JPS61103923A - Polymeric electrical conductor - Google Patents

Abstract

PURPOSE:To obtain the titled conductor highly stable to oxygen, free from any problems such as toxicity, by incorporating an inorganic electron acceptor in a polymer constituted by poly(arylenevinylene) derivative with the main chain having phenothiazine skeletor of specific formula. CONSTITUTION:First, a poly(arylenevinylene) derivative with its main chain having phenothiazine skeleton of formula III (n is positive integer) is prepared by the reaction between (A) 10-substituted-3,7-dihalophenothiazine of formula I (R is H or 1-16C alkyl; X is Br or I) and (B) divinylbenzene of formula II. Next, a polymer constituted by said derivative is exposed to a vapor of an inorganic electron acceptor (e.g., I2) to obtain the objective electrical conductor. EFFECT:Highly stable to oxygen, easy to apply to forming process. USE:Rectifying diodes, transistors, electrodes for solar cell, etc.

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to poly(
The present invention relates to a novel organic polymeric conductor based on a polymer comprising a (arylene vinylene) derivative. [Prior art] Conventionally, conjugated polymers such as polyacetylene, poly(halapenylene), poly(phenylene sulfide), and polypyrrole have been used as base materials for organic polymer conductors.
2. Description of the Related Art Organic polymer conductors are known in which electrical conductivity is increased by chemical doping, which is a treatment in which an electron acceptor, a so-called doping agent, is added to a polymer. However, unlike ordinary thermoplastic polymers, the above-mentioned polymers do not melt even when heated, but thermally decompose while remaining in a solid state, resulting in poor moldability and processability.Moreover, polyacetylene is insoluble, Due to its infusible nature, it has particularly poor processability and is unstable in air due to the action of oxygen. Furthermore, organic polymer conductors made of the above-mentioned polymers generally have drawbacks such as decreased conductivity and brittleness due to the influence of oxygen in the air. Therefore, various proposals have been made to improve the polymer as a base material for organic polymer conductors, such as thiophenediyl derivatives, 7landiyl derivatives (Japanese Patent Application Laid-Open No. 11327/1982), condensed 5,6
Polymers having complex members as repeating units (Japanese Patent Application Laid-open No. 1-2
7950), poly(alkylcarbazolyl) (Japanese Unexamined Patent Publication No. 84917/1983), and the like have been proposed. [Problems to be solved by the invention] In organic polymer conductors, the electron acceptor added to the base material made of the above polymer is a super strong acid such as A8Fg, which has a high affinity for the polymer. It is considered to be the most preferable in terms of providing high conductivity. In particular, the electron acceptor that can provide high conductivity in polyacetylene, poly(paraphenylene), and poly(phenylene sulfide) is A.
Limited to sF5 only. However, AaF'5 is extremely toxic, and as a conductor added to the base material, there is a problem in that it lacks safety for the human body. Therefore, conductors made of polyacetylene are unstable to oxygen in the air, and polyacetylene is unstable to oxygen in the air.
Conductors made of poly(phenylene sulfide) and poly(phenylene sulfide) also become highly sensitive to water and are unstable, returning to an insulating state due to moisture.When reacting with doping agents, cross-linking and ring melting reactions occur, making them impossible to process. It becomes a state. Furthermore, although conductors made of polypyrrole are relatively stable in air, they have the disadvantage of being brittle, and can only be used in very limited applications. Therefore, almost all known organic polymer conductors lack safety, are unstable in the air, and have poor processability. There is a problem in that it is not suitable for use as a component that requires high reliability. Under these circumstances, there is a need for organic polymer conductors that are environmentally safe, have stability, easy processability, and satisfy physical properties and can be used in a wide range of applications. [Means for Solving the Problems] Based on the recognition of the above problems, the present inventors conducted various studies and research on organic polymer conductors. As a result, polymers consisting of poly(arylenevinylene) derivatives having a phenothiazine skeleton main chain can be used as base materials for organic polymer conductors, especially polymers containing inorganic electron acceptors such as
It was discovered that it has a strong affinity for x, etc., and strongly adsorbs these electron acceptors, leading to the completion of the present invention as an organic polymer conductor that solves the above problems. . That is, the present invention consists of a poly(arylenevinylene) derivative having a phenothiazine skeleton in the main chain represented by the formula (where R is hydrogen, an alkyl group having 1 to 16 carbon atoms, and n is a positive integer) An object of the present invention is to provide an organic polymer conductor characterized by adding an inorganic electron acceptor to a polymer.In the present invention, a poly( Arylenevinylene) derivatives are disclosed in Japanese Patent Application Laid-Open No. 165423/1983, filed by the same applicant as the present invention, together with a method for producing them. Photoreceptors are useful for image forming devices, etc., and are used in combination with sensitizers, but they are also used as organic polymer conductors.

[Adds an inorganic electron acceptor. Since the derivative is a conjugated polymer having a pi-electron conjugated system, for example, 2°Brz, HtBO*, Son, MusFi,
ElbFi, PFi, BFs. C3xBOsH, (OFm)1SO4,5bC1i,
AIC! 1*, has a high affinity for inorganic electron acceptors such as FeC1m or HCl0* and strongly adsorbs these electron acceptors. It also has affinity for organic electron acceptors such as tetracyanoquinodimethane, tetracyanoethylene, and dichlorodicyanoquinone. Among the above-mentioned exemplified inorganic electron acceptors, preferable ones include 80S and 80S from the viewpoint of the method of addition to the polymer, conductivity as a conductor, stability, and safety for the human body and the environment. By the way, poly(hutsunilene vinylene) which does not contain a phenothiazine skeleton can be made into MoSA by adding
No improvement in lability was observed. The phenothiazine derivative represented by the formula (1) is a phenothiazine derivative represented by the formula (If) (wherein R is the same as above, and X is the same or different bromine or iodine). III) CH2-OH+0H-(
It is produced by reacting divinylbenzene represented by H2(III). This reaction typically requires a catalyst and a hydrogen halide scavenger. As a catalyst, a combination of a noble metal compound such as palladium acetate and a phosphorus compound such as doarylphosphine is suitable. Suitable hydrogen halide scavengers include amines such as tertiary amines, and basic salts such as sodium hydrogen carbonate and IJ cum. The starting compound is 10-substituted-3,7
-Dihalophenothiazine can be prepared by halogenating the phenothiazine with bromine or iodine chloride and then introducing a substituent, or
They can be prepared by halogenating 10-substituted-phenothiazines with bromine or iodine chloride. The thus obtained l〇-substituted dihalophenothiazine represented by formula (n) and divinylbenzene represented by formula (Iff) are combined with, for example, haladium acetate, triarylphosphone,
75 in the presence of a tertiary amine, preferably under a nitrogen atmosphere.
The reaction is carried out at a temperature of ~150°C. The degree of polymerization of the obtained polymer is preferably 5 or higher, particularly 10 or higher. Examples of triarylphosphines include tri-tolylphosphine, tris(2-methy/I/-5- 1-Butylphenyl)phosphine is preferably used, and is used in an amount of 1 to 10 mol per 1 mol of palladium acetate.The amount of palladium acetate used is 0.5 to 4 mol s of the amount of divinylbenzene used.
It is appropriate. Tertiary amines are useful as scavengers for generated hydrogen chloride, but triethylamine, trin-
Commonly used amines such as propylamine, tri-n-butylamine, etc. may be used, and the amount used is slightly in excess of the mole equivalent to the amount of hydrogen generated. Examples of reaction solvents include N,N-dimethylformamide, dimethylacetamide, and toluene. xylene, chlorobenzene, 0-dichlorobenzene, N
-Methyl-2-pyrrolidone, dimethyl sulfoxide, acetonitrile, etc. are used. In the production of the poly(arylene vinylene) derivative having a phenothiazine skeleton main chain represented by formula (1) in the present invention, the raw material 10- represented by formula (II) is used.
g-substituted-3,7-dihalophenothiazine has 1 to 16 carbon atoms
Each phenothiazine having an alkyl chain may be a combination of two or more. In the present invention, the method of adding an inorganic electron acceptor to a polymer is carried out by exposing the polymer to vapor of the electron acceptor. For example, the polymer powder can be exposed to the vapor of the electron acceptor in a closed container at room temperature to absorb the electron acceptor. Alternatively, the electron acceptor can be an organic solvent, such as hexane. The polymer can also be absorbed by immersing it in a solution dissolved in methylene chloride, nitromethane, or the like. Furthermore, the polymer and the electron acceptor may be mixed in a solid state. The heavy metal body used in the present invention can be molded by various molding methods such as compression molding, injection molding, and cast molding. The forms in which electron acceptors are added are powder, pellets,
film, sheet. It may be in any form, such as another molded body, and is not particularly limited. Furthermore, various molded bodies can be formed from powders, pellets, etc. to which electron acceptors are added. As mentioned above, the organic polymer conductor of the present invention can be converted into an organic polymer conductor by adding an inorganic electron acceptor that does not actually exhibit toxicity, and can be used in areas where toxicity does not occur. It is possible to add electron acceptors such as AaFg, which have toxicity problems, and the polymer has high thermal stability, making it an extremely excellent conductor material. [Examples of the Invention] The present invention will be specifically explained below using Examples, but the present invention is not limited to these Examples. Synthesis Example 1 Polymer of 10-ethyl-3,7-phenothiazinediylvinylene-1,4-7 22lenevinylene [Synthesis of 'A, 7-sipromo 10-ethylphenothiazine] 24 parts of sodium hydride (50% oily) (same parts by weight below) are added to 20 parts of dimethyl sulfoxide (hereinafter referred to as DMeo), heated to 70°C and stirred until no hydrogen generation is observed. After cooling to room temperature, add 1 while stirring in a water bath.
10 parts of phenothiazine dissolved in 5 parts of DMSO are added dropwise. After stirring for 30 minutes in a water bath, 5 parts of D
8.19 parts of ethyl iodide dissolved in MSO are added dropwise. After stirring at room temperature for 3 hours, crude crystals were obtained by pouring into a large amount of water. The obtained crude crystals were recrystallized from ethanol to give 10-
7.96 parts of ethylphenothiazine (yield 70%) was obtained. Melting point 104°C (11tto3-104°C). 7 parts of this 10-ethylphenothiazine are dissolved in 200 parts of acetic acid. While keeping the reaction temperature at 18℃,
Add 9.84 parts of bromine dissolved in 1 part of acetic acid dropwise and stir for 1 part to 1 hour. After stirring, pour into Daikei's aqueous sodium hydroxide solution to finally make it alkaline. The obtained crude crystals were recrystallized from ethanol to obtain 4.95 parts (yield: 42 inches) of 3,7-dipromo-10-ethylphenothiazine as pale yellow crystals. Melting point: 72°C. [:3.7- 3.7-Sipromo 10-ethylphenothiazine 1.5
4 parts, p-divinylbenzene 0.521 parts, tri-n-
A mixture consisting of 1.86 parts of butylamine, 0.018 parts of palladium acetate, 0.049 parts of tri-tolylphosphine, and 10 parts of N-methyl-2-pyrrolidone was heated at 120°C for 20 hours with stirring under a nitrogen atmosphere. . The reaction mixture was filtered while it was still hot to remove insoluble materials, and then reprecipitated twice in methanol to obtain 1.51 parts of a polymer having the following structure as an orange solid. CHsOFLg This orange polymer was further extracted with hot toluene for 30 hours using a Soxhlet extractor to obtain 1.41 parts of a polymer that was not extracted with hot toluene. Synthesis Example 2 In Synthesis Example 1, 3,7-dipromo-10-methylphenothiazine (melting point: 147°C) was synthesized using methyl iodide instead of ethyl iodide. continue,
3.7-dipromo-10-ethylphenothiazine [3.7-diproso-10-methylphenothiazine 1.
1.37 parts of a polymer having the following structure was obtained in the same manner as in Synthesis Example 1, except that 48 parts were used. Akira. Example 1 The orange polymer powder obtained in Synthesis Example was solidified using an infrared molding machine and molded into cylindrical pellets. When the electrical conductivity of this cylindrical pellet was measured, the electrical conductivity at room temperature was 4X10-''S/tan.Next, the polymer powder obtained in Synthesis Example 1 was heated to glass!J at room temperature. !!Exposed to iodine vapor in a closed container to obtain a powder containing 317 weights of iodine per polymer used.Iodine content was determined from the weight increase upon absorption of iodine.This powder was exposed to iodine vapor in the same manner as above. When the electrical conductivity of the obtained cylindrical pellet was measured, the electrical conductivity at room temperature was I
X 10-'s 7 cm. When this conductor is left in air at room temperature for one year,
There was no change in appearance, it was stable against oxygen in the air, and there was virtually no change in electrical conductivity. Example 2 Powder of the same polymer used in Example 1 was added to a concentration device at room temperature, allowed to absorb sulfuric acid for 30 minutes, and then thoroughly washed with methanol [to remove sulfuric acid adhering to the surface and remove the used polymer]. A powder containing No. 38 sulfuric acid per coalescence was obtained. This powder was solidified in the same manner as in Example 1, and the electrical conductivity of the obtained cylindrical pellet was measured, and it was found to be 3 x 10-7 at room temperature.
It was 8/crn. Even when this semiconductor was left in dry air at room temperature for one year, no change was observed in its appearance, it was stable against oxygen in the air, and its electrical conductivity remained essentially unchanged. Example 3 The polymer powder obtained in Synthesis Example 2 was solidified in the same manner as in Example 1, and the electrical conductivity of the obtained cylindrical pellet was measured. The electrical conductivity at room temperature was 5 x 10-"
It was B10n. This polymer powder was exposed to iodine vapor in the same manner as in Example 1 to obtain a powder containing 149 times 11 parts of iodine per polymer used. The iodine content was determined from the weight increase during iodine absorption. This powder was solidified in the same manner as described above, and the electrical conductivity of the resulting pellets was measured. The electrical conductivity was I x 10-'B/l:m at room temperature. When this conductor is left in air at room temperature for one year,
No visible change was observed; acid in the air. It was stable against the elements, and the electrical conductivity did not change substantially. [Effects of the Invention] According to the present invention, it is possible to produce a conductive material that has excellent stability against oxygen and is free from problems such as tetraprocity. The organic polymer isoelectric material of the present invention can be easily molded,
It can be provided as a film, a plate, or a composite thereof, and can be used in various fields, such as rectifying diodes, transistors, large-drop batteries, and electric currents for batteries, thereby expanding the field of application.

Claims (2)

[Claims] (1) Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (where R is hydrogen, an alkyl group having 1 to 16 carbon atoms, and n is a positive integer). ) An organic polymer conductor characterized by being formed by adding an inorganic electron acceptor to a polymer made of a derivative. (2) Inorganic electron acceptors are I_2, Br_2, H_2SO
_4, SO_3, AsF_5, SbF_5, PF_5,
BF_3, CF_3SO_3H, (CF_3)_2SO
_4, SbCl_5, AlCl_3, FeCl_3 or HClC_4.