reacted for 3 hours. The solvent and the like are removed under reduced pressure to obtain a viscous liquid. The terminal group is chloroformylation was confirmed by changes in the infrared absorption spectrum (disappears absorption around 1740 cm ^-1 derived from a carboxyl group, resulting newly absorbed 1792Cm ^-1 from chloroformyl group) . This was dissolved in 10 ml of dehydrated chloroform and slowly added dropwise to a solution of 1 g of reduced polyaniline completely dissolved in 30 ml of N-methyl-2-pyrrolidone under a nitrogen stream,
The reaction was carried out for 4 hours at room temperature. This solution was poured into 1 liter of dilute hydrochloric acid with stirring, the precipitate was filtered off, exposed to ammonia vapor and washed with water to remove hydrogen halide, and dried to obtain 2.78 g of the polyaniline derivative of the present invention. It was

When the infrared absorption spectrum was measured, it was 1645 cm ^-1 (C = O expansion / contraction), 2236 cm ^-1 (CN expansion / contraction), and 2850 to 295, which were attributable to the above-mentioned structure (II).
Absorption of 0 cm ^-1 (aliphatic C-H stretch) was observed. Further, 1600, 1500, 1300, 1170, 820
An absorption pattern peculiar to polyaniline (I) was observed at cm ^−1, and it was confirmed that the main chain had a polyaniline structure. From the reaction yield, the number of nitrogen atoms given to the branch of formula (II) was about 9% of the nitrogen atoms of polyaniline. k + 2
It was m + n = 130. In addition, a peak derived from a quinoid structure in the ¹³ C-NMR spectrum (chemical shift 138
From the ratio of the intensity of ppm / TMS) to the intensity of the peak derived from the benzenoid structure (chemical shift 122 ppm / TMS), m / (k + n) = 0.41.

1 g of the obtained polyaniline derivative was cut into 5 g of N-methyl-2-pyrrolidone and dissolved at room temperature, and a very flexible film was obtained by casting.
Further, when this film was dipped in a 20% aqueous solution of sulfuric acid for 24 hours and was doped and dried, the conductivity was 0.09 S / cm. Further, instead of N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, pyridine, chloroform, dichloroethane,
Similar processing was possible using an organic solvent such as dichloromethane or tetrahydrofuran.

[0037]

INDUSTRIAL APPLICABILITY The polyaniline derivative of the present invention is soluble in various organic solvents, and can be cast to obtain a self-supporting film having flexibility, and can be processed by coating or the like. It shows conductivity and is very useful for various purposes as electronic materials and conductive materials.

Claims (3)

[Claims] 1. The following formula (I): [In the formula, m is an integer of 0 or more, n is an integer of 2 or more] and the following formula (II): [In the formula, k is an integer of 1 to 2500, and X is the following structural formula (II
It is a polybutadiene-acrylonitrile copolymer structure represented by I), and x = 1 to 10, y = 1 to 10, y / (x + y) = 0.0
1-0.5, z = 5-15, and the terminal Z is 2-butenyl or hydrogen. ] The structural unit represented by
/ (K + n) = 0 to 100, k + m + n = 10 to 500
The polyaniline derivative is characterized in that 0, k / (k + 2m + n) = 0.0001 to 0.5. 2. A polyaniline treated with ammonia to give a soluble aniline polymer, and then treated with hydrazine to obtain the following formula (IV): [Wherein p is an integer of 10 to 5000] and a reduced polyaniline having a number average molecular weight of 2,000 to 500,000, which is a structural unit represented by the following general formula (V) HOOC-X (V). It is a polybutadiene-acrylonitrile copolymer structure represented by structural formula (III). ] The polyaniline derivative according to claim 1, wherein the polymer compound having a carboxyl group at one end is reacted in the presence of an equivalent amount or more of N, N'-disubstituted carbodiimides with respect to the carboxyl group. Manufacturing method. 3. A polyaniline treated with ammonia to obtain a soluble aniline polymer, and then treated with hydrazine to obtain the following formula (IV): [In the formula, p is an integer of 10 to 5,000] and a reduced polyaniline having a number average molecular weight of 2,000 to 500,000 consisting of a structural unit represented by the following formula (VI) YOC-X (VI) [wherein, X is the structure The polybutadiene-acrylonitrile copolymer structure represented by the formula (III), Y is chlorine or bromine. ] It is made to react with the high molecular compound which has a haloformyl group at one terminal shown by these.
A method for producing the polyaniline derivative of.