JPH05239207A - Polyaniline derivative and its production - Google Patents

Abstract

(57) [Summary] (Modified) [Object] To provide a polyaniline derivative that is soluble in an organic solvent and is capable of forming a flexible self-supporting film, and a method for producing the same. [Structure] A polyaniline derivative represented by the following formula. [Wherein, k is an integer of 1 or more; m and n are integers of 0 or more; k
+ M + n = 10 to 5000, k / (k + 2m + n) =
0.0001 to 0.4; m / (n + m) = 0 to 1; Al
k = average molecular weight having oxygen atoms at both ends 100 to 10
0000 polyether chains, A = (1) to (9) -SOp-R- (7), -SOp-R-SOp-
(8), -P (= X) (B)-(9) (R = divalent C
_1-30 hydrocarbon group, or its halogen or -COOM
Substituents (M = H, alkali _{metal, NH 4); X = O} ,
S; Y = S, NH; B = C _1-30 hydrocarbon group, C _1-30 alkoxy group; p = 0-2), Z = H, C _1-30 hydrocarbon group,
Acyl group or alkoxycarbonylmethyl group)]

Description

Detailed Description of the Invention

[0001]

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

[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 by heating, it has poor moldability and has a major drawback that it cannot be processed into a film.

For that purpose, for example, fibers of polymeric materials,
Impregnate a monomer 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, by devising the polymerization catalyst and reaction temperature, N-methyl-
Soluble polyaniline only in 2-pyrrolidone has been synthesized (M. Abe et al .; J. hem. So.
c. Chem. Commun. , 1989, 173
6). However, this polyaniline is hardly dissolved in other general-purpose organic solvents, and its application range is limited. In addition, polyaniline derivatives soluble in organic solvents have been synthesized using various aniline derivatives, but 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 it can be gelled.

[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 derivative that is soluble or gellable in an organic solvent and is capable of forming a flexible self-supporting film or fiber, and a method for producing the same. ..

[0005]

Means for Solving the Problems As a result of extensive studies to solve the above problems, the present inventor reacted a reduced polyaniline with a polyether compound having a functional group reactive with an aromatic secondary amine at the terminal. As a result, it was found that a polyaniline derivative having a branched 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 comprises a quinone diimine structural unit, an imino-1,4-phenylene structural unit, and an N-polyether branched chain-substituted imino-1,4-phenylene structural unit randomly bonded to each other. Is represented by the following formula (I).

[0007]

[Chemical 4] [Wherein k is an integer of 1 or more, m and n are integers of 0 or more, k + m + n = 10 to 5,000, and k / (k + 2m + n) = 0.0001 to 0.4, m
/ (N + m) = 0 to 1, Alk represents a polyether chain having oxygen atoms at both ends and an average molecular weight of 100 to 100,000, and A is a linkage selected from the following formulas (1) to (9). Represents a group,

[Chemical 5] (In the formula, R is a divalent hydrocarbon group having 1 to 30 carbon atoms, or a halogen or —COOM substitution product thereof (wherein M represents a hydrogen atom, Li, Na, K, Ca, Rb or NH ₄₎ . ), X represents an oxygen atom or a sulfur atom, Y represents a sulfur atom or NH, B represents a hydrocarbon group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms, and p is 0. To Z.), Z is a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, R ¹ C (=
O) — group or R ¹ OC (═O) CH ₂ — group (provided that
R ¹ represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group, a benzyl group, an aryl group, or a substitution product thereof. ) Represents a group selected from the group consisting of: ]

The method for producing a polyaniline derivative of the present invention comprises treating a soluble aniline polymer obtained by treating an aniline oxidized polymer with ammonia, and treating the soluble aniline polymer with an excess of hydrazine.
A reduced polyaniline having imino-1,4-phenylene as a structural unit and having a number average molecular weight of 2,000 to 500,000 is produced, and then the following formula (II) W-A ¹ -Alk-Z (II) In the formula, W represents a functional group selected from the following formulas (a) to (g),

[Chemical 6] (In the formula, Hal represents a halogen atom, and X, Y, B
And p have the same meaning as described above. ), A ¹ is a direct bond, a divalent hydrocarbon group having 1 to 30 carbon atoms or a halogen-substituted product thereof, -R-C (= X)-, -R-NHC (=
X) -, - R-SO p - , or -C (= X) - (wherein, R and X represents a) as defined above,.
However, when W represents an intramolecular carboxylic acid anhydride group of the formula (e), A ¹ represents a trivalent hydrocarbon group having 1 to 30 carbon atoms, and Alk and Z have the same meaning as described above. ]
It is characterized by reacting with a polyether compound having a functional group that reacts with an aromatic secondary amine at the end.

The present invention will be described in detail below. The polyaniline derivative of the present invention is characterized by having an N-polyether branched chain-substituted imino-1,4-phenylene structural unit represented by the following formula (III).

[Chemical 7] (In the formula, A, Alk, and Z have the same meanings as described above.)

In the present invention, the number of nitrogen atoms involved in the branched structure represented by the above formula (III) needs to be in the range of 0.01 to 40% of the nitrogen atoms of polyaniline. When the number of nitrogen atoms involved in the branched structure is higher than 40%, the generated polyaniline derivative has a problem that the conductivity is lowered. On the other hand, if it is less than 0.01%, the solubility is not much different from that of polyaniline.

In the structural unit represented by the above formula (III), the linking group A is selected from the formulas (1) to (9), and these linking groups also have solubility and film forming property. Including
It does not affect the physical properties of the polyaniline derivative of the present invention. In the case where the linking group has the formulas (1) to (5), (7) and (8), R represents a divalent hydrocarbon group having 1 to 30 carbon atoms, or a halogen or a -COOM substitution product thereof. More specifically, a divalent straight-chain or branched-chain aliphatic hydrocarbon group having 1 to 30 carbon atoms, an araliphatic hydrocarbon group and an aromatic hydrocarbon group, and a halogen or carboxyl group substitution thereof. You can raise your body.

Alk represents a polyether chain having oxygen atoms at both ends and having an average molecular weight of 100 to 100,000, and specifically, oxymethylene, oxyethylene, oxypropylene, oxytrimethylene, oxytetramethylene. Methylene, oxypentamethylene, oxyhexamethylene, oxymethylmethylene, oxymethylethylene, oxymethoxymethylethylene, oxyphenoxymethylmethylene, oxyethylethylene, oxyC ₃ ~
A polyether chain having an average molecular weight of 100 to 100,000 composed of at least one selected from the group consisting of C ₃₀ alkylethylene, oxy-2-methyl-trimethylene and oxy-2-methyl-tetramethylene as a structural unit. I can give you. Further, in the group represented by Z, examples of the hydrocarbon group having 1 to 30 carbon atoms include an alkyl group, an alkenyl group, a benzyl group and an aryl group.

In the present invention, specific examples of the branched structure represented by the formula (III) include the following formulas (III-1) to (II).
I-7) etc. can be illustrated.

[Chemical 8]

(In the formula, A ² represents an alkylene group having 1 to 4 carbon atoms, an alkenylene group having 4 or less carbon atoms, or a 1,2-phenylene group, and A ³ represents an alkylene group having 1 to 6 carbon atoms or a phenylene group. R ² and R ³ each represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, j represents an integer of 6 to 200, and Z has the same meaning as described above.)

The polyaniline derivative of the present invention is produced as follows. That is, aniline is used at a low temperature, for example, -20 to 20 using ammonium persulfate or the like as an oxidizing agent.
The aniline oxidation polymer obtained by oxidative polymerization at a temperature in the range of 50 ° C. is first treated with ammonia to obtain soluble polyaniline. Then, the soluble polyaniline is treated with an excess of hydrazine to give an imino-1,4-phenylene structure having a number average molecular weight of 2,000.
˜500,000 [measured with GPC (N-methyl-2-pyrrolidone solvent), polystyrene-reduced number average molecular weight] reduced polyaniline is obtained. In the hydrazine treatment, the soluble polyaniline is dispersed in water or methanol, and the amount is equivalent to or more than the nitrogen atom in the polyaniline, preferably 3
Double hydrazine is added under a nitrogen atmosphere, and the mixture is stirred at 0 to 30 ° C. for 24 hours or more.

The reduced polyaniline obtained is soluble in the following amide solvents. That is, N-methyl-2-
Pyrrolidone, N, N-dimethylacetamide, N, N-
It is soluble in dimethylformamide, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidinone and the like. However, it is almost insoluble in other general-purpose organic solvents such as chloroform or tetrahydrofuran. In the present invention, when the number average molecular weight of the polyaniline main chain is lower than 2,000, it becomes difficult to obtain a flexible self-supporting film or fiber from the finally formed polyaniline derivative. 5
If it exceeds 0,000, the solubility or swellability in a solvent becomes insufficient, which is not preferable in terms of workability such as casting and gel stretching.

In order to introduce a branched structure into the reduced polyaniline, a polyether compound having a functional group (W) which reacts with an aromatic secondary amine at the terminal represented by the above formula (II) is used. The main point of the present invention is to introduce a branched chain composed of a suitable polyether into the polyaniline main chain, and the linking group A between the branched chain and the polyaniline main chain is used.
The structure of does not significantly affect the physical properties of the derivative of the present invention, including solubility and film-forming property. Therefore, the end of the polyether compound before the reaction may be a functional group that reacts with the secondary aromatic amine.

Specific examples of the terminal functional group W of the polyether compound in the above formula (II) include an isocyanate group, an isothiocyanate group, a sulfinyl halide group,
Examples include sulfenyl halide group, sulfonyl halide group, oxirane ring, aziridine ring, thiirane ring, phosphinyl halide group, thiophosphinyl halide group, carboxyl group, haloformyl group, and intramolecular cyclic carboxylic acid anhydride group. You can Further, in the group represented by A ¹ , examples of the hydrocarbon group having 1 to 30 carbon atoms include a straight chain or branched chain aliphatic hydrocarbon group, an araliphatic hydrocarbon group and an aromatic hydrocarbon group. it can. As for Alk and Z, those exemplified above can be mentioned.

The polyether compound represented by the above formula (II) having a functional group capable of reacting with an aromatic secondary amine at the terminal is obtained, for example, by cationic polymerization, anionic polymerization, coordination polymerization of a cyclic ether or the like. An example is a polyether compound obtained by converting the terminal hydroxyl group of a polyether having a hydroxyl group at the terminal into a functional group that reacts with an aromatic secondary amine.

For example, poly (oxyethylene) cetyl ether, poly (oxyethylene) uryl ether, poly (oxymethylene) methyl ether, poly (oxyethylene) uric acid ester and poly (oxyethylene)
A starting material is a polyether having a hydroxyl group at one end such as stearic acid ester, and the terminal hydroxyl group is reacted with trimellitic anhydride or halogenated trimellitic anhydride to form a cyclic acid anhydride structure at the end. , Reacted with an excess of diisocyanate to have an end structure having an isocyanate structure, reacted with an excess of diisothiocyanate to have an end of an isothiocyanate structure, disulfinyl halide, disulphenyl halide or A compound having a sulfinyl halide, a sulfenyl halide, or a sulfonyl halide structure at each end by reacting with a disulfonyl halide, a halogenated hydrocarbon having a double bond at the end, for example, an allyl halide, or a double bond at the end. By reacting with a carboxylic acid having, for example, allyl acetic acid After forming a structure having a double bond at the terminal, this is reacted with INCO and then KOH to form an aziridine ring, or reacted with sulfur dichloride and then reduced to a thiirane ring. can give. Further, there can be mentioned a polyether compound obtained by reacting the terminal amino group of polyethylene oxide having an amino group at the terminal with phosgene to convert it into a terminal isocyanate group.

In the present invention, specific examples of the polyether compound represented by the formula (II) include a polyether compound represented by the following formula (II-1) having a carboxyl group at one end, and a formula (II-2). The polyether compound having a haloformyl group at one end can be mentioned. ^{HOOC-A 2 -CO-O- (} CHR 2 CHR 3 O) j -Z (II-1) Hal-CO-A 2 -CO-O- (CHR 2 CHR 3 O) j -Z (II-2) (In the formula, A ² , Hal, R ² , R ³ , Z and j have the same meanings as described above.)

The polyether compound having a haloformyl group at one end represented by the above formula (II-2) is, for example, a polyether compound having a carboxyl group at one end represented by the above formula (II-1), and its alkyl. It can be easily derived from an alkali metal or ammonium salt of an ester or carboxylic acid. More specifically, the formula (II-1)
When using a carboxylic acid represented by, by adding an equivalent amount or more of an inorganic halogen compound such as phosphoryl chloride, thionyl chloride, phosphorus pentachloride, phosphorus trichloride to the carboxylic acid, by reacting in an inert solvent such as benzene A polyether compound having a haloformyl group at one end can be obtained. In this case, zinc chloride, pyridine, iodine, triethylamine or the like may be added as a catalyst. Alternatively, with respect to the above-mentioned carboxylic acid, acid halides such as benzoyl chloride, phthalic acid chloride and oxalic acid chloride, α, α
-Dihalogenoethers, halogenated alkylamines, triphenylphosphine / carbon tetrachloride, pyrocatealkylphosphotrichloride, diethylhalophosphochloride, triphenylhalophosphobromide and other organic phosphorus halides, etc.,
It can be obtained by reacting an organic halide in an inert solvent such as benzene or chlorobenzene. Formula (II-
When the alkyl ester of carboxylic acid shown in 1) is used, the alkyl ester of carboxylic acid is reacted with triphenylhalophosphohalide or its complex with boron fluoride to have a haloformyl group at one end. A polyether compound can be obtained. Also,
When an alkali metal carboxylate or ammonium carboxylate is used, the carboxylate is reacted with an inorganic halide such as phosphoryl chloride or phosphorus pentachloride or a complex of thionyl chloride and dimethylformamide to give a polyamine having a haloformyl group at one end. An ether compound can be obtained.

Other specific examples of the polyether compound represented by the formula (II) in the present invention include the following formulas (II-3) to
The compound shown by (II-10) can be illustrated.

[Chemical 9] (In the formula, A ³ , Z, p and j have the same meaning as described above.)

Next, the reaction between the reduced polyaniline produced as described above and the polyether compound having a functional group which reacts with the aromatic secondary amine at the terminal represented by the above formula (II) will be described. The reaction of the present invention is carried out by different methods depending on the type of the functional group W. 1) When the functional group W is one of the formulas (a) to (e) In the amide solution of the reduced polyaniline, a polyether compound having a functional group that reacts with an aromatic secondary amine at the terminal or an organic solvent Is added and the stirring is continued under a nitrogen stream for 1 to 48 hours in the temperature range of -10 to 80 ° C. If necessary, pyridine or a tertiary amine such as triethylamine or diethylaniline, or ammonium chloride may be added to carry out the reaction. The reaction mixture is poured into alcohol or water and the polymer formed is precipitated. The polyaniline derivative of the present invention can be produced by further treating the obtained polymer with aqueous ammonia.

2) When the functional group W is represented by the above formula (f), a polyether compound having a carboxyl group at one end is dissolved in an amide solvent, and N, N in an equivalent amount or more based on the terminal carboxyl group is added thereto. The ′ -disubstituted carbodiimides were added to the mixture while cooling to −10 to 10 ° C., the stirring was continued at that temperature for 1 to 4 hours, and then the above reduced polyaniline was added. The reaction is continued by stirring for 6 hours. After completion of the reaction, the reaction mixture is poured into dilute hydrochloric acid to precipitate the formed polyaniline derivative. Since the obtained polyaniline derivative is doped with hydrochloric acid, the polyaniline derivative of the present invention can be produced by exposing it to ammonia vapor, washing it with water and dedoping.

The N, N'- used in the above reaction
The disubstituted carbodiimides are represented by the following formula (IV) R ⁴ —N═C═N—R ⁵ (IV) (wherein R ⁴ and R ⁵ may be the same or different, for example, methyl group, ethyl group , N-propyl group, i
-Substituted or unsubstituted alkyl groups such as propyl group, n-butyl group, t-butyl group and 3-dimethylaminopropyl group, cyclic alkyl groups such as cyclohexyl group, phenyl group, p-tolyl group, p-N, N -Dimethylaminophenyl group, p-chlorophenyl group, p-nitrophenyl group,
It represents a substituted or unsubstituted aryl group such as p-cyanophenyl group. ), More specifically, diethylcarbodiimide, diisopropylcarbodiimide, dicyclohexylcarbodiimide, diphenylcarbodiimide, di-p-tolylcarbodiimide, 1-
Examples include ethyl-3- (3-dimethylaminopropyl) carbodiimide and the like. In the above case, the amount of the N, N′-disubstituted carbodiimides used is preferably an equivalent amount or more with respect to the amount of the carboxyl group at one end of the polyether compound to be reacted.

3) When the functional group W is the above-mentioned formula (g), a polyether compound having a haloformyl group at one end is well mixed with a solvent (for example, an amide solvent such as chloroform) and the haloformyl group is used. Inert solvent)
Was added dropwise to the solution of the reduced polyaniline amide solvent described above, and the mixture was stirred at 0 to 80 ° C. for 1 to 10 hours, and then the reaction mixture was poured into dilute hydrochloric acid to precipitate the produced polyaniline derivative. Since the obtained polyaniline derivative is doped with hydrochloric acid, the polyaniline derivative of the present invention can be produced by exposing it to ammonia vapor, washing it with water and dedoping.

In the present invention, the amide solvent used in the reactions 1) to 3) is N-methyl-
2-pyrrolidone, N, N-dimethylacetamide, N,
Examples include N-dimethylformamide, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidinone and the like.

The polyaniline derivative of the present invention does not change the length of the polyaniline main chain during its production. Furthermore, the value of m / (n + m) can be controlled by oxidizing or reducing the obtained polyaniline derivative of the present invention. That is, when the polyaniline derivative of the present invention is oxidized using an oxidizing agent or electrochemically, m
When the polyaniline derivative of the present invention is reduced with a reducing agent or electrochemically, the value of m decreases. However, if the solubility in a solvent is important, it is preferable that the rigid quinonediimine structure is small, that is, m <n, and if the self-supporting property and flexibility of the film are important, m> n is preferable. Therefore, for the above reasons, the polyaniline derivative of the present invention is
The value of m / (n + m) suitable for film formation is usually in the range of 0.10 to 0.60. Note that m / (n +
m) is a peak derived from a quinoid structure in the ¹³ C NMR spectrum (chemical shift 138 ppm / TMS) and a peak derived from a benzenoid (chemical shift 122 ppm /
It can be determined from the respective intensity ratio with TMS).

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 can be dissolved in an ether solvent such as tetrahydrofuran, an amine solvent such as pyridine, and a polar solvent such as dimethyl sulfoxide. From this solution it is possible to produce free-standing films or fibers. Further, the processed product such as the film and the fiber shows a high electric conductivity of 10 ^{−3 to} 50 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 halogen compounds such as iodine, bromine, chlorine and iodine trichloride, sulfuric acid, hydrochloric acid, nitric acid, perchlorates, protic acids such as borofluoric acid, various salts of the above protic acids, and trichloride. Aluminum, iron trichloride, molybdenum chloride, antimony chloride, arsenic pentafluoride and other Lewis acids, acetic acid, trifluoroacetic acid, benzenesulfonic acid, p-toluenesulfonic acid and other organic acids, polyethylene sulfonic acid, polyethylene carboxylic acid, polyacryl Examples thereof include various compounds such as acids and polymer acids such as polystyrene sulfonic acid. The method of doping these compounds is not particularly limited, and any known method can be used. Generally, a derivative of polyaniline, a gel thereof or a molded product thereof and a dopant compound may be brought into contact with each other, and it can be carried out in a gas phase or a liquid phase. Alternatively, a method of electrochemically doping in a solution of the above-mentioned protonic acid or its salt can be used.

[0032]

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 100 ml and cooled to -5 ° C. On the other hand, concentrated hydrochloric acid 2
1.9 g and 6.28 g of ammonium persulfate were dissolved in water to make 100 ml. After cooling this solution to -10 ° C, the solution was slowly added dropwise to the above aniline solution,
The stirring was continued for 6 hours. The thus obtained aniline-oxidized polymer having a number average molecular weight of 12,000 (GPC, measured in a solvent of N-methyl-2-pyrrolidone, polystyrene equivalent number average molecular weight) was thoroughly washed with water, and then washed with aqueous ammonia. A dedoping process was performed. The soluble polyaniline thus obtained was dispersed in 200 ml of water, and the water content was 50 m under a nitrogen atmosphere.
1 hydrazine was added, and stirring was continued at room temperature for 24 hours, filtered and dried to obtain an off-white reduced polyaniline (number average molecular weight 12,000).

On the other hand, as a polyether having a carboxyl group at one end, poly (oxyethylene) diglycolic acid monomethyl ester (average molecular weight of about 3000, structural formula: HOOCCH ₂ -O- (CH ₂ CH ₂ O) _j CH ₂ CO ₂ CH ₃ ; j = about 6
0.825 g of 5) was dissolved in 10 ml of dehydrated benzene, 1 ml of oxalic acid chloride was added, and the mixture was heated at 50 ° C. for 2 hours and then at 80 ° C. for 1 hour to obtain benzene and unreacted oxalate. The substances and the like were distilled off to obtain 0.830 g of a polyether having a chloroformyl group at one end (2.5% of the chloroformyl group based on the nitrogen atom in polyaniline). The presence of chloroformyl groups, in the measurement of the infrared absorption spectrum, absorption of 1795 cm ^-1 was observed, and was confirmed from the fact that the absorption of 1770 cm ^-1 due to carboxylic acid has disappeared. The obtained polyether was dissolved in 10 ml of dehydrated chloroform, and 1 g of reduced polyaniline produced as described above was added to 50 m.
It was slowly added dropwise to a solution obtained by dissolving it in 1 N-methyl-2-pyridone, and the reaction was continued by stirring at room temperature for 4 hours. After completion of the reaction, the reaction solution was added to 1 liter of diluted hydrochloric acid while stirring, and the paper and the precipitate were filtered off. After further exposure to ammonia vapor, the product is washed with water to remove hydrogen halide and dried to give the polyaniline derivative 1.8 of the present invention.
20 g was obtained. (K + m + n = about 98)

The infrared absorption spectrum was measured and found to be 1650 cm due to the branched structure of the above formula (III).
^-1 (C = O stretching) and 2850 to 2950 cm ^-1 (aliphatic C-H stretching) were observed. In addition, 1600,
Absorption patterns peculiar to polyaniline 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 involved in the branched structure of formula (III) is about 2.5% of the nitrogen atoms of polyaniline (ie, k / (k +
It was 2m + n) = 0.025). Further, it was confirmed from the ¹³ C spectrum that m / (n + m) = 0.33. 1 g of the obtained polyaniline derivative 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 casting. Furthermore, when this film was immersed in a 20% sulfuric acid aqueous solution for 24 hours and was doped and dried, the conductivity was 0.5 S / cm. Also, instead of N-methyl-2-pyrrolidone,
Similar processing was possible using an organic solvent such as N-dimethylacetamide, N, N-dimethylformamide, pyridine, chloroform, dichloroethane, dichloromethane or tetrahydrofuran. Furthermore, this polyaniline derivative was soluble in water and alcohols such as methanol and ethanol, and could be processed.

Example 2 Instead of the polyether having a carboxyl group at one end used in Example 1, succinic acid mono (polyethylene glycol monolaurate) ester (molecular weight about 740, the above formula (II-1)) was used. At j = about 10) 0.
The same reaction was carried out using 812 g to obtain 1.780 g of the polyaniline derivative (k + m + n = about 100) of the present invention. This polyaniline derivative was soluble in the same organic solvent as in Example 8 and also soluble in water and alcohol, and could be processed in the same manner. The infrared absorption spectrum of the obtained polyaniline derivative was measured and found to be 1650 cm ^-1 (C = O stretching) due to the branched structure of the above formula (III), 2850 to 295.
Absorption of 0 cm ^-1 (aliphatic C-H stretch) was observed. Further, 1600, 1500, 1300, 1170, 82
An absorption pattern peculiar to polyaniline was observed at 0 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 branched structure of the formula (II) is about 10% (k / (k
It was + 2m + n) = 0.1). Further, it was confirmed from the ¹³ C spectrum that m / (n + m) = 0.34. 1 g of the obtained polyaniline derivative was added to N-methyl-
2-pyrrolidone 5 g, stirred at room temperature to dissolve,
A self-supporting film was made by casting. further,
When this film was immersed in a 20% sulfuric acid aqueous solution for 24 hours to be doped and dried, the conductivity was 0.3 S / cm.

Example 3 Instead of the polyether having a carboxyl group at one end used in Example 1, succinic acid mono (polyethylene glycol monolaurate ester) ester (molecular weight about 1386, the above formula (II-1)) was used. J = about 25)
The same reaction was performed using 0.812 g to give 1.790 g of the polyaniline derivative (k + m + n = about 99) of the present invention.
Got This polyaniline derivative was soluble in the same organic solvent as in Example 1 and also soluble in water and alcohol, and could be processed in the same manner.
The infrared absorption spectrum of the obtained polyaniline derivative was measured and found to be 1650 cm ^-1 (C = O stretching) due to the branched structure of the above formula (III), 2850 to 29.
Absorption of 50 cm ^-1 (aliphatic C-H stretch) was observed.
Further, 1600, 1500, 1300, 1170, 8
An absorption pattern peculiar to polyaniline was observed at 20 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 branched structure of formula (III) is about 5% (k / (k
+ 2m + n) = 0.05). Further, it was confirmed from the ¹³ C spectrum that m / (n + m) = 0.34. 1 g of the obtained polyaniline derivative was put into 5 g of N-methyl-2-pyrrolidone and stirred at room temperature to be dissolved to prepare a self-supporting film by casting. Further, this film was immersed in a 20% sulfuric acid aqueous solution for 24 hours to be doped and dried, and the conductivity was 0.5 S / cm.
Met.

Example 4 Instead of the polyether having a carboxyl group at one end used in Example 1, poly (oxyethylene) diglycolic acid monoethyl ester (structural formula: HOOCCH ₂ -O
-(CH ₂ CH ₂ O) _j CH ₂ CO ₂ C ₂ H ₅ ; molecular weight about 1000,
j = about 20) 2.195 g and the same reaction is carried out to give the polyaniline derivative of the present invention (k + m + n = about 10).
4) 2.10 g was obtained. This polyaniline derivative was soluble in the same organic solvent as in Example 1 and also soluble in water and alcohol, and could be processed in the same manner. The infrared absorption spectrum of the obtained polyaniline derivative was measured and found to be the above formula (III)
1650 cm ^-1 (C = O expansion and contraction) due to the branched structure of
Absorption of 2850 to 2950 cm ^-1 (aliphatic C-H stretch) was observed. Furthermore, 1600, 1500, 130
Absorption patterns peculiar to polyaniline were observed at 0, 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 branched structure of formula (III) was about 20% (k / (k + 2m + n) = 0.2) of the nitrogen atoms of polyaniline.
In addition, from the ¹³ C spectrum, m / (n + m) = 0.33
Was confirmed. 1 g of the obtained polyaniline derivative was put into 5 g of N-methyl-2-pyrrolidone and stirred at room temperature to be dissolved to prepare a self-supporting film by casting. Furthermore, when this film was immersed in a 20% sulfuric acid aqueous solution for 24 hours to be doped and dried, the conductivity was 0.07 S / cm.

Example 5 As a polyether having a carboxyl group at one end,
Poly (oxyethylene) diglycolic acid monoethyl ester (Structural formula: HOOCCH ₂ -O- (CH ₂ CH ₂ O) _j CH ₂ CO ₂ -C ₂ H
₅ ; 2.95 g of molecular weight of about 1000, j = about 20) was dissolved in 30 ml of N-methyl-2-pyrrolidone under a nitrogen stream and cooled to 0 ° C. Next, 0.453 g of dicyclohexylcarbodiimide was added, and stirring was continued for 1 hour at 0 ° C., 1 g of reduced polyaniline was further added, and the reaction was continued for 6 hours while gradually returning to room temperature. After completion of the reaction, the reaction solution was poured into 1 liter of dilute hydrochloric acid while stirring, and the precipitate was filtered off. After further exposing to ammonia vapor, washing with water to remove hydrogen halide, and drying to obtain the polyaniline derivative of the present invention (k + m + n = about 104) 3.
Obtained 082 g. This polyaniline derivative was prepared according to Example 1
It was soluble in the same organic solvent as in (1) and was also soluble in water and alcohol, and could be processed in the same manner. The infrared absorption spectrum of the obtained polyaniline derivative was measured and found to be 1650 cm ⁻¹ (C═O stretching) due to the branched structure of the above formula (III), 285
Absorption of ^{0 to} 2950 cm ^-1 (aliphatic C-H stretch) was observed. Furthermore, 1600, 1500, 1300, 11
An absorption pattern peculiar to polyaniline was observed at 70 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 branched structure of formula (III) is about 20% of the nitrogen atoms of polyaniline.
(K / (k + 2m + n) = 0.2). Also, ¹³
From the C spectrum, it was confirmed that m / (n + m) = 0.34. 1 g of the obtained polyaniline derivative was added to N
-Methyl-2-pyrrolidone was placed in 5 g, and the mixture was stirred at room temperature for dissolution to prepare a self-supporting film by casting. Further, this film was immersed in a 20% sulfuric acid aqueous solution for 24 hours to be doped and dried, and the conductivity was 0.0
It was 5 S / cm.

Example 6 As a polyether having a carboxyl group at one end,
4.39 g of poly (oxyethylene) diglycolic acid monoethyl ester (molecular weight about 1000, j = about 20) was dissolved in 30 ml of N-methyl-2-pyrrolidone under a nitrogen stream and cooled to 0 ° C. Next, 0.906 g of dicyclohexylcarbodiimide was added, stirring was continued for 1 hour at 0 ° C., 1 g of reduced polyaniline was further added, and the reaction was continued for 6 hours while gradually returning to room temperature. After completion of the reaction, the reaction solution was poured into 1 liter of diluted hydrochloric acid while stirring,
The precipitate was filtered off. After further exposing it to ammonia vapor, it is washed with water to remove hydrogen halide and dried to give the polyaniline derivative of the present invention (k + m + n = about 110) 5.2.
2 g was obtained. This polyaniline derivative was soluble in the same organic solvent as in Example 1 and also soluble in water and alcohol, and could be processed in the same manner. The infrared absorption spectrum of the obtained polyaniline derivative was measured and found to be 1650 cm ^-1 (C = O stretching) due to the branched structure of the above formula (III), 2850 to
Absorption of 2950 cm ^-1 (aliphatic C-H stretch) was observed. Further, 1600, 1500, 1300, 117
An absorption pattern peculiar to polyaniline was observed at 0,820 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 branched structure of formula (III) is about 40% of the nitrogen atoms of polyaniline.
(K / (k + 2m + n) = 0.4). Also, ¹³
From the C spectrum, it was confirmed that m / (n + m) = 0.35. 1 g of the obtained polyaniline derivative was added to N
-Methyl-2-pyrrolidone was placed in 5 g, and the mixture was stirred at room temperature for dissolution to prepare a self-supporting film by casting. Further, this film was immersed in a 20% sulfuric acid aqueous solution for 24 hours to be doped and dried, and the conductivity was 0.0
It was 1 S / cm.

Example 7 4.1 g of aniline and 21.9 g of concentrated hydrochloric acid were dissolved in water to 100 ml and cooled to -5 ° C. On the other hand, concentrated hydrochloric acid 2
1.9 g and 6.28 g of ammonium persulfate were dissolved in water to make 100 ml. After cooling this solution to -10 ° C, the solution was slowly added dropwise to the above aniline solution,
The stirring was continued for 6 hours. The thus obtained aniline-oxidized polymer having a number average molecular weight of 12,000 (GPC, measured in a solvent of N-methyl-2-pyrrolidone, polystyrene equivalent number average molecular weight) was thoroughly washed with water, and then washed with aqueous ammonia. A dedoping process was performed. The soluble polyaniline thus obtained was dispersed in 200 ml of water, and the water content was 50 m under a nitrogen atmosphere.
l of hydrazine was added, and stirring was continued at room temperature for 24 hours, filtered and dried to obtain an off-white reduced polyaniline (number average molecular weight 12,000). 1 g of the reduced polyaniline thus obtained was completely dissolved in 30 ml of N-methyl-2-pyrrolidone under a nitrogen stream.

On the other hand, polyethylene glycol monomethyl ether (manufactured by Aldrich, average molecular weight 2000)
Was reacted with an equimolar amount of trimellitic anhydride chloride in tetrahydrofuran to be esterified to obtain a polyether having an acid anhydride structure at the terminal. N-methyl-2-pyrrolidone solution (30 ml) of 1 g of the reduced polyaniline
2.39 g of a polyether having an acid anhydride structure at the end was added thereto under a nitrogen stream, and the reaction was continued at room temperature for 6 hours. This solution was poured into 1 liter of diluted hydrochloric acid with stirring, the precipitate was filtered off, exposed to ammonia vapor, washed with water to remove hydrogen halide, and dried to obtain the polyaniline derivative (k + m + n = about 103) 3.38 g was obtained.

The infrared absorption spectrum was measured and found to be 1650 cm due to the branched structure of the above formula (III).
^-1 (C = O stretching) and 2850 to 2950 cm ^-1 (aliphatic C-H stretching) were observed. In addition, 1600,
Absorption patterns peculiar to polyaniline 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 involved in the branched structure of formula (III) is about 10% of the nitrogen atoms of polyaniline (k / (k + 2m + n) =
It was 0.1). In addition, from the ¹³ C spectrum, m /
It was confirmed that (n + m) = 0.30. 1 g of the obtained polyaniline derivative 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 dipped in a 20% aqueous hydrochloric acid solution for 24 hours and was then dried, the conductivity was 0.2 S / cm. Also, N-
Instead of methyl-2-pyrrolidone, N-dimethylacetamide, N, N-dimethylformamide, pyridine,
Similar processing was possible using an organic solvent such as chloroform, dichloroethane, dichloromethane or tetrahydrofuran.

Example 8 Polyethylene glycol monomethyl ether (Aldr
ich, average molecular weight 2000) was reacted with an equimolar amount of hexamethylene diisocyanate in tetrahydrofuran to give a carbamic acid ester, and a polyether having an isocyanate group at the terminal was obtained. 2.17 g of the polyaniline derivative (k + m + n = about 99) of the present invention was obtained in the same manner as in Example 7 except that 1.19 g of the polyether having an isocyanate group at the terminal was used. The obtained polyaniline derivative was soluble in the same organic solvent as in Example 14 and could be processed in the same manner. The infrared absorption spectrum was measured and found to be 1650 cm ^-1 (C = O stretching) due to the branched structure of the above formula (III), 2
Absorption of 850 to 2950 cm ^-1 (aliphatic C-H stretch) was observed. Furthermore, 1600, 1500, 1300,
Absorption patterns peculiar to polyaniline were observed at 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 branched structure of the formula (III) was about 4.8% (k / (k + 2m + n) = 0.048) of the nitrogen atoms of polyaniline. In addition, from the ¹³ C spectrum, m / (n + m) = 0.
It was confirmed to be 33. 1 g of the obtained polyaniline derivative 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 dipped in a 20% aqueous hydrochloric acid solution for 24 hours and was then dried, the conductivity was 1.2 S / cm.

Example 9 Polyethylene glycol monomethyl ether (Aldr
ich, average molecular weight 5000) was reacted with equimolar m-benzenedisulfonyl chloride in tetrahydrofuran to give a sulfonic acid ester, and a polyether having a sulfonyl chloride group at the terminal was obtained. Polyether having a sulfonyl chloride group at the above terminal 0.
57 g was treated in the same manner as in Example 7 to obtain 1.51 g of the polyaniline derivative (k + m + n = about 98) of the present invention. The obtained polyaniline derivative was soluble in the same organic solvent as in Example 7, and could be processed in the same manner. When the infrared absorption spectrum was measured, 1351 and 1176c due to the branched structure of the above formula (III) were measured.
Absorption of m ^-1 (S = O stretching) and 2850 to 2950 cm ^-1 (aliphatic C-H stretching) was observed. In addition, 160
Absorption patterns peculiar to polyaniline were 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 involved in the branched structure of the formula (III) is about 1.0% (k / (k + 2m +) of the nitrogen atoms of polyaniline.
n) = 0.010). Further, it was confirmed from the ¹³ C spectrum that m / (n + m) = 0.33. 1 g of the obtained polyaniline derivative 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. Further, when this film was dipped in a 20% hydrochloric acid aqueous solution for 24 hours and was doped and dried, the conductivity was 1.1 S / cm.

Example 10 Polyethylene glycol monododecyl ether (produced by Tokyo Kasei Co., Ltd., molecular weight 1288) was reacted with 1.5 times mol of sodium hydride and then with 2 times mol of allyl chloride, and the end was allyl ether. Turned into This is further INC
The mixture was reacted with O for 24 hours at room temperature and refluxed in methanol for 3 hours. Next, KOH was added and refluxed for 4 hours to convert the terminal allyl group into an aziridine ring. Polyether 5.9 having an aziridine ring at the terminal obtained as described above
The same procedure as in Example 7 was carried out using 7 g to obtain 6.51 g of the polyaniline derivative (k + m + n = about 109) of the present invention. The obtained polyaniline derivative was soluble in the same organic solvent as in Example 7, and could be processed in the same manner. The infrared absorption spectrum was measured and found to be 2850 to 2950c due to the branched structure of the above formula (III).
m ^-1 (aliphatic C-H stretch) 3360, 3290 cm
Absorption of ^-1 (N-H stretching) was observed. In addition, 160
Absorption patterns peculiar to polyaniline were 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 involved in the branched structure of the formula (III) is about 37.0% of the nitrogen atoms of polyaniline (k / (k + 2m +
n) = 0.37). Further, it was confirmed from the ¹³ C spectrum that m / (n + m) = 0.35. 1 g of the obtained polyaniline derivative 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 dipped in a 20% hydrochloric acid aqueous solution for 24 hours and was then dried, the conductivity was 0.1 S / cm.

Example 11 Polyethylene glycol monododecanoic acid ester (manufactured by Tokyo Kasei Co., Ltd., molecular weight 655) is reacted with an equimolar amount of trimellitic acid chloride chloride in tetrahydrofuran to be esterified, and a polyether having an acid anhydride structure at the terminal end. Got
Polyether 1.8 having an acid anhydride structure at the above terminal
The same procedure as in Example 7 was carried out using 2 g to obtain 2.71 g of the polyaniline derivative (k + m + n = about 103) of the present invention. The obtained polyaniline derivative was soluble in the same organic solvent as in Example 7, and could be processed in the same manner. The infrared absorption spectrum was measured and found to be 1650 cm ⁻¹ (C═O) due to the branched structure of the above formula (III).
Expansion and contraction) and 2850 to 2950 cm ^-1 (aliphatic CH)
(Stretching) was observed. Furthermore, 1600, 150
Absorption patterns peculiar to polyaniline were observed at 0, 1300, 1170, and 820 cm ^−1, and it was confirmed that the main chain had a polyaniline structure. From the reaction yield, the formula (III)
The number of nitrogen atoms involved in the branched structure of the polyaniline is about 19.0% (k / (k + 2m + n) = 0.
19). In addition, from the ¹³ C spectrum, m / (n
It was confirmed that + m) = 0.34. 1 g of the obtained polyaniline derivative was added to N-methyl-2-pyrrolidone 5
It was melted by putting it in g and stirring at room temperature, and it was possible to form a film by spinning or stretching. In addition, this film 2
When it was dipped in a 0% hydrochloric acid aqueous solution for 24 hours and was then dried, the conductivity was 0.8 S / cm.

Example 12 Polyethylene glycol monostearate (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight: 725) was reacted with an equimolar amount of trimellitic anhydride chloride in tetrahydrofuran to be esterified, and a polyether having an acid anhydride structure at the end. Got The polyaniline derivative of the present invention (k + m + n = about 103) 2.91 was prepared in the same manner as in Example 7 except that 1.97 g of a polyether having an acid anhydride structure at the terminal was used.
g was obtained. The obtained polyaniline derivative was soluble in the same organic solvent as in Example 7, and could be processed in the same manner. When the infrared absorption spectrum was measured, it was 1650 cm due to the branched structure of the above formula (III).
^-1 (C = O stretching) and 2850 to 2950 cm ^-1 (aliphatic C-H stretching) were observed to be absorbed. In addition, 160
Absorption patterns peculiar to polyaniline were 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 involved in the branched structure of the formula (III) is about 19.0% (k / (k + 2m +) of the nitrogen atoms of polyaniline.
n) = 0.19). Further, it was confirmed from the ¹³ C spectrum that m / (n + m) = 0.34. 1 g of the obtained polyaniline derivative 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 dipped in a 20% aqueous hydrochloric acid solution for 24 hours and was then dried, the conductivity was 0.7 S / cm.

Example 13 Polyethylene glycol monononyl phenyl ether (manufactured by Tokyo Kasei Co., Ltd., molecular weight 440) was reacted with equimolar hexamethylene diisocyanate in tetrahydrofuran to give a carbamic acid ester, which had an isocyanate group at the end. Obtained ether. Using 2.67 g of the above-mentioned polyether having an isocyanate group, the same treatment as in Example 7 was carried out and the polyaniline derivative (k) of the present invention was used.
+ M + n = about 110) 3.57 g was obtained. The obtained polyaniline derivative was soluble in the same organic solvent as in Example 7, and could be processed in the same manner. The infrared absorption spectrum was measured and found to be 1650 cm ^-1 (C = O stretching) and 28 due to the branched structure of the formula (III).
Absorption of 50 to 2950 cm ^-1 (aliphatic C-H stretch) was observed. Furthermore, 1600, 1500, 1300, 1
Absorption patterns peculiar to polyaniline were 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 involved in the branched structure of formula (III) is about 3 of the nitrogen atoms of polyaniline.
It was 9.0% (k / (k + 2m + n) = 0.39). In addition, from the ¹³ C spectrum, m / (n + m) = 0.
It was confirmed to be 33. 1 g of the obtained polyaniline derivative 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 dipped in a 20% hydrochloric acid aqueous solution for 24 hours and was then dried, the conductivity was 0.1 S / cm.

Example 14 Polyethylene glycol monomethyl ether (Aldr
ich, average molecular weight 440) 1.5 times the molar Na
After reacting with H, it was reacted with sodium 4-chlorobutanesulfonate to convert the terminal into butyl ether sulfonate. This was further reacted with PCl ₅ to convert the terminal hydroxyl group of polyethylene glycol monomethyl ether to a chlorosulfonyl butyl ether group. This sulfonyl chloride formation is based on infrared absorption spectra of 1400, 1
It was confirmed by absorption at 180 cm ^-1 . Using 2.36 g of the obtained polyether and treating in the same manner as in Example 7, the polyaniline derivative of the present invention (k + m + n = about 101) 3.
06 g was obtained. The obtained polyaniline derivative was soluble in the same organic solvent as in Example 7, and could be processed in the same manner. When the infrared absorption spectrum was measured, 1351 due to the branched structure of the above formula (III),
1176 cm ^-1 (S = O expansion and contraction) and 2850 to 295
Absorption of 0 cm ^-1 (aliphatic C-H stretch) was observed. Further, 1600, 1500, 1300, 1170, 82
An absorption pattern peculiar to polyaniline was observed at 0 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 branched structure of formula (III) is about 9.1% (k / k) of the nitrogen atoms of polyaniline.
It was (k + 2m + n) = 0.091). Also, ¹³ C
From the spectrum, it was confirmed that m / (n + m) = 0.33. 1 g of the obtained polyaniline derivative 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.
Furthermore, when this film was dipped in a 20% aqueous hydrochloric acid solution for 24 hours and was then dried, the conductivity was 2.1 S / cm.
Met.

Example 15 Polypropylene glycol of diol type (molecular weight: about 10)
00, manufactured by Wako Pure Chemical Industries, Ltd.) was refluxed in water for 12 hours in the presence of potassium carbonate using platinum-activated carbon as a catalyst to convert both terminals into carboxyl groups. The number of terminal carboxyl groups was 2.01 by volumetric analysis. This is 1.
It was converted to a methyl ester by reacting with 1-fold mole of methanol. The obtained monomethyl ester product was separated through a silica gel column and treated with excess oxalyl chloride to chloroformate the carboxyl group at one end.
Chloroformylation is 1795c of infrared absorption spectrum
It was confirmed by absorption of m ⁻¹ . Using 1.1 g of polypropylene glycol monomethyl ether having a chloroformyloxy group at one end, the polyaniline derivative (k + m + n) of the present invention (about 1) was treated in the same manner as in Example 7.
01) 2.1 g was obtained. The obtained polyaniline derivative was soluble in the same organic solvent as in Example 7, and could be processed in the same manner. When the infrared absorption spectrum was measured, it was found that 1 due to the branched structure of the above formula (III)
650, 1734 cm ^-1 (C = O expansion and contraction) and 2850
Absorption of ˜2950 cm ⁻¹ (aliphatic C—H stretching) was observed. Further, 1600, 1500, 1300, 117
An absorption pattern peculiar to polyaniline was observed at 0,820 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 branched structure of formula (III) is about 10.0 of that of polyaniline.
% (K / (k + 2m + n) = 0.1). Also,
^{From the 13} C spectrum, it was confirmed that m / (n + m) = 0.33. 1 g of the obtained polyaniline derivative 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 dipped in a 20% aqueous hydrochloric acid solution for 24 hours and was then dried, the conductivity was 1.8 S /
It was cm.

Example 16 2.2 g of polyethylene glycol monononyl phenyl ether (manufactured by Tokyo Kasei Co., Ltd., average molecular weight 2000) was reacted with an excess of oxalyl chloride to give a terminal oxygen atom a chlorooxalyl group (Cl—C (═O)). A C (= O)-)-bonded polyether was synthesized. The chlorooxalyl group is
Infrared absorption spectrum of 1790, 1734 cm ^-1 (C =
(O stretching). 1. The obtained polyaniline derivative (k + m + n = about 100) was treated in the same manner as in Example 7 except that polypropylene glycol monomethyl ether having a chlorooxalyloxy group at one end thereof was used.
41 g was obtained. The obtained polyaniline derivative was soluble in the same organic solvent as in Example 7, and could be processed in the same manner. When the infrared absorption spectrum was measured, 1650 due to the branched structure of the above formula (III),
1734 cm ^-1 (C = O expansion and contraction) and 2850 to 295
Absorption of 0 cm ^-1 (aliphatic C-H stretch) was observed. Further, 1600, 1500, 1300, 1170, 82
An absorption pattern peculiar to polyaniline was observed at 0 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 branched structure of formula (III) is about 7.5% (k /
(K + 2m + n) = 0.075). Also, ¹³ C
From the spectrum, it was confirmed that m / (n + m) = 0.33. 1 g of the obtained polyaniline derivative 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.
Furthermore, when this film was dipped in a 20% hydrochloric acid aqueous solution for 24 hours and was then dried, the conductivity was 1.5 S / cm.
Met.

[0052]

INDUSTRIAL APPLICABILITY The polyaniline derivative of the present invention can be dissolved in various organic solvents, can be easily processed, and can obtain a flexible molded product such as a self-supporting film or fiber. You can Since these molded products show high conductivity by doping, the polyaniline derivative of the present invention is very useful for various applications such as electronic materials and conductive materials.

Claims (2)

[Claims] 1. A quinone diimine structural unit, imino-1,
A polyaniline derivative represented by the following formula (I) in which a 4-phenylene structural unit and an N-polyether branched chain-substituted imino-1,4-phenylene structural unit are randomly bonded. [Chemical 1] [Wherein k is an integer of 1 or more, m and n are integers of 0 or more, k + m + n = 10 to 5,000, and k / (k + 2m + n) = 0.0001 to 0.4, m
/ (N + m) = 0 to 1, Alk represents a polyether chain having oxygen atoms at both ends and an average molecular weight of 100 to 100,000, and A is a linkage selected from the following formulas (1) to (9). Represents a group, (In the formula, R is a divalent hydrocarbon group having 1 to 30 carbon atoms, or a halogen or —COOM substitution product thereof (wherein M represents a hydrogen atom, Li, Na, K, Ca, Rb or NH ₄₎ . ), X represents an oxygen atom or a sulfur atom, Y represents a sulfur atom or NH, and B represents 1 carbon atom.
Represents a hydrocarbon group of ˜30 or an alkoxy group of 1 to 30 carbon atoms, and p represents an integer of 0 to 2. ), Z is a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, R ¹ C (═O)
Group or R ¹ OC (═O) CH ₂ group (provided that R ¹
Represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group, a benzyl group, an aryl group, or a substitution product thereof. ) Represents a group selected from the group consisting of: ] 2. A soluble aniline polymer obtained by treating an aniline oxidized polymer with ammonia is treated with an excess of hydrazine to contain imino-1,4-phenylene as a structural unit in a number average molecular weight of 2,000. ~ 500,000 of reduced polyaniline is produced, and then the following formula (II) W-A ¹ -Alk-Z (II) [wherein, W is a function selected from the following formulas (a) to (g)) Represents a group, (In the formula, Hal represents a halogen atom, and X, Y, B
And p have the same meaning as described above. ), A ¹ is a direct bond, a divalent hydrocarbon group having 1 to 30 carbon atoms or a halogen-substituted product thereof, -R-C (= X)-, -R-NHC (=
X) -, - R-SO p - , or -C (= X) - (wherein, R and X represents a) as defined above,.
However, when W represents an intramolecular carboxylic acid anhydride group of the formula (e), A ¹ represents a trivalent hydrocarbon group having 1 to 30 carbon atoms, and Alk and Z have the same meaning as described above. ]
The method for producing a polyaniline derivative according to claim 1, wherein the polyaniline derivative is reacted with a polyether compound having a functional group that reacts with an aromatic secondary amine at the terminal.