JP3196186B2 - Pyrrole derivatives and polymers thereof - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel pyrrole derivative and a polymer thereof, and relates to a battery electrode material, a solar cell,
Photoelectrodes, sensors, nonlinear optical materials, electromagnetic shielding,
Provided is a conductive polymer compound applied to an antistatic material or the like.

[0002]

2. Description of the Related Art In recent years, organic conductive compounds having conductivity (for example, polypyrrole, polyaniline, polythiophene, etc.) have been applied to electric and electronic materials because of their unique properties. In addition, development of optical applications has been promoted at the same time due to the features as a conjugated polymer, and many reports have been made on organic conductive compounds. In particular, an aromatic condensed ring is directly introduced into the conductive polymer main chain from the effective use of the π-electron system, and its application is being developed from an electronic and optical viewpoint.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a novel conductive polymer which pays attention to the above viewpoints.

[0004]

According to the present invention, there is provided 1) a compound represented by the general formula [I]:

Embedded image (However, R ¹ and R ² may be the same or different and represent hydrogen, alkyl, substituted alkyl, alkoxy, substituted alkoxy, phenyl or substituted phenyl.) 2) General formula [II]

Embedded image (However, R ¹ and R ² are as defined above, and R ³ is R
^1, R ² and the same. A) a pyrrole derivative represented by the general formula [I] or [II] as a constituent unit. Among the above compounds, the substituted alkyl group, substituted alkoxy group and substituted phenyl group include those substituted with sulfonic acid, carboxylic acid, amino acid and the like. The monomer used in the present invention can be easily synthesized using the precursor described in JP-A-4-198168. That is, as shown in the following chemical formula 5, 2-pyrrolecarboxylic acid ester is easily obtained by heating under a nitrogen atmosphere in a protic solvent such as ethylene glycol using a base such as sodium hydroxide. be able to.

[0005]

Embedded image Here, R ¹ , R ² and R ³ are as described above, and R represents an alkyl group.

Since these monomers are relatively unstable in the air, it is desirable to carry out the reaction and purification operations in an atmosphere of an inert gas such as nitrogen and, if necessary, to block light.
As shown in the following chemical formula 6, the polymer can be obtained by subjecting the pyrrole derivatives [I] and [II] to electrolytic oxidation polymerization or chemical oxidation polymerization. Further, it can be copolymerized with a copolymerizable monomer.

[0007]

Embedded image

The solvent used for the electrolytic oxidation polymerization includes acetonitrile, tetrahydrofuran, dioxane, propylene carbonate, dimethylformamide and the like. As the electrolyte, commonly used ammonium salt, phosphonium salt, perchlorate, borate, sulfonate,
Sulfuric acid, hydrochloric acid, trifluoroacetic acid and the like are used. The anions of these electrolytes are incorporated into the polymer as dopants during electrolytic polymerization. When the electrode plate is immersed in a solution containing the monomers [I] and [II] and the electrolyte, and a voltage is applied by a constant potential method or a constant current method in a nitrogen atmosphere, a polymer is formed on the anode. Monomer concentration during polymerization, electrolyte concentration, current density,
The polymerization temperature and the like can be arbitrarily selected. In chemical oxidative polymerization, Lewis acids such as FeCl ₃ , H ₂ O ₂ , NH
_A polymer can be easily obtained with a conventional oxidizing agent such as a peroxide such as ₄ S ₂ O ₈ or a quinone.

[0009]

EXAMPLES The present invention will be described in more detail with reference to Examples, but it is needless to say that the present invention is not limited to these Examples. Example 1 (Synthesis of monomer) Ethyl 2-pyrrolecarboxylate [R ¹ = R ² = H, R = Et in general formula (Ia)] 0.3 g and 3 equivalents of NaO
H was placed in 20 ml of ethylene glycol and heated at 170-180 ° C. for 3.5 hours under a nitrogen atmosphere. The reaction mixture was cooled to room temperature, 50 ml of water and 50 ml of benzene were added,
The mixture was stirred well, and the generated insolubles were filtered. Then, Zemben was further added and extraction was performed three times. The benzene layer is thoroughly washed with water, dried over anhydrous MgSO ₄ , the benzene is distilled off, and the remaining crude product is purified by column chromatography to obtain the desired product (R ¹ = R ² = H in the general formula [I]). )
was gotten. The physical properties are as follows. m.p. 129-131 DEG C. UV-VIS 356, 264, 246, 227 (n
m) ¹ H NMR 7.01 (d, J = 2.5 Hz, 2H) 7.44-7.62 (m, 6H) 8.12 (bs, 1H) Elemental analysis Ca1c. C, 87.93 H, 4.74
N, 7.32 Found C, 88.19H, 4.99N, 7.31 The IR spectrum is shown in FIG.

Example 2 (Synthesis of polymer) 0.12 g of the monomer obtained in Example 1 and 1/3 equivalent of Me ₄ N.BF ₄ were dissolved in 35 ml of acetonitrile, and the electrode was attached. Bubbling with nitrogen,
Dissolved oxygen was removed. A voltage of 3.5 V was applied to react at room temperature for 24 hours. The black product formed on the anode was thoroughly washed with acetonitrile and dried to obtain 0.06 g of a polymer. Its electrical conductivity at room temperature was measured by the four probe method and found to be 3 × 10 ⁻² S / cm. FIG. 2 shows the IR spectrum. A similar reaction was carried out using tetrahydrofuran as the solvent and ClO ₄ ^{− as} the electrolyte to obtain a polymer. The electric conductivity was 3 × 10 ⁻¹ S / cm.

Example 3 (Synthesis of polymer) 0.0631 g of the monomer obtained in Example 1 was dissolved in 9 ml of acetonitrile, and 0.44 g and 0.0327 g of AlCl ₃ and CuCl were added, respectively, followed by N ₂ atmosphere. Stirred for 2 hours. Thereafter, air was passed through at room temperature for 24 hours, and the insoluble black powder was separated by filtration, washed with dil HCl, sufficiently washed with water and methanol, and dried to obtain 0.036 g of a polymer powder. This powder was pressed at a pressure of 200 kg / cm ² for 10 minutes to prepare a disk, and the electric conductivity was measured. As a result, 0.1 S / cm was obtained.

Example 4 (Synthesis of a polymer) 0.0617 g of the monomer obtained in Example 1 was dissolved in 5.5 ml of acetonitrile, and DDQ0.02 was dissolved in an N ₂ atmosphere.
21 g was added and reacted at room temperature for 7 hours. The insoluble black powder was separated by filtration and dried to obtain 0.015 g of a polymer powder. A disk was prepared in the same manner as in Example 3, and the electric conductivity was measured. As a result, 2.1 × 10 ^-2 S / cm was obtained.

Example 5 (Synthesis of polymer) Polymerization and post-treatment were carried out in the same manner as in Example 4, except that 0.0203 g of P-chloranil was added instead of DDQ. The obtained polymer was 0.026 g. When a disk was prepared and the electric conductivity was measured in the same manner as in Example 3, 1.7 × 10 ⁻⁵ S / cm was obtained.

[0014]

According to the present invention, a polymer having high conductivity and excellent stability can be easily obtained from a novel monomer, and these include an electrode material, a conductive material, a display material, a non-linear optical material, and an electromagnetic wave shield. It can be used for materials and antistatic materials.

[Brief description of the drawings]

FIG. 1 is a view showing an IR spectrum of a compound obtained in Example 1.

FIG. 2 is a view showing an IR spectrum of a polymer obtained in Example 2.

──────────────────────────────────────────────────続 き Continued on the front page (58) Fields surveyed (Int. Cl. ⁷ , DB name) C07D 209/94 C08G 61/12 H01B 1/12 C09K 3/00 C09K 3/16 CA (STN) REGISTRY (STN )

Claims (3)

(57) [Claims] 1. A compound of the general formula [I] A pyrrole derivative represented by the formula: However, R ¹ and R ² may be the same or different and represent hydrogen, alkyl, substituted alkyl, alkoxy, substituted alkoxy, phenyl or substituted phenyl. 2. A compound of the general formula [II] A pyrrole derivative represented by the formula: However, R ¹ and R ² are as defined in claim 1, and R ³ is the same as R ¹ and R ² . 3. A polymer containing the pyrrole derivative according to claim 1 as a structural unit.