JP2992149B2 - 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 polyaniline derivative soluble in an organic solvent and capable of forming a flexible self-supporting film and a method for producing the same.

[0002]

2. Description of the Related Art In recent years, polyaniline is a new electronic material,
For conductive materials, 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, and various terminal equipment. The application of is considered. However, in general, polyaniline has π
Since the conjugated system is highly developed, the main chain of the polymer is rigid and the interaction between the molecular chains is strong, and since there are many strong hydrogen bonds between the molecular chains, it is insoluble in most organic solvents. In addition, since they are not melted by heating, they have poor moldability and cannot be processed into films or the like. For this purpose, for example, fibers of a polymer material,
A base material having a desired shape such as a porous body is impregnated with a monomer composed of aniline, and the monomer is brought into contact with an appropriate polymerization catalyst, or is polymerized by electrolytic oxidation to form a conductive composite material. The monomer was polymerized in the presence of a thermoplastic polymer powder to obtain a similar composite material.

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 al .; J. Chem. So).
c., Chem. Commun., 1989, 1736). However, this polyaniline is hardly soluble in other general-purpose organic solvents,
The range of application was limited. In addition, synthesis of polyaniline derivatives soluble in organic solvents using various aniline derivatives has been performed, but a film having sufficient flexibility could not be formed.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned 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 even if the number of nitrogen atoms involved in the formation of a crosslinked structure is increased and can form a flexible self-supporting film, and a polyaniline derivative thereof. It is intended to provide a manufacturing method.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above problems, and as a result, by reacting polyaniline with a butadiene-acrylonitrile copolymer having a carboxyl group or a haloformyl group at both terminals, The inventors have found that a polyaniline derivative having a crosslinked structure which is soluble in an organic solvent and can form a flexible self-supporting film can be obtained, and the present invention has been completed.

The polyaniline derivative of the present invention has the following formula (I)

Embedded image (Where m and n are integers of 2 or more, m / n = 0.01 to 1)
00, m + n = 10-5000), and polyaniline having a number average molecular weight of 2,000-500,000 comprising a structural unit represented by the following formula (II):

Embedded image [In the formula, X represents a repeating unit of a butadiene-acrylonitrile copolymer structure represented by the following formula (III);

Embedded image (Y / (x + y) = 0.01-0.5, x> 0, y>
0, z = 5 to 15)], and the number of nitrogen atoms involved in the formation of the crosslinked structure is 0.01 to less than 15% of the nitrogen atoms in the polyaniline. Features.

On the other hand, the method for producing a polyaniline derivative according to the present invention comprises the following formula (IV) obtained by treating an aniphosphorylated polymer with ammonia to obtain a soluble polyaniline and then treating with an excess of hydrazine.

Embedded image (N is an integer of 10 to 5000), 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 (V):

Embedded image (Y / (x + y) = 0.01-0.5, x> 0, y>
0, z = 5 to 15) with a butadiene-acrylonitrile copolymer having carboxyl groups at both terminals in the presence of N, N'-disubstituted carbodiimide in an amount equivalent to or more than the carboxyl group. Or (b) the following formula (VI)

Embedded image ( Y represents chlorine or bromine, and y / (x + y) = 0.0
1-0.5, x> 0, y> 0, z = 5-15) butadiene having a haloformyl group at both terminals
It is characterized by reacting with an acrylonitrile copolymer.

The method for producing the polyaniline derivative of the present invention will be further described. The reduced polyaniline represented by the above formula (IV) and having a number average molecular weight of 2,000 to 500,000 is produced as follows. That is, using ammonium persulfate or the like as an oxidizing agent,
For example, an aniphosphorylated polymer obtained by oxidative polymerization at a temperature in the range of −20 to 50 ° C. is first treated with ammonia to obtain a soluble polyaniline. It is then treated with excess hydrazine. In this hydrazine treatment, soluble polyaniline is dispersed in water, and hydrazine equivalent to nitrogen atoms in the polyaniline is added in an amount of at least equivalent, preferably at least 3 times, under a nitrogen atmosphere.
Can be carried out by stirring. The reduced polyaniline thus obtained 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 tetradrofuran. is there.

Next, the reduced polyaniline is reacted with a butadiene-acrylonitrile copolymer having a carboxyl group at both ends represented by the above formula (V), or at the both ends represented by the above formula (VI). The reduced polyaniline is crosslinked by reacting with a butadiene-acrylonitrile copolymer having a haloformyl group. That is, a butadiene-acrylonitrile copolymer having a carboxyl group at both ends represented by the above formula (V) is dissolved in pyridine, and an N, N'-disubstituted carbodiimide having an equivalent or more of the terminal carboxyl group is added to -10. ~
The mixture is added while cooling to 10 ° C., and stirring is continued at that temperature for 1 to 4 hours. Then, the amide-based solution of the reduced polyaniline is added. The reaction mixture is poured into dilute hydrochloric acid and the resulting polymer precipitates. Since this polymer is doped with hydrochloric acid, the polyaniline derivative of the present invention can be produced by dedoping with ammonia water.

Alternatively, a butadiene-acrylonitrile copolymer having a haloformyl group at both terminals represented by the above (VI) is dissolved in chloroform, and the solution is slowly added dropwise to an amide-based solution of reduced polyaniline. Continue stirring for hours. The reaction mixture is poured into dilute hydrochloric acid and the resulting polymer precipitates. Since this polymer is doped with hydrochloric acid, the polyaniline derivative of the present invention can be produced by dedoping with ammonia water. Since the length of the polyaniline main chain of the polyaniline derivative of the present invention thus obtained does not change during the production, the value of m + n of the polyaniline represented by the above formula (I) is reduced to the reduced form represented by the above formula (IV) It becomes the same as the value of n of polyaniline. After completion of the crosslinking reaction, an oxidizing agent or a reducing agent is allowed to exist or electrochemically oxidized or reduced to form a polyaniline derivative m.
/ N can be adjusted to an appropriate value. That is, when the polyaniline derivative of the present invention is oxidized by an oxidizing agent or electrochemical oxidation, the value of m increases, and when the polyaniline derivative of the present invention is reduced by a reducing agent or electrochemical reduction, m increases. Decreases. The value of m / n is ¹³ C N
It can be determined from the respective intensity ratios of the peak derived from the quinoid structure (chemical shift: 138 ppm / TMS) and the peak derived from benzenoid (chemical shift: 122 ppm / TMS) in the MR spectrum.

In the above case, the amide solvent may be N-
Methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidinone and the like can be used.

The butadiene-acrylonitrile copolymer having a carboxyl group at both terminals represented by the above formula (V) used in the present invention includes, for example, Goodrid
Hycar CTBN (trade name) marketed by Ch. can be applied to the present invention.

The butadiene-acrylonitrile copolymer having haloformyl groups at both terminals represented by the above formula (VI) is a dicarboxylic acid or an ester of the dicarboxylic acid (an ester of a lower alcohol such as methyl or ethyl), or Dicarboxylic acid salts (alkali metal salts,
Ammonium salts and the like).
That is, it can be synthesized from a dicarboxylic acid as follows. (I) The present invention is achieved by adding an equivalent or more of an inorganic halogen compound such as phosphoryl chloride, thionyl chloride, phosphorus pentachloride, and phosphorus trichloride to the dicarboxylic acid and reacting the same in an inert solvent such as benzene or chlorobenzene. Butadiene-acrylonitrile copolymer having haloformyl groups at both ends can be obtained. In this case, zinc chloride, pyridine, iodine, triethylamine or the like may be added as a catalyst. (Ii) acid halides such as benzoyl chloride, phthalic acid chloride, oxalyl chloride, α, α-dihalogenoethers, halogenated alkylamines, triphenylphosphine / Organic halides such as organic phosphorus halides such as carbon tetrachloride, pyrocatechol phosphotrichloride, diethylhalophosphochloride, and triphenylhalophosphobromide are reacted in an inert solvent such as benzene or chlorobenzene. Can be obtained.

The dicarboxylic acid ester has a haloformyl group at both terminals used in the present invention by reacting the dicarboxylic acid ester with a triphenylphosphohalide or a complex thereof with boron fluoride. A butadiene-acrylonitrile copolymer can be obtained.

Further, from the carboxylate, the dicarboxylate is treated with an inorganic halogen compound such as phosphoryl chloride or phosphorus pentachloride or a complex of thionyl chloride and dimethylformamide to form haloformyl at both terminals used in the present invention. A butadiene-acrylonitrile copolymer having a group can be obtained. In addition to these, any reaction that can convert a carboxyl group into a haloformyl group can be applied without any problem, and a butadiene-acrylonitrile copolymer having a haloformyl group at both terminals used in the present invention is obtained. be able to.

The N, N'-disubstituted carbodiimides used in the present invention are represented by the following formula (VII): R'-N = C = NR "(VII), wherein R 'and R "may be the same or different, for example, a methyl group, an ethyl group, an n-propyl group,
an alkyl group such as an i-propyl group, an n-butyl group, a t-butyl group, a 3-dimethylaminopropyl group, a cyclic alkyl group such as a cyclohexyl group, or a phenyl group;
And aryl groups such as -tolyl group, m-tolyl group, pN, N-dimethylaminophenyl group, p-chlorophenyl group, p-nitrophenyl group and p-cyanophenyl group.

Specific examples include diethylcarbodiimide, diisopropylcarbodiimide, dicyclocarbodiimide, diphenylcarbodiimide, di-p-tolylcarbodiimide, 1-ethyl-3- (3'-dimethylaminopropyl) carbodiimide and the like.

In the polyaniline derivative of the present invention, the number of nitrogen atoms involved in the type of the crosslinked structure represented by the formula (II) may be in the range of 0.01 to less than 15% of the nitrogen atoms in the polyaniline. is necessary. If the number of nitrogen atoms involved in the formation of the crosslinked structure of formula (II) is higher than 15% of the nitrogen atoms in the polyaniline, gelation occurs in the polyaniline derivative solution and problems arise in the preparation of paints and the like. . Also, when it is lower than 0.01%,
Polyaniline derivatives with sufficient solubility could not be obtained,
Moreover, its flexibility is also insufficient.

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. It can be dissolved in ether solvents such as tetrahydrofuran, amine solvents such as pyridine, and polar solvents such as dimethyl sulfoxide. From this solution, it is possible to produce self-supporting films and fibers. In addition, processed products such as films and fibers
By doping with an acceptor dopant, 1
A high conductivity of 0 ^{-3 to} 10 S / cm can be exhibited.

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 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 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, or organic acids such as acetic acid, trifluoroacetic acid, benzenesulfonic acid, p-toluenesulfonic acid and the like can be mentioned.

The method of doping these compounds is not particularly limited, and is generally in a gas phase or a liquid phase.
Polyaniline derivative or its molded product and dopan
It can be carried out by contacting the bets compound. Or,
A method of electrochemically doping in a solution of the above-mentioned protonic acid or a salt thereof can also be used.

[0022]

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 ml
After cooling to −10 ° C., the solution was slowly dropped into the aniline solution, and stirring was continued at −10 ° C. for 6 hours. The thus obtained aniphosphorylated polymer having a number average molecular weight of 12,000 (GPC, measured in N-methyl-2-pyrrolidone solvent, number average molecular weight in terms of polystyrene) is sufficiently washed with water, and then dedoped with ammonia water. Was carried out to obtain a soluble polyaniline. The obtained soluble polyaniline 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 thus obtained reduced polyaniline (number average molecular weight: 12,000, m + n ＋ 130) was completely dissolved in 30 ml of N-methyl-2-pyrrolidone under a nitrogen stream. On the other hand, Hycar, a butadiene-acrylonitrile copolymer having carboxyl groups at both ends,
1.97 g of CTBN (molecular weight: about 3600, acrylonitrile component ratio: 10 mol%, manufactured by Goodrich) was added in 3 parts.
Dissolved in 0 ml pyridine and cooled to 0 ° C. 0.2266 g of dicyclohexylcarbodiimide was added and stirring was continued at 0 ° C. for 1 hour. The reduced polyaniline solution was added to the reaction solution, and the reaction was continued for 6 hours while gradually returning to room temperature. The obtained solution was poured into diluted hydrochloric acid (11) with stirring, and the formed precipitate was separated by filtration, further exposed to ammonia vapor, and washed with water to remove hydrogen halide.
After drying, 2.78 g of the polyaniline derivative of the present invention was obtained.

When the infrared absorption spectrum of the obtained polyaniline derivative was measured, it was found to be 1645 cm ⁻¹ (C = 0 expansion and contraction) and 2236 cm due to the structure of the above formula (II).
^-1 (CN stretching) and 2850-2950 cm ^-1 (aliphatic CH stretching) were absorbed. Further, 1600, 1
At 500, 1300, 1170, and 820 cm ⁻¹ , an absorption pattern specific to the polyaniline represented by the general formula (I) was observed, and it was confirmed that the main chain had a polyaniline structure. From the reaction yield, the number of nitrogen atoms involved in forming the crosslinked structure of the formula (II) was 9% of the nitrogen atoms in the polyaniline. Also, m / n determined from ¹³ C NMR spectrum
Was 0.42.

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

Example 2 In Example 1, Hycar CT which is a butadiene-acrylonitrile copolymer having carboxyl groups at both ends is used.
BN (molecular weight about 3600, acrylonitrile component ratio 27
Using 0.20 g of a mol% (manufactured by Goodrich) and 0.452 g of dicyclohexylcarbodiimide, 2.78 g of the polyaniline derivative of the present invention was obtained in the same procedure as described below. When the infrared absorption spectrum of the obtained polyaniline derivative was measured, 1
645 cm ^-1 (C = 0 stretch), 2236 cm ^-1 (CN
Stretching) and absorption at 2850-2950 cm ^-1 (aliphatic CH stretching) were observed. In addition, 1600, 1500,
At 1300, 1170 and 820 cm ⁻¹ , an absorption pattern peculiar to the polyaniline represented by the general formula (I) was observed, and it was confirmed that the main chain had a polyaniline structure. From the reaction yield, the number of nitrogen atoms involved in the formation of the crosslinked structure of the formula (II) was 0.8% of the nitrogen atoms in the polyaniline.
Also, as a result of measuring the ¹³ C NMR spectrum, m / n
Was 0.49.

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

Example 3 In Example 1, Hycar CT which is a butadiene-acrylonitrile copolymer having carboxyl groups at both ends is used.
BN (molecular weight about 3600, acrylonitrile component ratio 17
Using 5.93 g (mol%, manufactured by Goodrich) and 0.878 g of dicyclohexylcarbodiimide, 6.85 g of the polyaniline derivative of the present invention was obtained in the same manner as described below. When the infrared absorption spectrum of the obtained polyaniline derivative was measured, 1
645 cm ^-1 (C = 0 stretch), 2236 cm ^-1 (CN
Stretching) and absorption at 2850-2950 cm ^-1 (aliphatic CH stretching) were observed. In addition, 1600, 1500,
At 1300, 1170 and 820 cm ⁻¹ , an absorption pattern peculiar to the polyaniline represented by the general formula (I) was observed, and it was confirmed that the main chain had a polyaniline structure. From the reaction yield, the number of nitrogen atoms involved in the formation of the crosslinked structure of formula (II) was 13% of the nitrogen atoms in polyaniline. As a result of measuring a ¹³ C NMR spectrum, the value of m / n was 0.38.

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

Example 4 Hycar CTBN which is a butadiene-acrylonitrile copolymer having carboxyl groups at both ends (molecular weight: about 3600, acrylonitrile component ratio: 10 mol%, Go:
Odrich) was dissolved in 20 ml of dehydrated benzene, and 0.28 g of oxalyl chloride was added.
The reaction was carried out at 0 ° C. for 3 hours to produce a butadiene-acrylonitrile copolymer having haloformyl groups at both terminals.
The solvent was removed under reduced pressure to obtain a viscous liquid. The change in the infrared absorption spectrum of the terminal group was confirmed by the change in the infrared absorption spectrum (the absorption around 1740 cm ^-1 derived from the carboxyl group disappeared, and 1792 derived from the chloroformyl group was newly added).
cm ^-1 absorption). This was dissolved in 10 ml of dehydrated chloroform, 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, and reacted at room temperature for 4 hours. This reaction solution was poured into diluted hydrochloric acid (11) with stirring, and the formed precipitate was separated by filtration, further exposed to ammonia vapor, washed with water to remove hydrogen halide, and dried.
2.78 g of the polyaniline derivative of the present invention was obtained.

When the infrared absorption spectrum of the obtained polyaniline derivative was measured, it was found to be 1645 cm ⁻¹ (C = 0 expansion and contraction) and 2236 cm due to the structure of the above formula (II).
^-1 (CN stretching) and 2850-2950 cm ^-1 (aliphatic CH stretching) were absorbed. Further, 1600, 1
At 500, 1300, 1170 and 820 cm ⁻¹ , an absorption pattern peculiar to the polyaniline represented by the general formula (I) was observed, and it was confirmed that the main chain had a polyaniline structure. From the reaction yield, the number of nitrogen atoms involved in forming the crosslinked structure of the formula (II) was 9% of the nitrogen atoms in the polyaniline. In addition, when the ¹³ C NMR spectrum was measured, the value of m / n was 0.43.

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

[0033]

Industrial Applicability The polyaniline derivative of the present invention is soluble in various organic solvents and can obtain a flexible self-supporting film by casting, and can be processed by a method such as coating. It is. Processed products such as films show high conductivity due to doping, and thus are very useful as electronic materials and conductive materials for various uses.

Claims (3)

(57) [Claims] [Claim 1] The following general formula (I) (Where m and n are integers of 2 or more, m / n = 0.01 to 1)
(Polyaniline having a number average molecular weight of 2,000 to 500,000) comprising a structural unit represented by the following formula (II): [Wherein X represents a repeating unit of a butadiene-acrylonitrile copolymer structure represented by the following formula (III): (Y / (x + y) = 0.01-0.5, x> 0, y>
0, z = 5 to 15)], and the number of nitrogen atoms involved in the formation of the crosslinked structure is 0.01 to less than 15% of the nitrogen atoms in the polyaniline. Characteristic polyaniline derivatives. 2. The following formula (IV) obtained by treating an aniphosphorylated polymer with ammonia to obtain a soluble polyaniline and then treating with an excess of hydrazine. (N is an integer of 10 to 5000), 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 general formula (V): (Y / (x + y) = 0.01-0.5, x> 0, y>
0, z = 5 to 15) with a butadiene-acrylonitrile copolymer having carboxyl groups at both ends and a carboxyl group in the presence of an equivalent or more equivalent amount of N, N'-disubstituted carbodiimide. The method for producing a polyaniline derivative according to claim 1, wherein: 3. The aniphosphorylated polymer is treated with ammonia to form a soluble polyaniline, which is then treated with an excess of hydrazine to obtain the following formula (IV): (N is an integer of 10 to 5000) reduced polyaniline having a number average molecular weight of 2,000 to 500,000 consisting of a structural unit represented by the following general formula (VI): ( Y represents chlorine or bromine, and y / (x + y) = 0.0
1-0.5, x> 0, y> 0, z = 5-15) butadiene having a haloformyl group at both terminals
The method for producing a polyaniline derivative according to claim 1, wherein the reaction is carried out with an acrylonitrile copolymer.