JP2837427B2 - Electrically conductive organic polymer materials - Google Patents

Description

The present invention relates to an electrically conductive organic polymer material, and more particularly, to a heat-treated phenolic resin or an electron-donating dopant and / or The present invention relates to a method for producing an electrically conductive organic polymer powder material obtained by doping an electron-accepting dopant.

[Conventional technology]

The polymer material is excellent in moldability, lightness and mass productivity. Therefore, by utilizing these characteristics of the polymer material, an organic polymer material having electrical semiconductivity is demanded in many industrial fields including the electronics industry. The early organic semiconductors were difficult to form into a film or plate, and did not have the properties of an n-type or p-type impurity semiconductor. In recent years, organic semiconductors having relatively good moldability have been obtained, and these semiconductors can be converted into n-type or p-type organic semiconductors by doping them with an electron-donating dopant or an electron-accepting dopant. It became. A typical example of such an organic semiconductor is polyacetylene.

However, polyacetylene has a disadvantage that it is easily oxidized by oxygen. For this reason, it is difficult to handle in air, and it is not practical as an industrial material.

JP-A-59-3806 and JP-A-60-152554, which are filed by the applicant of the present application, describe a heat-treated aromatic condensation polymer composed of carbon, hydrogen and oxygen, wherein hydrogen atom / carbon atom Consisting of an insoluble and infusible substrate having a polyacene skeleton structure represented by an atomic ratio of 0.60 to 0.15, and an electron-donating doping agent or an electron-accepting doping agent, wherein the electric conductivity is higher than that of the undoped substrate. Large electrically conductive organic polymer materials have been proposed. The material is stable in air and is practical as an industrial material.

In this prior application, an insoluble and infusible substrate containing a polyacene-based skeletal structure is produced by heat-treating a phenolic resin molded body. However, in consideration of productivity, if a large amount of the compact is charged into an electric furnace at a high filling rate, there is a problem that only an inhomogeneous insoluble and infusible substrate such as crater-like blisters can be obtained. Was.

[Problems to be solved by the invention]

The present inventors have conducted intensive studies in view of the above problems, and as a result, a powdery phenolic resin obtained by agitating an aqueous solution of an initial condensate of a phenolic resin and an aqueous solution of zinc chloride with stirring. The inventors have found that the above-mentioned problems can be solved by heat-treating the zinc chloride composite in a non-oxidizing atmosphere, and have completed the present invention.

An object of the present invention is to provide a method for producing an electrically conductive organic polymer-based powder material that is economical and can be mass-produced.

Another object of the present invention is to provide a method for producing an electrically conductive organic polymer-based powder material which has a semiconductive or conductive electrical conductivity and has a high specific surface area, so that a large amount of dopant can be rapidly doped. To provide.

Still other objects and advantages will be apparent from the following description.

[Means for solving the problem]

The above-described object is to provide a composite powder of a phenolic resin and zinc chloride produced by subjecting a water-soluble phenolic resin precondensate and a zinc chloride to a condensation reaction in an aqueous medium with stirring, in a non-oxidizing atmosphere. It contains a polyacene-based skeletal structure obtained by heat treatment under the following conditions. The atomic ratio of hydrogen atoms / carbon atoms is 0.05 to 0.6, and the specific surface area value by the BET method is at least 600 m ² / g. A method for producing an electrically conductive organic polymer-based powder material, and a phenolic resin and zinc chloride formed by stirring and mixing a water-soluble phenolic resin precondensate and zinc chloride in an aqueous medium to cause a condensation reaction. Containing a polyacene-based skeleton structure obtained by heat-treating the composite under a non-oxidizing atmosphere, having an atomic ratio of hydrogen atoms / carbon atoms of 0.05 to 0.6, and a specific surface area value of at least 600 m ² / g by the BET method. Less than It is achieved by the method for manufacturing an electro-conductive organic polymer-based powder material insoluble infusible powder formed by doping an electron donating dopant and / or electron-accepting dopant to be.

As the phenolic resin used in the present invention,
(A) a condensate of an aldehyde with an aromatic hydrocarbon compound having a phenolic hydroxyl group, such as a phenol-formaldehyde resin, and (b) a xylene-modified phenol.
An aromatic hydrocarbon compound having a phenolic hydroxyl group, such as a formaldehyde resin (in which a part of phenol is substituted with xylene), may be mentioned.

The insoluble and infusible substrate in the present invention can be produced, for example, as follows.

First, a powdery phenolic resin / zinc chloride composite is prepared from an aqueous solution of an initial condensate of a phenolic resin and an aqueous solution of zinc chloride.

In the conventional method, the composite was manufactured as a molded plate by a two-stage method in which the above-mentioned raw materials were stirred and mixed while being sufficiently cooled to form a uniform mixed liquid of the raw materials, and then heated and cured. In the method, the condensation reaction is advanced by heat generated during mixing by forcibly stirring and mixing the raw materials without sufficient cooling, and by forced stirring,
The powder is pulverized to prepare the composite. The cooling or heating temperature conditions during stirring vary depending on the composition of the raw materials, but it is sufficient that heat is generated to such an extent that the condensation reaction proceeds. However, if the temperature of the reaction system is 20 ° C. or lower, it is preferable that the temperature be 20 ° C. or higher because problems such as easy precipitation of zinc chloride in the zinc chloride aqueous solution occur. The particle size of the obtained composite powder varies depending on the production conditions, but for the purpose of the present invention, it is preferable to produce the powder as a powder having a size of 100 μm or less. In addition, they may be obtained as secondary aggregates of these fine particles. The mixing amount of zinc chloride is preferably 1/2 to 10/1 by weight relative to the phenolic resin. When zinc chloride is less than 1/20, the particle size of the composite becomes 100 μm or more. Become.

The concentration of the aqueous zinc chloride solution also affects the shape and size of the mixture.
It is preferable to use in the range of. If the concentration is lower than 0.1, zinc chloride precipitates and solidifies, and uniform mixing cannot be performed. On the other hand, if it exceeds 1, the particle size becomes 100 μm or more, and it becomes difficult to obtain a homogeneous product in the subsequent heat treatment step when a large amount is charged into an electric furnace as described above.

Further, in order to control the condensation reaction under stirring, a substantially spherical phenolic resin such as Bellpearl (manufactured by Kanebo Co., Ltd.)
And the like may be mixed during the stirring and mixing. However, if the mixing amount of the substantially spherical phenolic resin is too large, the bulk density of the mixture decreases, and the productivity decreases.

The powdery phenolic resin thus obtained and the zinc chloride composite are subjected to a temperature of 400 to 800 ° C. in a non-oxidizing atmosphere, preferably to a temperature of 450 to 750 ° C., particularly preferably 500
Heat to a temperature of ~ 700 ° C. The aromatic condensation polymer causes a dehydrogenation dehydration reaction by the heat treatment, and a polyacene skeleton structure is formed by the condensation reaction of the aromatic ring.

This reaction is a kind of thermal condensation polymerization, and the degree of reactivity is represented by the atomic ratio represented by hydrogen atoms / carbon atoms (hereinafter referred to as H / C) in the final product. The H / C value of the insoluble infusible substrate is 0.05 to 0.6, preferably 0.15 to 0.50. When the value of H / C of the insoluble infusible substrate is larger than 0.6, the electric conductivity is low because the polyacene-based skeletal structure is not developed, while the H / C
When the value of C is smaller than 0.05, the amount of dopant that can be doped becomes small.

The obtained heat-treated body is sufficiently washed with water or diluted hydrochloric acid to remove the inorganic salt contained in the heat-treated body.

Thereafter, by drying this, the insoluble infusible substrate powder of the present invention is obtained.

The particle size of the thus obtained insoluble and infusible substrate powder of the present invention varies depending on the kind and composition of the raw materials or the production conditions in each step, but is usually 100 μm or less. In addition, they may be obtained as secondary aggregates of these fine particles.

Further, the insoluble infusible base powder has a specific surface area value of at least 600 m ² / g by the BET method.

If the specific surface value of the powder is less than 600 m ² / g, Cl
It is difficult to dope a large amount of a dopant having a large ionic radius, such as O ₄ ⁻ , BF ₄ −, or AsF ₅ , in a large amount and smoothly, and when used as an active adsorbent as described later, the amount of adsorption is undesirably reduced.

Since the insoluble and infusible base powder containing the polyacene-based skeleton structure has a very large specific surface area value of 600 m ² / g or more according to the BET method, it is considered that a gas such as oxygen invades and easily deteriorates. However, in reality, there is no change in physical properties and the like even when left in the air for a long time, and it is excellent in oxidation stability.

According to the present invention, an electrically conductive organic polymer powder material obtained by doping the insoluble and infusible substrate powder with an electron-donating dopant, an electron-accepting dopant, or both of these dopants is obtained.

That is, according to the present invention, a powdery phenolic resin / zinc chloride composite obtained by advancing a condensation reaction while stirring and mixing an aqueous solution of an initial condensate of a phenolic resin and an aqueous solution of zinc chloride is mixed in a non-oxidizing atmosphere. Hydrogen atom / carbon atom ratio of 0.6 obtained by heat treatment in
An insoluble infusible substrate powder containing a polyacene-based skeletal structure of from 0.05 to 0.05, and a specific surface area value of at least 600 m ² / g or more by a BET method, comprising an electron-donating dopant and / or an electron-accepting dopant. An electrically conductive organic polymer powder material is obtained.

As the electron donating dopant, a substance that easily separates electrons is used. For example, lithium, sodium, potassium,
A Group 1A metal of the periodic table, such as rubidium or cesium, is preferably used.

Similarly, as the electron donating dopant, tetra (C ₁
-C ₄ alkyl) ammonium cation example (CH _{3) 4} N ⁺
Alternatively, (C ₄ H ₉ ) ₄ N ⁺ can be used.

In addition, a substance that easily accepts electrons is used as the electron-accepting dopant. Such as fluorine, chlorine, bromine, halides such as _{iodine; AsF 5, PF 5, BF} 3, BCl 3, BBr 3, such as halogen compounds FeCl _3; SO ₃ or an oxide of such non-metallic elements of the N ₂ O _5; Alternatively, an anion derived from an inorganic acid such as H ₂ SO ₄ , HNO ₃ or HClO ₄ is preferably used.

As the doping method of such a dopant, essentially the same doping method as conventionally used for polyacetylene or polyphenylene can be used.

For example, when the dopant is an alkali metal, it can be doped by bringing a molten alkali metal or a vapor of the alkali metal into contact with an insoluble and infusible substrate powder, and, for example, an alkali metal naphthalene complex formed in tetrahydrofuran. The insoluble and infusible substrate may be brought into contact with and doped.

When the dopant is a halogen, a halogen compound or an oxide of a nonmetallic element, doping can be easily performed by bringing these gases into contact with the insoluble and infusible substrate powder.

When the doping agent is an anion derived from an inorganic acid, the doping can be carried out by impregnating the insoluble and infusible substrate powder with the inorganic acid.

It is also possible to form an insoluble infusible substrate powder into an electrode and electrochemically dope it with an electron donating dopant such as lithium and sodium or an electron accepting dopant such as ClO ₄ ⁻ and BF ₄ ^−. .

The doping agent is generally used in the insoluble infusible substrate powder of the present invention in a proportion of 10 ^-5 mol or more based on the repeating unit of the aromatic condensation polymer.

The insoluble infusible substrate powder obtained by the production method of the present invention thus obtained has a higher conductivity than the insoluble infusible substrate powder before doping (for example, 10 ^-12 to 10 ² Ω ^-1 · cm ^-1 ). high electrical conductivity, increases for example, several times to 10 ¹⁰ times greater than insoluble and infusible base powder before doping. When doped with an electron-donating dopant, an n-type semiconductor is provided, and when doped with an electron-accepting dopant, a p-type semiconductor is provided. According to the present invention, an electron-donating dopant and an electron-accepting dopant can be used together as a dopant. When these dopants are almost uniformly mixed in the insoluble and infusible base powder of the present invention, the dopant becomes p-type or n-type depending on which one of the dopants is present most.
For example, it becomes n-type when there are many electron-donating dopants, and becomes p-type when there are many electron-accepting dopants.

〔The invention's effect〕

The insoluble and infusible substrate containing the polyacene-based skeleton structure obtained by the production method of the present invention is mostly in the form of powder, and most of the other is a secondary agglomerate of fine powder which becomes powder by simple pulverization. Therefore, the material can be formed into an arbitrary shape such as a film shape, a plate shape, or a cylindrical shape by a method of adding a binder and the like, and is an extremely practical material.

By utilizing the high specific surface area value of the insoluble and infusible substrate powder obtained by the production method of the present invention, various chemical reactions occurring at the interface can be rapidly advanced. For example, it is suitable for an electrode material of a battery. In addition, since various physical adsorptions occur smoothly, uniformly and in large quantities, they are suitable as adsorbents or separation materials.

Further, since slight change in electric conductivity occurs due to adsorption of gas such as H ₂ O and O ₂ , it can be suitably used as a sensor material.

In addition, the insoluble and infusible base powder obtained by the production method of the present invention contains a polyacene-based skeletal structure, is excellent in chemical resistance, and has many pores, so that the molding is severe. It is also suitable as a filter medium used under conditions.

As described above, the insoluble and infusible substrate powder obtained by the production method of the present invention has excellent heat resistance and oxidation resistance, and has a high specific surface area. Organic semiconductor that can be doped in large quantities and uniformly, and has a chemically active function, and can be formed into any shape such as a film or plate with excellent mechanical strength, so it can be applied to various fields. It is an industrially useful material that can be used.

 Hereinafter, the present invention will be described specifically with reference to examples.

Example 1 (1) Production of an insoluble and infusible substrate containing a polyacene-based skeleton structure A water-soluble resol (60% concentration) was added to an aqueous zinc chloride solution (85%).
Concentration) at a ratio of 10:30, and stirring and mixing at 70 rpm using a DMV type universal mixing stirrer (manufactured by Sanei Seisakusho) equipped with a screw beater as a stirrer while heating at 40 ° C. The discoloration due to the curing reaction began to occur in about 30 minutes, and after 10 minutes, a powdery phenolic resin / zinc chloride composite of 100 μm or less was obtained. 10 kg of the composite was charged into a square electric furnace, and heated at a rate of 40 ° C./hour under a nitrogen stream to 500
Heat treatment was performed up to ° C. Next, the heat-treated product was washed with dilute hydrochloric acid, washed with water, and then dried to obtain an insoluble and infusible base powder.

The specific surface area value of the insoluble infusible substrate powder by the BET method is 230.
0 m ² / g, and the atomic ratio of hydrogen atom / carbon atom is 0.24
Met.

(2) To 100 parts of the insoluble and infusible base powder, 5 parts of polytetrafluoroethylene as a binder was added and kneaded sufficiently, followed by pressure molding into a plate having a thickness of 1 mm.

(3) Lithium is then added to propylene carbonate that has been sufficiently dehydrated.
ClO ₄ was dissolved to a solution of about 1.0 mol /. And the above solution is used as an electrolyte with lithium metal as a cathode,
(2) a sheet-like molded body as an anode of, about 1 hour COL ₄ by applying a voltage of approximately 4V between the two electrodes ^- doped with ions. The doping amount is Cl per carbon atom of the insoluble infusible substrate.
O ₄ ^- was decided to represent the number of ions.

In the present invention this ClO ₄ ^- number of ions are those obtained from the current value flowing in the circuit at the time of doping. The current value is 3.0
%Met.

Comparative Example 1 A uniform raw material mixed solution was prepared at the same composition ratio as in Example 1 while sufficiently cooling at a temperature of 20 ° C., poured into a mold of 50 × 50 × 5 mm, and cured at a temperature of 100 ° C. for 60 minutes. Proceed with the reaction,
A plate-like composite molded body having a thickness of about 5 mm was obtained. 10 kg of the composite molding
Was placed in the same square electric furnace as in Example 1, and heated at 40 ° C. under a nitrogen stream.
The temperature was raised at a rate of / hour and the heat treatment was performed up to 500 ° C.
A large amount of crater-like blisters were generated, making removal very difficult.

Examples 2 to 4 (1) Insoluble and infusible substrate powders were obtained in the same manner as in Example 1 with the mixed compositions shown in Table 1. In each case, the substrate powder was homogeneous, and no blistering or the like occurred.

(2) The substrate was formed into a molded plate in the same manner as in Example 1.
These molded plates had sufficient strength. Table 1 summarizes the specific surface area of the substrate, the hydrogen / carbon atom ratio, and the doping amount of the molded plate.

Examples 5 and 6 (1) 10 kg of the composite produced in the same manner as in Example 1 was charged into a rectangular electric furnace, and heated at a rate of 40 ° C./hour under a nitrogen stream and heat-treated to 400 ° C. . Further, 10 kg of the composite was heat-treated to 700 ° C under the same conditions to obtain an insoluble and infusible base powder. In both cases, the substrate powder was homogeneous and no blistering or the like occurred.

(2) The substrate was formed into a molded plate in the same manner as in Example 1.
These molded plates had sufficient strength. Table 2 summarizes the specific surface area of the substrate, the hydrogen / carbon atom number ratio, and the doping amount of the molded plate.

Example 7 (1) Production of an insoluble and infusible base powder containing a polyacene-based skeleton structure A water-soluble resol (75% concentration) was mixed with a spherical phenol resin (Bellepearl manufactured by Kanebo Co., Ltd.) and an aqueous zinc chloride solution (85%).
Phenolic resin / zinc chloride composite powder was obtained by adding 10/10/50 to the mixture at a ratio of 10/50 and stirring and mixing at 60 ° C. for 10 minutes. The composite was heat-treated under the same conditions as in Example 1 to obtain an insoluble and infusible base powder.

(2) The insoluble infusible base powder was formed into a molded plate in the same manner as in Example 1. The specific surface area of the substrate was 2,300 m ² / g, and the doping amount of ClO ₄ ⁻ ions in the molded plate was 3%.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Taneo Okamoto 2-15-24 Kamishinjo, Higashiyodogawa-ku, Osaka-shi, Osaka Masaru Seki (56) References JP-A-62-127341 (JP, A)

Claims (2)

(57) [Claims] 1. A composite powder of a phenolic resin and zinc chloride formed by stirring and mixing a water-soluble phenolic resin precondensate and zinc chloride in an aqueous medium to cause a condensation reaction. It contains a polyacene-based skeleton structure that is heat-treated under the following conditions, and has an atomic ratio of hydrogen atoms / carbon atoms of 0.
A method for producing an insoluble, infusible, electrically conductive organic polymer-based powder material having a specific surface area of at least 600 m ² / g by a BET method, which is from 0.05 to 0.6. 2. A composite powder of a phenolic resin and zinc chloride produced by stirring and mixing a water-soluble phenolic resin initial condensate and zinc chloride in an aqueous medium to cause a condensation reaction, and subjecting the mixture to a non-oxidizing atmosphere. It contains a polyacene-based skeleton structure that is heat-treated under the following conditions, and has an atomic ratio of hydrogen atoms / carbon atoms of 0.
An electrically conductive organic polymer obtained by doping an insoluble and infusible powder having a specific surface value of at least 600 m ² / g by BET method with an electron donating dopant and / or an electron accepting dopant which is from 0.05 to 0.6. Manufacturing method of powder based materials.