JPH03181477A - Monomer of electrically conductive polymer and production thereof - Google Patents

Abstract

NEW MATERIAL:A compound shown by formula I (n is 1 or 2; R is 1-6C straight-chain alkyl). EXAMPLE:3-Methoxyethoxyethoxythiophene. USE:A monomer of electrically conductive polymer. PREPARATION:A compound shown by formula II is coupled with 3- bromothiophene to give a compound shown by formula I. The coupling is carried out by reacting the compound shown by formula II with sodium in a solventless state or in a solvent (e.g. benzene, hexane, toluene or DMF) to give a sodium salt and then reacting the salt with 3-bromothiophene. An electrically conductive polymer obtained by polymerizing the compound shown by formula I by electrochemical or chemical method can make a substrate electrically conductive by dissolving the polymer and coating, etc., and is widely applicable as an electrically conductive material because of excellent stability of electrical conductivity.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a novel conductive polymer monomer and a method for producing the same.

(Prior Art) Research has been actively conducted on conductive polymers using electron-accepting or electron-donating substances as dopants in conjugated polymers such as polyacetylene, polyparaphenylene, polypyrrole, polythiophene, and polyaniline. It is being done.

The main polymerization methods for the conjugated polymers illustrated here include electrochemical polymerization and chemical polymerization.The former polymerization method generally yields polymers in the form of a film, while the latter polymerization method produces fibers. A solid or powdered polymer can be obtained.

However, conductive polymers made of the above polymer and dopant are generally insoluble in solvents and do not melt even when heated, so they have poor processability and are difficult to apply in a wide range of areas.

(Problems to be Solved by the Invention) Under the circumstances described above, there has been a demand for a novel monomer for obtaining a conductive polymer with high solvent solubility and stable conductivity.

(Means for Solving the Problems) As a result of intensive studies, the present inventors have found a means for solving the above problems and have completed the present invention.

That is, the object of the present invention is to solve the following general formula (1) (however,
In the formula, n is an integer of 1 or 2, and R represents a straight chain alkyl group having 1 to 6 carbon atoms. ), and also to provide a novel conductive polymer monomer represented by the following general formula (II) H○(CH,CH,○)nR...(IT) (wherein n is 1
or an integer of 2, R represents a straight-chain alkyl group having 1 to 6 carbon atoms) and 3-bromothiophene. It is something.

The coupling is carried out by reacting the compound represented by the above general formula (11) with sodium without a solvent or in a solvent to form a sodium salt, and then adding and reacting 3-bromothiophene. As the solvent, any type of inert organic solvent can be used, and specific examples include benzene, hexane, toluene, dimethylformamide, and diethyl ether. In the coupling reaction, sodium iodide, copper oxide,
It is also possible to use catalysts such as copper. The reaction temperature is not particularly limited, but is preferably a temperature close to the boiling point of the solvent or reaction system. The conductive polymer obtained by polymerizing the monomer of the present invention by an electrochemical method or a chemical method is dimethylformamide, dimethyl sulfoxide, γ-
It is also possible to make the substrate conductive by dissolving it in a wide range of solvents such as butyllactone, acetone, and acetonitrile, and applying methods such as coating. Furthermore, since the conductivity is stable, it can be widely applied as a conductive material.

(Examples) Hereinafter, the present invention will be specifically explained according to Examples, but the present invention is not limited to these Examples.

Example 1 Methyl calpitol LOOG was charged into a 300aQ four-loop flask equipped with a temperature needle, nitrogen blowing tube, condenser, and stirrer. Metallic sodium 5 under nitrogen stream
．． 20 g was added in small portions to produce the sodium salt of methylcarpitol. Copper oxide 2. Og and 60 mg of sodium iodide were added, followed by 16.3 g of 3-bromothiophene, and the mixture was reacted at 150°C for 10 hours. After the reaction, copper oxide is filtered off, excess methylcarpitol is extracted with water, and the organic layer is distilled under reduced pressure to obtain 1
5.9 g of 3-methoxyethoxyethoxythiophene was obtained. The boiling point of this product was 95-bm Hg. N
The MR measurement results are shown in Table 1.

Example 2 The procedure was carried out in exactly the same manner as in Example 1 except that ethyl cellosolve was used instead of methylcarpitol, and 12.6 g of 3
-Ethoxyethoxythiophene was obtained. The boiling point of this was 60-61'C/1 mrnHg. N
The measurement results of MR are shown in Table 1.

1 The procedure was carried out in exactly the same manner as in Example 1 except that butyl cellosolve was used in place of methylcarpitol.
-Butoxyethoxythiophene was obtained. The boiling point of this product was 118° C./4 miHg. The NMR measurement results are shown in Table 1.

The procedure of Example 1 was repeated except that ethyl carbitofur was used in place of ethyl carpitol, and 16.1 g of 3-ethoxyethoxyethoxythiophene was obtained. The boiling point of this product was 114° C. and 71 m+aHg. NMR
The measurement results are shown in Table 1. Example 5 1.5 g of 3-methoxyethoxythiophene was prepared in the same manner as in Example 1, except that methyl cellosolve was used instead of methyl carpitol and the reaction temperature was 130°C. Obtained. The boiling point of this product was 60° C. and 71 mmHg. N
The MR measurement results are shown in Table 1.

Example 6 30 g of hexyl cellosolve sodium salt prepared in advance and 200 g of toluene were charged into a reaction apparatus exactly the same as in Example 1, and 16.3 g of 3-bromothiophene and 2.5 g of copper oxide were added.
0g was added and the reaction was carried out at 110°C for 16 hours. Example 1
14.9 g of 3-hexyloxyethoxythiophene was obtained by treating in exactly the same manner as above. The boiling point of this thing is 113
The temperature was 10.5 mmHg. The NMR measurement results are shown in Table 1.

Example 7 The procedure of Example 6 was repeated except that 35 g of hexylcarpitol sodium salt was used instead of hexyl cellosolve sodium salt, to obtain 6.2 g of 3-hexyloxyethoxyethoxythiophene. The boiling point of this product was 140-142°C and 10.5 mmHg. NMR
The measurement results are shown in Table 1.

Example 8 Anhydrous ferric chloride 1.9 in 25 mQ of dry chloroform
While stirring under a nitrogen stream, 0.8 g of 3-methoxyethoxyethoxythiophene synthesized in Example 1 was added dropwise, and a polymerization reaction was carried out at 25° C. for 30 minutes. After the reaction, the produced polymer was filtered, washed with water, and diluted with methanol.
Washed twice.

Thereafter, it was dried at 50° C. for 24 hours under reduced pressure to obtain 1.1 g of poly-3-methoxyethoxyethoxythiophene.

Next, 0.1 g of this poly-3-methoxyethoxyethoxythiophene, vinyl chloride/vinyl acetate copolymer (VMC
H, manufactured by VCC) (7) 0.25 g of 30% MEK solution and 0.13 g of 20% ethyl acetate solution of isocyanate crosslinking agent (Coronate, manufactured by Nippon Polyurethane Industries)
was dissolved in 5.5 g of DMF and 4 g of butyl acetate,
It was made into a conductive coating liquid. This coating solution was applied to a 50 μm thick polyester film using a bar coater, and heated to 100°C.
and dried for 3 minutes. The conductivity of the coated surface of this polyester film was 3×10′Ω·□, and the conductivity after being stored in the air at 150° C. for 14 days was 6.2×IO′Ω·.

(Effects of the Invention) According to the present invention, a conductive polymer monomer with good processability and stable conductivity and a method for producing the same could be provided.

Claims (2)

[Claims] (1) The following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) (However, in the formula, n is an integer of 1 or 2, and R is a carbon number of 1 to 6.
represents a straight-chain alkyl group. ) A conductive polymer monomer represented by (2) Represented by the following general formula (II) HO(CH_2CH_2O)nR...(II) (wherein, n is an integer of 1 or 2, and R represents a straight chain alkyl group having 1 to 6 carbon atoms.) The general formula (
I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) (However, in the formula, n is an integer of 1 or 2, and R is a carbon number of 1 to 2.)
6 represents a straight chain alkyl. ) A manufacturing method for a conductive polymer monomer represented by