JPH07286035A - Soluble conductive polymer and its production - Google Patents

Abstract

PURPOSE:To obtain a soluble conductive polymer which can be obtained by a simple operation, is soluble in various solvents such as water, has self- dopability, therefore need not be doped and is excellent in processability and electrical and mechanical properties. CONSTITUTION:This polymer is one having a weight-average molecular weight of 500-1000000 and comprising structural units of the formula (wherein Ht is NH, S, O, Se or Te; R<1> is a linear or branched alkyl; X<1> is CO2, CONH, O, S or NH; R<2> is a 3-21 C pivalent (substituted) hydrocarbon group; and M is an atom which forms a positive counter ion when oxidized). This polymer is produced by chemically polymerizing the corresponding monomer in the presence of an oxidizing transition metal halide and treating the formed polymer with an acidic solution.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a conductive polymer having self-doping property, which is soluble and easy to process, a manufacturing method and a precursor.

[0002]

2. Description of the Related Art Organic polymer materials having electronic conductivity are
In recent years, antistatic materials, electromagnetic wave shielding materials, secondary batteries,
A wide range of applications such as capacitors and electrochromic display devices are under consideration. As electron conductive polymer,
Polyacetylene, polyaniline, polyphenylene vinylene, polypyrrole, polythiophene, etc. are known. Among them, N-methyl-2 is a material soluble in a solvent.
-Polyaniline soluble in pyrrolidone (M. Abe et.
al. J .; Chm. Soc. Chem. Comm
un. , 1989, 1736), polypyrrole having a substituent such as an alkyl group introduced therein, and polythiophene (M.-.
A. Sato, S .; Tanaka, K .; Kaeriya
ma: Synth. Met. (1987, 18, 229)
There is. It is known that a polymer such as polyphenylene vinylene is soluble in its precursor polymer.
Since these polymers can be formed into films by casting, application of various polymer films to antistatic materials and the like is being studied. However, in order to impart conductivity to the conductive polymer, it is necessary to treat it with an electron-accepting or electron-accepting compound after molding (hereinafter referred to as doping), soaking it in an acidic solution, exposing it to a dopant vapor, etc. However, this was a problem in terms of processing. Further, when a low molecular weight dopant is doped, there is a problem that dedoping is likely to occur due to immersion in a solvent or heating. As a means for solving the problems of these conductive polymers, a conductive polymer having a self-doping property (A.O. Patil et al. J. Am. Ch) in which a counter ion serving as a dopant is covalently bonded to a polymer is used.
em. Soc. 1987, 109, 1858-185.
9) has been proposed, but in the method for producing such a polymer (Japanese Patent Laid-Open No. 2-189333), chemical polymerization is performed in the presence of an oxidizable transition metal halide to remove a transition metal ion in the product. It was necessary to remove the produced transition metal hydroxide by filtering the polymer solution after the dissolution in the acid solution. Further, in order to obtain a highly conductive self-doping polymer without performing doping treatment after film formation or mixing of a polymer solution and a dopant, treatment with an ion exchange resin or the like is indispensable. Such filtration and ion exchange treatment of the polymer solution have been obstacles to the industrial production of the self-doping type conductive polymer.

[0003]

DISCLOSURE OF THE INVENTION The present invention eliminates the need for doping treatment which is soluble in a solvent such as water and is excellent in processability, has improved solvent resistance and heat resistance, and has excellent electrical and mechanical properties. Another object of the present invention is to provide a soluble conductive polymer.

[0004]

As a result of repeated studies to solve the above problems, the inventors of the present invention chemically polymerized a certain monomer in the presence of an oxidizable transition metal halide, and simply It was found that the transition metal halide was removed from the polymer by washing with a polar solvent and treated with an acidic solution to obtain a soluble self-doped conductive polymer, and the present invention was completed.

That is, the present invention has the general formula [I]

[Chemical 7] (Wherein Ht is NH, S, O, Se or Te, R ¹ is a linear or branched alkyl group, and X ¹ is CO ₂ , C
ONH, O, S, or NH, R ² represents an optionally substituted divalent hydrocarbon group having 3 to 21 carbon atoms, and M represents an atom which produces a positive counterion upon oxidation. ) Having a structural unit represented by
The present invention relates to a, 000,000 conductive polymer, a manufacturing method thereof, and a manufacturing method of a monomer.

More preferred specific examples of the soluble conductive polymer belonging to the general formula [I] include Ht of NH, S, and Se;
R ¹ is a methyl group; X ¹ is —COO— or —CONH
-; R ² is a linear alkyl group [that is,-(CH ₂ ).
_v- (where v is 3-12)]. A copolymer containing a monomer unit other than the monomer unit represented by the general formula [I] is also intended. Representative molecular weight inventions 13 to 103 (by weight), and a high molecular weight is preferable. Examples of the atom represented by M that produces a positive counterion upon oxidation include a hydrogen atom, an alkali metal, an alkaline earth metal, and an ammonium ion. Examples of the hydrocarbon substituent of R ² include a halogen atom, a nitro group, a hydroxyl group, a carboxyl group and an alkoxy group.

The method for producing a conductive polymer is represented by the general formula [II]

[Chemical 8] (In the formula, Ht, R ¹ , X ¹ , R ² and M have the same meanings as described above.) The compound is chemically polymerized in the presence of an oxidizing transition metal halide, and the polymer is treated with an acidic solution. Of the general formula [I ′]

[Chemical 9] (In the formula, Ht, R ¹ , X ¹ and R ² have the same meanings as described above.).

Examples of the transition metal halide used in the present invention include ferric oxide, molybdenum chloride, tungsten chloride, tin chloride, vanadium chloride, ruthenium chloride, antimony chloride and arsenic pentafluoride. As a polymerization method, a method of simply mixing a solution of a transition metal halide and a monomer represented by the general formula [II], a method of flowing a mixed solution of a transition metal halide and a monomer on a glass plate, and drying (hereinafter, a drying method And). In the polymerization by the drying method, it is necessary to select a solvent in order to suppress the reaction, but various alcohols, water and the like, or a mixed solvent thereof can be used for the production of the present polymer. Then, washing with a polar solvent is performed in order to remove the transition metal halide in the product. The solvent used at this time is not particularly limited as long as it can dissolve the transition metal halide used. At this point, the polymer has no solubility in water and the like, so that washing with water is also possible. Finally, the polymer is treated with an acidic solution by simply immersing it in an acidic solution. The acidic solution used is not particularly limited as long as it can exchange M of the general formula [I] for a hydrogen atom. Subsequently, the acid used for the treatment is removed by washing the polymer. The solvent used is a solvent that dissolves the acid used and does not dissolve the polymer. Acetone is used as the solvent for cleaning.
Tetrahydrofuran, various alcohols and the like can be preferably used. The polymer thus obtained is dissolved in water, methanol, DMF, NMP, acetic acid or the like, and a self-supporting conductive polymer film can be prepared by casting without any doping treatment. The conductivity of the resulting film without doping 10 ^-7 to 10 ⁰ s
It has a conductivity of about / cm. Furthermore, the conductivity can be improved by performing the doping. Examples of the compound to be doped include halides (iodine, bromine, iodine chloride, iodine bromide, etc.), Lewis acids (arsenic pentafluoride, phosphorus pentafluoride, antimony pentafluoride,
Boron difluoride, boron dichloride, boron dibromide, sulfur dioxide, etc., Bronsted acids (hydrogen fluoride, hydrogen chloride, fluorosulfonic acid, chlorosulfonic acid, perchloric acid, trifluorometasulfonic acid, toluene) Sulfonic acid, etc.),
Examples thereof include transition metal chlorides (ferric chloride, titanium tetrachloride, etc.), organic compounds (tetracyanoethylene, tetrafluorotetracyanoquinodimethane, tetrafluorobenzoquinone, etc.) and the like. Examples of the method of doping with these dopants include ordinary methods such as chemical doping and electrochemical doping. M of the general formula [I] of the obtained polymer solution is a desired alkali metal ion,
It can be changed to alkaline earth metal ions and ammonium ions. That is, sodium hydroxide in the polymer solution,
By adding a predetermined amount of a metal hydroxide solution such as potassium hydroxide, it is possible to change M of the general formula [I] to a desired alkali metal ion such as ammonium ion or potassium ion.

The monomer of the conductive polymer raw material of the present invention has a general formula [III]

[Chemical 10] (In the formula, Ht and R ¹ have the same meanings as described above, and X ² is C
Indicates O ₂ H, CONH ₂ , OH, SH or NH ₂ . )
And a compound represented by the general formula [IV]

[Chemical 11] (In the formula, X ³ represents a divalent hydrocarbon group having 2 to 20 carbon atoms, provided that one or more hydrogen atoms of the hydrocarbon are a halogen atom, a nitro group, a hydroxyl group, a carboxyl group or an alkoxy group. Which may be substituted with) in the presence of a base.

[0010]

EXAMPLES Next, the present invention will be described in more detail by way of examples. Example 1 Preparation of sodium 3- (4-methyl-3-pyrrolecarbonyloxy) propane sulfonate:

[Chemical 12] 2-Methylpyrrole-3-carboxylic acid 2 g was suspended in isopropanol 15 ml, and sodium methoxide 28% was added.
A uniform solution was prepared by adding 3.09 g of a methanol solution. Further, 1.95 g of 1,3-propane sultone was added here. After reacting at 70 ° C. for 20 minutes, the white crystals formed were collected by filtration to give 50% isopropanol.
The crystals were washed with ml. The crystals were dissolved in water and washed with ethyl acetate to remove unreacted 4-methylpyrrole-3-carboxylic acid, and the aqueous layer was evaporated to dryness to obtain 3.86 g of the desired product as white crystals. Yield 89% ¹ H-NMR (270 MHz DMSO-d ₆ ) TMS
Δ (ppm): 1.9-2.05 (2H,
m), 2.2 (3H, s), 2.5-2.7 (2H,
t), 4.1-4.25 (2H, t), 6.6 (1H,
s), 7.33 (1H, s), 11.1 (1H, br
s) IR (KBr, ν, cm ⁻¹ ): 1687s, 1209
s, 1159s, 1056s, m. p. 300 ° C Up

Example 2 Production of Conducting Polymer: 3-
Sodium (4-methylpyrrole-3-carbonyloxy) propanesulfonate 0.19 g and anhydrous ferric chloride 0.29 g were added to methanol / water (= 7 ml / 0.1 ml).
And was stirred. This homogeneous solution was poured onto a 64 cm ² glass plate, and the solvent was evaporated under reduced pressure at room temperature. Peel off the remaining black film from the glass plate, remove the anhydrous ferric chloride by washing with methanol until the washing liquid is no longer colored, and further remove the polymer film with a 6N HCl aqueous solution.
Soak for 5 minutes. The polymer film was washed with tetrahydrofuran until the washing liquid became neutral, and the polymer was dissolved in 20 ml of water. The obtained polymer aqueous solution was concentrated to obtain 3 g of a 3.6% polymer solution. The yield obtained from the solid content concentration and the solution amount was 62%. G of the polymer aqueous solution thus obtained
A PC measurement showed that the weight average molecular weight was 100,00.
0, converted to polystyrene sulfonate (0.1 M KCl aqueous solution was used for the moving layer). The resulting polymer solution was cast on a glass plate and the solvent was evaporated at room temperature. The polymer film thus obtained was peeled off from the glass plate and further heated at 110 ° C.
It was dried by leaving it in the oven for 2.5 hours. The conductivity of the obtained polymer film was measured by a DC four-terminal method, and it was 1.13 × without doping.
The conductivity was as high as 10 ^-1 s / cm. The conductivity is 3 × 10 ^-1 s / cm by further doping with iodine.
And improved.

Comparative Example 1 Production of Conductive Polymer (without Acid Solution Treatment): 4-Methylpyrrole-3-carboxylic Acid
0.19 g of sodium 3-propanesulfonate and 0.29 g of anhydrous ferric chloride were added to methanol / water (= 7 ml / 0.
1 ml) and stirred. 64c of this uniform solution
It was poured onto a m ² glass plate, and the solvent was evaporated under reduced pressure at room temperature. Peel off the remaining black film from the glass plate, and wash with methanol until the washing liquid is no longer colored to remove anhydrous ferric chloride, and 0.1 ml of 0.1 NaOH aqueous solution.
The polymer was thrown in and dissolved, but it was not completely dissolved. The undissolved polymer and the generated iron hydroxide were removed by filter paper filtration, and the polymer solution was passed through a proton type ion exchange resin. The resulting polymer solution was concentrated to 3.6
% Polymer solution was obtained. The yield determined from the solid content concentration and the solution amount was 31%. GPC measurement of the polymer aqueous solution thus obtained showed a weight average molecular weight of 51,000 and polystyrene sulfonate conversion (0.1M
KCl aqueous solution was used for the mobile phase). The polymer solution obtained in Comparative Example 1 was poured onto a glass plate, and the solvent was evaporated at room temperature. Peel off the polymer film thus obtained from the glass plate,
Furthermore, it was dried by leaving it in an oven at 110 ° C. for 2.5 hours. The conductivity of the obtained polymer film was measured by a DC four-terminal method to be 2.7 × 10 ^-2 s / cm.
And showed a lower conductivity than Example 2.

[0013]

EFFECT OF THE INVENTION The conductive polymer of the present invention can be obtained by a simple operation, is soluble in various solvents such as water, and has a self-doping property.
It is a conductive polymer with excellent electrical and mechanical performance.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Atsushi Yanagisawa 345 Yanagicho, Takada, Odawara-shi, Kanagawa Nippon Soda Co., Ltd. Odawara Research Institute (72) Inventor Masashi Kamiyama 345, Yanagicho, Takada, Odawara, Kanagawa Nippon Soda Co., Ltd. Odawara Research Center

Claims (3)

[Claims] 1. A compound represented by the general formula [I]: (In the formula, Ht is NH, S, O, Se or Te, R ¹ is a linear or branched alkyl group, and X ¹ is CO ₂ , C
ONH, O, S, or NH, R ² represents an optionally substituted divalent hydrocarbon group having 3 to 21 carbon atoms, and M represents an atom which produces a positive counterion upon oxidation. ) Having a structural unit represented by
, 000,000 conductive polymer. 2. A compound represented by the general formula [II]: (In the formula, Ht, R ¹ , X ¹ , R ² and M have the same meanings as described above.) The compound is chemically polymerized in the presence of an oxidative transition metal halide to treat the polymer with an acidic solution. The general formula [I '] is characterized by (In the formula, Ht, R ¹ , X ¹ and R ² have the same meanings as described above.) A method for producing a conductive polymer having a weight average molecular weight of 500 to 1,000,000 and having a structural unit. 3. A compound represented by the general formula [III]: (Wherein Ht and R ¹ have the same meanings as described above, and X ² represents CO ₂ H, CONH ₂ , OH, SH or NH ₂ ) and a compound of the general formula [IV] (In the formula, X ³ represents a divalent hydrocarbon group having 2 to 20 carbon atoms, provided that one or more hydrogen atoms of the hydrocarbon are a halogen atom, a nitro group, a hydroxyl group, a carboxyl group or an alkoxy group. Which may be substituted with a cyclic intramolecular oxysulfonic acid ester represented by the formula [II] (In the formulae, Ht, R ¹ , X ¹ , R ² and M have the same meanings as described above.)