JPH06100691A - Polyaniline derivative and its production - Google Patents

Abstract

PURPOSE:To obtain a polyaniline deriv. which is sol. or swellable in an org. solvent and gives a flexible self-supporting film or fiber excellent in heat resistance by combining specific structural units randomly. CONSTITUTION:A polyaniline deriv. is formed by randomly combining quinodiimine structural units and/or imino-1,4-phenylene structural units with N-polysiloxane-grafted imino-1,4-phenylene structural units and is represented by formula I wherein k>=1; m>=0; n>=0; k+m+n is 10-5,000; k/(k+2m+n) is 0.0001-0.5; m/(m+n) is 0-1; x is 1-200; R<1> is H, alkyl, or aryl; R is a direct bond, -(CH2)h-, -X-(CH2)j, etc. wherein X is O or S; and h and j are each 1-30 provided h+j is 2-30 Z is 1-5C alkyl or phenyl; and A is a direct bond, a group of formula II or III, etc. wherein X is as defined above; Y is 0, S, or -NH-; and R<2> is a 1-30C divalent hydrocarbon group or its halogenated deriv.

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 swellable in an organic solvent and is capable of forming a flexible, self-supporting film having excellent heat resistance and a method 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, optoelectronic conversion elements, optical memories, functional elements such as various sensors, display elements, various hybrid materials, transparent conductors, various terminal devices, etc. is being studied. However, in general, polyaniline has a highly developed π-conjugated system, so that the main chain of the polymer is rigid and the interaction between the molecular chains is strong, and many strong hydrogen bonds exist between the molecular chains. Since it is insoluble in the organic solvent and does not melt even when heated, it has poor moldability and cannot be processed into a film. For that purpose, for example, by impregnating a base material of a desired shape such as a fiber of a polymeric material or a porous body with a monomer and contacting this monomer with a suitable polymerization catalyst, or by polymerizing by electrolytic oxidation. A similar composite material has been obtained by producing a conductive composite material or alternatively by polymerizing a monomer in the presence of a thermoplastic polymer powder.

On the other hand, polyaniline soluble only in N-methyl-2-pyrrolidone has been synthesized by devising the polymerization catalyst and reaction temperature (M. Abe et al .;
J. Chem. Soc. Chem. Commun. ，
1989, 1736). However, this polyaniline is also insoluble in other general-purpose organic solvents, and its application range is limited. Although polyaniline derivatives soluble in an organic solvent have been synthesized by using various aniline derivatives, it was not possible to form a film having sufficient flexibility. Also. The introduction of a substituent such as an alkyl chain has been studied, but in that case, there is a problem that the heat resistance is lowered at the same time. On the other hand, if the polymer compound can be gelled, it can be processed by using techniques such as gel stretching, gel spinning, and gel molding.

[0004]

SUMMARY OF THE INVENTION The present invention is intended to solve the above problems in the prior art. That is, an object of the present invention is to provide a polyaniline derivative that is soluble or swellable in an organic solvent, and is capable of forming a flexible self-supporting film or fiber having excellent heat resistance, and a method for producing the same. To do.

[0005]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventor has found that polyaniline is dissolved in an organic solvent by reacting it with polysiloxane having a group reactive with an amino group at the terminal. Further, they have found that a polyaniline derivative having a graft structure capable of forming a flexible self-supporting film or fiber which is swellable and has excellent heat resistance is obtained, and the present invention has been completed.

In the polyaniline derivative of the present invention, one or both of the quinodiimine structural unit and the imino-1,4-phenylene structural unit are randomly bonded to the N-polysiloxane graft imino-1,4-phenylene structural unit. And is represented by the following formula (I).

[0007]

[Chemical 5] [In the formula, k is an integer of 1 or more, m and n are integers of 0 or more, and k + m + n = 10 to 5000, and
k / (k + 2m + n) = 0.0001 to 0.5, m /
(M + n) = 0 to 1, x is an integer of 1 to 200, R ¹ is a hydrogen atom, an alkyl group or an aryl group, and each R ¹ bonded to each silicon atom is different from each other. R may be a direct bond or a group-(CH
_{2) h -, - X- (} CH 2) h -, - (CH 2) h -X
- (CH _{2) j} -, or _{-X- (CH 2) h -X- (} C
H ₂ ) _j − (wherein X represents an oxygen atom or a sulfur atom, h and j are integers of 1 to 30, and h + j =
2 to 30), Z represents an alkyl group having 1 to 5 carbon atoms or a phenyl group, and A represents a direct bond or a linking group selected from the following formulas (1) to (9).

[0008]

[Chemical 6] {In the formula, X represents an oxygen atom or a sulfur atom, Y represents an oxygen atom, a sulfur atom or -NH-, and R ² is a divalent hydrocarbon group having 1 to 30 carbon atoms or a halogen-substituted product thereof or-. COOM substitution (M is hydrogen atom, L
represents i, Na, K, Cs, Rb or NH ₄ . ), B represents a hydrocarbon group having 1 to 30 carbon atoms or an alkoxy group, and p represents an integer of 0 to 2. }] In the polyaniline derivative of the present invention, the number of nitrogen atoms involved in branching of the N-polysiloxane graftimino-1,4-phenylene structural unit is preferably 0.01 to 50% of the nitrogen atoms of polyaniline.

The polyaniline derivative of the present invention is obtained by treating an aniline oxidation polymer with ammonia to obtain a soluble aniline polymer, and then treating with excess hydrazine.
A reduced polyaniline having imino-1,4-phenylene as a structural unit and having a number average molecular weight of 2000 to 500000 is represented by the following formula (II).

[0010]

[Chemical 7] [In the formula, W is a halogen atom or the following formula (a)-
Represents a functional group selected from (g)

[0011]

[Chemical 8] (Wherein X, Y, P and B have the same meanings as described above, and Ha
l represents a halogen atom. ) A ¹ is a direct bond, -R ^{2
-, - R 2 -NH-C} (= X) -, - R 2 -C (= X)
- or -R ² -SO _p - (provided that, R ^2, X and _p
Represents the same meaning as described above. When W represents an intramolecular carboxylic acid anhydride group (g), R ² represents a trivalent hydrocarbon group having 1 to 30 carbon atoms, and R, R ¹ ,
Z, k, m, n and x have the same meaning as described above. ] It can manufacture by reacting with the polysiloxane compound which has the functional group which reacts with the aromatic secondary amine shown in these terminals.

The method for producing the polyaniline derivative of the present invention will be further described. First, the reduced polyaniline having the number average molecular weight of 2,000 to 500,000 is obtained as follows. That is, aniline is used at a low temperature, for example, -2 using ammonium persulfate or the like as an oxidizing agent.
An aniline oxidation polymer obtained by oxidative polymerization at a temperature in the range of 0 to 50 ° C. is first treated with ammonia to obtain a soluble polyaniline. Then, this is treated with excess hydrazine to give a number average molecular weight of 2,000-50.
A reduced polyaniline of 30,000 [measured with GPC (N-methyl-2-pyrrolidone solvent), polystyrene-equivalent number average molecular weight] is obtained. The hydrazine treatment is carried out by dispersing a soluble polyaniline in water or methanol, adding hydrazine in an amount equal to or more than the nitrogen atom in the polyaniline, preferably 3 times or more under a nitrogen atmosphere, for 24 hours or more,
It can be performed by stirring at 0 to 30 ° C. The resulting reduced polyaniline is soluble in N-methyl-2-pyrrolidone or N, N-dimethylacetamide, but insoluble in other general-purpose organic solvents such as chloroform and tetrahydrofuran.

In order to introduce a branched chain into the N-position of this reduced polyaniline, it is reacted with a polysiloxane compound represented by the above formula (II) having a functional group (W) which reacts with an aromatic secondary amine at the terminal. It is necessary to let As the terminal functional group in the polysiloxane compound represented by the above formula (II), specifically, a halogenated alkyl group, a carboxyl group, a carbonyl halide group, an isocyanate group, an isothiocyanate group, a sulfenyl halide group,
Examples thereof include sulfinyl halide group, sulfonyl halide group, oxirane ring, aziridine ring, thiirane ring, phosphinyl halide group, thiophosphinyl halide group, and intramolecular cyclic carboxylic acid anhydride group.

In the polysiloxane compound represented by the above formula (II) used in the present invention, R is a spacer which is bonded to the linking group, and is a direct bond or a group-
_{(CH 2) h -, -} X- (CH 2) h -, - (CH 2)
_h -X- (CH _{2) j} - or -S- (CH _{2) h} -O
- (CH _{2) j} - (provided that, X represents an oxygen atom or a sulfur atom, h and j is an integer of 1 to 30, h
+ J = 2 to 30), and specific examples thereof include a methylene group, an ethylene group, a propylene group, an oxymethylene group, an oxyethylene group, and an oxytrimethylene group. The terminal group Z is a C1-C5 alkyl group such as a methyl group or an ethyl group, or a phenyl group.

Also, each R ¹ bonded to each silicon atom
Is a hydrogen atom, an alkyl group or an aryl group,
R ^{1 s} may be different from each other, and specific examples of the alkyl group and the aryl group include a methyl group,
Examples thereof include alkyl groups such as ethyl group and propyl group, and aryl groups such as phenyl group. For example, when each R ¹ represents a methyl group and a phenyl group, the polysiloxane chain may be a mixture of structural units represented by the following formula.

[Chemical 9]

Examples of commercially available products of the polysiloxane compound represented by the above formula (II) used in the present invention include:
FM, which is a polysiloxane having an epoxy group at one end
0511, FM05211, FM05325 (all manufactured by Chisso Co., Ltd., molecular weights of 1,000 and 5000, respectively).
And 10,000) such as TS having a halogen at the end
L9205 (manufactured by Toshiba Silicone Co., molecular weight 224.9 or 196.8) and the like can be mentioned.

The reaction between the reduced polyaniline obtained as described above and the polysiloxane compound represented by the above formula (II) is carried out by different methods depending on the kind of the terminal functional group. Next, those will be described in detail. Synthesis Example 1: Functional group W is a halogen atom or formula (a),
In the case of (g), an amide-based solution of the reduced polyaniline described above is used,
A polysiloxane having a terminal functional group such as a halogen hydrocarbon group is added to the terminal, and stirring is continued in a temperature range of 0 to 80 ° C. for 1 to 48 hours under a nitrogen stream. If necessary, pyridine or a tertiary amine such as triethylamine or diethylamine may be added to carry out the reaction. The reaction mixture is poured into alcohol or water and the polymer formed is precipitated. By further treating this polymer with aqueous ammonia, the polyaniline derivative of the present invention can be produced.

Synthesis Example 2: The functional group W has the formulas (b), (c),
In the case of (e) and (f), the above-mentioned amide solution of reduced polyaniline is added, for example,
An amide-based, ether-based, or ester-based solution of the polysiloxane compound having the above functional group is gradually added, and the temperature is in the range of -10 to 80 ° C under a nitrogen flow of 1 to 48.
Continue stirring for hours. If necessary, pyridine or a tertiary amine such as triethylamine or diethylamine may be added to carry out the reaction. The reaction mixture is poured into alcohol or water and the polymer formed is precipitated. By further treating this polymer with aqueous ammonia,
The polyaniline derivative of the present invention can be produced.

Synthetic Example 3: When the functional group W is of the formula (d) A polysiloxane compound having a carboxyl group at one end is dissolved in an amide solvent, and N, N'-dicarboxylic acid equivalent to the end carboxyl group is added thereto. Substituted carbodiimides with -10
Add while cooling to 0-10 ° C., continue stirring at that temperature for 1 to 4 hours, then add the above amide solution of reduced polyaniline and slowly return to room temperature for another 1
Continue stirring for ~ 48 hours. The reaction mixture is poured into alcohol and the polymer formed is precipitated. By further treating this polymer with aqueous ammonia, the polyaniline derivative of the present invention can be produced.

The N, N'-disubstituted carbodiimides used herein are represented by the following formula (III) R ³ -N = C = N-R ⁴ (III) (wherein R ³ and R ⁴ are the same or May be 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, cyclic alkyl group such as cyclohexyl group, phenyl group, p-tolyl group, m
-Tolyl group, p-N, N-dimethylaminophenyl group,
Exposing aryl groups such as p-chlorophenyl group, p-nitrophenyl group and p-cyanophenyl group. ), More specifically, diethylcarbodiimide, diisopropylcarbodiimide, dicyclohexylcarbodiimide, diphenylcarbodiimide, di-p.
-Tolyl carbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide and the like can be mentioned.

Further, the terminal carboxylic acid group of the polysiloxane having a terminal carboxylic acid group is converted into a haloformyl group,
The polyaniline derivative of the present invention can be produced according to the above-mentioned synthesis method 2. The conversion of this terminal carboxylic acid group to a haloformyl group is carried out by the following method from carboxylic acid, its carboxylic acid ester (ester of lower alcohol such as methyl or ethyl), or carboxylic acid salt (alkali metal salt, ammonium salt, etc.). It can be easily implemented. That is, from the carboxylic acid, an equivalent amount or more of an inorganic halogen compound such as phosphoryl chloride, thionyl chloride, phosphorus pentachloride or phosphorus trichloride is added to the carboxylic acid and reacted in an inert solvent such as benzene. A polysiloxane compound having a haloformyl group at the terminal can be obtained. In this case, zinc chloride, pyridine, iodine, triethylamine or the like may be added as a catalyst. Similarly, from carboxylic acids, acid halides such as benzoyl chloride, phthalic acid chloride, oxalic acid chloride, α, α-dihalogenoethers, halogenated alkylamines, triphenylphosphine / Add organic halides such as carbon tetrachloride, pyrocatetyl phosphotrichloride, ethylphosphodichloride, triphenylphosphotribromide, and other organic halides, and react in an inert solvent such as benzene or chlorobenzene. You can also get it.

From the carboxylic acid ester, a polysiloxane compound having a haloformyl group at the terminal used in the present invention can be obtained by using a triphenylphosphohalide or a complex thereof with boron fluoride for the carboxylic acid ester. it can. From the carboxylic acid salt, a polysiloxane compound having a haloformyl group at the terminal used in the present invention is prepared by using an inorganic halogen compound such as phosphoryl chloride or phosphorus pentachloride or a complex of thionyl chloride and dimethylformamide with respect to the carboxylic acid salt. Obtainable. In addition to these, any reaction may be used as long as it is a reaction capable of converting a carboxylic acid group to a haloformyl group, whereby a polysiloxane compound having a haloformyl group at the terminal used in the present invention can be obtained. .

In the case of the above reaction in the present invention, when an amide type solvent is used as the solvent, specifically, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexa Methylphosphoric triamide, 1,3-dimethyl-2-imidazolidinone, etc. can be used.

The polysiloxane having a functional group capable of reacting with an aromatic secondary amine at the end, which is represented by the above formula (II) and is used as a raw material in the present invention, has a functional group W at one end. Disiloxane is a cyclic siloxane trimer or tetramer and platinum black (Pt /
C), chloroplatinic acid, silver halide, and other noble metal-based catalysts can be used for the reaction. Also,
A disiloxane polymer having a hydroxyl group at one end (for example, FM0411, FM0421, FM0425: all manufactured by Chisso Corporation, molecular weights of 1,000 and 50, respectively).
00 and 10000, or XF3968: manufactured by Toshiba Silicone Co., Ltd., average degree of polymerization: about 350). Specifically, a terminal hydroxyl group is reacted with an acid anhydride to form a carboxylic acid structure, a terminal to form a cyclic acid anhydride structure by reacting with trimellitic anhydride or a halogenated trimellitic anhydride, Those with an acid halide structure by reacting with an excess diacid halide, those with an excess diisocyanate to form an isocyanate structure, and those with an excess diisothiocyanate to react with an end isothiocyanate React with a nato structure, disulfinyl halide, disulphenyl halide, or disulfonyl halide, and each end has a sulfinyl halide, sulfenyl halide, or sulfonyl halide structure, react with epihalohydrin to terminate the oxirane ring Or a halo having a double bond at the end. Hydrolyzed hydrocarbons, such as allyl halides, and carboxylic acids having a double bond at the end, such as allyl acetic acid, to form a structure having a double bond at the end, and then reacted with a peroxide to give aziridine. Examples thereof include those which form a ring, those which are reacted with sulfur dichloride and then reduced to form a thiirane ring, and the like. Furthermore, a siloxane polymer having a vinyl group at one end (for example, FM0231, FM0241, FM024
2; Frightened, p Chisso Co., Ltd., molecular weight 10 each
00, 5000 and 10000), and specifically, those formed by reacting with a peroxide to form an oxirane ring, those formed by reacting with INCO and then KOH to form an aziridine ring, Examples thereof include those obtained by reacting with sulfur dichloride and then reducing to form a thiirane ring.

In the polyaniline derivative of the present invention, since the length of the polyaniline main chain does not change during production, k
The value of + m + n becomes the same as the value of n of the reduced polyaniline as the starting material. Further, 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 with an oxidizing agent or by electrochemical oxidation, the value of m increases, and the polyaniline derivative of the present invention is obtained with a reducing agent or by electrochemical reduction. If is reduced, the value of m decreases. The value of m / (n + m) is the peak derived from the quinoid structure in the ¹³ C NMR spectrum (chemical shift 138 p.
intensity of pm / TMS (tetramethylsilane) and peak derived from benzenoid structure (chemical shift 122p
It can be obtained from the ratio of pm / TMS).

In the polyaniline derivative of the present invention, the nitrogen atoms involved in branching are preferably in the range of 0.01 to 50% on average of the nitrogen atoms of polyaniline. When the ratio of nitrogen atoms involved in branching is higher than 50%,
It becomes difficult to dissolve and swell, which causes problems in workability. If it is as small as 0.01%, the solubility will not be much different from that of polyaniline.

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, or a halogenated hydrocarbon solvent such as chloroform, dichloroethane or dichloromethane. Alternatively, 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. It is possible to produce free-standing films and fibers from this solution or gel. Further, the processed product such as the film or the fiber becomes high in conductivity of 10 ^{−3 to} 10 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, Examples thereof include various compounds such as Lewis acids such as iron trichloride, molybdenum chloride, antimony chloride and arsenic pentafluoride, and organic acids such as acetic acid, trifluoroacetic acid, benzenesulfonic acid and p-toluenesulfonic acid.

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

[0030]

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, it was slowly added dropwise to the above aniline solution, and -10 ° C.
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. Then, dedoping treatment was performed with aqueous ammonia to obtain a soluble polyaniline. Obtained reduced polyaniline (number average molecular weight 1
2,000, m + n = about 130) 1g under N flow
-Completely dissolved in 30 ml of methyl-2-pyrrolidone. In addition to this, polysiloxane FM0511 having an epoxy group at the end (manufactured by Chisso Corporation, molecular weight 1000, W
= Epoxy group, A ¹ = methylene group, R = -O-CH
₂ -, R ¹ = methyl, Z = methyl) 2.195G added by performing the 6 hours grafting reaction at 40 ° C. according to Synthesis method 1, a polyaniline derivative of the present invention 3.18
g was obtained.

When the infrared absorption spectrum was measured, it was 2980 cm ^-1 (methyl group C-H expansion and contraction), 1260 cm ^-1 (methyl group symmetrical bending angle) due to the branched structure, 1020.
Absorption of cm ^-1 (Si-O expansion and contraction) was observed. Furthermore, 1
600, 1500, 1300, 1170, 820 cm ^-1
The absorption pattern peculiar to polyaniline was observed in and it was confirmed that the main chain had a polyaniline structure. From the reaction yield, the number of nitrogen atoms involved in the cross-linked structure of the formula (II) is about 20% of the nitrogen atoms in polyaniline (k / (k + 2m +
n) was 0.2). Also, from the ¹³ C spectrum, m
/(N+m)=0.48.

1 g of the obtained polyaniline derivative was put into 9 g of N-methyl-2-pyrrolidone and dissolved to prepare 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 doped, the conductivity was 0.8 S / cm.
Met. When heated in the air, no weight loss was observed up to 350 ° C. Also, N-methyl-2
Even if an organic solvent such as N, N-dimethylacetamide, N, N-dimethylformamide, pyridine, chloroform, dichloroethane, dichloromethane or tetrahydrofuran was used instead of -pyrrolidone, the same processing was possible.

Example 2 In Example 1, TSL9205 (molecular weight 224.9, x = 1, which is a disiloxane having a chloromethyl group at the terminal, was used.
R ¹ = methyl group, Z = methyl group, W = chlorine atom, A = direct bond, R = trimethylene group; manufactured by Toshiba Silicone Co., Ltd.)
Using 1.234 g, the following procedure was followed to obtain 2.225 g of the polyaniline derivative of the present invention. When the infrared absorption spectrum was measured, it was found to be 298 due to the above-mentioned branched structure.
Absorptions of 0 cm ⁻¹ (methyl group C—H expansion and contraction), 1260 cm ⁻¹ (methyl group symmetrical bending angle), and 1020 cm ⁻¹ (Si—O expansion and contraction) were 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 is about 49% of the nitrogen atoms of polyaniline (k /
It was (k + 2m + n) = 0.49). In addition, from the ¹³ C spectrum, m / (n + m) = 0.44.

1 g of the obtained polyaniline derivative was put into 20 g of N-methyl-2-pyrrolidone and dissolved to prepare 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. Also, when heated in the atmosphere, 350
No weight loss was observed up to ° C. Further, similar processing is possible even when an organic solvent such as N, N-dimethylacetamide, N, N-dimethylformamide, pyridine, chloroform, dichloroethane, dichloromethane or tetrahydrofuran is used in place of N-methyl-2-pyrrolidone. It was

Example 3 FM041 which is a polysiloxane having a hydroxyl group at the terminal
1 (manufactured by Chisso Corp., molecular weight = about 1000, R ¹ = methyl group, Z = methyl group, R = trimethylene group, A ¹ = oxyethylene group, W = hydroxyl group) was reacted with succinic anhydride to produce a terminal. Polysiloxane having carboxyl group (R
_{= -O- (CH 2) 2 -O-} (CH 2) 3 -, A 1 = -
_{(CH 2) 2 -C (=} O) -, W = COOH) was obtained.
Using 1.207 g of this product, 2.200 g of the polyaniline derivative of the present invention was obtained by the procedure of Synthesis method 3 below.

The infrared absorption spectrum was measured and found to be 2980 cm ^-1 (methyl group C-
H stretch), 1734, 1650 cm ^-1 (C = O stretch),
1260 cm ^-1 (Methyl group symmetrical bending), 1020 cm ^-1
Absorption of (Si-O expansion and contraction) was observed. Furthermore, 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 was about 10% (k / (k + 2m + n) = 0.1) of the nitrogen atoms of polyaniline. Further, from the ¹³ C spectrum, m / (n + m) = 0.
It was 44. 1 g of the obtained polyaniline derivative was N-
It was put in 9 g of methyl-2-pyrrolidone and dissolved at room temperature to obtain a very flexible film or fiber. Furthermore, this film or fiber is added to 20% sulfuric acid
After being dipped for 4 hours and then dried, the conductivity is 0.5.
It was S / cm. When heated in the atmosphere, 3
No weight loss was observed up to 50 ° C. Further, instead of N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, pyridine,
Similar processing was possible using an organic solvent such as chloroform, dichloroethane, dichloromethane or tetrahydrofuran.

Example 4 FM041 which is a polysiloxane having a hydroxyl group at the terminal
1 (manufactured by Chisso Corp., molecular weight = about 1000, R ¹ = methyl group, Z = methyl group, R = trimethylene group, A ¹ = oxyethylene group, W = hydroxyl group) was reacted with anhydrous phthalic acid chloride. , polysiloxane _{(R = -O- (CH 2)} 2 -O- (CH 2 having an acid anhydride structure at the end) ₃ -, a ¹
_{=> C 6 H 3 -C (} = O) -, W = - (O =) C-O-
(= O)-) was obtained. Using 1.289 g of this,
Hereinafter, 2.200 g of the polyaniline derivative of the present invention was obtained by the procedure of Synthesis method 1.

The infrared absorption spectrum was measured and found to be 2980 cm ^-1 (methyl group C-
H stretch), 1650 cm ^-1 (C = O stretch), 1260c
m ⁻¹ (Methyl group symmetrical bending angle), 1020 cm ⁻¹ (Si—O
(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 number of nitrogen atoms involved in the branched structure is about 1 of the nitrogen atoms of polyaniline.
It was 0% (k / (k + 2m + n) = 0.1). Moreover, m / (n + m) = 0.46 from the ¹³ C spectrum. 1 g of the obtained polyaniline derivative was added to N-methyl-
It was put in 9 g of 2-pyrrolidone and dissolved at room temperature to obtain 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 0.9 S / cm.
Met. When heated in the air, no weight loss was observed up to 350 ° C. Also, N-methyl-2
The same processing was possible by using an organic solvent such as N, N-dimethylacetamide, N, N-dimethylformamide, pyridine, chloroform, dichloroethane, dichloromethane or tetrahydrofuran instead of -pyrrolidone.

Example 5 XF396 which is a polysiloxane having a hydroxyl group at the terminal
8 (manufactured by Toshiba Silicone Co., average degree of polymerization = 350, R ¹ =)
Methyl group, Z = methyl group, R = direct bond, A ¹ = direct bond, W = hydroxyl group) is reacted with ethyl chloroacetate and then with triphenylphosphine dichloride to give a polymorph having a chloroformyl group at the end. Siloxane (average molecular weight = 426, R ¹ = methyl group, Z = methyl group, R = direct bond, A ¹ = methylene group, W = chloroformyl group) was obtained. Using 0.936 g of this product, the polyaniline derivative of the present invention 1.9 was manufactured according to the procedure of Synthesis Method 2 below.
22 g was obtained.

The infrared absorption spectrum was measured and found to be 2980 cm ^-1 (methyl group C-
H stretch), 1650 cm ^-1 (C = O stretch), 1260c
m ⁻¹ (Methyl group symmetrical bending angle), 1020 cm ⁻¹ (Si—O
(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 number of nitrogen atoms involved in the branched structure is about 2 of the nitrogen atoms of polyaniline.
It was 0% (k / (k + 2m + n) = 0.2). Moreover, m / (n + m) = 0.46 from the ¹³ C spectrum. 1 g of the obtained polyaniline derivative was added to N-methyl-
It was put in 9 g of 2-pyrrolidone and dissolved at room temperature to obtain 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 doped, the conductivity was 0.1 S / cm.
Met. When heated in the air, no weight loss was observed up to 350 ° C. Also, N-methyl-2
Even if an organic solvent such as N, N-dimethylacetamide, N, N-dimethylformamide, pyridine, chloroform, dichloroethane, dichloromethane or tetrahydrofuran was used instead of -pyrrolidone, the same processing was possible.

Example 6 FM042, which is a polysiloxane having a hydroxyl group at the terminal
1 (manufactured by Chisso Corporation, molecular weight = about 2000, R ¹ = methyl group, Z = methyl group, R = trimethylene group, A ¹ = oxyethylene group, W = hydroxyl group) was first treated with phosphorus trichloride. To convert a terminal hydroxyl group into a chlorine atom, and then to react with silver cyanate to convert the terminal into an isocyanate, and to provide a polysiloxane having an isocyanate group at the terminal (average molecular weight =
About 2025, R ¹ = methyl group, Z = methyl group, R = trimethylene group, A ¹ = oxyethylene group, W = isocyanato group) were obtained. Using 1.111 g of this product, 2.022 g of the polyaniline derivative of the present invention was obtained in accordance with the procedure of Synthesis method 2 below.

The infrared absorption spectrum was measured and found to be 2980 cm ^-1 (methyl group C-
H expansion / contraction), 1655 cm ^-1 (C = O expansion / contraction), 1260c
m ⁻¹ (Methyl group symmetrical bending angle), 1020 cm ⁻¹ (Si—O
(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 number of nitrogen atoms involved in the branched structure is about 5 of the nitrogen atoms of polyaniline.
% (K / (k + 2m + n) = 0.05). Further, from the ¹³ C spectrum, m / (n + m) = 0.48. 1 g of the obtained polyaniline derivative was added to N-methyl-
It was put in 9 g of 2-pyrrolidone and dissolved at room temperature to obtain a very flexible film or fiber. Furthermore, when this film or fiber was dipped in a 20% aqueous solution of sulfuric acid for 24 hours and doped, the conductivity was 0.3 S / cm.
Met. When heated in the air, no weight loss was observed up to 350 ° C. Also, N-methyl-2
Even if an organic solvent such as N, N-dimethylacetamide, N, N-dimethylformamide, pyridine, chloroform, dichloroethane, dichloromethane or tetrahydrofuran was used instead of -pyrrolidone, the same processing was possible.

Example 7 FM042, which is a polysiloxane having a hydroxyl group at the terminal
1 (manufactured by Chisso Corporation, molecular weight = about 2000, R ¹ = methyl group, Z = methyl group, R = trimethylene group, A ¹ = oxyethylene group, W = hydroxyl group) was first treated with phosphorus trichloride. After converting the terminal hydroxyl group to chlorine atom and then reacting with sodium bisulfite to convert the terminal to sodium sulfonate group, it is treated with phosphorus oxytrichloride to convert the terminal to sulfonyl chloride and have a sulfonyl chloride group at the terminal. Polysiloxane (average molecular weight = about 2082,
R ¹ = methyl group, Z = methyl group, R = trimethylene group,
A ¹ = oxyethylene group, W = sulfonyl chloride group) was obtained. Using 2.285 g of this product, 3.022 g of the polyaniline derivative of the present invention was obtained in accordance with the procedure of Synthesis method 2 below.

The infrared absorption spectrum was measured and found to be 2980 cm ^-1 (methyl group C-
H stretch), 1351, 1176 cm ^-1 (S = O stretch),
1260 cm ^-1 (Methyl group symmetrical bending), 1020 cm ^-1
Absorption of (Si-O expansion and contraction) was observed. Furthermore, 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 was about 9% (k / (k + 2m + n) = 0.09) of the nitrogen atoms of polyaniline. Further, from the ¹³ C spectrum, m / (n + m) = 0.
It was 48. 1 g of the obtained polyaniline derivative was N-
It was put in 9 g of methyl-2-pyrrolidone and dissolved at room temperature to obtain a very flexible film or fiber. Furthermore, this film or fiber is added to 20% sulfuric acid
When it was dipped for 4 hours and then dried, the conductivity was 0.2.
It was S / cm. When heated in the atmosphere, 3
No weight loss was observed up to 50 ° C. Further, instead of N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, pyridine,
Similar processing was possible using an organic solvent such as chloroform, dichloroethane, dichloromethane or tetrahydrofuran.

[0045]

INDUSTRIAL APPLICABILITY The polyaniline derivative of the present invention can be swollen with various organic solvents, the obtained gel can be easily processed, and a flexible self-supporting film or fiber can be obtained. it can. Since the formed film or fiber shows 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 quinodiimine structural unit and imino-
A polyaniline derivative represented by the following formula (I), in which one or both of 1,4-phenylene structural units and N-polysiloxane graftimino-1,4-phenylene structural units are randomly bonded. [Chemical 1] [In the formula, k is an integer of 1 or more, m and n are integers of 0 or more, and k + m + n = 10 to 5000, and
k / (k + 2m + n) = 0.0001 to 0.5, m /
(M + n) = 0 to 1, x is an integer of 1 to 200, R ¹ is a hydrogen atom, an alkyl group or an aryl group, and each R ¹ bonded to each silicon atom is different from each other. R may be a direct bond or a group-(CH
_{2) h -, - X- (} CH 2) h -, - (CH 2) h -X
- (CH _{2) j} -, or _{-X- (CH 2) h -X- (} C
H ₂ ) _j − (wherein X represents an oxygen atom or a sulfur atom, h and j are each an integer of 1 to 30 and h + j = 2 to 30), and Z is a carbon number of 1
5 represents an alkyl group or a phenyl group, and A represents a direct bond or a linking group selected from the following formulas (1) to (9). [Chemical 2] {In the formula, X represents an oxygen atom or a sulfur atom, Y represents an oxygen atom, a sulfur atom or -NH-, and R ² is a divalent hydrocarbon group having 1 to 30 carbon atoms or a halogen-substituted product thereof or-. COOM substitution (M is hydrogen atom, L
represents i, Na, K, Cs, Rb or NH ₄ . ), B represents a hydrocarbon group having 1 to 30 carbon atoms or an alkoxy group, and p represents an integer of 0 to 2. }] 2. A number average molecular weight having imino-1,4-phenylene as a structural unit, which is obtained by treating an aniline-oxidized polymer with ammonia to obtain a soluble aniline polymer, and then treating with excess hydrazine. 2000-500000 reduced polyaniline is represented by the following formula (II): [In the formula, W is a halogen atom or the following formula (a)-
A functional group selected from (g) (In the formula, X, Y, P and B have the same meanings as described above, and H
al represents a halogen atom. ) A ¹ is a direct bond, -R
^{2 -, - R 2 -NH-} C (= X) -, - R 2 -C (=
X) - or -R ² -SO _p -. (Provided that, R ^2, X and _p represents an indicative) as defined above, provided that, W
Is an intramolecular carboxylic acid anhydride group (g), R ²
Represents a trivalent hydrocarbon group having 1 to 30 carbon atoms, R, R
¹ , Z, k, m, n and x have the same meanings as described above. ] The method for producing a polyaniline derivative according to claim 1, wherein the polyaniline derivative is reacted with a polysiloxane compound having a functional group that reacts with an aromatic secondary amine at the end.