JPH0598000A - Polyaniline derivative and its production - Google Patents

Abstract

PURPOSE:To produce a polyaniline derivative capable of being swollen in organic solvents, moldable or processable into a flexible self-supporting film and fibers. CONSTITUTION:An aniline oxidative polymer is treated with ammonia to give a soluble type polyaniline, which is then treated with an excessive amount of hydrazine to give a reduction type polyaniline of a formula I (n is 10-5,000), having 2,000-500,000 number-average molecular weight, which is reacted with a butadiene-acrylonitrile copolymer of formula II [y/(x+y)=0.01-0.5; x>0; y>0; Z=5-15] containing carboxyl groups at both ends or a butadiene-acrylonitrile copolymer of formula III containing haloformyl groups at both ends to give a polyaniline derivative comprising a polyaniline of formula IV (m and n are >=2; m/n=0.01-100; m+n=10-5,000) having 2,000-5000,000 number-average molecular weight as a main chain and a crosslinked structure of formula V (x is butadiene-acrylonitrile copolymer of formula VI) on the main chain wherein the number of nitrogen atoms in the crosslinked structure is 15-40% nitrogen atoms in the polyaniline.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyaniline derivative capable of swelling in an organic solvent and forming a flexible self-supporting film or fiber, and a method for producing the same.

[0002]

2. Description of the Related Art In recent years, 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 because there are many strong hydrogen bonds between the molecular chains, it is insoluble in most organic solvents. Moreover, 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. To that end, for example, fibers of polymeric materials,
A substrate having a desired shape such as a porous body is impregnated with a monomer consisting of aniline, and the monomer is brought into contact with a suitable polymerization catalyst, or is polymerized by electrolytic oxidation to form a conductive composite material, or A similar composite material was obtained by polymerizing the monomer in the presence of the thermoplastic polymer powder.

On the other hand, a 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. So.
c., Chem. Commun., 1989, 1736). However, this polyaniline is also almost insoluble in other general-purpose organic solvents,
The applicable range was limited. Further, polyaniline derivatives soluble in an organic solvent have been synthesized by utilizing various aniline derivatives, but it has not been possible to form a film having sufficient flexibility. On the other hand, if the polymer compound can be gelled, gel stretching or gel spinning,
It can be processed using a technique such as gel formation.

[0004]

SUMMARY OF THE INVENTION The present invention aims to solve the above-mentioned problems in the prior art. That is, the object of the present invention is to be swellable with an organic solvent even if the number of nitrogen atoms involved in the formation of a crosslinked structure is increased, and to form a flexible self-supporting film or fiber by gelling. A polyaniline derivative and a method for producing the same are provided.

[0005]

Means for Solving the Problems As a result of extensive studies to solve the above problems, the present inventors have made polyaniline react with a butadiene-acrylonitrile copolymer having a carboxyl group or a haloformyl group at both ends, It was found that a polyaniline derivative having a crosslinked structure capable of swelling with an organic solvent and capable of forming a flexible self-supporting film or fiber was obtained, and completed the present invention.

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

[Chemical 8] (In the formula, m and n are integers of 2 or more, m / n = 0.01 to 1
00, m + n = 10 to 5,000) having a number average molecular weight of 2,000 to 500,000 of a polyaniline as a main chain, the main chain having the following formula (II)

[Chemical 9] [In the formula, X represents a repeating unit of a butadiene-acrylonitrile copolymer structure represented by the following formula (III).

[Chemical 10] (Y / (x + y) = 0.01 to 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 15 to 40% of the nitrogen atoms in polyaniline. ..

On the other hand, in the method for producing a polyaniline derivative of the present invention, the aniline-oxidized polymer is treated with ammonia to give a soluble polyaniline, and then treated with an excess of hydrazine to obtain the following formula (IV).

[Chemical 11] (A) a reduced polyaniline having a number average molecular weight of 2,000 to 500,000 comprising a structural unit represented by (n is an integer of 10 to 5,000) (a) the following formula (V)

[Chemical formula 12] (Y / (x + y) = 0.01 to 0.5, x> 0, y>
0, z = 5 to 15) and a butadiene-acrylonitrile copolymer having a carboxyl group at both ends, in the presence of an equivalent amount or more of N, N′-disubstituted carbodiimides based on the carboxyl group. Or (b) the following formula (IV)

[Chemical 13] (Y represents chlorine or bromine, and y / (x + y) = 0.0
1-0.5, x> 0, y> 0, z = 5 to 15), and butadiene having haloformyl groups at both ends.
It is characterized by reacting with an acrylonitrile copolymer.

The production method of the polyaniline derivative of the present invention will be further described. The reduced polyaniline represented by the formula (IV) and having a number average molecular weight of 2,000 to 500,000 is produced as follows. That is, using aniline at a low temperature, using ammonium persulfate or the like as an oxidizing agent,
For example, an aniline oxidation 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, hydrazine equivalent to or more than nitrogen atom in polyaniline, preferably 3 times or more, is added in a nitrogen atmosphere for 24 hours or more at 0 to 30 ° C.
It can be carried out by stirring. The reduced polyaniline thus 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.

Next, the reduced polyaniline is reacted with a butadiene-acrylonitrile copolymer having carboxyl groups at both ends represented by the above formula (V), or at 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 a terminal carboxyl group and an equivalent amount or more of N, N'-disubstituted carbodiimides are dissolved in -10 -10
The mixture is cooled to 0 ° C., and the mixture is stirred at that temperature for 1 to 4 hours. Then, the amide solution of the reduced polyaniline is added, and the mixture is slowly stirred at room temperature and further stirred 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.

Alternatively, a butadiene-acrylonitrile copolymer having a haloformyl group at both ends as shown in the above (VI) is dissolved in chloroform and slowly added dropwise to an amide solution of reduced polyaniline, and the mixture is cooled to 1 to 24 at room temperature. Continue stirring for 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. Since the polyaniline derivative of the present invention thus obtained does not change the length of the polyaniline main chain during production, the value of m + n of the polyaniline represented by the above formula (I) is the reduced form represented by the above formula (IV). It becomes the same as the value of n of polyaniline. In addition, after the completion of the crosslinking reaction, m of the polyaniline derivative produced by allowing an oxidizing agent or a reducing agent to exist or electrochemically oxidizing or reducing it
/ 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 is increased, and when the polyaniline derivative of the present invention is reduced by a reducing agent or electrochemical reduction, m is increased. The value of decreases. The value of m / n is ¹³ C N
It can be determined from the intensity ratio of each peak of the quinoid structure (chemical shift 138 ppm / TMS) and the peak of benzenoid (chemical shift 122 ppm / TMS) in the MR spectrum.

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

Examples of the butadiene-acrylonitrile copolymer having a carboxyl group at both ends represented by the above formula (V) used in the present invention include, for example, Goodri.
Hycar CTBN (trade name) marketed by ch company is applicable to the present invention.

Further, the butadiene-acrylonitrile copolymer represented by the above formula (VI) having haloformyl groups at both ends is a dicarboxylic acid represented by the above formula (V), or an ester of the dicarboxylic acid (such as methyl or ethyl). It can be easily derived from an ester of a lower alcohol) or a salt of a dicarboxylic acid thereof (alkali metal salt, ammonium salt, etc.). That is, it can be synthesized from dicarboxylic acid as follows. (I) The present invention is carried out by adding an equivalent amount or more of an inorganic halogen compound such as phosphoryl chloride, thionyl chloride, phosphorus pentachloride or phosphorus trichloride to the dicarboxylic acid and reacting it in an inert solvent such as benzene or chlorobenzene. It is possible to obtain a butadiene-acrylonitrile copolymer having haloformyl groups at both ends used for. In this case, zinc chloride, pyridine, iodine,
Triethylamine or the like may be added as a catalyst. (Ii)
Acid halides such as benzoyl chloride, phthal chloride, oxalyl chloride, etc., α, α-dihalogenoethers, halogenated alkylamines, triphenylphosphine / carbon tetrachloride in an equimolar amount or more with respect to the dicarboxylic acid. Obtained by reacting an organic halide such as an organophosphorus halide consisting of chlorobenzene, chlorobenzene, chlorobenzene, etc. in an inert solvent such as benzene, chlorobenzene, etc. You can

From the dicarboxylic acid ester, a triphenylphosphohalide or its complex with boron fluoride is used in an equimolar amount or more with respect to the dicarboxylic acid ester to react at both ends of the present invention. A butadiene-acrylonitrile copolymer having a haloformyl group can be obtained.

Further, the dicarboxylic acid salt is reacted with an equimolar amount of an inorganic halogen compound such as phosphoryl chloride or phosphorus pentachloride or a complex of thionyl chloride and dimethylformamide, relative to the dicarboxylic acid salt, A butadiene-acrylonitrile copolymer having haloformyl groups at both ends used in the present invention can be obtained. In addition to these, any reaction that can convert a carboxyl group to a haloformyl group can be applied without any problem, and a butadiene-acrylonitrile copolymer having haloformyl groups at both ends used in the present invention can be 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), where R'and R ″ may be the same or different, for example, methyl group, ethyl group, n-propyl group,
Alkyl group such as i-propyl group, n-butyl group, t-butyl group, 3-dimethylaminopropyl group, or cyclic alkyl group such as cyclohexyl group, or phenyl group, p
Aryl groups such as -tolyl group, m-tolyl group, p-N, N-dimethylaminophenyl group, p-chlorophenyl group, p-nitrophenyl group and p-cyanophenyl group.

Specific examples thereof 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 formation of the crosslinked structure represented by the above formula (II) is 15 to 40 on average in the polyaniline.
It must be in the range of%. When the number of nitrogen atoms involved in the formation of the cross-linked structure of the formula (II) is higher than 40% of the nitrogen atoms in polyaniline, it becomes difficult to swell, which causes a problem in gel preparation. Also, 15
When it is lower than 0.1%, the polyaniline derivative is dissolved and a polyaniline derivative having sufficient gel strength cannot be obtained, and it is difficult to process it into a flexible self-supporting film or fiber.

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 swellable in ether solvents such as and tetrahydrofuran, amine solvents such as pyridine, and polar solvents such as dimethyl sulfoxide. A self-supporting film or fiber can be produced from a solution obtained by swelling the polyaniline derivative. Further, the processed product such as the film or the fiber can exhibit a high conductivity of 10 ⁻³ to 10 S / cm by doping with a dopant having an acceptor property.

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 Lewis acids such as iron trichloride, molybdenum chloride, antimony chloride and arsenic pentafluoride, and various compounds such as acetic acid, trifluoroacetic acid, benzenesulfonic acid and p-toluenesulfonic acid.

The method of doping these compounds is not particularly limited, and generally, in a gas phase or a liquid phase,
It can be carried out by contacting the polyaniline derivative, its gel or its molded product with the dopand compound. Alternatively, a method of electrochemically doping in the solution of the above-mentioned protonic acid or its salt can be used.

[0022]

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
After cooling to -10 ° C, the solution was slowly added dropwise to the above aniline solution, and stirring was continued at -10 ° C for 6 hours. The thus obtained aniline oxidized polymer having a number average molecular weight of 12000 (GPC, measured in a solvent of N-methyl-2-pyrrolidone, polystyrene equivalent number average molecular weight) was thoroughly washed with water, and then dedoped with aqueous ammonia. Then, soluble polyaniline was obtained. The obtained soluble polyaniline was dispersed in 200 ml of water, 50 ml of hydrazine was added under a nitrogen atmosphere, the mixture was continuously stirred at room temperature for 24 hours, filtered and dried to obtain an off-white reduced polyaniline.

1 g of the reduced polyaniline (number average molecular weight 12000, m + n≈130) thus obtained was completely dissolved in 30 ml of N-methyl-2-pyrrolidone under a nitrogen stream. On the other hand, Hycar, which is a butadiene-acrylonitrile copolymer having carboxyl groups at both ends,
CTBN (molecular weight of about 3600, acrylonitrile component ratio 10 mol%, manufactured by Goodrich) 3.94 g of 3
It was dissolved in 0 ml of pyridine and cooled to 0 ° C. 0.2266 g of dicyclohexylcarbodiimide was added and stirring was continued for 1 hour at 0 ° C. 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 resulting solution was poured into 11 diluted hydrochloric acid with stirring, the formed precipitate was filtered off, exposed to ammonia vapor and washed with water to remove hydrogen halide,
After drying, 4.78 g of the polyaniline derivative of the present invention was obtained.

The infrared absorption spectrum of the obtained polyaniline derivative was measured and found to be 1645 cm ^-1 (C = 0 expansion / contraction) and 2236 cm due to the structure of the above formula (II).
⁻¹ (CN stretching) and 2850 to 2950 cm ⁻¹ (aliphatic C—H stretching) were observed to be absorbed. Furthermore, 1600, 1
Absorption patterns peculiar to the polyaniline represented by the general formula (I) were observed at 500, 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 involved in the formation of the crosslinked structure of formula (II) was 19% of the nitrogen atoms in polyaniline. In addition, m / determined from ¹³ C NMR spectrum
The value of n was 0.34.

1 g of the obtained polyaniline derivative was put in 9 g of N-methyl-2-pyrrolidone, swollen and gelled to prepare a very flexible film or fiber. Further, when this film or fiber 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,
Similar processing was possible using an organic solvent such as dichloroethane, dichloromethane or tetrahydrofuran.

Example 2 Hycar CT, which is a butadiene-acrylonitrile copolymer having carboxyl groups at both ends in Example 1, was used.
BN (molecular weight about 3600, acrylonitrile component ratio 27
7.88 g of the polyaniline derivative of the present invention in the same procedure as described below, using 7.88 g of mol% (produced by Goodrich) and 0.9064 g of dicyclohexylcarbodiimide.
Obtained. The infrared absorption spectrum of the obtained polyaniline derivative was measured and found to be 1645 cm ⁻¹ (C = 0 expansion and contraction), 2236 cm ⁻¹ (C) due to the structure of the above formula (II).
N stretch), 2850 to 2950 cm ^-1 (aliphatic C-H)
(Stretching) was observed. Furthermore, 1600, 150
General formula (I) at ⁰ , 1300, 1170, 820 cm ^-1
The absorption pattern peculiar to polyaniline shown by 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 40% of the nitrogen atoms in polyaniline. The m / n value determined from the ¹³ C NMR spectrum was 0.21.

1 g of the obtained polyaniline derivative was put into 5 g of N-methyl-2-pyrrolidone and allowed to swell to produce a very flexible film or fiber. Furthermore, when this film or fiber was dipped in a 20% sulfuric acid aqueous solution for 24 hours and was then dried, the conductivity was 0.1 S / c.
It was m. Similar processing is also possible by using an organic solvent such as N, N-dimethylacetamide, N, N-dimethylformamide, pyridine, chloroform, dichloroethane, dichloromethane or tetrahydrofuran instead of N-methyl-2-pyrrolidone. It was

Example 3 Hycar CTBN which is a butadiene-acrylonitrile copolymer having carboxyl groups at both ends (molecular weight: about 3600, acrylonitrile component ratio: 17 mol%, Go:
odrich) 3.94 g was dissolved in 20 ml of dehydrated benzene and 0.58 g of oxalyl chloride was added to obtain 7
The reaction was carried out at 0 ° C. for 3 hours to form a butadiene-acrylonitrile copolymer having haloformyl groups at both ends, and the solvent and the like were removed under reduced pressure to obtain a viscous liquid. It was confirmed that the terminal group was chloroformylated by changing the infrared absorption spectrum (absorption near 1740 cm ⁻¹ derived from the carboxyl group disappeared, and 1792c newly derived from the chloroformyl group) was confirmed.
m ⁻¹ absorption occurred). This was dissolved in 10 ml of dehydrated chloroform and completely dissolved in 30 ml of N-methyl-2-pyrrolidone under a nitrogen stream to give reduced polyaniline 1.
It was slowly added dropwise to the solution of g and reacted at room temperature for 4 hours. The reaction solution was poured into 11 diluted hydrochloric acid with stirring, the formed precipitate was filtered off, exposed to ammonia vapor, washed with water to remove hydrogen halide, and dried.
4.57 g of the polyaniline derivative of the present invention was obtained.

The infrared absorption spectrum of the obtained polyaniline derivative was measured and found to be 1645 cm ^-1 (C = 0 expansion / contraction) and 2236 cm due to the structure of the above formula (II).
⁻¹ (CN stretching) and 2850 to 2950 cm ⁻¹ (aliphatic C—H stretching) were observed to be absorbed. Furthermore, 1600, 1
Absorption patterns peculiar to the polyaniline represented by the general formula (I) were observed at 500, 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 involved in the formation of the crosslinked structure of formula (II) was 18% of the nitrogen atoms in polyaniline. In addition, m / determined from ¹³ C NMR spectrum
The value of n was 0.35.

1 g of the obtained polyaniline derivative was put in 5 g of N-methyl-2-pyrrolidone and allowed to swell to produce a very flexible film or fiber. Furthermore, when this film or fiber was dipped in a 20% sulfuric acid aqueous solution for 24 hours and was then dried, the conductivity was 0.01 S /
It was cm. Similar processing is also possible by using an organic solvent such as N, N-dimethylacetamide, N, N-dimethylformamide, pyridine, chloroform, dichloroethane, dichloromethane or tetrahydrofuran instead of N-methyl-2-pyrrolidone. It was

[0031]

INDUSTRIAL APPLICABILITY The polyaniline derivative of the present invention can be swelled with various organic solvents and can be molded into a flexible self-supporting film or fiber. These molded products show high conductivity by doping, and are very useful as various electronic materials and conductive materials for various purposes.

Claims (3)

[Claims] 1. The following general formula (I): (In the formula, m and n are integers of 2 or more, m / n = 0.01 to 1
00, m + n = 10-5000) and having a number average molecular weight of 2,000-500,000 polyaniline as a main chain, the main chain is represented by the following formula (II): [In the formula, X represents a repeating unit of a butadiene-acrylonitrile copolymer structure represented by the following formula (III). [Chemical 3] (Y / (x + y) = 0.01 to 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 15 to 40% of the nitrogen atoms in polyaniline. Polyaniline derivative. 2. An aniline-oxidized polymer is treated with ammonia to obtain a soluble polyaniline, and then treated with an excess of hydrazine to obtain the following formula (IV): A reduced polyaniline having a number average molecular weight of 2,000 to 500,000, which comprises a structural unit represented by (n is an integer of 10 to 5000), is represented by the following general formula (V): (Y / (x + y) = 0.01 to 0.5, x> 0, y>
0, z = 5 to 15) and a butadiene-acrylonitrile copolymer having a carboxyl group at both ends and a carboxyl group and an equivalent amount or more of N, N′-disubstituted carbodiimides. The method for producing a polyaniline derivative according to claim 1, wherein 3. An aniline-oxidized polymer is treated with ammonia to obtain a soluble polyaniline, and then treated with an excess of hydrazine to obtain the following formula (IV): A reduced polyaniline having a number average molecular weight of 2,000 to 500,000 composed of structural units represented by the formula (n is an integer of 10 to 5,000) is 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 to 15), and butadiene having haloformyl groups at both ends.
The method for producing a polyaniline derivative according to claim 1, wherein the polyaniline derivative is reacted with an acrylonitrile copolymer.