KR20110001106A - Method of preparing polythiophene derivative and polythiophene derivative prepared using the same - Google Patents

Abstract

PURPOSE: A polythiophene derivative is provided to ensure excellent stability and conductivity by removing a side chain according to heating and lengthening a conjugation length. CONSTITUTION: A method for preparing a polythiophene derivative comprises the steps of: dissolving 3-bromoethyl thiophene in a solvent; adding sodium diethyldithiocarbamate trihydrate to the prepared solution; adding water to the mixed solution, extracting the mixture in an organic solvent phase, and removing moisture from the extracted solution; dissolving the obtained monomer in a solvent, adding FeCl3, and then stirring the mixture; and filtering the precipitate from the obtained solution.

Description

Method for preparing polythiophene derivatives and polythiophene derivatives produced therefrom TECHNICAL FIELD

The present invention relates to a method for producing a polythiophene derivative and a polythiophene derivative prepared through the same, and more particularly, because it is hardened and is not affected by other solvents, and the like, and has excellent stability. Side chain) is removed and consequently the conjugation length (conjugation length) is long, the present invention relates to a method for producing a polythiophene derivative having excellent electrical conductivity and a polythiophene derivative prepared through the same.

The conductive polymer refers to a polymer having electrical conductivity while maintaining the advantages of light and easy processing, which are the inherent characteristics of the polymer.

A polymer is a molecule having a very long chain of molecules as compared to a conventional low molecular material. When such polymer chains are gathered together to form an aggregate, a small solid is formed. This solid form may be fiber, plastic or rubber.

Polymer materials, such as plastics, which are widely used in real life because of their lightness and elasticity, have traditionally been known as insulators, but the discovery of polymer materials with high electrical conductivity enables the emergence of plastic products that can replace metals beyond the conventional concept of polymer materials. It is done.

The first conductive polymer found is polyacetylene, which is itself a semiconductor, but when treated with iodine it has an electrical conductivity comparable to that of metal.

Such conductive polymers have advantages of transparency, flexibility, portability, lightness, and low cost, and thus are widely applied to products such as displays and electronic devices. However, at present, the conductivity of the conductive polymer is low, its use is limited.

In order to overcome this problem, additives such as CNT are dispersed evenly on a polymer matrix or a polymer film, thereby preparing a composite having conductivity while maintaining properties of polymers such as heat resistance and chemical resistance.

On the other hand, in the case of the conductive polymer is often used to form a thin film and coating other materials thereon, if the stability is insufficient, such as melting or deformation in the process there is a problem that is difficult to use.

In order to solve the problems of the prior art as described above, the present invention is a hardening type, so it is not affected by other solvents and the like, and thus has excellent stability, a method of preparing a polythiophene derivative having excellent electrical conductivity, and a polythiophene prepared therefrom. It is an object to provide a derivative.

The present invention comprises the steps of dissolving (S1) 3-bromoethyl thiophene (3-bromoethyl thiophene) in a solvent; (S2) adding and mixing sodium diethyldithiocarbamate trihydrate to the solution prepared in step (S1); (S3) adding water to the mixed solution prepared in step (S2) and extracting with an organic solvent, and then removing and purifying water from the extracted solution; (S4) dissolving the monomer obtained in the step (S3) in a solvent, and then adding and stirring FeCl ₃ ; (S5) It provides a method for producing a polythiophene derivative, comprising the step of filtering the precipitate in the solution obtained in the step (S4).

The present invention also provides a polythiophene derivative prepared according to the method for producing the polythiophene derivative.

Polythiophene derivative prepared according to the above manufacturing method is represented by the following formula (1).

[Formula 1]

The invention also relates to (S1) 2-bromomethyl-2,3dihydro-thieno [3,4-b] [1,4] dioxine (2-Bromomethyl-2,3-dihydro-thieno [3]. , 4-b] [1,4] dioxine) in a solvent; (S2) adding and mixing sodium diethyldithiocarbamate trihydrate to the solution prepared in step (S1); (S3) adding water to the mixed solution prepared in step (S2) and extracting with an organic solvent, and then removing and purifying water from the extracted solution; (S4) dissolving the monomer obtained in the step (S3) in a solvent, and then adding and stirring FeCl ₃ ; And (S5) provides a method for producing a polythiophene derivative comprising the step of filtering the precipitate in the solution obtained in the step (S4).

The present invention also provides a polythiophene derivative prepared according to the method for producing the polythiophene derivative.

Polythiophene derivative prepared according to the above manufacturing method is represented by the following formula (2).

[Formula 2]

According to the manufacturing method of the polythiophene derivative of the present invention and the polythiophene derivative prepared through the same, it is hardened and is not affected by other solvents and the like, so that the stability is excellent, and side chains are removed by heating. As a result, the conjugation length is long, and thus the electrical conductivity is excellent.

Hereinafter, with reference to the accompanying drawings will be described in more detail the present invention. The terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary meanings and should be construed in accordance with the technical meanings and concepts of the present invention.

The present invention comprises the steps of dissolving (S1) 3-bromoethyl thiophene (3-bromoethyl thiophene) in a solvent; (S2) adding and mixing sodium diethyldithiocarbamate trihydrate to the solution prepared in step (S1); (S3) adding water to the mixed solution prepared in step (S2) and extracting with an organic solvent, and then removing and purifying water from the extracted solution; (S4) dissolving the monomer obtained in the step (S3) in a solvent, and then adding and stirring FeCl ₃ ; (S5) It provides a method for producing a polythiophene derivative, comprising the step of filtering the precipitate in the solution obtained in the step (S4).

According to the method for preparing the polythiophene derivative, first, 3-bromoethyl thiophene is dissolved in a solvent (S1).

In the step (S1), for example, an organic solvent such as ethanol, chloroform or THF may be preferably used.

Next, sodium diethyldithiocarbamate trihydrate is added to the solution prepared in step (S1) and mixed (S2).

The amount of sodium diethyldithiocarbamate trihydrate added in step (S2) is preferably 1.5 to 2.5 moles per mole of 3-bromoethyl thiophene.

Reaction of 3-bromoethyl thiophene and sodium diethyldithiocarbamate trihydrate is performed as in Scheme 1 below.

Scheme 1

Next, water is added to the mixed solution prepared in step (S2) and extracted with an organic solvent, and then water is removed from the extracted solution and purified (S3).

In the step (S3), an organic solvent such as ethyl ether, ethyl acetate, chloroform or THF may be preferably used when extracting the organic solvent.

In the step (S3), for example, a method such as column chromatography or recrystallization may be used when the extract is purified.

Next, after dissolving the monomer obtained in the step (S3) in a solvent, FeCl ₃ is added and stirred (S4).

When dissolving the monomer in the step (S4), for example, an organic solvent such as chloroform and THF may be preferably used.

The reaction in which the monomer is polymerized in step (S3) is shown in Scheme 2 below.

Scheme 2

The amount of FeCl ₃ added in the step (S3) is preferably 2 to 4 moles per mole of monomer.

Next, the precipitate is filtered from the solution obtained in step (S4) (S5). Through this step, it is possible to obtain a polythiophene derivative which is a product of the above polymerization process.

In this step, for example, the solution obtained in the step (S4) may be put in methanol, and the precipitate may be filtered out.

The polythiophene derivative prepared by the above manufacturing method is hardened and is not affected by other solvents and the like, so that the polythiophene derivative is not only excellent in stability, but also removes side chains upon heating, and consequently, the length of the conjugated bond. (conjugation length) is long, has the advantage of excellent electrical conductivity.

The invention also relates to (S1) 2-bromomethyl-2,3dihydro-thieno [3,4-b] [1,4] dioxine (2-Bromomethyl-2,3-dihydro-thieno [3]. , 4-b] [1,4] dioxine) in a solvent; (S2) adding and mixing sodium diethyldithiocarbamate trihydrate to the solution prepared in step (S1); (S3) adding water to the mixed solution prepared in step (S2) and extracting with an organic solvent, and then removing and purifying water from the extracted solution; (S4) dissolving the monomer obtained in the step (S3) in a solvent, and then adding and stirring FeCl ₃ ; And (S5) provides a method for producing a polythiophene derivative comprising the step of filtering the precipitate by putting the solution obtained in step (S4) to methanol.

According to the method for preparing the polythiophene derivative, first, 2-bromomethyl-2,3dihydro-thieno [3,4-b] [1,4] dioxine is dissolved in a solvent (S1).

In the step (S1), for example, an organic solvent such as ethanol, chloroform or THF may be preferably used.

Next, sodium diethyldithiocarbamate trihydrate is added to the solution prepared in step (S1) and mixed (S2).

The amount of sodium diethyldithiocarbamate trihydrate added in the step (S2) per mol of 2-bromomethyl-2,3-dihydro-thieno [3,4-b] [1,4] dioxine It is preferable that it is 1.5-2.5 mol.

The reaction of 2-bromomethyl-2,3dihydro-thieno [3,4-b] [1,4] dioxine with sodium diethyldithiocarbamate trihydrate is carried out as in Scheme 3 below.

Scheme 3

Next, water is added to the mixed solution prepared in step (S2) and extracted with an organic solvent, and then water is removed from the extracted solution and purified (S3).

In the step (S3), an organic solvent such as ethyl ether, ethyl acetate, chloroform or THF may be preferably used when extracting the organic solvent.

For purification of the extract in the step (S3), for example, a method such as column chromatography may be used.

Next, after dissolving the monomer obtained in the step (S3) in a solvent, FeCl ₃ is added and stirred (S4).

When dissolving the monomer in the step (S4), for example, an organic solvent such as chloroform and THF may be preferably used.

When the monomer is polymerized in the step (S3), a polythiophene derivative represented by Chemical Formula 2 is polymerized.

[Formula 2]

In the step (S3), the amount of FeCl ₃ added is preferably 2 to 4 moles per mole of monomer.

Next, the precipitate is filtered from the solution obtained in step (S4) (S5). Through this step, it is possible to obtain a polythiophene derivative which is a product of the above polymerization process.

In this step, for example, the solution obtained in the step (S4) may be put in methanol, and the precipitate may be filtered out.

Hereinafter, preferred examples are provided to aid the understanding of the present invention, but the following examples are merely for exemplifying the present invention, and it will be apparent to those skilled in the art that various changes and modifications can be made within the scope and spirit of the present invention. It is natural that such variations and modifications fall within the scope of the appended claims.

< Example >

Example  One

After dissolving 4.5 g of 3-bromoethyl thiophene in 60 ml of ethanol, 8.6 g of sodium diethyldithiocarbamate trihydrate is added. The mixed solution was stirred at room temperature for about 5 hours. Water was added to the reaction solution, followed by extraction with an organic solvent using ethyl ether. The remaining water was removed using MgSO4, and purified using column chromatography. About 2.6 g of product was obtained. NMR data of the synthesized monomer is shown in FIG.

1.5 g of the product (monomer) obtained above was dissolved in 30 ml of chloroform. 2 g of iron (III) chloride was added to the solution and stirred for 24 hours. The reaction solution was poured into methanol and the precipitate was filtered to give about 0.6 g of product. NMR data of the synthesized polymer is shown in FIG. 2. The TGA of the synthesized polymer is shown in FIG. 3.

Example  2

After dissolving 1 g of 3-bromoethyl thiophene in 40 ml of ethanol, 3.2 g of sodium diethyldithiocarbamate trihydrate are added. The mixed solution was stirred at room temperature for about 5 hours. Water was added to the reaction solution, followed by extraction with an organic solvent using ethyl ether. The remaining water was removed using MgSO ₄ , and purified using column chromatography. About 0.36 g of product was obtained.

The obtained monomer was dissolved in 20 ml of chloroform. 0.2 g of iron (III) chloride was added to the solution and stirred for 24 hours. The reaction solution was poured into methanol and the precipitate was filtered to give about 0.15 g of product.

< Experimental Example >

Experimental Example  One

The polythiophene derivative prepared according to Example 1 was heated at about 250 ° C. for 30 minutes to obtain a cured thin film. UV spectrum before and after thermosetting is shown in FIG. It can be seen from the UV spectrum that the conjugation length became longer after curing.

Experimental Example  2

The polythiophene derivative prepared according to Example 1 was heated at about 250 ° C. for 30 minutes to obtain a cured thin film. UV spectrum before and after thermosetting is shown in FIG. It can be seen from the UV spectrum that the conjugation length became longer after curing.

The long conjugation length after curing in Experimental Examples 1 and 2 was because the side chain of the polythiophene derivative was removed, thereby improving the electrical conductivity.

1 is a diagram showing NMR data of a monomer synthesized in Example 1. FIG.

2 is a diagram showing NMR data of a polythiophene derivative synthesized in Example 1. FIG.

3 is a diagram showing a TGA of a polythiophene derivative synthesized in Example 1. FIG.

4 is a view showing the UV spectrum before and after thermosetting of the polythiophene derivative prepared according to Example 1.

5 is a view showing the UV spectrum before and after thermosetting of the polythiophene derivative prepared according to Example 2.

Claims (18)

(S1) dissolving 3-bromoethyl thiophene in a solvent; (S2) adding and mixing sodium diethyldithiocarbamate trihydrate to the solution prepared in step (S1); (S3) adding water to the mixed solution prepared in the step (S2) and extracting the organic solvent, and then removing and purifying water from the extracted solution; (S4) dissolving the monomer obtained in the step (S3) in a solvent, adding and stirring FeCl ₃ ; (S5) Method for producing a polythiophene derivative, characterized in that it comprises the step of filtering the precipitate in the solution obtained in the step (S4). The method of claim 1, The solvent used in the step (S1) is a method for producing a polythiophene derivative, characterized in that selected from the group consisting of ethanol, chloroform and THF. The method of claim 1, The solvent used in the step (S4) is a method for producing a polythiophene derivative, characterized in that selected from the group consisting of chloroform and THF. The method of claim 1, The organic solvent used in the extraction into the organic solvent in the step (S3) is a method for producing a polythiophene derivative, characterized in that selected from the group consisting of ethyl ether, ethyl acetate, chloroform and THF. The method of claim 1, A method for producing a polythiophene derivative, characterized in that the amount of sodium diethyldithiocarbamate trihydrate is 1.5 to 2.5 moles per mole of 3-bromoethyl thiophene. The method of claim 1, The purification method used in the step (S3) is a method for producing a polythiophene derivative, characterized in that the column (column chromatography). The method of claim 1, The step (S5) is a method for producing a polythiophene derivative, characterized in that the step of filtering the precipitate by putting the solution obtained in the step (S4) to methanol. A polythiophene derivative prepared according to the method for producing a polythiophene derivative according to any one of claims 1 to 7. Polythiophene derivative represented by the following formula (1). [Formula 1]

(S1) dissolving 2-bromomethyl-2,3dihydro-thieno [3,4-b] [1,4] dioxine in a solvent; (S2) adding and mixing sodium diethyldithiocarbamate trihydrate to the solution prepared in step (S1); (S3) adding water to the mixed solution prepared in the step (S2) and extracting the organic solvent, and then removing and purifying water from the extracted solution; (S4) dissolving the monomer obtained in the step (S3) in a solvent, adding and stirring FeCl ₃ ; (S5) Method for producing a polythiophene derivative, characterized in that it comprises the step of filtering the precipitate in the solution obtained in the step (S4). The method of claim 10, The solvent used in the step (S1) is a method for producing a polythiophene derivative, characterized in that selected from the group consisting of ethanol, chloroform and THF. The method of claim 10, The solvent used in the step (S4) is a method for producing a polythiophene derivative, characterized in that selected from the group consisting of chloroform and THF. The method of claim 10, The organic solvent used in the extraction into the organic solvent in the step (S3) is a method for producing a polythiophene derivative, characterized in that selected from the group consisting of ethyl ether, ethyl acetate, chloroform and THF. The method of claim 10, The amount of sodium diethyldithiocarbamate trihydrate added is 1.5 to 2.5 moles per mole of 2-bromomethyl-2,3 dihydro-thieno [3,4-b] [1,4] dioxine Method of producing a polythiophene derivative. The method of claim 10, The purification method used in the step (S3) is a method for producing a polythiophene derivative, characterized in that the column (column chromatography). The method of claim 10, The step (S5) is a method for producing a polythiophene derivative, characterized in that the step of filtering the precipitate by putting the solution obtained in the step (S4) to methanol. A polythiophene derivative prepared according to the method for producing a polythiophene derivative according to any one of claims 10 to 16. Polythiophene derivative represented by the following formula (2). [Formula 2]

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