KR101478828B1 - Method for the terminal functionalization of polyalkylthiophene by using a click chemistry reaction - Google Patents

Abstract

The present invention relates to a method of functionalizing a polyalkylthiophene, which comprises: 1) reacting a 2-bromo-3-functional thiophene monomer represented by the following formula (1) with lithium diisopropylamide (LDA) composed of ZnCl _2), and [1,3-bis (diphenylphosphino) propane] dichloro nickel (ⅱ) ([1,3-bis (diphenylphosphino) propane] dichloronickel (ⅱ), Ni (dppp) Cl ₂₎ And reacting with a grignard reagent represented by the general formula (2) as a polymerization terminator to give a terminal alkyne represented by the following general formula (3) having a molecular weight distribution of 1.0 to 1.3 and a symmetric molecular weight distribution, A step of preparing a polyalkylthiophene having a group introduced therein; And 2) reacting the polyalkylthiophene of Formula 3 with an azide compound represented by the following Formula 4 in the presence of a copper / amine catalyst according to a click chemistry reaction, Lt; RTI ID = 0.0 > of: < / RTI >

CH≡C-MgBr

N ₃ -R ₂

In the above equations,

R ₁ is an alkyl group having ₁ to 12 carbon atoms,

R ₂ is selected from the group consisting of a halogen atom, an alkyl group having 1 to 50 carbon atoms, a vinyl group, an alkylhydroxyl group, an alkylaryl hydroxyl group, an aryl hydroxyl group, an alkyl carboxyl group, an aryl carboxyl group, an alkylaryl carboxyl group, A nitroalkyl group, an alkylaryl ester group, a haloalkyl group, a haloaryl group, a haloalkylaryl group, a nitroalkyl group, a nitroaryl group, a nitroalkylaryl group, an alkylamido group, an arylamido group, an alkylarylamido group, a cyanoalkyl group, A cyanoalkylaryl group, in which all oligomers or polymers having a terminal azido group are used, R ₂ has the corresponding oligomer or polymer form,

n is the degree of polymerization of the monomer of the polythiophene and is an integer of 10 to 100,000.

Polyalkyl thiophenes, terminal functionalization, click chemistry, Grignard reagents

Description

TECHNICAL FIELD [0001] The present invention relates to a method for functionalizing a polyalkylthiophene using a click chemistry,

The present invention relates to a method for selectively functionalizing the terminal of a polyalkylthiophene using a grignard reaction and a click chemistry reaction.

An advantage of the polythiophene-based compound as the electroluminescent and conductive polymer is that it is easy to control the luminescence color due to high thermal stability and mechanical strength and introduction of appropriate substituents. However, the polythiophene compound has a disadvantage that it is difficult to process due to its low solubility, has a short life span, and has low color purity. In order to improve the low solubility of the polythiophene compound, a method of substituting an alkyl group at the 3-position of the thiophene to improve the solubility thereof and then converting it into a conductive polymer that is easy to process has become popular. The conductive polymer produced by this method is a polyalkylthiophene, and a large substituent introduced into the main chain of thiophene is not only improved solubility but also increased torsional angle due to large steric hindrance, thereby restricting the conjugation length The luminescent color is controlled and the interaction between neighboring chains is suppressed to improve the luminous efficiency. In addition, since stereoregularity of a polythiophene compound largely affects its electrical and optical properties, it is important to obtain a polymer having stereoregularity with a low molecular weight distribution in order to improve light emission efficiency and color purity. In addition, by introducing an appropriate functional group into the side chain or terminal of the polythiophene, the morphology formed by the functional group such as the polar functional group and the interfacial property with the other compound to be added are improved as well as the advantages coming from the stereoregularity described above It is expected that the electrical and optical characteristics will be further improved.

Conventional polythiophene compounds are prepared by oxidative polymerization using FeCl ₃ or nickel-catalyzed coupling of Grignard reagents formed from the reaction of 2,5-dihalogenated thiophene with magnesium. However, these reactions are very difficult because of precise control of the molecular weight distribution due to the progress of the continuous reaction between the ends of the chain, and inevitably the functionalization of the chain ends is not completely completed, resulting in irregular electrical and electronic properties. It is pointed out that it is difficult to achieve the expected result. Such synthesis and polymerization problems are hindering the application of polythiophene compounds to semiconductor layers for organic thin film transistors. Accordingly, various studies have been actively made on the improvement of various physical properties by introducing various functional groups at the terminal of the polymer chain of the polythiophene compound.

On the other hand, "click chemistry" is an azide-alkyne ring addition reaction (cyclo addition), which has a very high thermodynamic driving force (generally 20 ㎉ / ㏖ or more) Carbon-heteroaromatic bonds. That is, the click chemistry can form an intermolecular bond at a high yield in reaction with a polymer such as an oligomer, a polymer and the like as well as a reaction with a low molecule due to a high reactivity.

Currently, the click chemistry has been applied to a variety of applications including, for example, the study of the cycloaddition of azide functionality and alkyne (Rostovtsev, VV, et al . , Angew . Chem . Int . Ed . 41: 2596-2599, 2002); Application of click chemistry through organic synthesis (Lee, LV, et al . , J. Am . Chem . Soc . 125: 9588-9589, 2003); The inventors of J. Am . Chem . Soc . 124: 14397-14402, 2002) have been continuously carrying out studies such as easy surface functionalization using click chemistry. At present, there is active research on the chemical reaction using general polymer and synthetic polymer. However, there is no research on the chemical reaction using conductive polymer compared to other polymers. Therefore, if the advantages of such click chemistry are applied to a conductive polyimide, a polythiophene-based polymer, and the terminal of the polythiophene-based polymer is functionalized with various kinds of functional groups such as a polar functional group, an oligomer and a polymer, It is expected to exhibit various properties and many applications can be made throughout the electronics industry.

Accordingly, it is an object of the present invention to provide a wider range of molecular weight distributions due to a polymer-to-polymer coupling reaction, which is a side reaction that occurs when a conventional polyalkyl thiophene compound is polymerized, and to provide functional groups such as polar functional groups, oligomers, and polymers at the ends of polyalkyl thiophene- A polyalkylthiophene compound having an alkyne group introduced at the terminal having a symmetric molecular weight distribution in the range of 1.0 to 1.3 is prepared by Grignard reaction and then a click chemical reaction is used And introducing various kinds of functional groups at the terminal to thereby easily functionalize the terminal of the polyalkyl thiophene compound at a high yield.

In order to achieve the above object,

1) preparing a polyalkylthiophene having a molecular weight distribution in the range of 1.0 to 1.3 and symmetrical with respect to the molecular weight and having an alkenyl group introduced at the terminal, using a grignard reagent as a polymerization terminator in the polymerization of polyalkylthiophene; And

2) a step of reacting the polyalkylthiophene with an azide compound having various functional groups according to a click chemistry reaction to introduce a functional group such as a polar functional group, an oligomer or a polymer to the end of the polyalkylthiophene , And a method for functionalizing a polyalkylthiophene terminal.

The method for functionalizing a polyalkylthiophene according to the present invention can be carried out by firstly using a Grignard reagent as a polymerization terminator in the polymerization of an alkylthiophene to eliminate a side reaction such as a coupling phenomenon caused by a polyalkylthiophene in a conventional method, A polyalkylthiophene having a narrow distribution and an alkyne group at the terminal which is symmetric to the left and the right is synthesized and reacted with an azide compound having various functional groups according to a click chemistry to prepare a polyalkylthiophene having a polar functional group, Functional terminals of the polythiophene can be functionalized by selectively introducing various functional groups such as the polythiophene and the polythiophene.

The present invention relates to a method for selectively functionalizing the terminal of a polyalkylthiophene.

Specifically, the method for functionalizing a polyalkylthiophene end according to the present invention comprises

1) reacting a 2-bromo-3-functional thiophene monomer represented by the following formula 1 with lithium diisopropylamide (LDA), zinc chloride (ZnCl ₂ ) and [1,3-bis (diphenylphosphino ) Propane] dichloro nickel (II) ([1,3-bis (diphenylphosphino) propane] dichloronickel (II), Ni (dppp) Cl ₂ ) To produce a polyalkylthiophene having a molecular weight distribution of 1.0 to 1.3 and a symmetrical molecular weight distribution with an alkyne group introduced at the end thereof represented by the following formula (3) by reacting with a Grignard reagent represented by the following formula ; And

2) reacting the polyalkylthiophene of Formula 3 with an azide compound represented by Formula 4 in the presence of a copper / amine catalyst according to a click chemistry reaction, Lt; RTI ID = 0.0 > polyalkylthiophene < / RTI >

≪ Formula 1 >

(2)

CH≡C-MgBr

(3)

≪ Formula 4 >

N ₃ -R ₂

≪ Formula 5 >

In the above equations,

R ₁ is an alkyl group having ₁ to 12 carbon atoms,

R ₂ is selected from the group consisting of a halogen atom, an alkyl group having 1 to 50 carbon atoms, a vinyl group, an alkylhydroxyl group, an alkylaryl hydroxyl group, an aryl hydroxyl group, an alkyl carboxyl group, an aryl carboxyl group, an alkylaryl carboxyl group, A nitroalkyl group, an alkylaryl ester group, a haloalkyl group, a haloaryl group, a haloalkylaryl group, a nitroalkyl group, a nitroaryl group, a nitroalkylaryl group, an alkylamido group, an arylamido group, an alkylarylamido group, a cyanoalkyl group, A cyanoalkylaryl group, in which all oligomers or polymers having a terminal azido group are used, R ₂ has the corresponding oligomer or polymer form,

n is the degree of polymerization of the monomer of the polythiophene and is an integer of 10 to 100,000.

Generally, among polythiophene compounds, polyalkylthiophene is a product obtained by introducing an alkyl chain at the 3-position of thiophene which is a monomer, which is excellent in solubility and stability and is excellent in processability, It is a conductive polymer having regularity. In particular, if functional terminals of polythiophene polymers are functionalized with various kinds of functional groups such as polar functional groups and oligomers and polymers, they are expected to exhibit various properties that could not be achieved by conventional conductive polymers. There will be.

Traditionally, terminal functionalization of polyalkylthiophenes has been described by Yamamoto polymerization (Liu, J, et al., Macromolecules 35: 9882-9889, 2002). The alkyl thiophene monomer was activated using lithium diisopropylamide (LDA) and zinc chloride (ZnCl ₂ ) (Diphenylphosphino) propane] dichloronickel (II), Ni (dppp) Cl ₂ ), which is an initiator initiator, 1,3-bis After the polymerization reaction is carried out, a thiophene monomer into which a previously prepared functional group has been introduced is added. Then, methanol was added to terminate the polymerization reaction, and the reaction product was separated by methanol precipitation. Finally, the reaction product was purified by using methanol, n-hexane, tetrahydrofuran (THF) Purification by Soxhlet extraction.

However, when the terminal of the alkylthiophene is functionalized according to the above reaction, it is difficult to synthesize the monomer into which the functional group is introduced, and when the polar functional group is introduced, it may affect the polymerization reaction and is difficult to introduce. In addition, since the polymerization reaction is terminated by methanol, a side reaction such as a coupling phenomenon occurs between the polymer chains at the terminal of the polymerized polyalkyl thiophene, and the molecular weight distribution changes asymmetrically to increase the molecular weight distribution.

Alternatively, the 2,5-dibromo-3-hexylthiophene monomer is reacted with tert-butylmagnesium chloride (t-BuMgCl), [1,3-bis (diphenylphosphino) propane] dichloronickel (II) After polymerization using a catalyst system composed of 1,3-bis (diphenylphosphino) propane] dichloronickel (II), Ni (dppp) Cl ₂ and Grignard reagent (R-MgBr), Grignard reagent R'-MgBr) (Jeffries-El, M, Macromolecules , 38: 10346-10352, 2005) have been reported. However, since this method substitutes bromine (Br) at both terminals of the polythiophene on the polymerization mechanism, the functional groups can be introduced into both ends or only at one terminal thereof, thereby suppressing coupling and side reaction between the polymer chains And it is difficult to introduce a polar functional group due to the nature of the Grignard reagent.

In order to overcome the above problems, the present inventors have synthesized a polyalkylthiophene having bromine (Br) at only one end by using a Yamamoto reaction and then reacted with a Grignard reagent instead of methanol as a polymerization terminator, It is confirmed that polyalkyl thiophenes whose molecular weight distributions of symmetrical type are controlled to a low level of 1.0 to 1.3 are obtained without side reactions such as coupling phenomenon caused by polyalkyl thiophene.

Specifically, step 1) in the method of functionalizing a polyalkylthiophene according to the present invention can be represented by the following reaction formula 1:

Wherein R ₁ and n are as defined above.

According to Scheme 1, the 2-bromo-3-functionalized thiophene monomer ( 1 ) is reacted with lithium diisopropylamide (LDA), zinc chloride (ZnCl ₂ ) and [1,3- ) Propane] dichloro nickel (II) ([1,3-bis (diphenylphosphino) propane] dichloronickel (II), Ni (dppp) Cl ₂ ) ( 2 ) to prepare a polyalkylthiophene ( 3 ) having a molecular weight distribution of 1.0 to 1.3 and an alkyne group introduced at the terminal, having a symmetrical molecular weight distribution.

The Grignard reagent used in the present invention is generally represented by the following formula (2), which is reacted with a terminal brominated polythiophene polymer polymerized using a 2-bromo-3-functional thiophene monomer represented by the following formula The alkynyl group of the Grignard reagent represented by the following formula (2) is substituted with the Br group at the terminal of the polyalkylthiophene, and a polyalkylthiophene having an alkynyl group introduced at the terminal represented by the following formula (3) is synthesized.

≪ Formula 1 >

(2)

CH≡C-MgBr

(3)

In the above formulas, R ₁ and n are as defined above.

Typical examples of the Grignard reagent represented by the general formula (2) reacting with the 2-bromo-3-functionalized thiophene monomer as described above include ethinyl magnesium bromide, which is an alkylthiophene 100 represented by the general formula to 50% by mol to 150% by mol based on 100% by mol.

In a preferred embodiment of the present invention, the 2-bromo-3-functionalized thiophene monomer is activated with lithium diisopropylamine (LDA) and zinc chloride (ZnCl ₂ ) The reaction is carried out in the presence of a poly (3-phosphino) propane] dichloro nickel (II) [Ni (dppp) Cl ₂ ], and the reactant is reacted with ethynyl magnesium bromide as a Grignard reagent, Hexylthiophene is obtained.

The polyalkylthiophene having a terminal functional group introduced therein is symmetrical in shape and has a molecular weight distribution of a constant value in a low range of 1.0 to 1.3, exhibiting excellent solubility and processability and having enhanced stereoregularity. In the present invention, by appropriately controlling the amount of [1,3-bis (diphenylphosphino) propane] dichloronickel (II) [Ni (dppp) Cl ₂ ] used in the polymerization reaction, The introduced polyalkyl thiophene can be synthesized.

The polyalkylthiophene having the functional group introduced at the terminal can be easily functionalized by introducing the desired functional group selectively using the click chemistry reaction represented by the following reaction formula (2).

Wherein R ₁ , R ₂ and n are as defined above.

According to Scheme 2, is reacted with an azide compound (4) having an alkyne group is introduced into the poly-alkylthiophene (3) a group versatility under the copper / amine catalyst at the terminal alkyne O groups of the polyalkyl thiophene-3 The polyalkylthiophene (5) having a functional group introduced at the terminal thereof is prepared by substituting the functional group of the zide compound (4). Copper bromide (CuBr), copper iodide (CuI), copper chloride (CuCl), copper tribromide (Cu (ph ₃ ) ₃ Br) and the like may be used as the copper component of the copper / amine catalyst suitable for the above reaction.

Click chemistry was first proposed by Professor Barry Sharpless of the United States in 2001 to create new drugs more effectively for new drug development (Sharpless, KB, et al . , Angew . Chem . Int. Ed . : 2004-2021, 2001), is a fast and irreversible reaction that binds small molecules to form larger molecules. Typical click chemistry is azide-alkyne cycloaddition, in which a molecule having an azide functional group at the molecular end is subjected to a "clicking" process under a catalyst consisting of copper and an amine And binds with various alkyne compounds.

In a preferred embodiment of the present invention, poly-3-hexylthiophene having an alkyne group introduced at its end is reacted with 4-vinylbenzyl azide in the presence of copper (CuBr) and dynonyl-dipyridinyl (dNbpy) To perform a click chemical reaction to form a triazole ring. As a result, poly-3-hexylthiophene containing a [1,2,3] -triazole ring having a vinyl group introduced at its terminal is synthesized.

As described above, the polyalkylthiophenes having various functional groups introduced at their terminals according to the present invention are excellent in solubility and processability, and have excellent stereoregularity at the terminal end It can be expected to be used for a semiconductor layer for an organic thin film transistor.

Hereinafter, the present invention will be described in more detail with reference to Examples. It is to be understood by those skilled in the art that these embodiments are only intended to further illustrate the present invention and that the scope of the present invention is not limited by these embodiments in accordance with the gist of the present invention.

Example  1: 3- Hexylthiophene  Produce

3-Bromothiophene (3 g, 18.4 mmol) and hexyl magnesium bromide were added in the same amount as in 3-bromothiophene to a solution of [1,3-bis (diphenylphosphine) propane] dichloronickel II) was added to a mixed solvent of 0.012 g of 0.12 mol% of 3-bromothiophene and reacted at 40 ° C for 4 hours. Subsequently, an excess amount of water and an ether solvent were added to the reaction mixture to separate the organic layer, and 3-hexylthiophene was obtained from the organic layer in a yield of 70% by distillation using a difference in boiling point.

^{1 H-NMR (300 MHz,} CDCl 3, ∂ ppm): 7.25 ppm (d, 1H), 6.95 ppm (t, 2H), 2.65 ppm (t, 2H), 1.65 ppm (m, 2H), 1.37 ppm ( m, 6H), 0.95 ppm (t, 3H)

Example  2: 2- Bromo -3- Hexylthiophene  Preparation of monomers

3 g (17.8 mmol) of 3-hexylthiophene prepared in Example 1 was dissolved in 30 ml of dimethyl amide, N-bromosuccinimide was added in the same amount as 3-hexylthiophene, For 3 hours. Subsequently, dimethylchloride and an excess amount of water were added to the reaction mixture to separate an organic layer, and the organic layer was purified by column chromatography to obtain a 2-bromo-3-hexylthiophene monomer in a yield of 81%.

^{1 H-NMR (300 MHz,} CDCl 3, ∂ ppm): 7.20 ppm (d, 1H), 6.85 ppm (d, 1H), 2.65 ppm (t, 2H), 1.63 ppm (m, 2H), 1.35 ppm ( m, 6H), 0.95 ppm (t, 3H)

Example  3: At the end Alkin Giga  Introduced Poly 3 - Hexylthiophene  Produce

2 g (8.1 mmol) of the 2-bromo-3-hexylthiophene monomer prepared in Example 2 was dissolved in 20 ml of tetrahydrofuran (THF) with 1.15 ml of diisopropylamine purified in the same amount as the monomer, -Butyllithium (4.8 ml) was added to the solvent obtained by stirring at room temperature for 5 minutes, and the mixture was reacted at -78 ° C (reactor containing dry ice / acetone) for 1 hour. Subsequently, 1.16 g of zinc chloride was added to the reaction product in the same amount as the monomer, and the reaction was carried out at -70 ° C for 1 hour. Thereafter, a 0.65 mol% ratio of 2-bromo-3-hexylthiophene monomer in an ice- And 0.029 g of [1,3-bis (diphenylphosphine) propane] dichloronickel (II) were added and reacted at room temperature for 30 minutes. Then, 0.972 ml of 6 mol% ethynyl magnesium bromide was added to the reaction mixture, and the mixture was reacted for 10 minutes to complete the polymerization. The reaction mixture was precipitated in methanol, and the reaction product was separated, filtered and dried in a vacuum oven at 25 ° C. The dried product was purified through a soxhlet extraction method using methanol, hexane and tetrahydrofuran to obtain poly-3-hexylthiophene having an alkenyl group at the terminal thereof in a yield of 81%.

^{1 H-NMR (300 MHz,} CDCl 3, ∂ ppm): 6.95 ppm (s, 1H), 3.14 ppm (s, 1H), 2.75 ppm (t, 2H), 1.70 ppm (t, 2H), 1.38 ppm ( m, 6H), 0.98 ppm (t, 3H)

Example  4: 4- Vinyl benzyl Azid's  Produce

2 g (13.1 mmol) of 4-vinylbenzyl chloride was dissolved in 20 ml of dimethyl amide, 1.28 g of sodium azide was added in the same amount, and the mixture was reacted at room temperature for 24 hours. Subsequently, dimethylchloride and an excess amount of water were added to the reaction product, and the organic layer was separated to obtain 4-vinylbenzyl azide in a yield of 85%.

^{1 H-NMR (300 MHz,} CDCl 3, ∂ ppm): 7.65 ppm (d, 2H), 7.35 ppm (d, 2H), 6.75-6.85 ppm (m, 1H), 5.83 ppm (d, 1H), 5.38 ppm (d, 1 H), 4.20 ppm (s, 2 H)

Example  5: [1,2,3] - Triazole  Containing a ring Poly 3 - Hexylthiophene  Produce

1 mg (6.67 x 10 ^-2 mmol) of the 4-vinylbenzyl azide prepared in Example 4 was dissolved in 5 ml of tetrahydrofuran with 2.9 mg (2.0 x 10 ^-2 mmol) of copper bromide and 4,4'-dino Was added to a mixed solvent of 16.35 mg (4.0 x 10 ^-2 mmol) of 4,4'-dinonyl-2,2'-dipyridyl, dNbpy and stirred at room temperature for 30 minutes Then, 0.1 mg of poly-3-hexylthiophene having an alkyne group introduced into the terminal prepared in Example 3 was added, and the reaction was carried out at room temperature for 44 hours. The reaction product was separated by precipitation in methanol, followed by filtration and drying in a vacuum oven at 25 ° C. to obtain poly-3-hexylthiophene containing a [1,2,3] -triazole ring having a vinyl group at the end thereof in a yield of 75% ≪ / RTI > Thus, the vinyl group introduced at the terminal by a click chemistry reaction [1, 2,3] exhibited ¹ H-NMR spectrum of poly-3-hexyl silti comprising a triazole ring thiophene in Fig.

¹ H-NMR (300 MHz, CDCl ₃ , ppm): 7.15 ppm (d), 7.05 ppm (d), 6.95 ppm (s, 1H), 5.72 ppm (d), 5.25 ppm t, 2H), 1.70 ppm (t, 2H), 1.38 ppm (m, 6H), 0.98 ppm (t,

Experimental Example  1: Measurement of molecular weight distribution

The poly-3-hexylthiophene to which the alkyne group was introduced at the terminal prepared in Example 3 was obtained not by polymerizing the 2-bromo-3-hexylthiophene monomer and terminating the reaction using methanol but by using a grignard reagent To terminate the reaction while suppressing the side reaction in which coupling occurs at the high molecular weight terminal. The molecular weight of the poly-3-hexylthiophene thus prepared was measured by GPC, and as a result, it was confirmed that the weight average molecular weight was 15,400 and the molecular weight distribution was 1.3 as shown in FIG.

Experimental Example  2: MALDI - TOF  Mass spectrometry using mass spectrometry

3-hexylthiophene ( FIG. 3 ) in which an alkene group was introduced at the terminal prepared in Example 3 and a [1,2,3] -triazole ring in which a vinyl group was introduced at the terminal by click chemistry in Example 5 The molecular weight change of the poly-3-hexylthiophene ( FIG. 4 ) containing was analyzed by a MALDI-TOF mass spectrometer.

As a result, as shown in Figs. 3 and 4 , the mass spectrometric analysis of the poly-3-hexylthiophene to which the alkyne group was introduced had a [1,2,3] -triazole ring containing a vinyl group at the terminal In the mass spectrometry of poly (3-hexylthiophene), the molecular weight of the triazole functional group increased by 159.12 g / mol, which was 3236.81? 3395.90, 3403.26? 3562.13, 3570.03? 3729.15, 3736.34? 3895.61, 3902.65? 4061.78 and 4068.71? 4393.83. ≪ / RTI >

Experimental Example  3: elemental analysis

Elemental analysis of poly-3-hexylthiophene containing a vinyl group-introduced [1,2,3] -triazole ring at the terminal prepared in Example 5 was carried out using an elemental analyzer (Fisons Instrument, EA1180) The mass ratio of sulfur (S) of 3-hexylthiophene to nitrogen (N) of the introduced triazole ring was calculated. As a result, it was found that the poly-3-hexylthiophene, into which the triazole ring was introduced by click chemistry, Respectively.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the invention. something to do. It is therefore intended that the scope of the invention be defined by the claims appended hereto and their equivalents.

1 is a ¹ H-NMR spectrum of poly-3-hexylthiophene containing a [1,2,3] -triazole ring having a vinyl group at its terminal by a click chemistry reaction according to the present invention,

FIG. 2 shows a GPC spectrum of poly-3-hexylthiophene containing a [1,2,3] -triazole ring having a vinyl group introduced at the terminal by a click chemical reaction according to the present invention,

FIG. 3 is a MALDI-TOF mass spectrometry spectrum of poly-3-hexylthiophene having an alkyne group introduced at the terminal by Grignard reaction according to the present invention,

FIG. 4 is a MALDI-TOF mass spectrometry of poly-3-hexylthiophene containing a [1,2,3] -triazole ring having a vinyl group at the end thereof by a click chemistry reaction according to the present invention.

Claims (4)

1) reacting a 2-bromo-3-functional thiophene monomer represented by the following formula 1 with lithium diisopropylamide (LDA), zinc chloride (ZnCl ₂ ) and [1,3-bis (diphenylphosphino ) Propane] dichloro nickel (II) ([1,3-bis (diphenylphosphino) propane] dichloronickel (II), Ni (dppp) Cl ₂ ) To produce a polyalkylthiophene having a molecular weight distribution of 1.0 to 1.3 and a symmetrical molecular weight distribution with an alkyne group introduced at the end thereof represented by the following formula (3) by reacting with a Grignard reagent represented by the following formula ; And 2) a polyalkylthiophene having an alkyne group introduced at the end of the formula 3 is reacted with an azide compound represented by the following formula (4) in the presence of a copper / amine catalyst according to a click chemistry to introduce a functional group A method for functionalizing a polyalkylthiophene, comprising: preparing a polyalkylthiophene represented by the following formula (5): ≪ Formula 1 >

(2) CH≡C-MgBr (3)

≪ Formula 4 > N ₃ -R ₂ ≪ Formula 5 >

In the above equations, R ₁ is an alkyl group having ₁ to 12 carbon atoms, R ₂ is selected from the group consisting of a halogen atom, an alkyl group having 1 to 50 carbon atoms, a vinyl group, an alkylhydroxyl group, an alkylaryl hydroxyl group, an aryl hydroxyl group, an alkyl carboxyl group, an aryl carboxyl group, an alkylaryl carboxyl group, A nitroalkyl group, an alkylaryl ester group, a haloalkyl group, a haloaryl group, a haloalkylaryl group, a nitroalkyl group, a nitroaryl group, a nitroalkylaryl group, an alkylamido group, an arylamido group, an alkylarylamido group, a cyanoalkyl group, A cyanoalkylaryl group, in which all oligomers or polymers having a terminal azido group are used, R ₂ has the corresponding oligomer or polymer form, n is the degree of polymerization of the monomer of the polythiophene and is an integer of 10 to 100,000. The method according to claim 1, Wherein the polyalkylthiophene having an alkyne group introduced at the terminal of Formula 3 has an average molecular weight of 3,000 to 100,000 Da. The method according to claim 1, Wherein the Grignard reagent is used in an amount of 50 to 150 mol% based on 100 mol% of the polyalkyl thiophene to which the alkyne group is introduced at the terminal in the step 1). The method according to claim 1, Step 2) a copper component of the copper / amine catalyst in is selected from the group consisting of copper bromide (CuBr), copper iodide (CuI), copper chloride (CuCl) and hydrobromic three benzyl copper _{(Cu (ph 3) 3 Br} ) Lt; RTI ID = 0.0 > polyalkylthiophenes. ≪ / RTI >

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