KR20210073908A - Nanofiber based organic-inorganic composite photocatalyst and process for producing the same - Google Patents

Abstract

The present invention relates to an organic-inorganic composite photocatalyst based on nanofibers in which conjugated polymer nanoparticles are introduced into titanium dioxide nanofibers. More specifically, the present invention relates to: a photocatalyst that is easy to reuse by manufacturing the photocatalyst that is active in visible light by complexing a visible light region where there is no activity of titanium dioxide with conjugated polymer nanoparticles capable of absorbing visible light, and turning the titanium dioxide into nanofibers; and a manufacturing method thereof.

Description

Nanofiber-based organic-inorganic composite photocatalyst and manufacturing method thereof { Nanofiber based organic-inorganic composite photocatalyst and process for producing the same }

The present invention relates to a photocatalyst prepared by introducing conjugated polymer nanoparticles into titanium dioxide nanofibers and a method for preparing the same. It relates to a fiber-based photocatalyst that can be easily reused and a method for manufacturing the same, which can be applied to organic dye decomposition and oxidation/reduction reactions of organic compounds, and is an organic/inorganic nanofiber-based organic/inorganic catalyst that is easy to recover after reaction It relates to a composite photocatalyst and a method for preparing the same.

Nanomaterials have a size of 100 nm or less, and in particular, nanofibers can be defined as a one-dimensional flexible solid phase having a diameter of 100 nm or less and an aspect ratio of 100:1 or more. Recently, with the rapid development of nanomaterial-related technologies, fibers that are thinner and thinner than existing microfibers are being developed. As a method of manufacturing nanofibers, relatively simple equipment design and economical electrospinning are used. Nanofibers can express new functions through precise structural design that is controlled in nano size on the inside, outside, and surface of the fiber, and these nanofibers are promoting high functionality through particle or structure control.

The nanofiber web composed of nanofibers has the advantage of being porous, having a large specific surface area and light weight compared to the volume, and since it is a structure composed of fibers, it has the advantage of being flexible and can be applied in a wide variety of applications. have. In particular, as well-being products are in the spotlight, nanopowders and photocatalysts are applied in real life to produce products that are applied to household products such as building materials, home appliances, and cosmetics. Research to apply sterilization, deodorization, and electromagnetic wave shielding properties to post-treatment is being actively conducted.

On the other hand, in the photocatalyst field, research is being conducted to complex photocatalyst particles into nanofibers so that they can be reused with a large surface area, but the photocatalytic efficiency is low due to the low content of photocatalytic particles introduced into the nanofibers. In addition, although research on manufacturing photocatalytic metals into nanowires is being conducted, the photocatalytic properties of metals are very expensive, so there is a limit to their industrial application, and the technology for manufacturing nanofibers with a spinning device is extremely rare.

Among the photocatalyst materials, titanium dioxide absorbs only an ultraviolet region corresponding to less than 4% of sunlight and has a disadvantage in that it cannot use solar energy efficiently, but its catalytic activity is higher than other semiconducting photocatalyst materials. Research is being conducted to make it possible to absorb up to the visible light range. Examples thereof include low molecular weight organic dyes, noble metals, metal ions and non-metal ions. When exposed to light for a long period of time, low molecular weight organic dyes have a disadvantage that they cannot be reused due to low light stability due to low light stability. Precious metals are very expensive, so their use is limited commercially, and metal ions and non-metal ions are Since it is immobilized with a relatively weak interaction force such as van der Waals force, electron movement at the interface of the complex is not smooth.

The conjugated polymer has relatively high photostability compared to low molecular weight organic materials such as organic dyes, and structurally, because saturated and unsaturated bonds exist alternately, p-orbitals overlap to form delocalized π-electrons, and as a result It has optical and electrical conductivity properties. In addition, since the conjugated polymer can control the energy bandgap and electrical properties as desired from the design of the chemical structure, the cases of applying the semiconducting properties of the conjugated polymer to the photocatalyst field are increasing.

This semiconducting photocatalyst is a clean material that can convert solar energy into chemical energy, can decompose environmental pollutants such as dyes and low molecular weight organic compounds, and is a self-cleaning material that can decompose bacteria and microorganisms. is diverse The self-cleaning function is due to the strong oxidizing power of reactive oxygen species (ROS) generated on the surface of the photocatalyst, but the overall mechanism is a series of redox surfaces involving not only reactive oxygen species but also valence-to-hole, conduction-band electrons, etc. Reactions occur in a complex chain. The semiconductor photocatalyst absorbs light to excite electrons from the valence band to the conduction band, and the generated charge pair moves to the interface to cause electron transition, thereby accompanying various types of oxidation/reduction reactions. In addition, the reactive oxygen species is a chemically reactive molecule including an oxygen atom, and the types include superoxide (O ₂ ^- ), hydrogen peroxide (H ₂ O ₂ ), and hydroxyl radical (·OH).

However, most of the conventional photocatalyst materials are mainly used in a solution, dispersed in a solid, or coated or deposited on a glass slide. However, when used in a solution, its use is limited because the photocatalyst can be used in a dissolved state in a solvent, and in the case of colloids that disperse solids, additional processes such as filtration or centrifugation are involved, and when discarded after the reaction Because it exists in a colloidal state in the waste fluid, it acts as a disadvantage from an environmental point of view. When a glass slide is used, it is cumbersome to melt the catalyst material or dissolve it in a solvent for coating, and since the catalyst material cannot penetrate the medium of the reaction system, it is very disadvantageous in terms of surface area. That is, the solvent affinity of the catalyst surface is a very important factor in the catalytic activity of a heterogeneous catalyst, which means that the specific surface area of the catalyst has a very large effect on the catalyst activity because the catalytic reaction occurs on the catalyst surface.

Therefore, in the present invention, the support component itself is made into nanofibers with a photocatalytic material to eliminate the need for a support. It is advantageous, has excellent absorbency to the medium of the reaction system, and can be easily recovered because the nanofiber web can be retrieved and reused. In addition, an organic-inorganic composite photocatalyst based on nanofibers that overcomes the limitations of existing titanium dioxide by complexing conjugated polymer nanoparticles with excellent photostability to have activity in the visible light range, and a method for manufacturing the same and using the photocatalyst We present a photocatalytic reaction.

(Prior Document 0001) Korea Patent Registration No. 10-1562254: Polymer nanofibers having photocatalytic activity in the visible light region and method for manufacturing the same (Prior Document 0002) Korean Patent No. 10-1406587: Method for manufacturing a tin oxide nanofiber composite photocatalyst with nitrogen-doped zinc oxide protrusions attached to the surface using a single nozzle simultaneous electrospinning method (Prior Document 0003) Korean Patent Registration No. 10-1641123: Flexible nanostructured photocatalyst in which PVDF nanofiber layer and titanium dioxide nanoparticles are combined and method for manufacturing the same

The present invention synthesizes a conjugated polymer having absorption in the visible light region, prepares it as nanoparticles, and prepares an organic-inorganic composite photocatalyst based on nanofibers introduced by electrostatic force into titanium dioxide nanofibers, and a photocatalyst using the same It is intended to provide a response. Another object of the present invention is to provide a method for preparing an organic-inorganic composite photocatalyst based on a nanofiber that can be recovered and reused.

The organic-inorganic composite photocatalyst based on the nanofibers of the present invention for achieving the above object is a conjugated polymer nanoparticle having a structure of Formula 1 or Formula 2 below; and titanium dioxide nanofibers into which the conjugated polymer nanoparticles are introduced, and an organic-inorganic composite photocatalyst based on the nanofibers can be used for the photocatalytic reaction.

[Formula 1]

[Formula 2]

In addition, the photocatalytic reaction is any one of a decomposition reaction of an organic dye, an oxidation reaction of an organic compound, and a reduction reaction of an organic compound, and the organic dye is rhodamine B, methylene blue, methylorange. ), the oxidation reaction of the organic compound targets any one of benzylamine derivatives and furoic acid, and the reduction reaction of the organic compound preferably targets 4-nitrophenol.

And the method for producing an organic-inorganic composite photocatalyst based on the nanofibers of the present invention includes a first step (S100) of preparing a conjugated polymer having a structure of Formula 1 or Formula 2; a second step (S200) of preparing a conjugated polymer nanoparticle solution using the conjugated polymer prepared in the first step; A third step of preparing a titanium dioxide nanofiber spinning solution (S300); A fourth step (S400) of producing a nanofiber web by electrospinning the spinning solution prepared in the third step; a fifth step (S500) of heat-treating and firing the nanofiber web prepared in the fourth step; A sixth step (S600) of amine treatment of the heat-treated and fired nanofiber web in the fifth step; and a seventh step (S700) of immersing the amine-treated nanofiber web in the sixth step in the conjugated polymer nanoparticle solution prepared in the second step (S700).

In the organic-inorganic composite photocatalyst based on the nanofibers of the present invention, the nanoparticles of the conjugated polymer and the titanium dioxide nanofibers are immobilized by electrostatic attraction to increase the reactants and the reaction surface area of the catalytic reaction, thereby improving the catalytic efficiency. It is not easily desorbed during the reaction and has excellent stability. In addition, since the electron movement between the nanoparticles of the conjugated polymer and the titanium dioxide nanofiber is easy, the titanium dioxide nanofiber exhibits catalytic activity in the visible light region. In particular, since the organic-inorganic composite photocatalyst based on the nanofiber is obtained in the form of a nanofiber web, it has a large specific surface area and has the advantage of easy recovery after use. And since it can be reused by drying after washing, it has a very large economic saving effect.

1 is a flowchart of a method for manufacturing an organic-inorganic composite photocatalyst based on nanofibers according to the present invention;
2 is a graph showing the dye decomposition rate (%) according to the reuse of the organic-inorganic composite photocatalyst based on the nanofiber of the present invention;
3 is a graph showing the conversion rate (%) according to reuse using the nanofiber-based organic-inorganic composite photocatalyst of the present invention.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, the present invention is not limited to the embodiments disclosed below, but can be implemented in various different forms, and the following examples allow the disclosure of the present invention to be complete, and the scope of the invention to those of ordinary skill in the art It is provided to fully inform In addition, in the drawings for convenience of description, the size of the components may be exaggerated or reduced. In the drawings, variations of the illustrated shape can be expected, for example depending on manufacturing technology and/or tolerances. Accordingly, the present invention should not be construed as limited to the specific shape of the regions shown herein, but should include, for example, manufacturing-induced shape changes.

Hereinafter, an organic-inorganic composite photocatalyst based on the nanofibers of the present invention and a photocatalytic reaction using the same will be described in detail.

The method for manufacturing an organic-inorganic composite photocatalyst based on nanofibers according to the present invention, as shown in FIG. 1 , includes a first step (S100) of preparing a conjugated polymer; a second step of dissolving the conjugated polymer prepared in the first step in an organic solvent to prepare nanoparticles in tertiary distilled water (S200); A third step of preparing a nanofiber spinning solution (S300); A fourth step of manufacturing a nanofiber web by electrospinning the spinning solution of the third step (S400); A fifth step (S500) of heat-treating and firing the nanofiber web of the fourth step; A sixth step (S600) of functionalizing an amine group on the nanofiber web of the fifth step; A seventh step (S700) of immersing the amine-treated nanofiber web of the sixth step in the conjugated polymer nanoparticle solution of the second step (S700); it is preferable to include

The conjugated polymer used in the first step is preferably a compound composed of a repeating unit represented by the following formula (1) or (2).

[Formula 1]

In Formula 1, Z is _{any one of C, CR 1} R ₂ , N, S, O, NR ₃ , and SO ₂ , wherein R ₁ , R ₂ , R ₃ are different or the same as each other, and each independently at least one Halogen is a substituted or unsubstituted straight-chain or branched alkyl group or alkoxy group having 1 to 12 carbon atoms.

[Formula 2]

In addition, in Formula 2, R ₄ , R ₅ is H, OR ₆ , R ₇ , R ₆ , R ₇ are different or the same as each other, and each independently one or more halogens are substituted or unsubstituted straight chain or branched chain It is a C1-C12 alkyl group or an alkoxy group. Preferably, R ₄ , R ₅ is n-hexyl, n-heptyl, n-octyl, n-decyl, n-dodecyl, n-ethylhexyl, n-hexyloxy, n-heptyloxy, n-octyloxy, n-decyloxy and 2-ethylhexyloxy, or a combination thereof. The values of X and Y represent the composition of each repeating unit in mole fraction, where X is a real number from 0 to 0.99, and Y is 1-X.

,

,

,

,

,

중 어느 하나인 것이 바람직하다. In addition, in Formula 1 or Formula 2 below, Ar is

,

,

,

,

,

Any one of them is preferable.

In addition, according to the present invention, the molecular weight of the conjugated polymer is not particularly limited, but it is preferable that the number average molecular weight is 3,000 to 100,000, and the range of the number average molecular weight is appropriately adjusted according to the properties required for the use, such as solubility. can be used by

The conjugated polymer represented by Formula 1 or 2 used in the present invention is prepared by a Suzuki coupling reaction, but is not limited thereto, and may be prepared through various synthetic routes.

The second step in the method for producing an organic-inorganic composite photocatalyst based on nanofibers is a method for preparing the conjugated polymer represented by Chemical Formula 1 or 2 into nanoparticles, and is specifically as follows. A solution of 1 mg to 5 mg of the conjugated polymer represented by Formula 1 or 2 in 1 mL of an organic solvent having miscibility with water is prepared, specifically, the organic solvent is tetrahydrofuran (THF) It is preferable to use, but is not limited thereto.

Next, the solution of the conjugated polymer prepared as described above is rapidly injected into 10 to 15 mL of tertiary distilled water under ultrasonication, and the sonication time is preferably 30 minutes to 1 hour. In order to evaporate the organic solvent dissolved in the tertiary distilled water as described above, nitrogen gas or argon gas is injected for 30 minutes to 1 hour, and then the conjugated polymer nanoparticle solution is filtered with a filter of 0.45 micrometer or less. The size of the nanoparticles of the conjugated polymer prepared in the manufacturing process preferably has a diameter of 20 to 90 nanometers, but is not limited thereto, and can be appropriately adjusted in consideration of the diameter of the nanofiber to be composited.

In the third step, a method for preparing a spinning solution of titanium dioxide nanofibers is specifically as follows. Polyvinylpyrrolidone (PVP) is used as a template polymer so that titanium dioxide can be maintained in the form of fibers, but any polymer having fiber-forming ability can be used. Next, in order to maximize the catalytic efficiency, a block copolymer (P123) composed of three blocks of polyethylene glycol and polypropylene glycol was used as a surfactant capable of imparting mesoporosity of titanium dioxide, but a block copolymer used as a surfactant Either can be used. The PVP and P123 were dissolved in ethanol to prepare a fibrous structure solution, titanium dioxide precursor titanium isopropoxide (TTIP) and an acid catalyst were added to the solution, and ^{at a temperature of 80 to 100 o} C for 1 hour. After heating, it can be cooled to room temperature to prepare a spinning solution of titanium dioxide nanofibers.

The fourth step is a step for producing a titanium dioxide nanofiber, specifically as follows. The spinning solution of the titanium dioxide nanofiber prepared in the third step is injected into a syringe and a stainless needle having a diameter of 18 to 24 gauge is inserted, specifically, the spinning solution is evenly spun It is preferable that the needle tip be in the form of a cut-off that is not sharpened in order to be used. Next, the syringe into which the spinning solution is injected is installed in a syringe pump capable of applying a certain pressure, and specifically, it is preferable that the flow rate is 0.5 to 1 mL/h. The positive electrode is connected to the needle of the syringe into which the spinning solution is injected, and the opposite negative electrode is connected to a collector plate. Specifically, it is preferable to easily recover the nanofibers by laying aluminum foil on the collection plate, It is preferable to use a device that allows the nanofibers to be evenly stacked by moving left and right. The voltage applied to the electrospinning is preferably 10 to 20 kV and can be appropriately adjusted according to the diameter of the fiber, the viscosity of the spinning solution, the capacity of the spinning solution according to the diameter of the spinning needle, and the speed of the pump to be injected, and the spinning time is the minimum It is easy to recover the nanofibers and post-process them for 4 to 10 hours.

In the present invention, although the electrospinning method is adopted to manufacture the nanofiber, it is not limited thereto, and any process capable of forming the nanofiber is possible.

In the fifth step of the present invention, in the prepared in the fourth step, the residual solvent and moisture are removed from the nanofiber web composed of the nanofibers prepared in the fourth step, and the unreacted titanium dioxide precursor Heat treatment (baking) at a temperature of ^{100 to 150 o} C to induce an additional sol-gel reaction is performed for 1 hour to 6 hours. Next, the structure polymer and surfactant present in the heat-treated nanofibers are removed, and a calcination process is performed at ^{500 to 700 o C to provide a unique crystal lattice of titanium dioxide.} That is, the nanofibers are placed in a crucible, put in a furnace, and fired for at least 6 hours to prepare mesoporous titanium dioxide nanofibers. In this case, the diameter of the nanofiber is preferably 100 to 200 nm.

The sixth step is an amine treatment of the nanofiber web prepared in the fifth step, wherein the mesoporous titanium dioxide nanofibers are put in ethanol and 3-aminopropyltriethoxysilane ((3-Aminopropyl)triethoxysilane, APTES) After the addition of the reaction by slowly rolling (rolling) or stirring for 4 to 6 hours. After that, it is taken out, washed with ethanol, and heat-treated at a temperature of ^{100 to 150 o C for 2 to 6 hours.}

The following seventh step is a step of combining the conjugated polymer nanoparticles prepared in the second step with the nanofibers prepared in the sixth step, and the sixth step is to add the conjugated polymer nanoparticles prepared in the second step to the solution. of amine-treated titanium dioxide nanofibers are immersed, and reacted by rolling or stirring slowly for 4 to 6 hours. After that, it is taken out, washed with tertiary distilled water, and dried.

The photocatalytic reaction using the organic-inorganic composite photocatalyst based on the nanofibers of the present invention prepared as described above includes a decomposition reaction of an organic dye and an oxidation or reduction reaction of an organic compound. In this case, the organic dye is preferably any one of rhodamine B, methylene blue, and methyl orange, and the organic compound used in the oxidation reaction is any one of a benzylamine derivative and a furoic acid derivative. Preferably, the organic compound used in the reduction reaction is preferably any one of 4-nitrophenol derivatives.

The photocatalytic reaction using the organic-inorganic composite photocatalyst based on the nanofibers of the present invention may proceed as follows. That is, the organic-inorganic composite photocatalyst based on the prepared nanofibers is immersed in a 20 ml vial containing an aqueous organic dye solution or a reaction solution of an oxidation/reduction reaction, and then irradiated with an LED lamp while stirring. Here, the distance between the LED lamp and the vial is 5 to 10 cm, the intensity of the light source is in the range of 5 to 10 mA, and the reaction solution is recovered by time to obtain UV/Vis absorption spectrum or nuclear magnetic resonance (NMR) spectrum. to identify the product of the decomposition of the dye or the oxidation/reduction reaction. It is also possible to confirm the reaction process by thin layer chromatography (TLC).

The organic-inorganic composite photocatalyst based on nanofibers according to the present invention has a reusable feature. That is, after carrying out the catalytic reaction with the photocatalyst, it is removed, washed with a solvent, and reused.

The mechanism of the catalytic reaction in the photocatalytic reaction as described above is as follows. Electrons present in the valence band of the conjugated polymer are excited into the conduction band by a light source having a wavelength of 300 to 700 nm, and the electrons generated in this process move to the titanium dioxide nanofiber to exhibit the unique high catalytic activity of titanium dioxide. do. In this process, the triplet oxygen present in the vicinity is converted into reactive oxygen species by the moved holes and electrons. Since the generated reactive oxygen species acts as a strong oxidizing agent, it can not only decompose dyes such as rhodamine B, methylene blue, and methyl orange, but also convert benzoic acid by oxidation of benzaldehyde and oxidative coupling of benzylamine. By producing an N-benzyl-1-phenylmethanediamine derivative, the 4-nitrophenol derivative can be converted into 4-aminophenol in the presence of sodium borohydride. It is also possible to convert furoacids to furanones.

Hereinafter, the present invention will be described in detail as examples. However, these Examples are for describing the present invention in detail, and the scope of the present invention is not limited to these Examples.

[ manufacturing example One] conjugation Preparation of polymer (S100)

[ manufacturing example 1-1] Formula 1 fluorene conjugation Preparation of polymers

In order to prepare a fluorene-based conjugated polymer of Formula 1, 0.558 g (1 mmol) of 9,9-dioctyl fluorene-2,7-diboronic acid bis(1,3-propanediol) ester and 1, 0.235.9 g (1 mmol) of 4-dibromobenzene and 0.059 g (0.05 mmol) of tetrakis(triphenylphosphine)palladium catalyst were mixed with 10 mL of dehumidified toluene and 7 mL of 2 MK ₂ CO ₃ It was dissolved in the mixed solution and refluxed at 90° C. for 48 hours. After the reaction, it was cooled to room temperature, poured into methanol to precipitate a solid, and the precipitate was filtered. The solid obtained by filtration was washed sequentially with methanol, acetone, and water in that order and dried. The obtained precipitate had a number average molecular weight of 10,000 or more, and a green conjugated polymer was prepared.

In the conjugated polymer (hereinafter, CP-1) prepared in Preparation Example 1-1, Z is CR ₁ R _{2 ,} wherein R ₁ , R ₂ is an alkyl group having 8 carbons, and Ar is benzene .

And the CP-1 prepared as described above was confirmed by using ^{1 H-NMR as follows.}

¹ H NMR (300 MHz, CDCl ₃ ) δ=7.6~7.8 ppm (10H, aromatic), 3.3 ppm (4H, alkyl group), 2.2 ppm (4H, alkyl group), 2.17 ppm (4H, alkyl group), 1.34-0.94 ppm (22H, alkyl group)

[ manufacturing example 1-2] of Formula 1 fluorene conjugation Preparation of polymers

To prepare a fluorene-based conjugated polymer of Formula 1, 0.558 g (1 mmol) of 9,9-dioctyl fluorene-2,7-diboronic acid bis(1,3-propanediol) ester and 5, 0.288 g (1 mmol) of 8-dibromoquinoxaline and 0.058 g (0.05 mmol) of a tetrakis (triphenylphosphine) palladium catalyst were dissolved in 5 ml of dehumidified toluene, followed by 2 MK ₂ CO ₃ 3 ml and water After adding 2 ml, 2 to 3 drops of Aliquat 336 were added and refluxed at 90° C. for 48 hours. After the reaction, it was cooled to room temperature, poured into methanol to precipitate a solid, and the precipitate was filtered. The precipitate obtained by filtration was washed sequentially with methanol, acetone, and water in that order and dried to prepare a green conjugated polymer having a molecular weight of 30,000 or more.

In the conjugated polymer (hereinafter, CP-2) prepared in Preparation Example 1-2, Z is CR ₁ R _{2 ,} wherein R ₁ , R ₂ is an alkyl group having 8 carbons, Ar is quinoxyline to be.

And the CP-2 prepared as described above was confirmed by using ^{1 H-NMR as follows.}

¹ H NMR (300 MHz, CDCl ₃ ) δ = 7.87-7.69 ppm (m, 10H, aromatic), 2.13 ppm (s, 4H, alkyl), 1.28-0.8 ppm (30H, alkyl).

[ manufacturing example 1-3] of Formula 1 fluorene conjugation Preparation of polymers

To prepare a fluorene-based conjugated polymer of Formula 1, 0.558 g (1 mmol) of 9,9-dioctyl fluorene-2,7-diboronic acid bis(1,3-propanediol) ester and 5, After dissolving 0.44 g (1 mmol) of 8-dibromo-2,3-diphenylquinoxaline and 0.058 g (0.05 mmol) of tetrakis(triphenylphosphine)palladium catalyst in 5 ml of dehumidified toluene, 2 MK _{After adding 3 ml of 2} CO ₃ and 2 ml of water, 2-3 drops of Aliquat 336 were added and refluxed at 90° C. for 48 hours. After the reaction, it was cooled to room temperature, poured into methanol to precipitate a solid, and the precipitate was filtered. The precipitate obtained by filtration was washed sequentially with methanol, acetone, and water in that order and dried to prepare a green conjugated polymer having a molecular weight of 30,000 or more.

In the conjugated polymer (hereinafter, CP-3) prepared in Preparation Example 1-3, Z is CR ₁ R _{2 ,} wherein R ₁ , R ₂ is an alkyl group having 8 carbons, Ar is 2, It is 3-diphenylquinoxaline.

And the CP-3 prepared as described above was confirmed by using ^{1 H-NMR as follows.}

¹ H NMR (300 MHz, CDCl ₃ ) δ = 7.78-7.64 ppm (m, 18H, aromatic), 2.13 ppm (s, 4H, alkyl) 1.27-0.81 ppm (m, 26H, alkyl).

[ manufacturing example 1-4] of Formula 1 fluorene conjugation Preparation of polymers

To prepare a fluorene-based conjugated polymer of Formula 1, 0.558 g (1 mmol) of 9,9-dioctyl fluorene-2,7-diboronic acid bis(1,3-propanediol) ester and 4, 0.294 g (1 mmol) of 7-dibromobenzo[c][1,2,5]thiadiazole and 0.059 g (0.05 mmol) of tetrakis(triphenylphosphine)palladium catalyst in 10 mL of dehumidified of toluene and 7 mL of _{a mixed solution of 2 MK 2} CO ₃ , and refluxed at 90° C. for 48 hours. After the reaction, it was cooled to room temperature, poured into methanol to precipitate, and the precipitate was filtered. . The precipitate obtained by filtration was washed sequentially with methanol, acetone, and water in that order and dried to prepare a yellow conjugated polymer having a molecular weight of 10,000 or more.

In the conjugated polymer (hereinafter, CP-4) prepared in Preparation Example 1-4, Z is CR ₁ R _{2 ,} wherein R ₁ , R ₂ is an alkyl group having 8 carbons, Ar is 2, 1,3-benzothiadiazole.

And the CP-4 prepared as described above was confirmed by using ^{1 H-NMR as follows.}

¹ H NMR (300 MHz, CDCl ₃ ) δ=8.06 ppm (8H, aromatic), 3.32 ppm (4H, alkyl), 2.17 ppm (4H, alkyl), 1.3-0.94 (m, 26H, alkyl).

[ manufacturing example 1-5] Formula 1 fluorene conjugation Preparation of polymers

To prepare a fluorene-based conjugated polymer of Formula 1, 0.65 g (1 mmol) of 2,7-dibromo-9,9-bis(6-bromohexyl)fluorene and 4,7-bis[5-( 0.552 g (1 mmol) of 4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)thiophen-2-yl]benzo-2,1,3-thiazole ) and tetrakis (triphenylphosphine) palladium catalyst 0.059 g (0.05 mmol) were _{dissolved in a mixed solution of 10 mL of toluene and 7 mL of 2 MK 2} CO ₃ dehumidified, and at 90° C. for 48 hours. refluxed. After the reaction, it was cooled to room temperature, poured into methanol to precipitate, and the precipitate was filtered. The precipitate obtained by filtration was washed sequentially with methanol, acetone, and water in that order and dried to prepare a red conjugated polymer having a molecular weight of 10,000 or more.

In the conjugated polymer (hereinafter, CP-5) prepared in Preparation Example 1-5, Z is CR ₁ R _{2 ,} wherein R ₁ , R ₂ is an alkyl group having 8 carbons, and Ar is biscis It is enylbenzothiazole.

And the CP-5 prepared as described above was confirmed by using ^{1 H-NMR as follows.}

¹ H NMR (300 MHz, CDCl ₃ ) δ=8.14-8.16 ppm (12H, aromatic), 3.32 (2H, alkyl group), 2.03 (2H, alkyl group), 1.56-0.8 ppm (m, 30H, alkyl group).

[ manufacturing example 1-6] Formula 1 fluorene conjugation Preparation of polymers

To prepare a fluorene-based conjugated polymer of Formula 1, 0.558 g (1 mmol) of 9,9-dioctyl fluorene-2,7-diboronic acid bis(1,3-propanediol) ester and 5, 7-dibromo- cyeno[3,4-b ]pyrazine 0.294 g (1 mmol) and tetrakis(triphenylphosphine)palladium catalyst 0.058 g (0.05 mmol) were dissolved in 5 ml of dehumidified toluene After 2 MK ₂ CO ₃ 3 ml and 2 ml of water were added, 2 to 3 drops of Aliquat 336 were added and refluxed at 90° C. for 48 hours. After the reaction, it was cooled to room temperature, poured into methanol to precipitate a solid, and the precipitate was filtered. The precipitate obtained by filtration was washed sequentially with methanol, acetone, and water in that order and dried to prepare a purple conjugated polymer having a molecular weight of 10,000 or more.

In the conjugated polymer (hereinafter, CP-6) prepared in Preparation Example 1-6, Z is CR ₁ R _{2 ,} wherein R ₁ , R ₂ is an alkyl group having 8 carbons, and Ar is between It is nopyrazine.

And the CP-6 prepared as described above was confirmed by using ^{1 H-NMR as follows.}

¹ H NMR (300 MHz, CDCl ₃ ) δ=8.14~8.16 ppm(m, 8H, aromatic), 3.30-3.32(m, 2H, alkyl group), 2.13-2.2(s, 6H, alkyl group), 1.56~0.8 ppm (m, 26H, an alkyl group).

[ manufacturing example 1-7] Formula 2 phenylene conjugation Preparation of polymers

1,4-bis(octyloxy)-2,5-dibromobenzene 492 mg (1 mmol) and 1,4-benzenediboronic acid bis(pinacol) to prepare a phenylene-based conjugated polymer of Formula 2 0.165 g (0.5 mmol) of the ester and 0.029 g (0.05 mmol) of tetrakis (triphenylphosphine) palladium catalyst were dissolved in 10 mL of dehumidified toluene and 7 mL of 2 MK ₂ CO ₃ mixed solution, It was refluxed at 90 °C for 48 hours. After the reaction, it was cooled to room temperature, poured into methanol to precipitate, and the precipitate was filtered. The precipitate obtained by filtration was washed sequentially with methanol, acetone, and water in this order and dried to prepare a conjugated polymer having a molecular weight of 10,000 or more.

In the conjugated polymer (hereinafter, CP-7) prepared in Preparation Example 1-7, R ₄ , R ₅ are alkoxy having 8 carbons, and Ar is benzene.

And the CP-7 prepared as described above was confirmed by using ^{1 H-NMR as follows.}

¹ H NMR (300 MHz, CDCl ₃ ) δ = 7.2 to 8.1 ppm (6H, aromatic), 3.92 ppm (4H, alkyl group), 3.4 to 3.2 ppm (16H, alkyl group), 1.78 to 1.8 ppm (8H, alkyl group), 1.47 ppm (6H, alkyl group)

[ manufacturing example 1-8] of Formula 2 phenylene conjugation Preparation of polymers

1,4-bis(octyloxy)-2,5-dibromobenzene 492 mg (1 mmol), 1,4-benzenediboronic acid bis(pinacol) to prepare a phenylene-based conjugated polymer of Formula 2 0.165 g (0.5 mmol) of ester, 0.144 g (0.5 mmol) of 5,8-dibromoquinoxaline and 0.058 g (0.05 mmol) of tetrakis(triphenylphosphine)palladium catalyst were mixed with 10 mL of dehumidified toluene It was dissolved in 7 mL of _{a mixed solution of 2 MK 2} CO ₃ , and refluxed at 90° C. for 48 hours. After the reaction, it was cooled to room temperature, poured into methanol to precipitate, and the precipitate was filtered. The precipitate obtained by filtration was washed sequentially with methanol, acetone, and water in this order and dried to prepare a conjugated polymer having a molecular weight of 10,000 or more.

In the conjugated polymer (hereinafter, CP-8) prepared in Preparation Example 1-8, R ₄ , R ₅ are alkoxy having 8 carbons, and Ar is quinoxaline.

And the CP-8 prepared as described above was confirmed as follows by using ^{1 H-NMR.}

¹ H NMR (300 MHz, CDCl ₃ ) δ=7.28 to 8.1 ppm (6H, aromatic), 3.92 ppm (4H, alkyl group), 3.8 to 3.4 ppm (16H, alkyl group), 1.76 to 1.82 ppm (8H, alkyl group), 1.23 ppm (6H, alkyl group)

[ manufacturing example 1-9] Formula 2 phenylene conjugation Preparation of polymers

1,4-bis(octyloxy)-2,5-dibromobenzene 492 mg (1 mmol), 1,4-benzenediboronic acid bis(pinacol) ester to prepare a phenylene-based conjugated polymer of Formula 2 Dehumidify 0.165 g (0.5 mmol), 0.22 g (0.5 mmol) of 5,8-dibromo-2,3-diphenylquinoxaline and 0.058 g (0.05 mmol) of tetrakis(triphenylphosphine)palladium catalyst It was dissolved in a mixed solution of 10 mL of toluene and 7 mL of 2 MK ₂ CO ₃ , and refluxed at 90° C. for 48 hours. After the reaction, it was cooled to room temperature, poured into methanol to precipitate, and the precipitate was filtered. The precipitate obtained by filtration was washed sequentially with methanol, acetone, and water in this order and dried to prepare a conjugated polymer having a molecular weight of 10,000 or more.

In the conjugated polymer (hereinafter, CP-9) prepared in Preparation Example 1-9, R ₄ , R ₅ are alkoxy having 8 carbons, and Ar is 2,3-diphenylquinoxaline.

And the CP-9 prepared as described above was confirmed by using ^{1 H-NMR as follows.}

¹ H NMR (300 MHz, CDCl ₃ ) δ=7.28 to 8.1 ppm (10H, aromatic), 3.92 ppm (4H, alkyl group), 3.7 to 3.5 ppm (16H, alkyl group), 1.78 to 1.83 ppm (8H, alkyl group), 1.47 ppm (6H, alkyl group)

[ manufacturing example 1-10] of Formula 2 phenylene conjugation Preparation of polymers

1,4-bis(octyloxy)-2,5-dibromobenzene 492 mg (1 mmol) and 1,4-benzenediboronic acid bis(pinacol) to prepare a phenylene-based conjugated polymer of Formula 2 0.330 g (0.5 mmol) of ester, 0.294 g (0.5 mmol) of 4,7-dibromobenzo[c][1,2,5]thiadiazole and 0.058 g of tetrakis(triphenylphosphine)palladium catalyst ( 0.05 mmol) was dissolved in a mixed solution of 10 mL of dehumidified toluene and 7 mL of 2 MK ₂ CO ₃ , and refluxed at 90° C. for 48 hours. After the reaction, it was cooled to room temperature, poured into methanol to precipitate, and the precipitate was filtered. The precipitate obtained by filtration was washed sequentially with methanol, acetone, and water in this order and dried to prepare a conjugated polymer having a molecular weight of 10,000 or more.

In the conjugated polymer (hereinafter, CP-10) prepared in Preparation Example 1-10, R ₄ , R ₅ are alkoxy having 8 carbons, and Ar is 2,1,3-benzothiazole .

And the CP-10 prepared as described above was confirmed by using ^{1 H-NMR as follows.}

¹ H NMR (300 MHz, CDCl ₃ ) δ=7.27 to 8.3 ppm (5H, aromatic), 3.94 ppm (4H, alkyl group), 3.23 to 3.42 ppm (16H, alkyl group), 1.76 to 1.82 ppm (8H, alkyl group), 1.38 ppm (6H, alkyl group)

[ manufacturing example 1-11] Formula 2 phenylene conjugation Preparation of polymers

1,4-bis(octyloxy)-2,5-dibromobenzene 492 mg (1 mmol) and 1,4-benzenediboronic acid bis(pinacol) to prepare a phenylene-based conjugated polymer of Formula 2 0.165 g (0.5 mmol) of ester, 0.229 g (0.5 mmol) of 4,7-bis(5-bromothiophen-2-yl)benzo[c][1,2,5]thiadiazole and tetrakis ( Triphenylphosphine) palladium catalyst 0.058 g (0.05 mmol) was dissolved in a mixed solution of 10 mL of dehumidified toluene and 7 mL of 2 MK ₂ CO ₃ , and refluxed at 90° C. for 48 hours. After the reaction, it was cooled to room temperature, poured into methanol to precipitate, and the precipitate was filtered. The precipitate obtained by filtration was washed sequentially with methanol, acetone, and water in this order and dried to prepare a conjugated polymer having a molecular weight of 10,000 or more.

In the conjugated polymer (hereinafter, CP-11) prepared in Preparation Example 1-11, R ₄ and R ₅ are alkoxy having 8 carbons, and Ar is bisthienylbenzothiazole.

And the CP-11 prepared as described above was confirmed by using ^{1 H-NMR as follows.}

¹ H NMR (300 MHz, CDCl ₃ ) δ=7.32-8.17 ppm (7H, aromatic), 3.92 ppm (4H, alkyl group), 3.2-3.48 ppm (16H, alkyl group), 1.78-1.8 ppm (8H, alkyl group), 1.47 ppm (6H, alkyl group)

[ manufacturing example 1-12] of Formula 2 phenylene conjugation Preparation of polymers

1,4-bis(octyloxy)-2,5-dibromobenzene 492 mg (1 mmol), 1,4-benzenediboronic acid bis(pinacol) to prepare a phenylene-based conjugated polymer of Formula 2 0.330 g (1 mmol) of ester, 0.294 g (1 mmol) of 5,7-dibromo-thieno [3,4-b ] pyrazine and 0.058 g (0.05 mmol) of tetrakis (triphenylphosphine) palladium catalyst It was dissolved in a mixed solution of 10 mL of dehumidified toluene and 7 mL of 2 MK ₂ CO ₃ , and refluxed at 90° C. for 48 hours. After the reaction, it was cooled to room temperature, poured into methanol to precipitate, and the precipitate was filtered. The precipitate obtained by filtration was washed sequentially with methanol, acetone, and water in this order and dried to prepare a conjugated polymer having a molecular weight of 10,000 or more.

In the conjugated polymer (hereinafter, CP-12) prepared in Preparation Example 1-12, R ₄ , R ₅ are alkoxy having 8 carbons, and Ar is thienopyrazine.

And the CP-12 prepared as described above was confirmed by using ^{1 H-NMR as follows.}

¹ H NMR (300 MHz, CDCl ₃ ) δ = 7.76 ~ 8.5 ppm (5H, aromatic), 3.81 ppm (4H, alkyl group), 3.38 ~ 3.6 ppm (16H, alkyl group), 1.76 ~ 1.82 ppm (8H, alkyl group), 1.44 ppm (6H, alkyl group)

[ manufacturing example 2] conjugation Preparation of polymer nanoparticles (S200)

Each of the conjugated polymers CP-1 to CP-12 of Preparation Example 1 was dissolved in a THF solvent at a concentration of 2 mg/mL to prepare a conjugated polymer solution, and then 1 mL of the conjugated polymer solution was added to 12 mL of tertiary distilled water under an ultrasonic environment. put in quickly After mixing well the conjugated polymer solution and tertiary distilled water under an ultrasonic environment for 30 minutes, nitrogen gas is injected for 15 minutes to evaporate THF of the nanoparticle solution. After filtering the nanoparticle solution using a cellulose filter having a size of 0.45 μm, finally, conjugated polymer nanoparticles (hereinafter CPN) were prepared. That is, conjugated polymer nanoparticles CPN-1 to CPN-12 were prepared using conjugated polymer (hereinafter CP) CP-1 to CP-12, respectively.

[ manufacturing example 3] Preparation of titanium dioxide nanofiber spinning solution (S300)

As a fiber structure polymer, 2.4 g of PVP and 1 g of surfactant P123 were dissolved in 25.4 mL of ethanol by rolling for 6 hours. After slowly adding 2.4 mL of TTIP, a titanium dioxide precursor, to the PVP polymer solution, ^{it was stirred at 80 o} C until it became transparent. After confirming that the solution was uniformly mixed, 2.4 mL of acetic acid, an acid catalyst, was quickly injected, the reactor lid was closed ^{, and the mixture was stirred under reflux at 80 o} C for 1 hour, and the reactor was cooled to room temperature to prepare a spinning solution.

[ manufacturing example 4] Titanium dioxide through electrospinning of nanofiber web Manufacturing (S400)

The spinning solution prepared in Preparation Example 3 is placed in a 12 mL syringe and installed in a syringe pump. In this case, a cut-off stainless steel spinning needle with a flat needle tip was used for the syringe, and the diameter of the needle was 18 gauge. Next, each electrode was connected to the collecting plate and the spinning needle, and the applied voltage was 13 kV, the distance between the spinning needle and the collecting plate was 15 cm, and the collecting plate moved left and right to reciprocate to collect nanofibers, and a syringe The speed of the pump was 0.6 mL/h and spinning was performed for 6 hours.

[ manufacturing example 5] mesoporous and titania the crystal lattice titanium dioxide with of nanofiber web Manufacturing (S500)

After recovering the titanium dioxide nanofibers collected in Preparation Example 4, the residual solvent and moisture are removed, and the temperature of ^{120 o C to induce an additional sol-gel reaction of the unreacted titanium dioxide precursor.} Heat treatment (baking) was performed for 6 hours. Next, the titanium dioxide nanofiber web not only gives mesoporosity to the titanium dioxide nanofiber by removing the structural polymer and surfactant present in the heat-treated nanofiber, but also gives the intrinsic crystal lattice (anatase or rutile) of titanium dioxide. was put in a crucible, put in a heating furnace, and ^{calcined at 550 o} C for 6 hours to prepare a mesoporous titanium dioxide nanofiber-web (Mesoporous Titaniumdioxide Nanofiber-web, hereinafter MTF).

[ manufacturing example 6] amine group functionalized titanium dioxide of nanofiber web Manufacturing (S600)

In order to introduce an amine group to the mesoporous titanium dioxide nanofiber prepared in Preparation Example 5, 20 mg of the mesoporous titanium dioxide nanofiber was placed in 30 mL of ethanol, 400 μL of APTES was added, and then slowly rolled for 6 hours, This was taken out, washed with ethanol, and ^{heat-treated at a temperature of 120 °} C for 2 hours to prepare an amine functionalized titanium dioxide nanofiber web (Amine functionalized Mesoporous TiO ₂ Nanofiber-web, hereinafter MTF-NH ₂ ).

[ manufacturing example 7] conjugation Preparation of organic-inorganic composite in which polymer nanoparticles are composited with titanium dioxide nanofibers (S700)

_{20 mg each of the MTF-NH -2} prepared in Preparation Example 6 was immersed in 10 mL of each solution of the conjugated polymer nanoparticles CPN-1 to CPN-12 prepared in Preparation Example 2, reacted by rolling slowly for 6 hours, and retrieved 3 It was washed with distilled water and dried to prepare CPN-1-MTF to CPN-12-MTF.

In the present invention, the organic-inorganic composite photocatalyst prepared as described above can be applied to photocatalytic reactions such as decomposition of organic dyes, oxidation of organic compounds, or reduction of organic compounds.

The photocatalytic reaction may include: preparing an organic dye solution or an oxidation reaction solution of an organic compound or a reduction reaction solution of an organic compound; immersing an organic-inorganic composite photocatalyst in which conjugated polymer nanoparticles are complexed to titanium dioxide nanofibers in any one of the solutions; and irradiating light to any one of the solutions as a light source; etc. will be carried out.

The organic dye is preferably any one of rhodamine B, methylene blue, and methyl orange, and the organic compound used in the oxidation reaction is a benzylamine derivative, benzaldehyde, and furoic acid. acid) derivatives, and the organic compound used in the reduction reaction is preferably any one of 4-nitrophenol derivatives.

The photocatalytic reaction method using the organic-inorganic composite photocatalyst of the present invention is as follows. The prepared organic-inorganic composite photocatalyst is immersed in a 20 ml vial containing an organic dye aqueous solution or an oxidation/reduction reaction solution, and then irradiated with an LED lamp while stirring. Light irradiation is possible with any light source having a wavelength of 300 to 700 nm, such as LED lamps, xenon lamps, and solar simulators. Specifically, to irradiate visible light only, irradiate with LED lamps, or install a UV cut filter on xenon lamps and solar simulators. It is preferable to use During the photocatalytic reaction, the distance between the solar simulator and the vial is 5 to 10 cm, the intensity of the light source is in ^{the range of 15 to 25 W/m 2} , and the reaction solution is recovered by time to obtain UV/Vis absorption spectrum or nuclear magnetic resonance spectroscopy (nuclear magnetic resonance). Resonance (NMR) spectrum confirms the product of decomposition of dye or oxidation/reduction reaction. It is also possible to confirm the reaction process by thin layer chromatography (TLC).

Hereinafter, the photocatalytic reaction of the organic-inorganic composite photocatalyst of the present invention will be described in detail through examples using the nanofiber-based organic/inorganic composite photocatalyst of the present invention, that is, CPN-1-MTF to CPN-12-MT.

[ Example 1] Dye decomposition reaction

Rhodamine B, methylene blue, and methyl orange (refer to Chemical Formulas 3 to 5 below), which are commercially available dyes, are dissolved in water to prepare a reaction solution at a concentration of 20 ppm. 10 mL of the dye reaction solution prepared at a concentration of 20 ppm is put into a 20 mL vial, and organic-inorganic composite photocatalysts CPN-1-MTF to CPN-12 based on the nanofibers of the present invention prepared as described above -MTF was put into the reaction solution of the dye by 10 mg, respectively, and the dye decomposition reaction of Examples 1-1 to 1-12 was performed.

[Formula 3]

Rhodamine B

[Formula 4]

Methylene blue

[Formula 5]

methyl orange

In the dye decomposition reaction of Examples 1-1 to 1-12, visible light (22 W/m ² , λ>450 nm) was irradiated for 2 hours, and the distance between the light source and the dye solution was 5 cm.

After light irradiation, the absorbance of the reaction solution was measured using a uv-vis absorption spectrometer, and the absorbance was converted into concentration through a calibration curve to calculate the dye decomposition rate (%) based on [Equation 1] below. The maximum absorption wavelength of each dye is 544 nm for rhodamine B, 665 nm for methylene blue, and 500 nm for methyl orange.

[Equation 1]

[Comparative Example 1]

In Comparative Examples 1-1 to 1-12, 10 mg of the conjugated polymer nanoparticles CPN-1 to CPN-12 nanoparticles prepared in Preparation Example 2 were directly dispersed in a dye reaction solution to measure the dye decomposition rate (%). .

[Comparative Example 2]

In Comparative Example 2, 10 mg of the titanium dioxide nanofiber web prepared in Preparation Example 5 was directly immersed in the dye reaction solution to measure the dye decomposition rate (%).

At this time, when measuring the dye degradation rate (%) in Comparative Examples 1 to 2, other conditions are the same as in Example 1, and the measurement results of the dye degradation rate (%) performed in Example 1 and Comparative Examples 1 and 2 are shown in Table 1 shown in

Example Dye degradation rate (%) Rhodamine B methylene blue methyl orange Example 1-1 99.8 99.5 76 Example 1-2 99.3 99.3 74.5 Examples 1-3 99.1 99 73 Examples 1-4 99.7 99.2 78.2 Examples 1-5 99 99.1 76 Examples 1-6 99.4 99.8 74 Examples 1-7 99.2 99 77.6 Examples 1-8 99 99.4 77.3 Examples 1-9 99.6 99 72.4 Examples 1-10 99.5 99.1 71.9 Examples 1-11 99 99.6 70 Examples 1-12 99.7 99.4 72.6 Comparative Example 1-1 50.2 48.3 22.1 Comparative Example 1-2 51 44 25 Comparative Example 1-3 53.6 46.2 30.1 Comparative Example 1-4 52.4 38 31 Comparative Example 1-5 54 39.7 28 Comparative Example 1-6 51.5 42 24.6 Comparative Example 1-7 52 50.1 25 Comparative Examples 1-8 53.4 49 26.6 Comparative Example 1-9 56 47.3 20.2 Comparative Example 1-10 57.2 42.5 22 Comparative Example 1-11 54 48.3 23.6 Comparative Example 1-12 56.6 51 24 Comparative Example 2 17.2 12.3 8.9

As shown in Table 1, dye degradation rates of Examples 1-1 to 1-12 using CPN-1-MTF to CPN-12-MTF, which are organic-inorganic composite photocatalysts based on nanofibers according to the present invention ( %), more than 99% of rhodamine B and methylene blue were decomposed, and more than 70% of methyl orange was decomposed.

In contrast, the conjugated polymer nanoparticles CPN-1 to CPN-12 of Comparative Examples 1-1 to 1-12 were directly mixed in the reaction solution of the dye without complexing with the nanofiber, and then the dye decomposition rate (%) was As a result of the measurement, in the case of rhodamine B and methylene blue, it can be confirmed that the dye decomposition rate (%) is 50% or less. In Comparative Examples 1-1 to 1-12, since there is no titanium dioxide nanofiber, the separated electron-holes do not move and are recombined and emit fluorescence. In addition, in the case of Comparative Example 2, titanium dioxide showed a low dye decomposition rate because it did not absorb visible light.

[ Example 2] Oxidative coupling reaction of benzylamine derivatives

After dissolving 1 mmol of the benzylamine derivative as shown below in 5 mL of acetonitrile, a reaction solution was prepared. CPN-1-MTF to CPN-12-MTF, which are organic-inorganic composite photocatalysts based on the nanofibers of the present invention prepared as described above, were added to the reaction solution by 20 mg, respectively, in Examples 2-1 to 2- The oxidative coupling reaction of 12 was carried out.

At this time, when the benzylamine derivative as a reactant is converted into a product, a dibenzylimine derivative, a chemical reaction formula can be expressed by the following Formula 2.

.

[Equation 2]

The reaction solution of Examples 2-1 to 2-12 ^{was irradiated with visible light (22 W/m 2} , λ>450 nm) for 4 hours to carry out a conversion reaction, wherein the distance between the light source and the reaction solution was 5 cm.

After light irradiation, the solvent of the reaction solution was evaporated and removed, and then analyzed by ^{nuclear magnetic resonance spectrum (1} H NMR, 300 MHz, CDCl _{3 ).}

In nuclear magnetic resonance spectral analysis, the conversion rate was determined by the area ratio of the hydrogen spectrum of the benzyl-position carbon of the benzylamine derivative (reactant) at 3.48 ppm and the hydrogen spectrum of the benzyl-position carbon of the dibenzyl imine derivative (product) at 4.8 ppm. Calculated. The conversion rate (%) can be calculated from Equation 3 below.

[Equation 3]

In [Equation 3], Xb is the area of the hydrogen spectrum of the benzyl site carbon of the dibenzylamine derivative as a product, and Xd represents the area of the hydrogen spectrum of the benzyl site carbon of the benzylamine derivative as the reactant.

[Comparative Example 3]

In Comparative Examples 3-1 to 3-12, the conversion rate (%) was measured by directly mixing 20 mg each of the conjugated polymer nanoparticles CPN-1 to CPN-12 prepared in Preparation Example 2 into the reaction solution of the benzylamine derivative. . .

[Comparative Example 4]

In Comparative Example 4, 20 mg of the titanium dioxide nanofiber web prepared in Preparation Example 5 was directly immersed in a reaction solution of a benzylamine derivative to measure the conversion rate (%).

At this time, in Comparative Examples 3-1 to 3-12 and Comparative Example 4, when the conversion rate (%) was measured, other conditions were the same as in Example 2, and the conversion rates performed in Example 2 and Comparative Examples 3 and 4 ( %) are shown in Tables 2 and 3.

Example Conversion rate (%)

Example 2-1 95.4 98 94.6 96.3 Example 2-2 93 95 94 97 Example 2-3 91.2 94.3 96 98.2 Example 2-4 94.2 95.3 95.3 93.4 Example 2-5 95 96.1 96 94.2 Example 2-6 93.4 94 94 91 Example 2-7 94 93 96.3 96.5 Examples 2-8 96.4 98.3 92 94 Examples 2-9 92.3 96.3 90.3 95 Example 2-10 90 92 91.8 96.3 Example 2-11 91 94.2 92 94.2 Example 2-12 94 95 93.3 92 Comparative Example 3-1 0.5 0.6 1.2 1.6 Comparative Example 3-2 0.2 1.2 0.5 0.8 Comparative Example 3-3 1.2 1.3 0.7 0.6 Comparative Example 3-4 1.0 0.8 1.3 1.5 Comparative Example 3-5 1.8 0.9 One 1.3 Comparative Example 3-6 0.6 1.2 0.9 One Comparative Example 3-7 1.3 1.3 0.7 0.9 Comparative Example 3-8 2 0.8 1.3 0.7 Comparative Example 3-9 1.5 One 1.5 1.3 Comparative Example 3-10 1.2 2.1 One 1.3 Comparative Example 3-11 0.2 1.9 0.9 1.5 Comparative Example 3-12 1.3 1.7 1.3 0.6 Comparative Example 4 One 1.3 1.4 1.6

Example Conversion rate (%)

Example 2-1 82.3 37.1 79.2 Example 2-2 83 40.2 78.6 Example 2-3 84 41.3 81.3 Example 2-4 88 38 80.2 Example 2-5 85.9 39 83 Example 2-6 84.2 37.3 86.5 Example 2-7 79.2 39 79.3 Examples 2-8 77.8 42.3 76.0 Examples 2-9 80.2 41.2 77.2 Example 2-10 81 40.8 75.3 Example 2-11 84.3 45.2 76 Example 2-12 88 42 72 Comparative Example 3-1 0.2 0.5 0.4 Comparative Example 3-2 0.3 0.4 0.3 Comparative Example 3-3 0.2 0.4 0.6 Comparative Example 3-4 0.1 0.08 0.3 Comparative Example 3-5 0.2 0.6 0.4 Comparative Example 3-6 0.6 0.2 0.4 Comparative Example 3-7 0.5 0.1 0.5 Comparative Example 3-8 0.6 0.1 0.1 Comparative Example 3-9 0.2 0.07 0.09 Comparative Example 3-10 0.1 0.3 0.08 Comparative Example 3-11 0.2 0.5 0.6 Comparative Example 3-12 0.6 0.5 0.4 Comparative Example 4 0.4 0.6 0.6

As shown in Tables 2 and 3, conversion rates (%) of Examples 2-1 to 2-12 using the organic-inorganic composite photocatalyst CPN-1-MTF to CPN-12-MTF based on the nanofibers of the present invention ), it shows that the oxidative coupling reaction of various benzylamine derivatives is possible through the conversion (%) of 37.1 to 98.3%.

In contrast, 20 mg of the conjugated polymer nanoparticles CPN-1 to CPN-12 of Comparative Examples 3-1 to 3-12 and Comparative Example 4 were directly mixed with the reaction solution of benzylamine without using titanium dioxide nanofibers. Or, as a result of measuring the conversion rate (%) after immersing the titanium dioxide nanofiber into which the conjugated polymer nanoparticles are not introduced, it can be confirmed that almost no conversion from the benzylamine derivative to the dibenzylimine derivative has occurred.

)을 형성하면서 강력한 산화제로 작용하여 벤질아민을 산화시켜 중간체를 형성하고, 주변에 존재하는 또다른 벤질아민과 커플링반응하여 다이벤질이민 유도체를 형성하는 메커니즘이다. 따라서, 가시광을 흡수하는 공액화 고분자 나노입자 또는 이산화티타늄 나노섬유 한 가지만 존재하게 되면 활성산소종을 원활하게 형성시킬 수 없기 때문에 현저히 낮은 전환율을 나타낸다.As described in the dye decomposition, the oxidative coupling reaction of benzylamine is when visible light is irradiated to the nanofiber-based organic-inorganic composite photocatalyst, the electrons of the conjugated polymer nanoparticles absorbing the visible light are excited, and the excited electrons are the titanium dioxide nano As it moves to the fibers, dissolved oxygen dissolved in air or solvent is converted into superhydroxy radicals (

), acts as a strong oxidizing agent to oxidize benzylamine to form an intermediate, and is a mechanism for forming a dibenzylimine derivative by coupling with another benzylamine present in the vicinity. Therefore, when only one of the conjugated polymer nanoparticles or titanium dioxide nanofibers absorbing visible light is present, the active oxygen species cannot be smoothly formed, and thus the conversion rate is significantly low.

[ Example 3] puroic acid oxidation reaction

After dissolving 1 mmol of puroic acid as follows in 5 mL of water, a reaction solution was prepared. CPN-1-MTF to CPN-12-MTF, which are organic-inorganic composite photocatalysts based on the nanofibers of the present invention prepared as described above, were put into the reaction solution by 20 mg, respectively, in Examples 3-1 to 3- 12 was carried out.

In this case, the chemical reaction formula at the time of conversion from the furo acid as a reactant to a furanone as a product can be expressed as in Equation 4 below.

[Equation 4]

The reaction solution of Examples 3-1 to 3-12 ^{was irradiated with visible light (22 W/m 2} , λ>450 nm) for 4 hours to carry out a conversion reaction, wherein the distance between the light source and the reaction solution was 5 cm.

After light irradiation, the water in the reaction solution was evaporated to remove it, and then analyzed by ^{nuclear magnetic resonance spectrum (1} H NMR, 300 MHz, D _{2 O).}

In nuclear magnetic resonance spectral analysis, the conversion rate was calculated from the area ratio of the hydrogen spectrum of furo acid (reactant) at 7.67, 7.25, and 65.7 ppm and the spectrum of furanone (product) hydrogen at 7.42 and 6.25 ppm. The conversion rate (%) can be calculated from Equation 5 below.

[Equation 5]

[Comparative Example 5]

In Comparative Examples 5-1 to 5-12, the conversion rate (%) was measured by directly mixing 20 mg of each of the conjugated polymer nanoparticles CPN-1 to CPN-12 prepared in Preparation Example 2 in a reaction solution of puroic acid.

[Comparative Example 6]

In Comparative Example 6, 20 mg of the titanium dioxide nanofiber web prepared in Preparation Example 5 was directly immersed in a reaction solution of furoic acid to measure the conversion rate (%).

At this time, the other conditions when measuring the conversion rate (%) in Comparative Examples 5-1 to 5-12 and Comparative Example 6 were the same as in Example 3, and the conversion rates performed in Example 3 and Comparative Examples 5 and 6 ( %) is shown in Table 4.

Example Conversion rate (%) comparative example Conversion rate (%) Example 3-1 96.2 Comparative Example 5-1 0.3 Example 3-2 94 Comparative Example 5-2 0.6 Example 3-3 93 Comparative Example 5-3 1.2 Example 3-4 92 Comparative Example 5-4 1.6 Example 3-5 91.9 Comparative Example 5-5 1.4 Example 3-6 91 Comparative Example 5-6 0.8 Example 3-7 97 Comparative Example 5-7 One Example 3-8 94.6 Comparative Example 5-8 1.6 Example 3-9 95 Comparative Example 5-9 0.9 Example 3-10 92.3 Comparative Example 5-10 2.1 Example 3-11 90 Comparative Example 5-11 0.5 Example 3-12 88 Comparative Example 5-12 0.6 Comparative Example 6 1.3

As shown in Table 4, as a result of measuring the conversion rates (%) of Examples 3-1 to 3-12 using the photocatalyst complexes CPN-1-MTF to CPN-12-MTF of the present invention, all were 88% or more conversion was measured.

In contrast, the conjugated polymer nanoparticles CPN-1 to CPN-12 of Comparative Examples 5-1 to 5-12 and Comparative Example 6 were directly mixed with the reaction solution of puroic acid without using titanium dioxide nanofibers, or , As a result of measuring the conversion rate (%) after immersing 20 mg of titanium dioxide nanofibers in which the conjugated polymer nanoparticles are not introduced, it can be confirmed that almost no conversion of puroic acid to difuranone occurs.

In addition, when only one conjugated polymer nanoparticle or titanium dioxide nanofiber is present, active oxygen species cannot be smoothly formed, so it cannot function as an oxidizing agent, so in Comparative Example 5, furo acid shows a low conversion rate to difuranone it can be seen that

[ Example 4] 4- of nitrophenol reduction reaction

After preparing a solution of 1,100 ppm of 4-nitrophenol as shown below, 11 mL each was put into a 20 mL vial, and sodium borohydride was added to prepare a reaction solution. Then, CPN-1-MTF to CPN-12-MTF, which are organic-inorganic composite photocatalysts based on the nanofibers of the present invention, were added to the reaction solution to prepare the reaction solutions of Examples 4-1 to 4-12. .

In this case, the overall chemical reaction formula when the reactant, 4-nitrophenol, is converted to the product, 4-aminophenol, can be expressed as in Equation 6 below.

[Equation 6]

The reaction solution of Examples 4-1 to 4-12 ^{was irradiated with visible light (22 W/m 2} , λ>450 nm) for 4 hours to carry out a conversion reaction, wherein the distance between the light source and the reaction solution was 5 cm.

After light irradiation, the conversion rate (%) of the reaction solution was measured using a uv-vis absorption spectrometer. That is, when 4-nitrophenol (reactant) is converted to 4-aminophenol (product), the absorbance decreases at 400 nm, which is the maximum absorption wavelength of 4-nitrophenol. The conversion (%) to 4-aminophenol can be calculated.

[Equation 7]

[Comparative Example 7]

In Comparative Examples 7-1 to 7-12, the conversion rate (%) was measured by mixing 20 mg each of the conjugated polymer nanoparticles CPN-1 to CPN-12 prepared in Preparation Example 2 in the 4-nitrophenol reaction solution.

[Comparative Example 8]

In Comparative Example 8, 20 mg of the titanium dioxide nanofiber web prepared in Preparation Example 5 was directly immersed in a reaction solution of furoic acid to measure the conversion (%).

At this time, other conditions when measuring the conversion rate (%) in Comparative Examples 7-1 to 7-12 and 8 are the same as in Example 4, and the conversion rate (%) performed in Example 4 and Comparative Examples 7 and 8 The measurement results are shown in Table 5.

Example Conversion rate (%) comparative example Conversion rate (%) Example 4-1 87.3 Comparative Example 7-1 0.3 Example 4-2 91 Comparative Example 7-2 0.8 Example 4-3 98.8 Comparative Example 7-3 0.07 Example 4-4 94.5 Comparative Example 7-4 0.1 Example 4-5 81.5 Comparative Example 7-5 0.6 Example 4-6 82.4 Comparative Example 7-6 0.08 Example 4-7 85 Comparative Example 7-7 0.2 Examples 4-8 82.6 Comparative Examples 7-8 0.5 Examples 4-9 81 Comparative Example 7-9 0.7 Example 4-10 85.4 Comparative Example 7-10 0.06 Examples 4-11 89.8 Comparative Example 7-11 0.8 Example 4-12 84 Comparative Example 7-12 0.7 Comparative Example 8 1.2

As described in Table 5, the result of measuring the conversion rate (%) of Examples 4-1 to 4-12 using the nanofiber-based organic-inorganic composite photocatalyst CPN-1-MTF to CPN-12-MTF of the present invention , both were measured to have more than 81% conversion.

In contrast, 20 mg of the conjugated polymer nanoparticles CPN-1 to CPN-12 of Comparative Examples 7-1 to 7-12 were directly mixed in the reaction solution, and then the conversion (%) was measured. It can be seen that the conversion of phenol to 4-aminophenol hardly occurred. In addition, as a result of measuring the conversion rate (%) after immersing 20 mg of the titanium dioxide nanofiber of Comparative Example 8 directly in the reaction solution, it can also be confirmed that the conversion from 4-nitrophenol to 4-aminophenol hardly occurred.

In the reduction reaction of 4-nitrophenol, an oxidation-reduction reaction is accompanied in the presence of a reducing agent. At this time, if active oxygen species that can serve as a necessary oxidizing agent are not efficiently generated, the reduction conversion rate is lowered. Therefore, when only one conjugated polymer nanoparticle or titanium dioxide nanofiber is present, it cannot function as an oxidizing agent because active oxygen species cannot be smoothly formed, so in Comparative Examples 7 and 8, 4-nitrophenol was 4-amino It can be seen that the reduction conversion to phenol is low.

[ Example 5] Absorption member type photocatalytic reuse experiment

[Example 5-1] Reuse experiment in dye decomposition reaction

A reuse experiment was performed during dye decomposition using CPN-3-MTF (photocatalyst using conjugated polymer nanoparticles of Preparation Example 1-3), which is an organic-inorganic composite photocatalyst based on the nanofibers of the present invention. Rhodamine B, methylene blue and methyl orange used in the present invention were each dissolved in water to prepare reaction solutions of Examples 5-1-1 to 5-1-3 at a concentration of 20 ppm. After that, 10 ml of the reaction solution and 10 mg of CPN-3-MTF, an organic/inorganic composite photocatalyst based on nanofibers, were put together in a 20 ml vial and visible light for 2 hours (22 W/m ² , λ>450 nm) A dye decomposition reaction was carried out by irradiating the light, and the distance between the light source and the dye solution was 5 cm.

After irradiating with light for 2 hours, the CPN-3-MTF was taken out, washed with water, dried, immersed in the new reaction solution, and irradiated with light under the same conditions for 2 hours to carry out a dye decomposition reaction. The dye decomposition reaction was performed a total of 4 times, and the absorption spectrum of the reaction solution was measured after the reaction.

The dye decomposition rate (%) was measured based on Equation 1 using the absorption spectrum of the reaction solution measured as described above. At this time, the change of the absorption spectrum of the reaction solution according to the number of reuse of CPN-3-MTF, which is an organic-inorganic composite photocatalyst based on nanofibers, is shown in (a) to (c) of FIG. 2 . That is, (a) to (c) of FIG. 2 shows CPN-3-MTF which is an organic-inorganic composite photocatalyst based on nanofibers using the reaction solutions of Examples 5-1-1 to 5-1-3. It shows the change in absorbance at the maximum absorption wavelength of the reaction solution according to the number of times of reuse.

Looking at (a) of Figure 2, in the case of the reaction solution of rhodamine B, in the case of CPN-3-MTF, which is an organic-inorganic composite photocatalyst based on the nanofibers of the present invention, even when reused 4 times (%) This was found to be 95.3%. In addition, in the case of methylene blue and methyl orange, the dye decomposition rates (%) were measured to be 93.1% and 70.2%, respectively, even when CPN-3-MTF, which is the absorption-free photocatalyst, was reused 4 times. That is, it can be seen that the organic-inorganic composite photocatalyst based on the nanofibers of the present invention can be reused by still maintaining high dye decomposition efficiency even after being reused 4 times.

[Example 5-2] Reuse experiment in organic chemical reaction

An organic chemical reaction reuse experiment was conducted using CPN-3-MTF, an organic-inorganic composite photocatalyst based on the nanofibers of the present invention. That is, benzylamine, furonic acid and 4-nitrophenol were each prepared at a concentration of 1 mmol to prepare reaction solutions of Examples 5-2-1 to 5-2-3. When preparing the reaction solution, acetonitrile was used as a solvent for the benzylamine, and water was used as a solvent for the furonic acid and 4-nitrophenol.

5 ml of the reaction solutions of Examples 5-2-1 to 5-2-3 prepared as described above were put into a 20 ml vial, and CPN-3-MTF, which is an organic-inorganic composite photocatalyst based on nanofibers, respectively was immersed in 20 mg. Thereafter, the reaction was carried out by irradiating visible light (22 W/m ² , λ>450 nm) for 4 hours, and the distance between the light source and the dye solution was 5 cm.

After 4 hours of light irradiation, CPN-3-MTF, which is an organic-inorganic composite photocatalyst based on nanofibers, was taken out, washed with each solvent, dried, immersed again in the new reaction solution, and irradiated with light for 4 hours again. The reaction was carried out a total of 4 times, and after the reaction was removed by evaporation of the solvent of the reaction solution, Examples 5-2-1 and 5-2-2 were analyzed by nuclear magnetic resonance spectroscopy, and in Example 5-2-3, The conversion rate was calculated by measuring the absorption spectrum.

The conversion rates (%) of the benzylamine, furonic acid and 4-nitrophenol to each product were calculated through Equations 3, 5, and 7 above, and each conversion reaction is shown in Equations 8 to 11 below.

That is, the change in the conversion rate (%) of the reaction solution according to the number of reuse of CPN-3-MTF, which is an organic-inorganic composite photocatalyst based on nanofibers, is shown in (a) to (d) of FIG. 3 and Table 9. That is, (a) to (c) of FIG. 3 shows CPN-3-MTF which is an organic-inorganic composite photocatalyst based on nanofibers using the reaction solutions of Examples 5-2-1 to 5-2-4. It shows the conversion rate (%) in the number of reuses.

3 (a) to (c) and Table 6, even in the case of benzylamine, furonic acid, and 4-nitrophenol, the conversion rates (%) of dibenzylimine, furanone, and 4-aminophenol were the above. Even when CPN-3-MTF, an organic-inorganic composite photocatalyst based on nanofibers, was reused 4 times, 85.7%, 83.3%, and 82% were measured, respectively. That is, it can be seen that the absorption member-type photocatalyst of the present invention can be reused because it still shows a high conversion rate (%) of organic compounds even after being reused 4 times.

[Equation 8]

[Equation 9]

[Equation 10]

[Equation 11]

Example 5-2-1 Example 5-2-2 Example 5-2-3 number of reuses Conversion rate (%) 1 ^st 99.2 99.7 98 2 ^nd 98.4 85 96.4 3 ^rd 94 88 87 4 ^th 85.7 83.3 82

As described above, the organic-inorganic composite photocatalyst based on nanofibers using the conjugated polymer of the present invention is porous and has a surface area unlike a solution-phase photocatalyst used by dissolving in a solvent or a dispersed-phase photocatalyst used by dispersing in a solvent. Because it is complexed with conjugated polymer nanoparticles that have excellent affinity for water or polar solvents based on a wide titanium dioxide nanofiber and can exhibit photocatalytic activity by absorbing visible light, it has excellent wettability in the reaction system, so that the interaction with reactants and The catalytic efficiency is improved under visible light irradiation by increasing the reaction surface area. In addition, since the process of reabsorbing light by scattering is repeated by fixing the conjugated polymer nanoparticles having a photocatalytic function by absorbing visible light to the titanium dioxide nanofiber, a small amount of conjugated polymer nanoparticles is introduced It has the advantage of exhibiting high-efficiency photocatalytic properties even though it is used, and since the photocatalyst itself is composed of nanofibers, it is easy to recover after use and can be reused. And, as long as the conjugated polymer having the desired absorption wavelength is manufactured as nanoparticles, it can be introduced into the titanium dioxide nanofiber by electrostatic force, so the manufacturing process is simple and convenient, and the shape of the absorption member can be freely changed as needed. Because it can be deformed, it has a wide range of applications.

Although the present invention has been described with reference to the embodiments shown in the drawings, which are merely exemplary, those skilled in the art will understand that various modifications and equivalent other embodiments are possible therefrom. Therefore, the true technical protection scope of the present invention should be determined by the technical spirit of the appended claims.

Claims (7)

Conjugated polymer nanoparticles having a structure of Formula 1 or Formula 2 below; and
An organic-inorganic composite photocatalyst based on nanofibers comprising; titanium dioxide nanofibers introduced with the conjugated polymer nanoparticles.

[Formula 1]

In Formula 1, X is _{any one of C, CR 1} R ₂ , N, S, O, NR ₃ , and SO ₂ , wherein R ₁ , R ₂ , R ₃ are different or the same as each other, and each independently at least one halogen is a substituted or unsubstituted straight-chain or branched chain, an alkyl group or alkoxy group having 1 to 12 carbon atoms,

[Formula 2]

In Formula 2, R ₄ , R ₅ is any one of H, OR ₆ , and R ₇ , wherein R ₆ , R ₇ are different or the same as each other, and each independently one or more halogens are substituted or unsubstituted straight chain or branched chain. It is a chain of 1 to 12 alkyl or alkoxy groups. Preferably, R ₄ , R ₅ is n-hexyl, n-heptyl, n-octyl, n-decyl, n-dodecyl, n-ethylhexyl, n-hexyloxy, n-heptyloxy, n-octyloxy, n-decyloxy and 2-ethylhexyloxy, or a combination thereof. In addition, the values of X and Y represent the composition of each repeating unit in mole fraction, where X is a real number from 0 to 0.99, Y is 1-X,
And, in Formula 1 or Formula 2 below, Ar is

,

,

,

,

,

any one of
Photocatalytic reaction using the organic-inorganic composite photocatalyst based on the nanofiber of claim 1
3. The method according to claim 2,
The photocatalytic reaction is a photocatalytic reaction, characterized in that any one of a decomposition reaction of an organic dye, an oxidation reaction of an organic compound, and a reduction reaction of an organic compound.
4. The method according to claim 3,
The organic dye is rhodamine B (Rhodamine B), methylene blue (methylene blue), photocatalytic reaction, characterized in that any one of methyl orange (methylorange).
4. The method according to claim 3,
The oxidation reaction of the organic compound is a photocatalytic reaction, characterized in that targeting any one of a benzylamine derivative and a furoic acid.
4. The method according to claim 3,
The reduction reaction of the organic compound is a photocatalytic reaction, characterized in that 4-nitrophenol is targeted.
A first step (S100) of preparing a conjugated polymer having a structure of Formula 1 or Formula 2 below;
a second step (S200) of preparing a conjugated polymer nanoparticle solution using the conjugated polymer prepared in the first step;
A third step of preparing a titanium dioxide nanofiber spinning solution (S300);
A fourth step (S400) of producing a nanofiber web by electrospinning the spinning solution prepared in the third step;
a fifth step (S500) of heat-treating and firing the nanofiber web prepared in the fourth step;
A sixth step (S600) of amine treatment of the heat-treated and fired nanofiber web in the fifth step; and
A seventh step (S700) of immersing the amine-treated nanofiber web in the sixth step in the conjugated polymer nanoparticle solution prepared in the second step (S700); Method for manufacturing organic-inorganic composite photocatalyst

[Formula 1]

In Formula 1, X is _{any one of C, CR 1} R ₂ , N, S, O, NR ₃ , and SO ₂ , wherein R ₁ , R ₂ , R ₃ are different or the same as each other, and each independently at least one halogen is a substituted or unsubstituted straight-chain or branched chain, an alkyl group or alkoxy group having 1 to 12 carbon atoms,

[Formula 2]

In Formula 2, R ₄ , R ₅ is any one of H, OR ₆ , and R ₇ , wherein R ₆ , R ₇ are different or the same as each other, and each independently one or more halogens are substituted or unsubstituted straight chain or branched chain. It is a chain of 1 to 12 alkyl or alkoxy groups. Preferably, R ₄ , R ₅ is n-hexyl, n-heptyl, n-octyl, n-decyl, n-dodecyl, n-ethylhexyl, n-hexyloxy, n-heptyloxy, n-octyloxy, n-decyloxy and 2-ethylhexyloxy, or a combination thereof. In addition, the values of X and Y represent the composition of each repeating unit in mole fraction, where X is a real number from 0 to 0.99, Y is 1-X,

In addition, in Formula 1 or Formula 2 below, Ar is

,

,

,

,

,

any one of

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