JPS61174226A - Doped ladder polymer and its production - Google Patents

Abstract

PURPOSE:To produce the titled polymer having a high electric conductivity and suited as a material for battery electrodes, solar batteries, etc., by treating a specified ladder polymer with an electron-accepting compound. CONSTITUTION:A ladder polymer mainly consisting of repeating units of formula I is treated by exposure to an atmosphere of a vapor of an electron-accepting compound such as a halogen, SbF5, AsF5 or TiCl4 at a pressure of 1mmHg-10 atm for 1min-1,000hr or it is treated by immersion in a solution (of a concentration of 0.1g/l - saturated concentration) formed by dissolving said electron- accepting compound in an inert solvent (e.g., acetone) at -30-100 deg.C for 1min-100hr.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel conductive polymer and a method for producing the same. More specifically, the present invention relates to a doped heteroacene polymer comprising a pyrazine ring-containing heteroacene polymer and an electron-accepting compound, and a method for producing the same.

In recent years, when polyacetylene is doped with an electron-accepting substance (electron-accepting dopant) or an electron-donating substance (electron-donating dopant), a charge transfer complex formation reaction occurs and high electrical conductivity (electronic conductivity) can be developed. Since its discovery, organic polymers that can exhibit such conductivity have attracted attention.

The reason why these polymers have come to show high electrical conductivity through doping is that these polymers and electron-accepting bepans 1~ or electron-donating polymers have a conjugated double bond-based ladder-type polymer. Focusing on the electron-donating property and conjugation property of It was discovered that the material exhibits electrical conductivity, and the present invention was achieved.

That is, the present invention provides: 1. A doped ladder polymer formed from a ladder polymer mainly consisting of repeating units represented by the following formula [I] and an electron-accepting compound, and 2. The ladder-shaped polymer mainly composed of repeating units represented by formula [1] is treated with an electron-accepting compound.

5tiful, E. L. Mainen,
Macromolecules.

", 3.6 (, 1968), it can be synthesized as shown in the following formula.

In the present invention, doping means adding an electron-accepting compound as described below to the ladder polymer.
This refers to the fact that the ladder-shaped polymer itself has improved electrical conductivity compared to its original electrical conductivity, not only when they form a chemical bond with each other, such as a complex, but also when they are simply in a mixed state. It also includes things that exist in .

Examples include Lewis acids with electron-accepting compounds used in the present invention.

In the present invention, the desired electrical conductivity is expressed by the interaction between the ladder polymer and the electron-accepting compound,
The height of electrical conductivity varies greatly depending on the type and amount of electron-accepting compound. The amount of the electron-accepting compound is 5 to 500 parts by weight, preferably 10 to 400 parts by weight, based on 100 parts by weight of the ladder polymer. Otherwise, the desired electrical conductivity will not be achieved, and conversely, even if more than that amount is added, not only will the electrical conductivity not be expected to improve, but in some cases, the electrical conductivity will decrease, which is not preferable.

However, the magnitude of electrical conductivity should be controlled depending on the application, and it goes without saying that it is not necessarily evaluated based on height alone.

The treatment method for causing the ladder-type polymer to interact with the electron-accepting compound, ie, the doping method, is carried out as follows.

(1) In the case of electron-accepting compounds that are gases themselves or have vapor pressure, such as halogens, antimony pentafluoride, or sulfur trioxide, expose them to the vapor atmosphere.
So-called vapor phase doping, such as 1, is used.

,,゛ In the gas phase doping method, the doping amount can be controlled by the temperature of the dopant atmosphere, the dopant partial pressure, and the doping time. The temperature varies depending on the type of dopant, but is generally between -30 and 250 degrees Celsius.
The temperature is preferably 0 to 200°C. If it is less than that, the doping rate will be slow, and if it is more than that, it will be difficult to control or cause deterioration of the polymer, which is not preferable. Also, the partial pressure of the dopant is 1 mm HO
It is carried out in the range of ~10 atm, preferably 10 mm t-l Q ~5 atm. Below that, doping is generally slow, and above that, increasing the pressure has no effect, which is not preferable. Although the doping time depends on the type of dopant, temperature, and dopant partial pressure, it is generally carried out in a range of 1 minute to 1000 hours, preferably 5 minutes to 500 hours.

The inert solvent used in wet doping is one that reacts with the electron-accepting compound to deactivate its ability as an electron-accepting compound, and ketones such as ladder-type polymer ketones, cyclohexanone, and hexane. Hydrocarbons such as heptane, petroleum ether, cyclohexane, benzene, toluene, xylene.

-Tils, ethyl acetate, butyl acetate, cellosolve acetate,
Esters such as isoamyl acetate, alcohols such as methanol, ethanol, isopropanol, butanol,
Examples include aprotic polar solvents such as dimethylformamide, dimethylacetamide, dimethylsulfoxide, and N-methylpyrrolidone, and other solvents such as nitromethane and acetate-1-21-lyl.

Of course, these solvents are appropriately selected depending on the solubility and type of the dopant. The immersion temperature for 1 hour is not particularly limited, but generally 0.1 g/ρ to saturation concentration, preferably 1 g/fl to saturation concentration, -30 to 100°C, preferably 0 to 80°C, 2 hours is 1 The treatment time ranges from minutes to 100 hours, preferably from 5 minutes to 80 hours.

After the ladder-shaped polymerization volume is formed into a disk, sheet, or powder, it can be given high electrical conductivity by doping with the electron-accepting compound.

71 The doped ladder-type polymers obtained in the present invention not only exhibit high electrical conductivity but also can be easily formed into various molded bodies, and can be used as various molded bodies, for example, All "parts" on the right side refer to "parts by weight" for battery electrodes, solar cell materials, electromagnetic shielding casings, etc. Note that the doping amount (%) is expressed as the weight part of the doped dopant relative to the weight part of the polymer before doping.

Synthesis Example 1 Poly(1,6-cyhydropyrazine[2,3-41quinoxaline-2,3,8-1-lylu 7-(2H)-ylidene-7,8-dimethylidene] (represented by the above formula A method for synthesizing a ladder-shaped polymer (consisting of repeating units) is shown below.

2.31 parts of 1,2,4.5-tetraaminobenzene 4-base M salt was added to 264 parts of 116% polyphosphoric acid, and hydrogen chloride was added at 80°C for 2 hours and at 140°C for 2 hours under a nitrogen stream. was removed. Then 1.12 parts of 2,5-dihydroxy-〇-benzoquinone was added. After stirring at 180° C. for 12 hours and cooling, the reaction mixture was poured into ice water and the black-purple precipitate was filtered off. After washing and drying, the ladder-shaped polymer was
．． I got 4 copies. The logarithmic viscosity of the obtained polymer was 0,126j
/g (0.5g/d) Sulfuric acid, 30 The ladder-shaped polymer obtained in Synthesis Example 1 was pressed at a pressure of 2J/ci using an infrared tablet molding machine to form a tablet with a diameter of 12.5M and a thickness of about 500μm. A disk-shaped sample was prepared.The conductivity of this sample in the undoped state was 5.8X 10' S/cm.This sample was used for vapor phase doping with bromine.The sample was coated with carbon-based conductive paint. Two terminals were attached using gold wire and bromine doping was performed at 40°C.

Picoammeter 41 made by Yokogawa Hikolet Packard Neel
Changes in conductivity were investigated online using 40B. The conductivity was saturated after 14 minutes. The conductivity at this time is 2.1×1
It was 0'S/cm.

Example 2

Claims (1)

[Claims] 1. The following formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼A doped polymer formed from a ladder-shaped polymer mainly consisting of repeating units represented by [I] and an electron-accepting compound. Ladder type polymer. 2. A doped ladder characterized by treating a ladder-shaped polymer mainly consisting of repeating units represented by the following formula [I] ▲Mathematical formulas, chemical formulas, tables, etc.▼[I] with an electron-accepting compound Method for producing type polymers.