JPS6185440A - Polyaminopyridine - Google Patents

Abstract

PURPOSE:A compound useful for various devices, producible at low cost, stable in air, showing highly electrical conductivity when it is doped with a dopant, obtained by treating aminopyridine with an oxidizing agent or a salt, followed by treating it with an acid or a halide. CONSTITUTION:A polyaminopyridine having a structural unit shown by the formula I and/or formula II (one of Z1, Z2, and Z3 is nitrogen, and the rest two are carbon; Y1 is H, or <=6C hydrocarbon; Y<->2 is anion; R is H or <=6C saturated hydrocarbon) as an essential structural unit. It is obtained by treating aminopyridine with an oxidizing agent such as aluminum chloride, etc., or a salt such as Bu4NCl4, etc., followed by treating it with a protonic acid or methyl iodide, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel polymers. More specifically, the present invention relates to a novel polymer that is stable in air and that can be used to perform electrical conductivity by doping with a suitable dopant.

Polyacetylene and polypyrrole (typically conductive polymers) are materials with high industrial utility value because their conductivity changes from 1olo to 102S/CIl+ by doping 1J with an appropriate dopane. It is.

However, polyacetylene has the disadvantage of being unstable in air, and polypyrrole has the disadvantage that a polymer that provides high conductivity can only be obtained by a unique polymerization method called electrolysis, which is disadvantageous in terms of 'El cost. I have it.

The present inventors have conducted intensive research to obtain a new conductive polymer that overcomes these drawbacks. It has been found that it is stable in air, exhibits high 7"9 properties by doping with an appropriate dopant, and can be manufactured at a relatively low cost.

Therefore, the present defense is the following ti4 structure! Position 11 (11Jj, 7, is a polyaminopyridine with IJ (2) as an essential structural unit.

((14) One of Z+, Z2, and Z3 is nitrogen and the remaining two are carbon. Also, Y+ is hydrogen or a hydrocarbon group with 6 or less carbon atoms, and Y2O is an ion. and R is hydrogen or a saturated hydrocarbon group having 6 or less carbon atoms.) Specific examples of the anion Y20 include halogen ion, BF4 ion, BR'4 ion (R'1, L having 6 or less carbon atoms). saturated hydrocarbon group or [yo phenyl group], Pro ion, acetate ion, SO4 ion, 1-1sO4 ton, CF3 CoO+', ton, perchlorate ion, or A
Examples include S Fa ions.

The polyaminopyridine of the present invention is, for example, F;L! Synthesized by the manufacturing method.

A. Treat aminopyridine with a suitable oxidizing agent for 1°.

B. Treating aminopyridine with an appropriate salt.

The blue polyaminopyridine is treated with a suitable acid or halide by the method described in C, A or μB.

Examples of suitable oxidizing agents mentioned in A above include catalysts used in a series of reactions called Friedel-Crafts reactions in synthetic organic chemistry, such as aluminum chloride, zinc chloride, tin chloride, and chloride. copper, iron trichloride,
Examples of trifluoride include boron and iodine. ) or protic acids (eg sulfur mHc104.HBF4).

Examples of suitable salts mentioned in B above include ammonium persulfate,
3u 4 NCfLs, Et 4 NBF4.

Mention may be made of salts such as NaC 04 and Na BF4.

Examples of suitable salts or halides mentioned in C above include the aforementioned protonic acids or methyl amino acids, and ``furkyl halogens'' such as r-do.

Examples of the aminopyridine referred to in Δ and B include 2-aminopyridine, 3-aminopyridine, 4-7minopyridine, N-methylaminopyridine, and N-ethylaminopyridine, but 2-aminopyridine is electrically conductive. This is preferred because it provides a para-cleaved polymer with high properties.

The polyaminopyridine of the present invention is stable in air, exhibits high electrical conductivity when doped with an appropriate dopant, and can be produced at relatively low cost, so it has high industrial applicability. For example, it can be used as a secondary battery, a secondary battery, a solar cell, a photoconductive material, or various devices.

Hereinafter, the present invention will be described in more detail with reference to various colors.

The produced polymer was analyzed by elemental analysis, infrared analysis, solid state NMR and DSC methods.

Examples 1 to 3 20 g (0.21 mol) of 2-aminopyridine was added to 100 ml of needle! The mixture was dissolved in water and added dropwise to the oxidizing agent shown in Table 1 at 0°C. The reaction was stopped after flushing with water at 43° C. for 10 hours, thoroughly washed with ether and benzene, and then dried under reduced pressure.

The color of the polymer was initially brown, then turned brown, and then further changed to brownish brown.

Further, it was confirmed by DSC measurement that the produced polymer had a melting point (decomposition point) of 300° C. or higher.

Next, the resulting polymer is doped with iodine, and the conductivity is σ■2
The results are shown in Table 1.

Example 4 20 q (0.21 mol) of 2-aminopyridine in 1 mol of water
It was dissolved in 00d. In this solution, dissolve 0.1 mol of ammonium, which is a salt, in 200 d of water. : Oil was added dropwise at 0°C. After 10 hours, the resulting polymer was thoroughly washed with water and dried under reduced pressure.

Examples 5 to 6 A polymer was obtained in the same manner as in Example 1 except that the compound shown in Table 2 was used instead of 2-aminopyridine.

Example 7 5 U of polyaminopyridine obtained in the same manner as in Example 4 was added to 10 liters of water.
0al! 0.3 mol of methyl iodide was added, and the mixture was reacted at room temperature for 15 hours. After thorough washing with reaction water, it was dried under reduced pressure. It was confirmed by elemental analysis and infrared analysis that the product was a salt of methyl iodide having some of the structural units (2).

(Margin below) Table 1 Table 2

Claims (1)

[Claims] A polyaminopyridine having the following structural units (1) and/or (2) as essential constituent units. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(2) [Among the constituent units, one of Z_1, Z_2, and Z_3 is nitrogen and the remaining two are carbon . Further, Y_1 is hydrogen or a hydrocarbon group having 6 or less carbon atoms, Y_2^■ represents an anion, and R is hydrogen or a saturated hydrocarbon group having 6 or less carbon atoms. ]