JPH06256509A - Polyaniline-polyether block copolymer and its production - Google Patents

Abstract

PURPOSE:To produce a copolymer containing a specified polyaniline block (partly oxidized unit), soluble in an organic solvent or capable of gelation and capable of forming a flexible and self-supporting film or fiber. CONSTITUTION:This polyaniline-polyether block copolymer is represented by formula I [A is a polyaniline block represented by the formula H(NHAR)n ; Ar is 1,4-phnylene or its halogen-substituted group, etc., (n) is 10 to 5000; R<1> is a 1 to 30C alkylene; R<2> is a 1 to 30C alkylene, an alkylenecarbonyl, an alkenylene, a 6 to 30C arylene, etc. In the case R<2> contains a carbonyl, this group is bonded to the terminal oxygen of the polyether block; (k) is 10 to 1000] and having 2000 to 1000000 number-average molecular weight. The partly oxidized block may contain a structural unit of formula II (Q is 2,5- cyclohexadien-1,4-ylidene, etc.). This copolymer is synthesized by oxidative polymerization of aniline its halogen-, alkoxy-or alkyl-substitute in the presence of a polyether having amino groups on both the terminals of formula III.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyaniline-polyether block copolymer which is soluble or gellable in an organic solvent and can form a flexible self-supporting film, and a method for producing the same. Regarding

[0002]

2. Description of the Related Art In recent years, polyaniline has been used as a new electronic material and conductive material for battery electrode materials, antistatic materials,
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. are being studied. However, in general, polyaniline has a highly developed π-conjugated system, so that the polymer main chain is rigid, the interaction between the molecular chains is strong, and many strong hydrogen bonds exist between the molecular chains. Since it is almost insoluble in organic solvents and does not melt even when heated, it has poor moldability and cannot be processed into a film.

For that purpose, for example, fibers of polymeric materials,
Impregnate a base material of a desired shape such as a porous body with a monomer,
This monomer is polymerized by contact with a suitable polymerization catalyst or by electrolytic oxidation to form a conductive composite material, or alternatively, the monomer is polymerized in the presence of a thermoplastic polymer powder to prepare a similar composite material. I was getting. On the other hand, N-methyl-
Polyaniline soluble only in 2-pyrrolidone has been synthesized (M. Abe et al .; J. Chem. So.
c. Chem. Commun. , 1989, 173
6). However, this polyaniline was hardly dissolved in other general-purpose organic solvents, and its application range was limited. Although polyaniline derivatives soluble in organic solvents have been synthesized by utilizing various aniline derivatives, it was not possible to provide a film having sufficient flexibility. On the other hand, it is known that a polymer compound can be processed by using techniques such as gel stretching, gel spinning, and gel formation, if gelation is possible.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above situation in the prior art. That is, an object of the present invention is to provide a polyaniline-polyether block copolymer which is soluble or gellable in an organic solvent and can form a flexible self-supporting film or fiber, and a method for producing the same. To provide.

[0005]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventor has found that aniline is oxidatively polymerized in the presence of a polyether having amino groups at both ends to obtain both polyethers. It was found that a block copolymer having a structure in which a polyaniline chain extends from a terminal amino group can be dissolved or gelled in an organic solvent and can form a flexible self-supporting film or fiber. The invention was completed.

The polyaniline-polyether block copolymer of the present invention is represented by the following formula (I). ^{A-NH-R 2 - (} O-R 1) k -O-R 2 -NH-A (I) wherein, A is polyaniline block or partial oxidation thereof represented by the formula (II), H -(NH-Ar) _n- (II) (In the formula, Ar represents a 1,4-phenylene group or its halogen, alkoxy or alkyl-substituted product, and n is 1
It represents an integer of 0 to 5000. ) R ¹ represents an alkylene group having 1 to 30 carbon atoms, R ² represents an alkylene group having 1 to 30 carbon atoms, an alkylene carbonyl group, an alkenylene group or an alkenylene carbonyl group, or an arylene carbonyl group or arylene having 6 to 30 carbon atoms. Represents a carbonyl group, provided that when R ² has a carbonyl group,
The carbonyl group bonds to the terminal oxygen of the polyether block. k represents an integer of 10 to 1000. )]

The polyaniline-polyether block copolymer of the present invention has the following formula (III) H ₂ N—R ² — (O—R ¹ ) _k —O—R ² —NH ₂ (III) (wherein R ¹ , R ² and k have the same meanings as defined above.) Oxidative polymerization of aniline or its halogen, alkoxy or alkyl-substituted product in the presence of a polyether having amino groups at both ends. Can be manufactured by.

The present invention will be described in detail below. The polyaniline-polyether block copolymer represented by the above formula (I) of the present invention has a number average molecular weight of 2,000 to
1,000,000, preferably 2,100-230,
000, and the polyaniline block preferably has a number average molecular weight of 900 to 100,000, and the polyether block preferably has a number average molecular weight of 300 to 30,000. In the polyaniline-polyether block copolymer represented by the above formula (I) of the present invention, the group R ¹ in the polyether block is an alkylene group having 1 to 30 carbon atoms and they are bonded via an ether bond. is doing. Examples of the alkylene group include methylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene,
Examples thereof include linear or branched alkylene groups such as 2-methylpentamethylene and hexamethylene.

The linking group R ¹ for connecting the polyether block and the polyaniline block is an alkylene group or alkylenecarbonyl group having 1 to 30 carbon atoms, an alkenylene group or alkenylenecarbonyl group, or 6 carbon atoms.
Represents an arylene group or an arylenecarbonyl group of 30. Incidentally. When R ² has a carbonyl group, the carbonyl group is bonded so as to be adjacent to the terminal oxygen of the polyether block. As a specific example of R ² ,
Methylene, methylenecarbonyl, ethylene, ethylenecarbonyl, propylene, propylenecarbonyl, trimethylene, trimethylenecarbonyl, tetramethylene, tetramethylenecarbonyl, pentamethylene, 2-methylpentamethylene, hexamethylene, cyclohexylene,
Linear, branched or cyclic alkylene groups such as decamethylene, alkenylene groups such as vinylene, propenylene, butenylene and pentenylene, p-phenylene, m-phenylene, o-phenylene, phenylenecarbonyl, tolylene, biphenylene, naphthylene and other arylene groups. The group is raised.

The polyaniline block represented by the formula (II) of the polyaniline-polyether block copolymer of the present invention is capable of reversible electron transfer. Therefore, it is possible to use a protonic acid, a protonic acid salt, an electron-accepting substance, or electrochemically oxidize. On the other hand, the oxidized polyaniline block contains a base, an electron-donating substance,
It is possible to dedope or reduce by using a reducing agent or by electrochemically reducing. In this case, the structure of the polyaniline block will take a structure according to various states (oxidation, reduction). Further, this change can be caused not only in the entire polyaniline block but also in a part of the polyaniline block. A typical partial structure in that case is shown by the following formula. However, regarding the doping state, the case where a protonic acid is used is illustrated, but when another acid or an electron-accepting substance is used, a structure corresponding to each is taken.

[0011]

[Chemical 1] (In the formula, Ar has the same meaning as defined above, and Q is 2,5-
Cyclohexadiene-1,4-ylidene or a halogen, alkoxy or alkyl substituted product thereof, and HA represents a protic acid)

Such a change is described, for example, in E. M. Gen
ies et al. , Synth. Met. 36 (1
990) 139-182 and the like, which is an essential property of the polyaniline block. Therefore, even if the structure of the polyaniline block is changed by a substance that changes the electronic state of the main chain, such as oxidation or reduction, or doping or dedoping, or a substance that transfers or receives hydrogen, the present invention is not limited in any way. .

The polyaniline-polyether block copolymer of the present invention can be produced, for example, by the following method. That is, ammonium persulfate is added to an aqueous solution of a polyether having amino groups at both ends, this is kept at 0 ° C., and an aqueous solution of aniline or its derivative in hydrochloric acid is added thereto with stirring. In this case, the amount of ammonium persulfate, which is an oxidizing agent, is adjusted so as to be 0.1 to 10 times mol, and most typically 0.9 to 1.5 times mol, with respect to aniline or its derivative to be added. Also, the amount of hydrochloric acid is 0.9 to 100 times the molar amount of aniline or its derivative used, and in the most typical case 0.9 to
Prepare so that the molar ratio is 5 times. 1 to the obtained mixture
Continue stirring at 0 ° C. for 48 hours, most typically 6 hours. The formed solid matter is filtered off and further subjected to dedoping treatment with 5% aqueous ammonia to obtain the polyaniline-polyether block copolymer of the present invention having the main structure of the formula (IV-2). Further, if necessary, a reducing agent such as hydrazine is acted on to reduce the polyaniline block to obtain the polyaniline-polyether block copolymer of the present invention having the main structure of the formula (IV-3). .

Since the product after the dedoping treatment may contain polyaniline which is not block-copolymerized, it may be purified if desired. For example, a solvent that does not dissolve polyaniline, but does dissolve the polyaniline-polyether block copolymer of the present invention, for example,
It may be purified by extraction with chloroform or the like.

When a polyether having amino groups at both ends which is insoluble in water is used as a raw material, the polyether is dissolved in a solvent which is resistant to oxidation (benzene, nitrobenzene, dichloromethane, etc.) and then dissolved. Add an oxidizing agent that is active in the solvent, such as iron chloride, then add aniline or its derivative, and add 1 at 0 ° C.
The reaction may be performed for up to 48 hours, whereby the polyaniline-polyether block copolymer of the present invention can be obtained.

In the present invention, the polyether having amino groups at both ends used as a raw material is a polyether represented by the following formula (III).
Polyoxyethylenediamine (PEO amine) # 400 [R ¹ = ethylene, manufactured by Kawaken Fine Chemicals Co., Ltd.,
R ² = triethylene, k = about 7 to 9], # 6000 [R
¹ = ethylene, R ² = triethylene, k = about 178 to 1
89], and Erasmer 1000 [polytetramethylene oxide-di-p-aminobenzoate, R ¹ = tetramethylene, R ² = p-, manufactured by Ihara Chemical Industry Co., Ltd.
Phenylene carbonyl _{(-C 6 H 4 -C (=} O) -),
k = about 12 to 14] and the like are preferably used. It is also possible to use a polyether having amino groups formed at the terminals by aminoetherifying or aminoacylating the terminal hydroxyl groups of the polyether having hydroxyl groups at both ends.

The aniline or its derivative used in the present invention includes aniline, o-anisidine, m-
Examples include anisidine, o-toluidine, m-toluidine, o-ethylaniline, o-chloroaniline, m-chloroaniline and the like.

The polyaniline-polyether block copolymer of the present invention produced as described above is a block copolymer of a polyaniline block having a high solvent solubility and a polyaniline block having functions such as conductivity and various chromisms. It is characterized in that it is polymerized. Further, the polyether block has a function of imparting elasticity and flexibility in the bulk. Therefore, the polyaniline-polyether block copolymer of the present invention comprises an amide-based solvent such as N-methyl-2-pyrrolidone or N, N-dimethylacetamide, a halogenated hydrocarbon solvent such as chloroform, dichloroethane or dichloromethane, or tetrahydrofuran. And the like can be dissolved or gelled with an ether solvent such as, an amine solvent such as pyridine, and a polar solvent such as dimethyl sulfoxide. From this solution or gel it is possible to produce self-supporting films and fibers. Further, the processed product such as this film or fiber shows a high conductivity of 10 ⁻³ to 10 ² S / cm when doped with an acceptor dopant.

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, Lewis acids such as iron trichloride, molybdenum chloride, antimony chloride and arsenic pentafluoride, organic acids such as acetic acid, trifluoroacetic acid, benzenesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, camphor sulfonic acid, polyethylene Various compounds such as polymeric acids such as sulfonic acid, polyethylene carboxylic acid, polyacrylic acid and polystyrene sulfonic acid can be mentioned. The method of doping these compounds is not particularly limited, and any known method can be used. One is polyaniline-polyether block copolymer, its solution,
It suffices to bring the gel or the molded product thereof into contact with the dopant compound, and it can be carried out in the gas phase or the liquid phase. Alternatively, a method of electrochemically doping in the solution of the above-mentioned protonic acid or its salt can be used.

[0020]

EXAMPLES The present invention will be described below with reference to examples. Example 1 PEO amine # 400 which is a polyether having amino groups at both ends [R ¹ = ethylene, R ² = triethylene,
k = about 7-9] was dissolved in 30 ml of water, 24.5 g of ammonium persulfate was added and dissolved, and the mixture was kept at 0 ° C. Aniline (10 g) and concentrated hydrochloric acid (50 ml) were dissolved in water (50 ml), cooled to 0 ° C., and added dropwise to the above polyether-containing solution. After dropping for 1 hour, 0 hours for 6 hours
Stirring was continued at ° C. The produced solid substance was separated by filtration and dedoped with 5% aqueous ammonia. The product was extracted with chloroform to obtain the polyaniline-polyether block copolymer of the present invention. The yield was 10.1 g.
When the infrared absorption spectrum was examined, 1600, 150
Absorption of polyaniline 0,1300,1170,820cm ^-1 (corresponding to the structure of formula (IV-2)) was observed, also the absorption of ethylene was observed in 2800~2950cm ^-1. Also, in view of the yield, n = about 25. The number average molecular weight of this block copolymer is about 5,000.
It was 0. 1 g of the obtained polyaniline-polyether block copolymer was put in 5 g of N-methyl-2-pyrrolidone and dissolved by stirring at room temperature, and it was possible to form a film by spinning or stretching. Furthermore, when this film was exposed to hydrochloric acid vapor for 4 hours to be doped, the conductivity was 0.8.
It was S / cm. Also, similar processing is 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. there were.

Example 2 PEO Amine # 600 instead of PEO Amine # 400
0 [R ¹ = ethylene, R ² = triethylene, k = about 17
8-189] and ammonium persulfate 2.45.
g, aniline 1 g, and hydrochloric acid 30 ml were used in Example 1
According to this, 1.68 g of a polyaniline-polyether block copolymer of the present invention was obtained. When the infrared absorption spectrum was investigated, 1600, 1500, 1300, 1170,
Infrared absorption of polyaniline (corresponding to the structure of formula (IV-2)) was observed at 820 cm ^−1, and 2800 to 2950.
Absorption of ethylene was observed at cm ^-1 . Further, in view of the yield, n = about 30. The average molecular weight of this block copolymer was about 14,000. 1 g of the obtained polyaniline-polyether block copolymer was N-
It was dissolved in 5 g of methyl-2-pyrrolidone and stirred at room temperature, and it was possible to form a film by spinning or stretching.
Further, when this film was exposed to hydrochloric acid vapor for 4 hours to be doped, the conductivity was 0.9 S / cm. Further, instead of N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide,
Similar processing was possible using organic solvents such as pyridine, chloroform, dichloroethane, dichloromethane and tetrahydrofuran.

Example 3 Erasmer 1000 which is a polyether having amino groups at both ends [polytetramethylene oxide-di-p-aminobenzoate, R ¹ = tetramethylene, R ² = p-
Phenylene carbonyl _{(-C 6 H 4 -C (=} O) -),
k = about 12 to 14] 1 g was dissolved in 30 ml of chloroform, 3.2 g of iron (III) chloride was added and dissolved, and the mixture was kept at 0 ° C. 1.8 g of aniline was dissolved in 10 ml of chloroform, cooled to 0 ° C., and added dropwise to the solution containing the above polyether. After dripping over 1 hour, 6 hours at 0 ° C
The stirring was continued at. The produced solid substance was separated by filtration and dedoped with 5% aqueous ammonia. From this, the polyaniline-polyether block copolymer of the present invention was extracted with chloroform. The yield was 1.47 g. ・ By examining the infrared absorption spectrum, 1600, 1500, 1300,
Polyaniline (Formula (IV-2) at 1170 and 820 cm ^-1
(Corresponding to the structure of)
Absorption of ethylene was observed at ˜2950 cm ⁻¹ . Also, in view of the yield, n = about 20. The number average molecular weight of this block copolymer was about 4,900. 1 g of the obtained polyaniline-polyether block copolymer was put into 5 g of N-methyl-2-pyrrolidone and dissolved by stirring at room temperature, and it was possible to form a film by spinning or stretching. Furthermore, when this film was exposed to hydrochloric acid vapor for 4 hours to be doped, the conductivity was 0.15 S / c.
It was m. Also, similar processing is 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. there were.

Example 4 As a polyether having amino groups at both ends, a diol type polypropylene glycol (average molecular weight 300
0, manufactured by Wako Pure Chemical Industries, Ltd., k = about 22) and 4-fold molar 4-
A product obtained by reacting with aminobenzoic acid to form 4-aminobenzoic acid ester at the terminal (average molecular weight of about 3238, R ¹ = propylene, R ² = -C ₆ H ₄ -C (= O)-) was used. 1 g of the above polyether was used in place of PEO amine # 400 in Example 1, 9.80 g of ammonium persulfate, 4.0 g of aniline and 3 g of hydrochloric acid were used.
Using 0 ml, 4.37 g of the polyaniline-polyether block copolymer of the present invention was obtained according to Example 1. When the infrared absorption spectrum was examined, 1600, 1
Infrared absorption was observed in the polyaniline 500,1300,1170,820cm ^-1 (corresponding to the structure of formula (IV-2)), also the absorption of ethylene was observed in 2800~2950cm ^-1. Further, the yield was n = about 60. The number average molecular weight of this block copolymer is about 1
It was 5,000. 1 g of the obtained polyaniline-polyether block copolymer was put in 5 g of N-methyl-2-pyrrolidone and dissolved by stirring at room temperature, and it was possible to form a film by spinning or stretching. Further, when this film was exposed to hydrochloric acid vapor for 4 hours to be doped, the conductivity was 1.0 S / cm. Further, instead of N-methyl-2-pyrrolidone, N, N-dimethylacetamide,
Similar processing was possible using an organic solvent such as N, N-dimethylformamide, pyridine, chloroform, dichloroethane, dichloromethane and tetrahydrofuran.

Example 5 A polyaniline-polyether block copolymer of the present invention was obtained in the same manner as in Example 2 except that 2 g of aniline and 4.9 g of ammonium persulfate were used. The yield is 2.
It was 36 g. When I examined the infrared absorption spectrum,
1600, 1500, 1300, 1170, 820cm
^-1 infrared absorption polyaniline (corresponding in structure to Formula (IV-2)) was observed at, also the absorption of ethylene was observed in 2800～2950Cm ^-1. Further, the yield was n = about 60. The number average molecular weight of this block copolymer was about 20,000. 1 g of the obtained polyaniline-polyether block copolymer was added to N-methyl-2.
-Pyrrolidone (5 g) was dissolved by stirring at room temperature, and it was possible to form a film by spinning or stretching. Furthermore, when this film was exposed to hydrochloric acid vapor for 4 hours to be doped, the conductivity was 2.8 S / cm. Also, similar processing is 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. there were.

[0025]

INDUSTRIAL APPLICABILITY The polyaniline-polyether block copolymer of the present invention can be dissolved or gelled in various organic solvents, and can be processed to obtain a flexible self-supporting film or fiber. And shows high conductivity by doping, and is very useful for various applications as an electronic material and a conductive material.

Claims (3)

[Claims] 1. A polyaniline-polyether block copolymer having a number average molecular weight of 2,000 to 1,000,000 represented by the following formula (I). ^{A-NH-R 2 - (} O-R 1) k -O-R 2 -NH-A (I) wherein, A is polyaniline block or partial oxidation thereof represented by the formula (II), H -(NH-Ar) _n- (II) (In the formula, Ar represents a 1,4-phenylene group or its halogen, alkoxy or alkyl-substituted product, and n is 1
It represents an integer of 0 to 5,000. ) R ¹ has 1 to 30 carbon atoms
R ² represents an alkylene group having 1 to 30 carbon atoms, R ² is an alkylene group having 1 to 30 carbon atoms, an alkylenecarbonyl group, an alkenylene group or an alkenylenecarbonyl group, or 6 to 30 carbon atoms.
Represents an arylene group or an arylene carbonyl group, provided that when R ² has a carbonyl group, the carbonyl group is bonded to the terminal oxygen of the polyether block. k represents an integer of 10 to 1000. )] 2. The polyaniline-polyether block copolymer according to claim 1, wherein the partially oxidized polyaniline block contains a structural unit represented by the following formula (II-1). -NH-Ar-NH-Ar-N = Q = N-Ar- (II-1) (In the formula, Ar has the same meaning as defined above, and Q is 2,5-
Cyclohexadiene-1,4-ylidene or a halogen, alkoxy or alkyl substituted product thereof. ) 3. The following formula (III) H ₂ N—R ² — (O—R ¹ ) _k —O—R ² —NH ₂ (III) (wherein R ¹ , R ² and k are as defined above). And the halogen, alkoxy or alkyl-substituted aniline thereof is oxidatively polymerized in the presence of a polyether having the same meaning as the above) and having amino groups at both ends. Method for producing polyether block copolymer.