KR100954191B1 - Thiophene monomer having containing diketone, polythiophene, polythiophene copolymer and metal-coordinated polythiophene complex and a preparing method of the same - Google Patents

Abstract

The present invention provides a thiophene derivative compound comprising a diketone represented by the following formula (1) and a method for producing the same. The present invention also provides polythiophene and copolymers thereof synthesized from the thiophene derivative compounds, and metal-coordinated polymer metal complexes:

[Formula 1]

Wherein R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrogen, a hydroxyl group, a halogen atom, a halide, an alkyl group having 1 to 50 carbon atoms, an alkylhydroxyl group, an alkylarylhydroxyl group, or an arylhydroxyl group , Alkylcarboxyl group, arylcarboxyl group, alkylarylcarboxyl group, alkylester group, arylester group, alkylarylester group, haloalkyl group, haloaryl group, haloalkylaryl group, nitroalkyl group, nitroaryl group, nitroalkylaryl group, alkylamide , Arylamide, alkylarylamide, cyanoalkyl group, cyanoaryl group and cyanoalkylaryl group.

Diketones, polythiophenes, conductive polymers, electrically conductive metal polymer composites

Description

Thiophene monomers comprising diketone, polythiophene, polythiophene copolymer and metal coordination polythiophene polymer metal complex synthesized therefrom, and a method for preparing the same.THE PHHOPHENE MONOMER HAVING CONTAINING DIKETONE COORDINATED POLYTHIOPHENE COMPLEX AND A PREPARING METHOD OF THE SAME}

1 is a polythiophene copolymer synthesized by adjusting the molar ratio of thiophene monomer and 3-decylthiophene prepared in Example 3 to 40 to 60 and copper coordination to the polythiophene copolymer prepared in Example 4. Shows an infrared spectral spectrum of the polymer metal composite.

FIG. 2 is a diagram showing an ultraviolet spectral spectrum of a polymer metal composite in which copper is coordinated with the polythiophene copolymer prepared in Example 4. FIG.

Figure 3 is a view showing the results of pyrolysis analysis of the polymer metal complex copper is coordinated to the polythiophene copolymer prepared in Example 4.

[Industrial use]                         

The present invention relates to thiophene monomers, polythiophene, polythiophene copolymers and metal-coordinated polythiophene polymer metal composites and methods for their preparation. More specifically, the thiophene monomer having the electrical conductivity of the main chain and the metal introduction characteristics through the diketone of the side chain, polythiophene, polythiophene copolymer and metal coordination polythiophene polymer derived therefrom It relates to a metal composite and a method for producing the same.

[Private Technology]

Today, with the development of science and technology, informatization has greatly influenced the daily lives of individuals beyond the industrial and defense fields, and is rapidly expanding all over the world. In the information age, the development of the electronics, telecommunications, and defense industries is inevitable, which tends to be developed as a complex, diversified, lightweight, compact, and thinner electronic equipment. It is becoming. And it is pursued by the extension of the electromagnetic frequency band which they use.

As a result, the electromagnetic interference between the electromagnetic waves in the electrical and electronic materials and circuits has emerged as a major problem in the technical aspect, and the environmental debate is gradually spreading. In general, electromagnetic shielding has been made by metal or metal oxide materials, which are well known for their electrical properties, but are heavy, opaque, difficult to process into thin films, difficult to realize desired colors, expensive, and shield electromagnetic waves by reflecting electromagnetic waves. Although there are disadvantages in that there is no electromagnetic wave absorbing capacity, there is a great need for the development of new high performance electromagnetic shielding and absorbing materials that can replace these metal and metal oxide materials.

As part of this, fiber-reinforced composite materials, materials that have been treated with conductive materials on plastics, and materials that have conductive fillers mixed with plastics have been researched and developed as substitutes for metals and metal oxides. Recently, as the regulation of electromagnetic interference in Korea and abroad is in full swing, general fiber-reinforced composite materials and various plastic materials are difficult to effectively respond to related regulations, and thus, interest in conductive polymers and composite materials having added conductivity to these materials has been greatly increased. . Representative examples of such electrically conductive polymers include polyaniline, polythiophene, polypyrrole, polyparaphenylene, polyparaphenylenevinylene, polyacetylene, polyazomethine and the like.

Polyaniline, polypyrrole and polythiophene derivatives of conventional electrically conductive polymers have been attracting much attention because they are easy to polymerize, have relatively high electrical conductivity, and have excellent physical properties such as oxidation stability. In addition to the electrical conductivity of these polymers have anticorrosive properties and electrochromic properties can be applied to electronic materials, anticorrosive coatings, smart windows and the like.

However, the polymer compound having a conjugated double bond in the main chain as described above has many limitations in processing due to insoluble and insoluble properties due to mutual attraction between electrons included in the double bond. To this end, efforts have been made to improve the processability of conductive polymers.As a part of them, polymers can be polymerized by introducing doped or substituted monomers into doped polymers with a large molecular weight dopant to reduce the mutual attraction of the polymers, and polymers prepared by introducing a water-soluble dopant. There have been attempts to dissolve in an organic solvent or water using a method such as hydrolysis. However, this was so limited that only a very small amount of solution had limited commercialization. Therefore, recent studies have attempted to produce conductive polymers in dispersible forms rather than attempting to dissolve conductive polymers in solvents to overcome these limitations.

The present invention has been made to solve the above-mentioned problems of the prior art, an object of the present invention to provide a thiophene monomer having a metal conduction characteristics through the diketone of the side chain and the electrical conductivity of the main chain and a method for producing the same. It is for.

Another object of the present invention is to provide a polythiophene, polythiophene copolymer derived from a thiophene monomer, and a method for preparing the same.

It is still another object of the present invention to provide a metal coordination polythiophene polymer metal composite and a method of manufacturing the same.

The present invention to achieve the above object, the present invention provides a thiophene derivative compound having a diketone as a side and a method for producing the same.

The present invention also provides polythiophene and polythiophene copolymers synthesized from thiophene derivative compounds and methods for their preparation.

The present invention also relates to an electrically conductive metal-coordinated polythiophene polymer metal composite prepared by reacting a polythiophene or polythiophene copolymer with a metal in solution to introduce a metal into a diketone of a side branch of the polythiophene polymer, and a method for producing the same. To provide.

Hereinafter, the present invention will be described in more detail.                     

According to a first preferred embodiment of the present invention, there is provided a thiophene derivative compound having a diketone represented by the following Chemical Formula 1, and a method for preparing the same:

[Formula 1]

Wherein R ₁ , R ₂ , R ₃ , and R ₄ each independently represent a hydrogen, a hydroxyl group, a halogen atom, a halide, an alkyl group having 1 to 50 carbon atoms, an alkylhydroxyl group, an alkylarylhydroxyl group, and arylhydroxyl. Real group, alkyl carboxyl group, arylcarboxyl group, alkyl aryl carboxyl group, alkyl ester group, aryl ester group, alkyl aryl ester group, haloalkyl group, haloaryl group, haloalkylaryl group, nitroalkyl group, nitroaryl group, nitroalkylaryl group, alkyl Amide, arylamide, alkylarylamide, cyanoalkyl group, cyanoaryl group, and cyanoalkylaryl group. Unless stated otherwise in the specification of the present invention, an alkyl group means alkyl having 1 to 50 carbon atoms, and aryl means aryl having 6 to 24 carbon atoms.

The thiophene derivative compound of Formula 1 is prepared through the following process: tosylation 2- (3-thienyl) of 2- (3-thienyl) ethanol; R ₁ , R ₂ , R ₃ , and R ₄ of the hydroxy acetophenone of Formula 1a are each independently hydrogen, a hydroxyl group, a halogen atom, a halide, an alkyl group having up to 50 carbon atoms, and an alkyl hydroxy. Real group, alkyl aryl hydroxyl group, aryl hydroxyl group, alkyl carboxyl group, aryl carboxyl group, alkyl aryl carboxyl group, alkyl ester group, aryl ester group, alkyl aryl ester group, haloalkyl group, haloaryl group, haloalkylaryl group, nitroalkyl group Substituted with a substituent selected from the group consisting of nitroaryl groups, nitroalkylaryl groups, alkylamides, arylamides, alkylarylamides, cyanoalkyl groups, cyanoaryl groups, and cyanoalkylaryl groups; Reacting the tosylated 2- (3-thienyl) acetone with substituted hydroxy acetophenone to prepare a material having a ketone; The ketone-containing material is reacted with ethyl acetate to prepare a thiophene derivative compound of formula 1 having diketone:

[Formula 1a]

According to a second preferred embodiment of the present invention, there is provided a polythiophene of formula (2) and a polythiophene copolymer of formula (3) synthesized from the thiophene derivative compound represented by the formula (1) and a method for preparing the same:                     

[Formula 2]

[Formula 3]

Wherein R ₁ , R ₂ , R ₃ , R ₄ , and R ₅ are each independently hydrogen, a hydroxyl group, a halogen atom, a halide, an alkyl group having 1 to 50 carbon atoms, an alkyl hydroxyl group, an alkylaryl hydroxyl group, Aryl hydroxyl group, alkyl carboxyl group, aryl carboxyl group, alkyl aryl carboxyl group, alkyl ester group, aryl ester group, alkyl aryl ester group, haloalkyl group, haloaryl group, haloalkylaryl group, nitroalkyl group, nitroaryl group, nitroalkylaryl Group, alkylamide, arylamide, alkylarylamide, cyanoalkyl group, cyanoaryl group and cyanoalkylaryl group, n has a value of 2 to 100,000 as the degree of polymerization, and x is a molar ratio of 0.0 to 0.0 It is in the range of 1.0.

The polythiophene of Chemical Formula 2 is synthesized by polymerizing the thiophene monomer of Chemical Formula 1 using an oxidizing agent in a solution phase. In the polythiophene copolymer of Formula 3, the thiophene monomer of Formula 1 is used as the main monomer and the thiophene substituted with R ₅ at position 3 is used as a comonomer to adjust the molar ratio of the two monomers to use an oxidizing agent in solution. Synthesized by polymerization. The polythiophene of Formula 2 and the polythiophene copolymer of Formula 3 according to the present invention are characterized by excellent thermal and environmental stability and the polymer backbone having a pi-conjugated structure, and at the same time It has high solubility because it has various side branches in position, so it is easy to dissolve in various organic solvents or organic solvent / water mixed solution, and has excellent processability.

In the polythiophene of Formula 2 and the polythiophene copolymer of Formula 3, the polymer main chain has a pi-conjugated structure, so that the conductive properties can be realized by doping with various dopants. The polymers are doped with organic solvents or mixed solutions of organic solvents / water, almost all acids and salts and iodine, and are preferably chloride, perchloride or tetrafluoro which can generate anions in organic solvents or mixed solutions of organic solvents / water. It may be doped with one or more dopants selected from borate, para-toluene sulfonate, trifluoromethane sulfonate, hexafluorophosphate, polystyrene sulfonate group and cationically sodium group.

 As described above, in the doping of the polythiophene of Formula 2 and the polythiophene copolymer of Formula 3 with the dopant, all acid solutions and organic solvents may be used, and preferably hydrochloric acid, phosphoric acid, nitric acid, tetra Fluoroborate acid, para-toluene sulfonate acid, trifluoromethane sulfonate acid, hexafluorophosphate acid, polystyrene sulfonate, chloroform, acetonitrile, nitromethane, tetrahydrofuran, methacresol Eggplant or more than one can be used.

According to a third preferred embodiment of the present invention, the electrical conductivity by introducing a metal into the diketone of the side branches of the polythiophene polymer by reacting the polythiophene of the formula (2) or the polythiophene copolymer of the formula (3) in a solution phase Provided are a metal coordination polythiophene polymer metal composite and a method of manufacturing the same. The polythiophene copolymer of Formula 3 and the polymer metal complex excluding the metal are represented by the following Formula 4:                     

[Formula 4]

Wherein R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are as defined in Chemical Formulas 1 to 3, n has a value of 2 to 100,000 as the degree of polymerization, and x is a molar ratio in the range of 0.0 to 1.0. have.

The metal used to prepare the metal coordination polymer metal composite may be any metal, in particular alkali metals such as Li, Na, K, and Rb on the periodic table, alkaline earth metals such as Mg, Ca, Sr and Ba, divalent or 3 Preferred are transition metals having valence electrons.

The polymer metal composite has a pi-conjugated structure in which the polymer main chain is used for electric electronic devices and electronic control devices by utilizing the electric conduction properties by doping of various dopants and the electrically conductive polymer metal hybrid composite properties of side branches by metal coordination. Applicability to materials and electrically conductive polymer metal hybrid composites are also expected to be useful as polymer catalysts.

Example

Hereinafter, a preferred embodiment of the present invention. However, the following examples are only presented to aid the understanding of the present invention, and the present invention is not limited to the following examples.

Example 1 Synthesis of Thiophene Monomer of Formula 1

First, in a nitrogen atmosphere, the reaction vessel is maintained at 0 ° C., 2- (3-thienyl) ethanol and p-TSC (para-toluenesulphonic chloride) are added, and then chloroform and pyridine are added. After the reaction was carried out for several minutes to several hours, ether and distilled water were added, washed several times with hydrochloric acid solution, washed with 5% NaHCO ₃ and water, the organic layer was separated, the solvent was removed under reduced pressure, and then tosyl was introduced. Toluene-4-sulfonic acid 2-thiophen-3-yl-ethyl ester was synthesized. As a second step, a ketone is introduced into the tosylated thiophene derivative. Toluene-4-sulfonic acid 2-thiophen-3-yl-ethyl ester is obtained by dispersing the basic catalyst NaH in DME (ethylene dimethyl glycol ether). And p-hydroxy acetophenone dissolved in DME and added. After the addition is complete, reflux is carried out for 3 to 5 days to complete the reaction and the resulting mixture is concentrated under reduced pressure. An excess of ethyl acetate and water is added to the concentrated mixture to separate the organic layer, and a small amount of water remaining in the organic layer is removed with MgSO ₄ . The solvent in the resulting mixture was removed and 3- (ethyloxyacetophenyl) thiophene was synthesized using a silica column using hexane and ethyl acetate as developing solvents. As a third step, NaH was dispersed in DME, and 3- (ethyloxyacetophenyl) thiophene and excess ethyl acetate were added to the dispersed mixture to reflux for 3 to 7 days to complete the reaction, and the resulting mixture was completed. Is concentrated at reduced pressure. The concentrated material is diluted with excess ether and washed several times with water. The ether organic layer was separated, extracted with concentrated hydrochloric acid solution and methylene chloride, a small amount of water was removed with MgSO ₄ , the solvent was removed, and hexane and ethyl acetate were used as developing solvents. (Ethyloxyacetylacetophenyl) thiophene was synthesized.

¹ H NMR (δ, CDCl 3), 7.92 (m, 2H, Ph-H), 7.27 (t, 1H, Ph-H), 709. (s, 1H, Ph-H), 7.02 (t, 1H, Ph -H), 6.92 (t, 2H, Ph-H), 6.01 (s, 1H, vinyl), 4.25 (t, 2H, methylene), 3.17 (t, 2H, methylene), 2.16 (s, 3H, methyl)

Example 2: Polythiophene Synthesis

Dissolve 3- (ethyloxyacetylacetophenyl) thiophene, which is the thiophene monomer synthesized in Example 1, in chloroform or acetonitrile solvent, and then ferric chloride, which is an oxidizing agent, in a ratio of 1 to 4 times the monomer equivalent ratio. After reacting for a time and forming a precipitate in methanol, it was dried in a vacuum oven at 60 ℃ to synthesize a polythiophene containing a diketone polythiophene having a weight average molecular weight range of 1,000-100,000 depending on the reaction time.

Example 3: Polythiophene Copolymer Synthesis

The thiophene monomer synthesized in Example 1, 3- (ethyloxyacetylacetophenyl) thiophene and 3-decylthiophene were adjusted in the same equivalence ratio or equivalence ratio, so that ferric chloride as an oxidizing agent was used in a monomer equivalent ratio of 1 to 4 times for 15 minutes. The reaction was carried out for 24 hours to form a precipitate in methanol, which was then filtered and dried in a vacuum oven at 60 ° C. A copolymer of polythiophene-poly (3-decylthiophene) having a weight average molecular weight in the range of 1,000-100,000 was synthesized depending on the reaction time.

Example 4 Synthesis of Metal Coordination Polythiophene Polymer Metal Composite

After dissolving the polythiophene of Example 2 and the polythiophene copolymer of Example 3 in a chloroform solvent, cooperacetate was dissolved in a small amount of methanol, and then added to react for 1 hour to 5 days at a temperature range of 30-100 ° C. The precipitate was formed in methanol to synthesize an electroconductive polymer metal complex coordinating diketone and copper of polythiophene or a copolymer thereof.

Example 5: Identification of Synthetic Polymer Metal Composites

In Example 3, whether the synthesis of the polythiophene copolymer synthesized by adjusting the molar ratio of the thiophene monomer, 3- (ethyloxyacetylacetophenyl) thiophene and 3-decylthiophene to 40 to 60 was determined by infrared spectroscopy and ultraviolet ray. Confirmed by spectroscopy and pyrolysis. The results are shown in Figs. 1 to 3 in turn.

In Example 4, the molar ratio of thiophene monomer, 3- (ethyloxyacetylacetophenyl) thiophene and 3-decylthiophene was adjusted to 40 to 60, and copolymers of polythiophene and poly (3-decylthiophene) Synthesis of the electrically conductive polymer metal complex in which copper is coordinated to diketone of was confirmed by infrared spectroscopy, ultraviolet spectroscopy and pyrolysis analysis. The results are shown in Figs. 1 to 3 in turn. 1 to 3, P3EAET-co-P3DT (40:60) is a polythiophene copolymer synthesized by adjusting the molar ratio of 3- (ethyloxyacetylacetophenyl) thiophene and 3-decylthiophene to 40 to 60. P3EAET-co-P3DT (40:60, Cu) and P3EAET-co-P3DT (40:60) -Cu com mean an electrically conductive metal complex with copper coordinates, and P3EAET-co-P3DT (40). : 60) + Cu means a mixture of P3EAET-co-P3DT (40:60) and copper to check for coordination.

In the infrared spectral spectrum of FIG. 1, the peaks near 1250 cm ⁻¹ and 1180 cm ^{−1 show} thiophene formation of a polymer by substitution at positions 2 and 5, 1600-1500 In the vicinity of cm ⁻¹ , vibration patterns of benzene and thiophene rings overlap. The most prominent peak is the peak corresponding to the diketone at 1610 cm ^-1 when the metal is not coordinated, but shifted to 1600 cm ^-1 by relatively heavy copper when the copper is coordinated It can be seen.

When the copper is not coordinated as a spectrum obtained by the ultraviolet spectroscopy of FIG. 2, the characteristic peak does not appear in the short wavelength region, but when the ligand is formed, diketone and copper are coordinated at 310 nm to show the characteristic peak. In addition, although the characteristic peak was confirmed using the polymer mixture synthesized with copper to confirm the coordination, it can be seen that the copper is coordinated because the characteristic peak is not seen.

In the thermal analysis graph of FIG. 3, decomposition occurs at a higher temperature when copper is coordinated than when it is not coordinated. This is because diketone and copper coordination require more thermal energy to thermally decompose these ligands, and the weight loss is almost constant for polymers that are not coordinated above 400 ° C, and continuously for weights of coordinated polymers. Is decreasing, indicating that copper remains after decomposition.

The polythiophene derivative according to the present invention can improve conduction properties by coordinating a metal by using a diketone introduced into the side chain and electrical conduction characteristics by the main chain, and even after coordinating a metal after preparing a copolymer. It exhibits considerable solubility in organic solvents and is very good in thermal stability. Therefore, the polythiophene derivative of the present invention has high utility in additives for antistatic and anticorrosive coatings, for electric and electronic devices, and for electromagnetic wave control devices and systems.

All simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

Claims (5)

Thiophene derivative compound comprising a diketone to the side branch represented by the formula (1): [Formula 1]

Wherein R ₁ , R ₂ , R ₃ , and R ₄ are hydrogen. Tosylation of 2- (3-thienyl) of 2- (3-thienyl) ethanol; Reacting the tosylated 2- (3-thienyl) acetone with hydroxy acetophenone of Formula 1a to prepare a material having a ketone; A method for preparing a thiophene derivative compound according to claim 1 comprising the step of reacting a substance having the ketone with ethyl acetate: [Formula 1a]

R ₁ , R ₂ , R ₃ , and R ₄ in Formula 1a are hydrogen. A polymer selected from the group consisting of polythiophene of formula 2 and polythiophene copolymer of formula 3 synthesized from the thiophene derivative compound of claim 1 [Formula 2]

[Formula 3]

Wherein R ₁ , R ₂ , R ₃ , and R ₄ are hydrogen, R ₅ is hydrogen or an alkyl group having 1 to 50 carbon atoms, n has a value of 2 to 100,000 as a degree of polymerization, and x is a molar ratio.   A polymer metal composite formed by coordinating a metal and a polymer selected from the group consisting of polythiophene of Formula 2 and polythiophene copolymer of Formula 3. The polymer metal composite of claim 4, wherein the metal is an alkali metal, an alkaline earth metal, or a transition metal.

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