KR101432247B1 - Quasi-solid polymer electrolyte for dye-sensitized solar cell, hole transport material contained in same, and dye-sensitized solar cell containing the electrolyte - Google Patents

Abstract

The present invention provides a quasi-solid polymer electrolyte including a hole transporting material (HTM), a polymer for a solid electrolyte, and a liquid electrolyte, and provides a novel hole transporting material contained in the quasi-solid polymer electrolyte. The present invention also provides a dye-sensitized solar cell comprising the quasi-solid polymer electrolyte.

Description

TECHNICAL FIELD [0001] The present invention relates to a quasi-solid polymer electrolyte for a dye-sensitized solar cell, a hole transport material contained therein, and a dye-sensitized solar cell including the electrolyte. BACKGROUND ART < RTI ID = 0.0 > SOLAR CELL CONTAINING THE ELECTROLYTE}

The present invention relates to a quasi-solid polymer electrolyte for a dye-sensitized solar cell, a hole transport material contained therein, and a solar cell including the quasi-solid polymer electrolyte.

Since solar cells use infinitely clean solar energy, they are emerging as environmentally friendly alternative energy sources. Solar cells can directly convert sunlight to current (voltage), and can be divided into inorganic solar cells using p-n junctions of semiconductors and organic solar cells made mainly of organic materials. Of these, organic solar cells are not only cost-effective, environment-friendly, and indoors, but also transparent, thin, and light in order to realize a power window. In such organic solar cells, dye-sensitized solar cells (hereinafter referred to as DSSCs) using a dye-sensitization process in which a dye absorbing visible light is adsorbed to a semiconductor having a wide band gap have.

DSSCs generate currents on the following principle. First, when the sunlight (visible light) is absorbed, the dye molecules generate electron-hole pairs, and the generated electrons are injected into the conductive band of the semiconductor oxide electrode. The injected electrons are transferred to the transparent conductive film through the interface between nanoparticles to generate electric current. At this time, holes generated in the dye molecules are reduced again by receiving electrons by the oxidation-reduction electrolyte.

On the other hand, liquid electrolytes and ionic liquid electrolytes have been used as the electrolytes used in DSSCs, but various studies have been conducted to overcome them because they have drawbacks in terms of safety, efficiency, and processability. That is, a method of solidifying an electrolyte by adding an organic hardener to a liquid electrolyte, a method of solidifying an electrolyte using a polymer, a method of producing a quasi-solid electrolyte by using a high viscosity ionic liquid, a method of forming an organic HTM (hole transporting materials) To replace the electrolyte with an electrolyte.

Examples of the solid polymer used in the method of solidifying an electrolyte using a polymer include polyethylene oxide (PEO), polypropylene oxide (PPO), polyphosphorane, polysiloxane and polyvinylidene fluoride-co-hexafluoropropylene (PVDF -HFP), and the like. Of these, polyethylene oxide, which is a representative polymer, has a high molecular weight and thus has high crystallinity. Therefore, there is a drawback that it exhibits low ionic conductivity and diffusion coefficient at room temperature.

The electrolyte in the quasi-solid phase is impregnated with an organic electrolyte in a solid polymer composed of a polymer, an organic solvent, and a salt. In a quasi-solid electrolyte, a polymer forms a three-dimensional network structure by chemical bonding due to a chemical bond or intermolecular interaction, and thus forms a swollen body capable of holding and holding solvent molecules in the film. However, at the molecular level, the ionic conductivity of the polymer electrolyte is ~ 10 ^-3 S / cm or higher, so that the processability and stability of the solid polymer electrolyte and the high ionic conductivity of the liquid electrolyte I have everything. However, the mechanical strength is weak, there is still a sealing problem, and there are many difficulties in applying to a role-to-roll process.

Also, a method of replacing an organic HTM such as triarylamine, polythiophene, PEDOT, PANI-DBSA, OMe-TAD with an electrolyte has been introduced. Organic HTM has advantages such as roll-to-roll process, advantage of large size and excellent processability. On the other hand, due to its high molecular weight, it causes pore filling problem, absorbs visible light, .

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems of the prior art, and it is an object of the present invention to improve electric conductivity by increasing an uncrystallized region, enlarging a free volume and moving a polymer chain, Thereby providing high ionic conductivity; TiO ₂ / dye / electrolyte interface and Pt / electrolyte interface, thereby promoting electron transfer; It is possible to penetrate to the TiO ₂ interface without problems of pore filling; It is an object of the present invention to provide a quasi-solid polymer electrolyte for a dye-sensitized solar cell which reduces the recombination of electrons occurring at the interface between a semiconductor layer made of TiO ₂ and an electrolyte containing iodine.

It is another object of the present invention to provide a novel hole transport material which is contained in a quasi-solid polymer electrolyte and provides the above-mentioned effect.

It is another object of the present invention to provide a dye-sensitized solar cell including the quasi-solid polymer electrolyte and having excellent efficiency.

The present invention provides a quasi-solid polymer electrolyte comprising a hole transporting material (HTM), a polymer for a solid electrolyte, and a liquid electrolyte.

The present invention provides a compound represented by the above formula (1)

[Chemical Formula 1]

In the above formula

X is C1-C15 alkyl substituted or unsubstituted with C1-C15 alkoxy; A C1 to C15 alkyl group substituted or unsubstituted with C1 to C15 alkoxy, a C1 to C15 alkoxy group substituted or unsubstituted with a C1 to C15 alkyl group, and a C1 to C15 alkoxy group substituted with a C1 to C15 alkoxy group C5 < / RTI > to C20 aryl or heteroaryl, which is unsubstituted or substituted with a substituent selected from the group consisting of < RTI ID = 0.0 & A C1 to C15 alkyl group substituted or unsubstituted with C1 to C15 alkoxy, a C1 to C15 alkoxy group substituted or unsubstituted with a C1 to C15 alkyl group, and a C1 to C15 alkoxy group substituted with a C1 to C15 alkoxy group A C6-C22 arylalkyl or heteroarylalkyl which is substituted or unsubstituted with a substituent selected from the group consisting of R < 1 > Or -O-R < 1 > wherein the definition of R < 1 &

R2, R3, R4, R5, R6 and R7 are each independently hydrogen; C1 to C15 alkyl substituted or unsubstituted with C1 to C15 alkoxy; C1-C15 alkoxy optionally substituted with C1-C15 alkyl; C1 to C15 alkoxy substituted with C1 to C15 alkoxy; A C1 to C15 alkyl group substituted or unsubstituted with C1 to C15 alkoxy, a C1 to C15 alkoxy group substituted or unsubstituted with a C1 to C15 alkyl group, and a C1 to C15 alkoxy group substituted with a C1 to C15 alkoxy group C5 < / RTI > to C20 aryl or heteroaryl, which is unsubstituted or substituted with a substituent selected from the group consisting of < RTI ID = 0.0 & Or a C1-C15 alkyl substituted with C1-C15 alkoxy, a C1-C15 alkoxy optionally substituted with C1-C15 alkyl, and a C1-C15 alkoxy group substituted with C1-C15 alkoxy Or a C6-C22 arylalkyl or heteroarylalkyl group substituted or unsubstituted with a substituent selected from the group consisting of

R8 is a bond or absent,

R9 and R10 are methylene groups substituted or unsubstituted with one or two C1-C5 alkyl groups or are absent;

Ar is a C5 to C20 aromatic ring or aromatic heterocycle, said heterocycle containing one to three heteroatoms selected from the group consisting of O, S and N;

m is an integer from 0 to 5;

n, o and p are each independently 0 or 1;

Provided that when Ar is an aromatic hetero ring, at least one of R4, R5, R6 and R7 may be absent.

The present invention also provides a novel hole transport material (HTM) represented by the above formula (1).

The present invention also provides a dye-sensitized solar cell comprising the quasi-solid polymer electrolyte.

Since the quasi-solid polymer electrolyte of the present invention is prepared by mixing a hole transporting material (HTM), a polymer for a solid electrolyte and a liquid electrolyte, it is possible to increase the free-form area, enlarge the free volume, And provides a high ion conductivity by further improving the electric conductivity by the hole transfer phenomenon by the hole transport material (HTM). In addition, it has a low resistance at the TiO ₂ / dye / electrolyte interface and the Pt / electrolyte interface, thereby providing an effect of promoting electron migration. In addition, the use of a hole transport material (HTM) having a small molecular weight provides an advantage of penetration to the TiO ₂ interface without problems of pore filling. Further, the hole transporting material (HTM) provides an effect of reducing the recombination of electrons occurring at the interface between the semiconductor layer composed of TiO ₂ and the electrolyte containing iodine.

The present invention also provides a novel hole transport material (HTM) having excellent functions as described above.

In addition, the dye-sensitized solar cell of the present invention including the quasi-solid polymer electrolyte has a high ionic conductivity, exhibits a low resistance at the TiO ₂ / dye / electrolyte interface and the Pt / electrolyte interface, and thus provides excellent efficiency.

1 shows the current-voltage curves of the dye-sensitized solar cells prepared in Example 14 (electrolyte-E3), Comparative Example 3 (electrolyte-E1) and Comparative Example 4 (electrolyte-E2) of the present invention.
2 shows the photoelectric conversion efficiency (IPCE) of the dye-sensitized solar cell produced in Example 14 (electrolyte-E3), Comparative Example 3 (electrolyte-E1) and Comparative Example 4 (electrolyte-E2) of the present invention.
FIG. 3 shows the current-voltage curves of the dye-sensitized solar cells of Examples 14 to 18 prepared with quasi-solid polymer electrolytes containing different concentrations of hole transporting material (BMPC) (Examples 9 to 13) .
4 is a graph showing the charge transfer resistance of the electrolyte prepared in Example 9 (E3), Comparative Example 1 (E1) and Comparative Example 2 (E2) cm < ² >).
5 shows an equivalent circuit set to obtain the internal resistance of the electrolyte prepared in Example 9 (E3), Comparative Example 1 (E1) and Comparative Example 2 (E2) in a solar cell (Rs: R1 _CT : charge transfer resistance of Pt / electrolyte interface, R2 _CT : charge transfer resistance of TiO ₂ / dye / electrolyte interface).

Best Mode for Carrying Out the Invention

The present invention relates to a semi-solid polymer electrolyte for a dye-sensitized solar cell comprising a hole transporting material (HTM), a solid electrolyte polymer and a liquid electrolyte.

In the quasi-solid polymer electrolyte of the present invention, the hole transporting material (HTM) may be contained in an amount of preferably 5 to 30 parts by weight, more preferably 10 to 25 parts by weight, based on 100 parts by weight of the polymer for a solid electrolyte . If the amount of the hole transporting material is less than 5 parts by weight, it is difficult to obtain the effect of the addition of the hole transporting material. If the amount of the hole transporting material is more than 30 parts by weight, the ionic conductivity of I ^- / I ₃ ^- The efficiency is lowered.

In the quasi-solid polyelectrolyte of the present invention, the solid electrolyte polymer may include, but is not limited to, polyethylene oxide (PPO), polyvinylidene fluoride (PVDF), polyvinylidene fluoride ), Poly (methyl methacrylate), poly (acrylonitrile), polyphosphazene, polysiloxane, polyvinylidene fluoride-co-hexafluoropropylene (PVdF-HFP) Poly (ephichlorohydrin-co-ethylene oxide), etc. In particular, the polymer for solid electrolytes may be composed of PEO and PPO.

The polymer for a solid electrolyte may be contained in an amount of 5 to 60 parts by weight, more preferably 7 to 20 parts by weight, based on 100 parts by weight of the liquid electrolyte. When the polymer for solid electrolyte is contained in an amount of less than 5 parts by weight, it is difficult to form a quasi-solid polymer electrolyte. When the amount of the polymer is more than 60 parts by weight, the electrolyte becomes too hard and the mobility of electrons may be deteriorated.

In the quasi-solid polymer electrolyte of the present invention, the liquid electrolyte may be any of those known in the art without any limitation. A-butylpyridine (tBP), etc. - generally liquid electrolytes, but it is not limited to, acetonitrile, LiI, I _2, 1,2- dimethyl-3-propyl imidazolium iodide (DMPII), 4- tetrahydro .

In the quasi-solid polymer electrolyte of the present invention, the hole transporting material may be any of those known in the art without limitation. In particular, a compound represented by the following formula 1 may be preferably used.

The present invention relates to a compound having a hole transporting property represented by the following Formula 1:

[Chemical Formula 1]

In the above formula

X is C1-C15 alkyl substituted or unsubstituted with C1-C15 alkoxy; A C1 to C15 alkyl group substituted or unsubstituted with C1 to C15 alkoxy, a C1 to C15 alkoxy group substituted or unsubstituted with a C1 to C15 alkyl group, and a C1 to C15 alkoxy group substituted with a C1 to C15 alkoxy group C5 < / RTI > to C20 aryl or heteroaryl, which is unsubstituted or substituted with a substituent selected from the group consisting of < RTI ID = 0.0 & A C1 to C15 alkyl group substituted or unsubstituted with C1 to C15 alkoxy, a C1 to C15 alkoxy group substituted or unsubstituted with a C1 to C15 alkyl group, and a C1 to C15 alkoxy group substituted with a C1 to C15 alkoxy group A C6-C22 arylalkyl or heteroarylalkyl which is substituted or unsubstituted with a substituent selected from the group consisting of R < 1 > Or -O-R < 1 > wherein the definition of R < 1 &

R2, R3, R4, R5, R6 and R7 are each independently hydrogen; C1 to C15 alkyl substituted or unsubstituted with C1 to C15 alkoxy; C1-C15 alkoxy optionally substituted with C1-C15 alkyl; C1 to C15 alkoxy substituted with C1 to C15 alkoxy; A C1 to C15 alkyl group substituted or unsubstituted with C1 to C15 alkoxy, a C1 to C15 alkoxy group substituted or unsubstituted with a C1 to C15 alkyl group, and a C1 to C15 alkoxy group substituted with a C1 to C15 alkoxy group C5 < / RTI > to C20 aryl or heteroaryl, which is unsubstituted or substituted with a substituent selected from the group consisting of < RTI ID = 0.0 & Or a C1-C15 alkyl substituted with C1-C15 alkoxy, a C1-C15 alkoxy optionally substituted with C1-C15 alkyl, and a C1-C15 alkoxy group substituted with C1-C15 alkoxy Or a C6-C22 arylalkyl or heteroarylalkyl group substituted or unsubstituted with a substituent selected from the group consisting of

R8 is a bond or absent,

R9 and R10 are methylene groups substituted or unsubstituted with one or two C1-C5 alkyl groups or are absent;

Ar is a C5 to C20 aromatic ring or aromatic heterocycle, said heterocycle containing one to three heteroatoms selected from the group consisting of O, S and N;

m is an integer from 0 to 5;

n, o and p are each independently 0 or 1;

Provided that when Ar is an aromatic hetero ring, at least one of R4, R5, R6 and R7 may be absent.

In Formula 1,

As the C1-C15 alkyl contained in each substituent, methyl, ethyl, propyl, butyl, pentyl, heptyl, heptyl or octyl group is preferable, and C1-C15 alkoxy is preferably methoxy, ethoxy, Butoxy, pentoxy, hexoxy or heptoxy group.

Examples of the C1-C15 alkyl group substituted by C1-C15 alkoxy include butoxymethyl, butoxyethyl, hexoxymethyl, and heptoxymethyl. Examples of the C1-C15 alkyl group include C1-C15 Examples of the alkoxy group include 2-ethylheptyloxy, 3-ethylheptyloxy, 2-methylbutyloxy, 2-ethylpentyloxy and 3-ethylpentyloxy groups, and C1-C15 Include 3-methoxyphenoxy, 3-ethoxypentoxy, 3-propoxypentoxy, 2-methoxyhexyl, 2-ethoxyheptoxy, 2-propoxyheptoxy and the like .

The aryl or heteroaryl group of C5 to C20 and the aryl or heteroaryl group of the C6 to C22 arylalkyl or heteroarylalkyl group include, but are not limited to, phenyl, naphthyl, thiophenyl, anthracyl , Imidazole, pyridine, oxazole, thiazole, quinoline, EDOT (3,4-ethylenedioxythiophene) and the like.

Examples of the Ar include, but are not limited to, phenyl, naphthalene, anthracene, imidazole, pyridine, oxazole, thiazole, quinoline and EDOT.

The alkyl chains included in the substituents of the present invention may be in the form of branched or branched chains.

Specific examples of the compound represented by the formula (1) having the novel hole transporting property of the present invention are as follows:

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

[Chemical Formula 9]

Wherein X, R2, R3, R4, R5, R6, R7 and m are as defined in the above formula (1).

Specific examples of the hole transporting materials of the above formulas (2) to (9) are as follows:

9- (2-butoxyethyl) -3,6-bis (4-methoxyphenyl) -9H-carbazole,

4- [N, N-di (4- (2-ethyl) hexyloxyphenyl) amino] -1-butoxymethylbenzene,

4- [N, N-di (4- (2-ethyl) hexyloxyphenyl) amino] -3,5-dimethyl- 1-butoxymethylbenzene,

N, N-bis (4- (2-ethylhexyloxy) phenyl) naphthalen-1-

N, N-bis (4- (2-ethylhexyloxy) phenyl) naphthalen-1-

N- (4- (2-butoxyethyl) phenyl) -7- (2- ethylhexyloxy) -N- (7- (2- ethylhexyloxy) -9,9-dimethyl- Yl) -9,9-dimethyl-9H-fluoren-2-amine,

9- (4-butoxyphenyl) -3,6-bis (4-methoxyphenyl) -9H-carbazole,

9- (4-Butoxy-3,5-dimethylphenyl) -3,6-bis (4-methoxyphenyl) -9H-carbazole.

9-4-hexyl-3,6-bis (4-methoxyphenyl) -9H-carbazole

Hereinafter, the hole transporting property and the production method of the compounds represented by the above Chemical Formulas 1 to 9 will be described.

[ (2) ]

The compound of Formula 2 is characterized by containing a carbazole. Since it contains a nitrogen atom having a non-covalent electron pair in the structure and a double bond, the hole transport ability is excellent.

9- (2-butoxyethyl) -3,6-bis (4-methoxyphenyl) -9H-carbazole (BMPC) among the compounds included in Formula 2 can be prepared by the following Reaction Scheme 1. Further details are described in Example 1 below.

[ Scheme 1 ]

[ (3) ]

The compound of Formula 3 is characterized by having a triphenylamine structure. Since it contains a nitrogen atom having a non-covalent electron pair in its structure and a double bond, the hole transport ability is excellent.

4-di (4- (2-ethyl) hexyloxyphenyl) amino-1-butoxymethylbenzene in the compound of Formula 3 can be prepared by the following Reaction Scheme 2. Further details are described in Example 2 below.

[ Scheme 2 ]

[ Formula 4 ]

The compound of Formula 4 is characterized by having a triphenylamine structure. Since the compound contains a nitrogen atom and a double bond having a non-covalent electron pair in the structure, the hole transporting ability is excellent.

The 4- [N, N-di (4- (2-ethyl) hexyloxyphenyl) amino] -3,5-dimethyl-1-butoxymethylbenzene in the compound of Formula 4 is prepared by the following Reaction Formula 3 . More details are described in Example 3.

[Reaction Scheme 3]

[ Formula 5 ]

The compound of Formula 5 is characterized by containing a naphthalene and diphenylamine structure. Since the compound contains a nitrogen atom having a non-covalent electron pair and a double bond in the structure, the hole transport ability is excellent.

The 4- (2-butoxyethyl) -N, N-bis (4- (2-ethylhexyloxy) phenyl) naphthalen-l-amine in the compound of Chemical Formula 5 can be prepared by the following Reaction Scheme 4 . More details are described in Example 4.

[Reaction Scheme 4]

[ 6 ]

The compound of formula (6) is characterized by containing a difluorene and phenylamine structure, and has a hole-transporting ability because it contains a nitrogen atom and a double bond having a non-covalent electron pair in the structure.

(4- (2-butoxyethyl) phenyl) -7- (2-ethylhexyloxy) -N- Dimethyl-9H-fluoren-2-yl) -9,9-dimethyl-9H-fluoren-2-amine can be prepared by the following Reaction Scheme 5. More details are described in Example 5.

[Reaction Scheme 5]

[ Formula 7 ]

The compound of formula (7) is characterized by containing a carbazole. Since it contains a nitrogen atom having a non-covalent electron pair in the structure and a double bond, the hole transport ability is excellent.

9- (4-butoxyphenyl) -3,6-bis (4-methoxyphenyl) -9H-carbazole in the compound of Formula 7 can be prepared by the following Reaction Scheme 6. More details are described in Example 6.

[Reaction Scheme 6]

[ 8 ]

The compound of formula (8) is characterized by containing a carbazole. Since it contains a nitrogen atom having a non-covalent electron pair in the structure and a double bond, the hole transport ability is excellent.

9- (4-Butoxy-3,5-dimethylphenyl) -3,6-bis (4-methoxyphenyl) -9H-carbazole in the compound of Formula 8 can be prepared by the following Reaction Scheme 7 . More details are described in Example 7.

[Reaction Scheme 7]

[Chemical Formula 9]

The compound of formula (9) is characterized by containing a carbazole. Since it contains a nitrogen atom and a double bond having a non-covalent electron pair in the structure, the hole transport ability is excellent.

9-4-Hexyl-3,6-bis (4-methoxyphenyl) -9H-carbazole in the compound of Formula 9 can be prepared by the following Reaction Scheme 8. More details are described in Example 8.

[Reaction Scheme 8]

The present invention also provides a hole transport material (HTM) comprising the compound represented by the above formula (1). The compound represented by Formula 1 has excellent hole transporting properties (HTM) and therefore can be preferably used as a hole transporting material (HTM).

The present invention also relates to a dye-sensitized solar cell comprising the quasi-solid polymer electrolyte.

Since the dye-sensitized solar cell of the present invention includes the quasi-solid polymer electrolyte as described above, it has excellent ion conductivity and has a small charge transfer resistance at the Pt / electrolyte interface and TiO ₂ / dye / electrolyte interface, Respectively. Further, by using the quasi-solid polymer electrolyte, the design of the battery is easy, and leakage of the electrolytic solution is prevented, which is a safe feature.

In the present invention, the dye-sensitized solar cell may have the following configuration, but not limited thereto:

A first electrode comprising a conductive transparent substrate;

A light absorbing layer formed on one surface of the first electrode;

A second electrode disposed opposite to the first electrode on which the light absorbing layer is formed; And

Wherein the electrolyte is located in a space between the first electrode and the second electrode.

The materials constituting the solar cell will be described as follows.

The first electrode comprising the conductive transparent substrate is made of indium tin oxide, fluorine tin oxide, ZnO-Ga ₂ O ₃ , ZnO-Al ₂ O ₃ And a translucent electrode formed of at least one material selected from the group consisting of tin oxide, and tin oxide.

The light absorbing layer includes semiconductor fine particles and dyes. The semiconductor fine particles are formed of nanoparticle oxides such as titanium dioxide (TiO ₂ ), tin dioxide (SnO ₂ ), and zinc oxide (ZnO) . The dye adsorbed on the semiconductor fine particles may be used without limitation as long as it absorbs light in the visible light region, forms a strong chemical bond with the surface of the nano-oxide, and has heat and optical stability. As a representative example, a ruthenium-based organometallic compound can be mentioned.

The second electrode may be the same as the first electrode, or a conductive layer formed of platinum or the like on the light-transmitting electrode of the first electrode may be used.

DETAILED DESCRIPTION OF THE INVENTION

Hereinafter, the present invention will be described in detail by way of examples. However, these embodiments are provided to explain the present invention more clearly and not to limit the scope of the present invention. The scope of the present invention will be determined by the technical idea of the following claims.

Example .

Reagents used

Hexane, dichloromethane, ethyl acetate, ethyl alcohol, benzene, tetrahydrofuran, potassium carbonate (potassium carbonate). Anhydrous magnesium sulfate, sodium hydroxide, triethylamine, hydrochloric acid, ammonium chloride, celite, toluene, potassium hydroxide, ether, and nitric acid were used. (0), 4-methoxybromobenzene, dimethyborate, tetrabutylammonium bromide, tetrabutylammonium bromide, tetrabutylammonium iodide, (I), 4-iodoanisole, aniline, 9-bromo-10-methoxyanthracene, 1-bromo-4-methylpyridinium chloride, 1, 10-phenanthroline, phosphoryl chloride, lithium aluminum hydride, n-butyl iodide, 2- (naphthalen-1-yl) acetic acid, Sn, borane, 5-iodo-2-methoxy-1,3-dimethylbenzene, Cu-bronze, 18-crown-6, 1,2-dichlorobenzene, iodine, 6- Iodomethane, sodium sulfate, acetonitrile, 1,2-dimethyl-3-propylimidazolium iodide, LiI, I ₂ , Tetra Butyl ammonium hexafluorophosphate, a molecular weight M _n of PEO 1,000,000, and a molecular weight of _n 725M of PPG [Poly (propylene glycol)] was used as the purchased from Aldrich, more reagents were used without any purification.

Identification of synthesized compounds

All new compounds were identified by ¹ H-NMR, ¹³ C-NMR and FT-IR. ¹ H-NMR was recorded using a Varian 300 spectrometer and all chemical mobilities were recorded in ppm for tetramethylsilane, an internal standard. IR spectra were measured with KBr pellet using a Perkin-Elmer Spectrometer.

Example  1: 9- (2- Butoxyethyl ) -3,6- Bis (4- Methoxyphenyl ) -9H- Carbazole  synthesis

1-1: 2- (9H- Carbazole -9-yl) ethanol Synthesis of

The carbazole (3.5 g, 20.9 mmole) was dissolved in 100 mL of tetrahydrofuran using a round flask, and the reaction vessel was cooled to 0 占 폚 and then sodium hydride (0.75 g, 31.4 mmole) was added. After stirring at room temperature for 1 hour, 2-iodoethanol (4.7 g, 27.2 mmole) was slowly added dropwise. After stirring at room temperature for 12 hours, distilled water was added to the reaction vessel to terminate the reaction. The solvent was removed and the residue was extracted with ethyl acetate and washed several times with distilled water. The organic layer was dried over anhydrous magnesium sulfate, filtered, and then the organic solvent was removed under reduced pressure, followed by separation by column chromatography.

_{^{1 H NMR (300MHz, CDCl 3}} ) δ 4.08-4.1 (t, -CH 2, 2H), 4.48-4.52 (t, -CH 2, 2H), 7.26 (m, -Ar, 2H), 7.47-7.48 ( m, -Ar, 4H), 8.09-8.12 (d, -Ar, 2H)

1-2: 9- (2- Butoxyethyl ) -9H- Carbazole  synthesis

(3.0 g, 14.2 mmole) was dissolved in 100 mL of tetrahydrofuran using a round-bottomed flask, and the reaction vessel was cooled to 0 占 폚. Then, sodium hydride (0.51 g, 21.3 mmole). After stirring at room temperature for 12 hours, distilled water was added to the reaction vessel to terminate the reaction. The solvent was removed and the residue was extracted with ethyl acetate and washed several times with distilled water. The organic layer was dried over anhydrous magnesium sulfate, filtered, and then the organic solvent was removed under reduced pressure, followed by separation by column chromatography.

_{^{1 H NMR (300MHz, CDCl 3}} ) δ 1.83-1.94 (t, -CH 3, 3H), 1.27-1.29 (m, -CH 2, 2H), 1.44-1.50 (m, -CH 2, 2H), 3.35 _{-3.40 (t, -CH 2, 2H} ), 3.78-3.82 (t, -CH 2, 2H), 4.47-4.52 (t, -CH 2, 2H), 7.22-7.28 (m, -Ar, 2H), 7.41-7.49 (m, -Ar, 4H), 8.10-8.13 (d, -Ar, 2H)

1-3: 3, 6- Dibromo -9- (2- Butoxyethyl ) -9H- Carbazole  synthesis

(1.81 g, 8.6 mmole) was dissolved in 50 mL of tetrahydrofuran using a round-bottomed flask, and N-bromosuccinimide (3.06 g, 17.2 mmole) was added And the mixture was stirred at room temperature for 3 hours. After completion of the reaction, the solvent was removed and the reaction mixture was extracted with ethyl acetate and washed several times with distilled water. The organic layer was dried over anhydrous magnesium sulfate, filtered, and then the organic solvent was removed under reduced pressure, followed by separation by column chromatography.

_{^{1 H NMR (300MHz, CDCl 3}} ) δ 1.83-1.94 (t, -CH 3, 3H), (m, -CH 2, 2H), 1.44-1.50 (m, -CH 2, 2H), 3.28-3.32 ( _{t, -CH 2, 2H),} 3.71-3.75 (t, -CH 2, 2H), 4.36-4.40 (t, -CH 2, 2H), 7.29-7.32 (d, -Ar, 2H), 7.51-7.54 (dd, -Ar, 4H), 8.0 (s, -Ar, 2H)

1-4: 9- (2- Butoxyethyl ) -3,6- Bis (4- Methoxyphenyl ) -9H- Carbazole  synthesis

(0.23 g, 0.5 mmole), potassium carbonate (potassium carbonate, 0.18 g, 1.3 mmole), tetrakis (triphenylphosphine) palladium ) Palladium (0) (0.11 g, 0.1 mmole) was dissolved in 60 ml of toluene / tetrahydrofuran / H ₂ O (3: 1: 1) and the mixture was refluxed and stirred at 80 ° C for 17 hours. After completion of the reaction, the reaction mixture was extracted with ethyl acetate and washed several times with distilled water. The organic layer was dried over anhydrous magnesium sulfate, filtered, and then the organic solvent was removed under reduced pressure, followed by separation by column chromatography.

_{^{1 H NMR (300MHz, CDCl 3}} ) δ 1.81-1.86 (t, -CH 3, 3H), 1.23-1.28 (m, -CH 2, 2H), 1.48-1.55 (m, -CH 2, 2H), 3.36 _{-3.38 (t, -CH 2, 2H} ), 3.88 (s, -OCH3, 3H), 4.51-4.53 (t, -CH 2, 2H), 7.01-7.03 (d, -Ar, 4H), 7.48-7.51 (d, -Ar, 2H), 7.63-7.65 (m, -Ar, 6H), 8.27

Example 2 : 4- Di (4- (2-ethyl) hexyloxyphenyl) amino -One- Butoxymethylbenzene  synthesis

2-1: 4- Methoxyphenyl Of boronic acid  synthesis

1-Bromo-4-methoxybenzene (15.0 g, 80.2 mmole) is dissolved in 150 mL of tetrahydrofuran and the temperature is lowered to -78 DEG C under nitrogen reflux. Butyl lithium (5.65 g, 88.2 mmole) was slowly added dropwise while maintaining a low temperature, and the mixture was stirred for 1 hour. Trimethylborate (16.7 g, 160.4 mmole) is slowly added dropwise. The mixture was further stirred for 1 hour while keeping the temperature at low temperature, then slowly raised to room temperature, and stirred at room temperature for 12 hours. After completion of the reaction, the pH was adjusted to 2 with a 6M aqueous hydrochloric acid solution, extracted with ethyl acetate, and washed several times with distilled water. The organic layer was dried over anhydrous magnesium sulfate, filtered, and the organic solvent was removed under reduced pressure. The residue was dissolved in a small amount of tetrahydrofuran, and n-hexane was added dropwise at 0 ° C to precipitate crystals, which were then filtered and dried.

_{^{1 H NMR (300MHz, CDCl 3}} ) δ 3.81 (s, 3H, -OCH 3), 6.89-6.91 (d, -Ar, 2H), 7.72-7.74 (d, -Ar, 2H)

2-2: 1- (2- Ethylhexyloxy )-4- Of iodobenzene  synthesis

4-iodophenol (15 g, 68.18 mmol), potassium carbonate (24.5 g, 177.26 mmol) and 2-ethylhexyl bromide (17.12 g, 88.63 mmol) were added to a 250 mL round-bottomed flask and dissolved in 50 mL of acetonitrile Was refluxed and stirred for 24 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, acid-treated with 70 mL of 2 molar hydrochloric acid aqueous solution, extracted with methylene chloride, and washed several times with distilled water. The organic layer was dried over MgSO ₄ , the solvent was removed under reduced pressure, and the product was isolated by column chromatography. The yield was 93%.

_{^{1 H NMR (CDCl 3 ppm.}} ): Δ7.55-7.52 (d, 2H, Ar-H), 6.69-6.66 (d, 2H, Ar-H), 3.80-3.79 (d, 2H, CH 2 -O ), 1.73-1.67 (m, 1H, (CH 2) 3 -H), 1.53-1.28 (m, 8H, -CH 2), 0.97-0.88 (t, 6H, -CH 3).

2-3: 1-Di (4- (2-ethyl) Hexyloxyphenyl ) Synthesis of aminobenzene

Iodobenzene (19.03 g, 59.06 mmol), aniline (2.5 g, 26.84 mmol), copper chloride (0.27 g, 2.68 mmol), 1 , Phenanthroline (0.48 g, 2.68 mmol) and potassium hydroxide (9.04 g, 161.07 mmol) were added. 20 mL of purified toluene was added under nitrogen, and the mixture was refluxed and stirred at 125 ° C for 24 hours. When the reaction was completed, the reaction mixture was cooled to room temperature, extracted with toluene and washed several times with distilled water. The organic layer was dried over MgSO ₄ , the solvent was removed under reduced pressure, and the product was isolated by column chromatography (silica, CH ₂ Cl ₂ : hexane = 2: 3). The yield was 80%.

_{^{1 H NMR (CDCl 3 ppm.}} ): Δ7.23-7.21 (t, 1H, Ar-H), 6.85-6.81 (t, 2H, Ar-H), 6.79-6.75 (d, 4H, Ar-H) , 6.63-6.61 (d, 2H, Ar -H), 6.55-6.52 (d, 4H, Ar-H), 3.80-3.79 (d, 4H, CH 2 -O), 1.73-1.67 (m, 2H, ( CH ₂ ) ₃ -H), 1.53-1.28 (m, 16H, -CH ₂ ), 0.97-0.88 (t, 12H, -CH ₃ ).

2-4: 4-Di (4- (2-ethyl) Hexyloxyphenyl ) Synthesis of aminobenzaldehyde

POCl ₃ (3.28 g, 21.04 mmol) and DMF (30 mL) were added to a 250 mL flask, the temperature was lowered to 0 캜, POCl ₃ (3.28 g, 21.04 mmol) was added dropwise and the mixture was refluxed for 1 hour. N, N-di-4- (2-ethylhexyloxy) phenylaminobenzene (5 g, 20.38 mmol) was added thereto, followed by reflux stirring at room temperature for 12 hours. When drying was complete, POCl ₃ (3.28 g, 21.04 mmol) and 30 mL of DMF were added to the flask using a syringe under nitrogen reflux. Then 20 mL of DMF was added to the dropping funnel and then slowly dropped at 0 ° C. After dropping was completed, the mixture was refluxed and stirred at 90 DEG C for 24 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, extracted with MC, and washed several times with distilled water. The organic layer was dried over anhydrous magnesium sulfate, the solvent was removed under reduced pressure, and the product was isolated by column chromatography (silica, CH ₂ Cl ₂ : hexane = 2: 3). The yield was 80%.

_{^{1 H NMR (CDCl 3 ppm.}} ): Δ9.9 (s, 1H, HC = O), 7.09-7.07 (d, 2H, Ar-H), 6.85-6.82 (d, 2H, Ar-H), 6.77 -6.74 (d, 4H, Ar- H), 6.54-6.52 (d, 4H, Ar-H), 3.80-3.79 (d, 4H, CH 2 -O), 1.73-1.67 (m, 2H, (CH 2 _{) 3 -H), 1.53-1.28 (m} , 16H, -CH 2), 0.97-0.88 (t, 12H, -CH 3).

2-5: 4-Di (4- (2-ethyl) Hexyloxyphenyl ) Synthesis of aminobenzyl alcohol

A dropping funnel containing 4-di (4- (2-ethyl) hexyloxy-phenyl) aminobenzaldehyde (0.51 g, 13.50 mmol) was placed in a 250 mL Schlenk flask containing LiAlH ₄ (5 g, 9.44 mmol) Lt; / RTI > After drying was completed, each 50 mL of purified diethyl ether was added to the flask and dropping funnel using a syringe under nitrogen reflux and slowly added dropwise at 0 ° C. After the dropwise addition was completed, the mixture was refluxed and stirred at 50 DEG C for 24 hours. When the reaction was completed, the temperature was lowered to room temperature and acid-treated with 2M HCl aqueous solution. After the acid treatment was completed, the reaction mixture was extracted with ethyl acetate and washed several times with distilled water. The organic layer was dried over anhydrous magnesium sulfate, the solvent was removed under reduced pressure, and the product was isolated by column chromatography (silica, CH ₂ Cl ₂ ). The yield was 80%.

_{^{1 H NMR (CDCl 3 ppm.}} ): Δ7.09-7.07 (d, 2H, Ar-H), 6.85-6.82 (d, 2H, Ar-H), 6.77-6.74 (d, 4H, Ar-H) , 6.54-6.52 (d, 4H, Ar -H), 4,61 (s, 2H, CH 2), 3.80-3.79 (d, 4H, CH 2 -O), 3.65-3.62 (t, 1H, OH) 1.73-1.67 (m, 2H, (CH 2) 3 -H), 1.53-1.28 (m, 16H, -CH 2), 0.97-0.88 (t, 12H, -CH 3).

2-6: 4- Di (4- (2-ethyl) hexyloxyphenyl) amino -One- Butoxymethylbenzene  synthesis

A dropping funnel equipped with 4-di (4- (2-ethyl) hexyloxy-phenyl) aminobenzyl alcohol (5 g, 9.44 mmol) was placed in a 250 mL Schlenk flask containing NaH (0.54 g, 14.16 mmol) And dried under vacuum. After drying was completed, 30 mL of purified THF was added to the flask and dropping apparatus using a syringe under nitrogen reflux, and then slowly added dropwise at 0 ° C. After the dropping was completed, reflux was carried out at 100 ° C for 24 hours, and then, using a syringe, n-butyl iodide (2.8 g, 14.16 mmol) was added. After the reaction was completed, the temperature was lowered to room temperature and acid treatment was performed with 2M HCl aqueous solution. After acid treatment was completed, it was extracted with MC and washed several times with distilled water. The organic layer was dried over anhydrous magnesium sulfate, the solvent was removed under reduced pressure, and the product was isolated by column chromatography (silica, CH ₂ Cl ₂ ). The yield was 80%.

_{^{1 H NMR (CDCl 3 ppm.}} ): Δ7.09-7.07 (d, 2H, Ar-H), 6.85-6.82 (d, 2H, Ar-H), 6.77-6.74 (d, 4H, Ar-H) , 6.54-6.52 (d, 4H, Ar -H), 4.8 (s, 2H, CH 2), 3.80-3.79 (d, 4H, CH 2 -O), 3.65-3.62 (t, 1H, OH) 1.73- 1.67 (m, 8H, (CH 2) 3 -H, CH 2), 1.53-1.28 (m, 16H, -CH 2), 0.97-0.88 (m, 15H, -CH 3).

Example 3: 4- Di (4- (2-ethyl) hexyloxyphenyl) amino -3,5-dimethyl-1- Butoxymethylbenzene  synthesis

3-1: 1- Di (4- (2-ethyl) hexyloxy) phenylamino Synthesis of 2,6-dimethylbenzene

The compound was prepared in the same manner as in Example 2-3, except that 2,6-dimethylaniline was used instead of aniline.

_{^{1 H NMR (CDCl 3 ppm.}} ): Δ7.23-7.21 (t, 1H, Ar-H), 6.85-6.81 (t, 2H, Ar-H), 6.79-6.75 (d, 4H, Ar-H) , 6.63-6.61 (d, 2H, Ar -H), 6.55-6.52 (d, 4H, Ar-H), 3.80-3.79 (d, 4H, CH 2 -O), 2.12 (s, 6H, Ar-CH _{3), 1.73-1.67 (m, 2H} , (CH 2) 3 -H), 1.53-1.28 (m, 16H, -CH 2), 0.97-0.88 (t, 12H, -CH 3).

3-2: 4- Di (4- (2-ethyl) hexyloxy) phenylamino -3,5- Of dimethylbenzaldehyde  synthesis

Instead of 1-di (4- (2-ethylhexyloxy) phenyl) -N- (4- (2-ethylhexyloxy) Amino-2,6-dimethylbenzene, the compound was prepared in the same manner as in Example 2-4.

_{^{1 H NMR (CDCl 3 ppm.}} ): Δ9.9 (s, 1H, HC = O), 7.09-7.07 (d, 2H, Ar-H), 6.85-6.82 (d, 2H, Ar-H), 6.77 -6.74 (d, 4H, Ar- H), 6.54-6.52 (d, 4H, Ar-H), 3.80-3.79 (d, 4H, CH 2 -O), 2.12 (s, 6H, Ar-CH 3) , 1.73-1.67 (m, 2H, ( CH 2) 3 -H), 1.53-1.28 (m, 16H, -CH 2), 0.97-0.88 (t, 12H, -CH 3).

3-3: 4- Di (4- (2-ethyl) hexyloxyphenyl) amino -3,5- Dimethylbenzyl  Synthesis of alcohol

(4- (2-ethyl) hexyloxyphenyl) amino-3,5-dimethylbenzaldehyde was used instead of 4-di (4- , The compound was prepared.

_{^{1 H NMR (CDCl 3 ppm.}} ): Δ7.09-7.07 (d, 2H, Ar-H), 6.85-6.82 (d, 2H, Ar-H), 6.77-6.74 (d, 4H, Ar-H) , 6.54-6.52 (d, 4H, Ar -H), 4.61 (s, 2H, CH 2), 3.80-3.79 (d, 4H, CH 2 -O), 3.65-3.62 (t, 1H, OH) 2.12 ( _{s, 6H, Ar-CH 3} ), 1.73-1.67 (m, 2H, (CH 2) 3 -H), 1.53-1.28 (m, 16H, -CH 2), 0.97-0.88 (t, 12H, -CH ₃ ).

3-4: 4- Di (4- (2-ethyl) hexyloxyphenyl) amino -3,5-dimethyl-1- Butoxymethylbenzene  synthesis

(2-ethylhexyloxyphenyl) amino-3,5-dimethylbenzyl alcohol was used instead of 4-di (4- (2-ethylhexyloxyphenyl) aminobenzyl alcohol in Example 2 -6. ≪ / RTI >

_{^{1 H NMR (CDCl 3 ppm.}} ): Δ7.09-7.07 (d, 2H, Ar-H), 6.85-6.82 (d, 2H, Ar-H), 6.77-6.74 (d, 4H, Ar-H) , 6.54-6.52 (d, 4H, Ar -H), 4.8 (s, 2H, CH 2), 3.80-3.79 (d, 4H, CH 2 -O), 3.65-3.62 (t, 1H, OH), 2.12 (s, 6H, Ar-CH 3), 1.73-1.67 (m, 8H, (CH 2) 3 -H), 1.53-1.28 (m, 16H, -CH 2), 0.97-0.88 (m, 15H, - CH _3).

Example  4: 4- (2- Butoxyethyl ) -N, N- Bis (4- (2-ethylhexyloxy) phenyl) naphthalene -L-amine

4-1: 2- (4- Nitronaphthalene -1-yl) acetic acid

2- (naphthalen-1-yl) acetic acid (10.0 g, 53.7 mmol) dissolved in acetic acid (20 ml) was slowly added dropwise to the nitric acid at 25-30 ° C. The mixture was stirred at the same temperature for 2 hours and stored at 20 ° C for one day. When yellow crystals were formed, they were recrystallized again with acetic acid. The yield was 28%.

^{1 H NMR (300 MHz, CDCl} 3) δ (TMS, ppm: δ 3.93 (s, 2H, -CH2), 7.24 (d, 1H, Ar-H), 7.57 (t, 1H, Ar-H), 7.80 (d, 1H, Ar-H), 7.99 (d, 1H, Ar-H), 8.60 (d, 1H Ar-H).

4-2: Synthesis of 2- (4-aminonaphthalen-1-yl) acetic acid

The compound 1 (5.00 g, 21.6 mmol) obtained in Example 4-1, Sn (3.30 g, 27.8 mmol) and hydrochloric acid (20 ml) were refluxed and stirred at 80 ° C for 2 hours. The resulting reaction product was washed with hydrochloric acid and then recrystallized. The yield was 86%.

^{1 H NMR (300 MHz, CDCl} 3) δ (TMS, ppm: δ 3.93 (s, 2H, -CH 2), 5.85 (s, 2H, -NH2), 6.42 (d, 1H, Ar-H), 6.93 (d, 1H, Ar-H), 7.34-7.45 (m, 2H, Ar-H), 8.00-8.21 (m, 1H, Ar-H).

4-3: Synthesis of 2- (4-aminonaphthalen-1-yl) ethanol

Borane (1.0 M in THF, 16.5 mL, 16.5 mmol) was slowly added dropwise to tetrahydrofuran in which the compound 2 of Example 4-2 (0.83 g, 4.11 mmol) was dissolved under nitrogen reflux and stirred. After 1 hour, the reaction was terminated by adding distilled water to the mixture, extracted with ethyl acetate, and washed several times with distilled water. The organic layer was dried over anhydrous sodium sulfate and the solvent was removed under reduced pressure to obtain crystals. The yield was 62%.

^{1 H NMR (300 MHz, CDCl} 3) δ (TMS, ppm: δ 3.18 (t, 2H, -CH 2 -), 3.88 (t, 2H, HO-CH 2 -), 4.78 (s, 1H, -OH ), 5.85 (s, 2H, -NH 2), 6.42 (d, 1H, Ar-H), 6.93 (d, 1H, Ar-H), 7.34-7.45 (m, 2H, Ar-H), 8.00- 8.21 (m, 1H, Ar-H).

4-4: 1- (2- Ethylhexyloxy )-4- Iodobenzene  synthesis

4-iodophenol (15 g, 68.18 mmol), potassium carbonate (24.5 g, 177.26 mmol) and DMF (70 mL) were added and the mixture was refluxed for 2 hours. After stirring, 2-ethylhexyl bromide (17.12 g, 88.63 mmol) And refluxed and stirred for 24 hours. When the reaction was completed, the temperature was lowered to room temperature, acid-treated with 70 mL of 2 M hydrochloric acid aqueous solution, extracted with dichloromethane, and washed several times with distilled water. The organic layer was dried over anhydrous magnesium sulfate, the solvent was removed under reduced pressure, and the product was isolated by column chromatography (silica, dichloromethane: hexane = 3: 2). The yield was 93%.

^{1 H NMR (300 MHz, CDCl} 3) δ (TMS, ppm): 0.97-0.88 (t, 6H, -CH 3), 1.53-1.28 (m, 8H, -CH 2), 1.73-1.67 (m, 1H , (CH ₂ ) ₃ -H), 3.80-3.79 (d, 2H, CH ₂ -O), 6.69-6.66 (d, 2H, Ar-H), 7.55-7.52 (d, 2H, Ar-H).

4-5: 2- (4- ( Bis (4- (2-ethylhexyloxy) phenyl) amino ) Naphthalen-1-yl) ethanol

The compound 4 (4.00 g, 2.25 mmol), Compound 3 (1.00 g, 5.34 mmol), Cu-Bronze alloy 0.08 g, 0.10 mmol, 18-crown-6 (0.17 g, 0.12 mmol) g, 24.2 mmol) was dissolved in 1,2-dichlorobenzene, refluxed for 2 days, and stirred. After completion of the reaction, the mixture was extracted with dichloromethane and water several times. The organic layer was dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure. The residue was purified by silica column chromatography (dichloromethane-hexane = 2: 1) Respectively. The yield was 59%.

^{1 H NMR (300 MHz, CDCl} 3) δ (TMS, ppm): 0.96 (12H, m, -CH 3), 1.20-1.35 (16H, m, -CH 2 -), 1.98 (2H, m, -CH -), 3.18 (2H, m , -CH 2 -), 3.88-4.03 (6H, m, -CH 2 -), 4.78 (1H, s, -OH), 6.32-6.62 (8H, m, Ar-H ), 6.93 (1H, d, Ar-H), 7.34-7.45 (2H, m, Ar-H). 8.02-8.21 (2H, m, Ar-H)

4-6: 4- (2- Butoxyethyl ) -N, N- Bis (4- (2-ethylhexyloxy) phenyl) naphthalene -One- Amine  synthesis

A dropping funnel containing compound 5 (3.00 g, 5.03 mmol) was placed in a 250 mL Schlenk flask containing sodium hydride (0.18 g, 7.50 mmol) and dried under vacuum. After drying was completed, the purified DMF was added to the flask and dropping device in 30 mL increments under nitrogen reflux, and then slowly added dropwise at 0 ° C. After refluxing and stirring at 100 ° C for 24 hours, n-butyl iodide (1.70 g, 9.24 mmol) was added. After the reaction was completed, the temperature was lowered to room temperature and acid treatment was performed with a 2M hydrochloric acid aqueous solution. After the acid treatment was completed, the reaction mixture was extracted with dichloromethane and washed several times with distilled water. The organic layer was dried over anhydrous magnesium sulfate, the solvent was removed under reduced pressure, and the product was isolated by column chromatography (dichloromethane). The yield was 74%.

_{1H NMR (300 MHz, CDCl 3} ) δ (TMS, ppm): 0.96 (15H, m, -CH 3), 1.20-1.35 (20H, m, -CH 2 -), 3.16-3.37 (4H, m, - _{CH 2 -), 3.88-4.03 (6H} , m, -CH 2 -), 6.32-6.62 (8H, m, Ar-H), 6.93 (1H, d, Ar-H), 7.34-7.45 (2H, m , Ar-H). 8.02-8.21 (2H, m, Ar-H).

Example 5 : N- (4- (2- Butoxyethyl ) Phenyl ) -7- (2- Ethylhexyloxy ) -N- (7- (2- Ethylhexyloxy ) -9,9-dimethyl-9H- Fluorene Yl) -9,9-dimethyl-9H- Fluorene -2- Amine  synthesis

5-1: 6- Iodo -9H- Fluorene 3-ol

(5.00 g, 27.6 mmol) was dissolved in a boiling solvent (acetic acid: water: sulfuric acid / 100: 20: 3) and H ₅ IO ₆ (1.10 g, 4.83 mmol) and I ₂ 2.30 g, 9.06 mmol). After 4 hours, the resulting precipitate was filtered, and the filtrate was washed with 2M aqueous sodium carbonate solution and water. The resulting crystals were recrystallized in hexane. The yield was 72%.

^{1 H NMR (300 MHz, CDCl} 3) δ (TMS, ppm): 4.12 (2H, s, -CH 2), 6.75 (1H, d, Ar-H), 7.31-7.38 (3H, m, Ar-H ), 7.66 (1H, d, Ar-H), 8.22 (1H, s, Ar-H).

5-2: 6- Iodo -9,9-dimethyl-9H- Fluorene 3-ol

T-BuO ^- K ⁺ (2.40 g, 21.4 mmol) was added to the cooled anhydrous tetrahydrofuran in which the compound 1 (3.00 g, 30.1 mmol) was dissolved, followed by stirring at room temperature for 1.5 hours. Iodomethane (2.78 g, 19.6 mmol) was added and stirred for two hours. The resulting KI was filtered, and the solvent was removed to obtain crystals in a yield of 70%.

^{1 H NMR (300 MHz, CDCl} 3) δ (TMS, ppm): 1.67 (6H, s, -CH 3), 6.75 (1H, s, Ar-H)), 7.31-7.38 (3H, m, Ar- H), 7.66 (1H, d, Ar-H), 8.22 (1H, s, Ar-H).

5-3: 3- (2- Ethylhexyloxy ) -6- Iodo -9,9-dimethyl-9H- Fluorene  synthesis

The compound 2 (22.9 g, 68.18 mmol), potassium carbonate (24.5 g, 177.26 mmol) and DMF (70 mL) were added and the mixture was refluxed and stirred for 2 hours. 2-Ethylhexyl bromide (17.12 g, 88.63 mmol) And the mixture was refluxed and stirred for 24 hours. After the reaction was completed, the temperature was lowered to room temperature, acid-treated with 70 mL of 2M hydrochloric acid, extracted with dichloromethane, and washed several times with distilled water. The organic layer was dried over anhydrous magnesium sulfate, the solvent was removed under reduced pressure, and the product was isolated by column chromatography (silica, dichloromethane: hexane = 2: 1). The yield was 82%.

^{1 H NMR (300 MHz, CDCl} 3) δ (TMS, ppm): 0.96 (6H, t, -CH 3), 1.25-1.33 (8H, m, -CH 2 -), 1.67 (6H, s, -CH _{3), 3.78-4.11 (2H, m} , -CH 2 -), 6.79 (1H, d, Ar-H), 7.32-7.44 (3H, m, Ar-H), 7.66 (1H, d, Ar-H ), 8.22 (1H, s, Ar-H).

5-4: 2- (4- (Bis (7- (2- Ethylhexyloxy ) -9,9-dimethyl-9H- Fluorene Yl) amino) phenyl) ethanol

Cu-Sn alloy (0.10 g, 1.57 mmol) and 18-crown-6 (0.24 g, 0.91 mmol) were added to the above compound 3 (7.20 g, 16.1 mmol) ) And potassium carbonate (4.43 g, 32.1 mmol) were dissolved in 1,2-dichlorobenzene, and the mixture was refluxed for 2 days and stirred. After completion of the reaction, the mixture was extracted with dichloromethane and distilled water several times. The organic layer was dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure. The residue was purified by silica column chromatography (dichloromethane-hexane = 2: 1) Respectively. The yield was 59%.

^{1 H NMR (300 MHz, CDCl} 3) δ (TMS, ppm): 0.96 (12H, m, -CH 3), 1.25-1.35 (16H, m, -CH 2 -), 1.67 (12H, s, -CH _{3), 1.98 (2H, m} , -CH-), 2.75 (2H, t, -CH 2 -), 3.63 (2H, t, -CH 2 -), 3.78-4.12 (4H, m, -CH 2 - ), 4.78 (1H, s, -OH), 6.41 (2H, m, Ar-H). (2H, d, Ar-H), 6.73-6.88 (6H, m, Ar-H), 7.35 (2H, s, Ar-H), 7.44-7.60 (4H, m, Ar-H).

5-5: N- (4- (2- Butoxyethyl ) Phenyl ) -7- (2- Ethylhexyloxy ) -N- (7- (2- Ethylhexyloxy ) -9,9-dimethyl-9H- Fluorene Yl) -9,9-dimethyl-9H- Fluorene -2- Amine  synthesis

A dropping funnel containing 3.00 g (3.86 mmol) of compound 4 was placed in a 250 mL Schlenk flask containing sodium hydride (0.14 g, 5.83 mmol) and dried under vacuum. When drying was complete, 30 mL of purified DMF was added to the flask and dropping funnel under nitrogen reflux and slowly added dropwise at 0 ° C. After refluxing and stirring at 100 DEG C for 24 hours, n-butyl iodide (1.30 g, 7.06 mmol) was added. After the reaction was completed, the temperature was lowered to room temperature and acid-treated with 2M HCl aqueous solution. After the acid treatment was completed, the reaction mixture was extracted with dichloromethane and washed several times with distilled water. The organic layer was dried over anhydrous magnesium sulfate, the solvent was removed under reduced pressure, and the product was isolated by column chromatography. The yield was 64%.

^{1 H NMR (300 MHz, CDCl} 3) δ (TMS, ppm): 0.96 (15H, m, -CH 3), 1.25-1.46 (20H, m, -CH 2 -), 1.67 (12H, s, -CH _{3), 1.98 (2H, m} , -CH-), 2.75 (2H, t, -CH 2 -), 3.37 (2H, t, -CH 2 -), 3.70-3.78 (6H, m, -CH 2 - ), 6.41 (2H, m, Ar-H). (2H, d, Ar-H), 6.73-6.88 (6H, m, Ar-H), 7.35 (2H, s, Ar-H), 7.44-7.60 (4H, m, Ar-H).

Example  6: 9- (4- Butoxyphenyl ) -3,6- Bis (4- Methoxyphenyl ) -9H- Carbazole  synthesis

6-1: 9- (4- Methoxyphenyl ) -9H- Carbazole  synthesis

To a round-bottomed flask were added carbazole (7 g, 41.86 mmole), 4-iodoanisole (12.74 g, 54.42 mmole), copper iodide (1.99 g, 10.47 mmol), K ₂ CO ₃ (34.72 g, 251, , 18-crown-6 (1.11 g, 4.19 mmol) were dissolved in 30 ml of 1,2-dichlorobenzene, and the mixture was stirred at 180 ° C for 24 hours. Then, copper and salts were filtered using a filter paper and extracted with ethyl acetate. Washed several times. The organic layer was dried over anhydrous magnesium sulfate, the solvent was removed under reduced pressure, and the product was isolated by column chromatography.

¹ H NMR (300 MHz, CDCl ₃ )? 3.90 (s, -OMe, 3H), 8.13 (d, Ar-H, 2H), 7.44 2H), 7.32 (d, Ar-H, 2H), 7.27

6-2: 3,6- Dibromo -9- (4- Methoxyphenyl ) -9H- Carbazole  synthesis

9- (4-methoxyphenyl) -9H-carbazole (3 g, 11.22 mmole) was dissolved in 30 ml of MC, N-bromosuccinimide (3.39 g, 22.44 mmole) was added and the mixture was stirred at room temperature for 4 hours. The reaction was terminated by adding distilled water, extracted with ethyl acetate, and washed several times with distilled water. The organic layer was dried over anhydrous magnesium sulfate, the solvent was removed under reduced pressure, and the product was isolated by column chromatography.

¹¹ H NMR (300MHz, CDCl ₃ H), 7.36 (d, Ar-H, 2H), 7.10 (m, Ar-H) -H, 2H), 7.06 (d, Ar-H, 2H)

6-3: 4- (3,6- Dibromo -9H- Carbazole -9-yl) phenol

The 3,6-dibromo-9- (4-methoxyphenyl) -9H-carbazole (3 g, 6.96 mmole) is dissolved in 30 mL of dichloromethane and the reaction temperature is lowered to 0 캜. Of BBr ₃ (1.65mL, 17.40mmol) at 0 ℃ further was slowly added and the mixture was stirred for 3 hours. Water was added in an amount of 3 equivalents of BBr ₃ to terminate the reaction, extracted with ethyl acetate, and washed several times with distilled water. The organic layer was dried over anhydrous magnesium sulfate, the solvent was removed under reduced pressure, and the product was isolated by column chromatography.

¹ H NMR (300 MHz, CDCl ₃ ) 8.13 (s, Ar-H, 2H), 7.65 (d, Ar-H, 2H), 7.36 2H), 7.06 (d, Ar-H, 2H)

6-4: 4- (3,6- Bis (4- Methoxyphenyl ) -9H- Carbazole -9-yl) phenol

To a 250 mL round flask was added 4- (3,6-dibromo-9H-carbazol-9-yl) phenol (2 g, 4.80 mmol), 4- methoxyphenylboronic acid (2.19 g, 14.39 mmol) (1.99 g, 14.39 mmole) and tetrakis (triphenylphosphorine) palladium (0) (0.55 g, 0.1 mmole) were added and 60 ml of toluene / ethanol / H ₂ O (3: 1: 1) was added under nitrogen reflux The post-treatment temperature is raised to 80 DEG C and reflux agitated for 48 hours. After completion of the reaction, the reaction mixture was extracted with ethyl acetate and washed several times with distilled water. The organic layer was dried over anhydrous magnesium sulfate, the solvent was removed under reduced pressure, and the product was isolated by column chromatography.

¹ H NMR (300 MHz, CDCl ₃ ) 3.88 (s, -OCH ₃ , 6H), 7.01-7.03 (d, -Ar, 4H), 7.06 2H), 7.48-7.51 (d, -Ar, 2H), 7.63-7.65 (m, -Ar, 6H), 8.27

6-5: 9- (4- Butoxyphenyl ) -3,6- Bis (4- Methoxyphenyl ) -9H- Carbazole  synthesis

To a 250 mL round flask was added 4- (3,6-bis (4-methoxyphenyl) -9H-carbazol-9-yl) phenol (2 g, 3.79 mmol) and 20 mL anhydrous tetrahydrofuran under nitrogen reflux After dissolution, the reaction vessel is cooled to 0 占 폚. After cooling was complete, sodium hydride (0.17 g, 5.7 mmole) was added and stirred at room temperature for 1 hour, then 2-iodobutanol (1.7 g, 5.8 mmole) was slowly added dropwise. After stirring at room temperature for 24 hours, distilled water was added to the reaction vessel to stop the reaction. After completion of the reaction, the reaction mixture was extracted with ethyl acetate, and the organic layer was washed with distilled water several times. Upon completion of washing, the organic layer was dried over anhydrous magnesium sulfate, the solvent was removed under reduced pressure, and the product was isolated by column chromatography.

_{^{1 H NMR (300MHz, CDCl 3}} ) 1.83-1.94 (t, -CH 3, 3H), (m, -CH 2, 2H), 1.44-1.50 (m, -CH 2, 2H), 3.28-3.32 (t _{, -CH 2, 2H), 3.88} (s, -OCH3, 6H), 7.01-7.03 (d, -Ar, 4H), 7.06 (d, Ar-H, 2H), 7.10 (m, Ar-H, 2H , 7.48-7.51 (d, -Ar, 2H), 7.63-7.65 (m, -Ar, 6H), 8.27

6-6: 9- (4- Butoxyphenyl ) -3,6- Dibromo -9H- Carbazole  synthesis

In a 250 mL flask, 4- (3,6-dibromo-9H-carbazol-9-yl) phenol (2 g, 4.8 mmole) was added and dissolved in 20 mL of anhydrous tetrahydrofuran under nitrogen reflux. The vessel was cooled to 0 < 0 > C. After cooling was complete, sodium hydride (0.14 g, 5.92 mmole) was added and stirred at room temperature for 1 hour and then l-iodobutane (0.84 g, 4.56 mmole) was slowly added dropwise. After stirring at room temperature for 24 hours, distilled water was added to the reaction vessel to stop the reaction. After completion of the reaction, the reaction mixture was extracted with ethyl acetate, and the organic layer was washed with distilled water several times. Upon completion of washing, the organic layer was dried over anhydrous magnesium sulfate, the solvent was removed under reduced pressure, and the product was isolated by column chromatography.

¹ H NMR (300 MHz, CDCl ₃ ) 8.13 (s, Ar-H, 2H), 7.65 (d, Ar-H, 2H), 7.36 2H), 7.06 (d, Ar -H, 2H), 1.83-1.94 (t, -CH 3, 3H), (m, -CH 2, 2H), 1.44-1.50 (m, -CH 2, 2H), _{3.28-3.32 (t, -CH 2, 2H} )

6-7: 9- (4- Butoxyphenyl ) -3,6-di (1H- Imidazole -1-yl) -9H- Carbazole  synthesis

To a 250 mL round flask was added 9- (4-butoxyphenyl) -3,6-dibromo-9H-carbazole (3 g, 6.34 mmole), imidazole (1.04 g, 15.22 mmol), copper iodide , 1.27 mmole), 1,10-phenanthroline (0.23 g, 1.27 mmole) and potassium carbonate (5.26 g, 38.04 mmol) were added to the solution, and 20 mL of para-xylene was added under nitrogen reflux to dissolve And the mixture was refluxed and stirred at 150 ° C for 24 hours. The reaction was terminated by adding distilled water, extracted with ethyl acetate, and the organic layer was washed several times with distilled water. Upon completion of washing, the organic layer was dried over anhydrous magnesium sulfate, the solvent was removed under reduced pressure, and the product was isolated by column chromatography.

_{^{1 H NMR (300MHz, CDCl 3}} ) 1.83-1.94 (t, -CH 3, 3H), (m, -CH 2, 2H), 1.44-1.50 (m, -CH 2, 2H), 3.28-3.32 (t _{, -CH 2, 2H), 3.88} (s, -OCH 3, 6H), 7.14-7.17 (d, Ar-H, 2H), 7.36-7.49 (m, -Ar, 10H), 7.91 (s, -Ar , ≪ / RTI > 2H), 8.13 (d, -Ar, 2H)

6-8: 9- (4- Butoxyphenyl ) -3,6-bis (2,3- Dihydrothiethano [3,4-b] [1,4] dioxin -5-yl) -9H- Carbazole

To a 250 mL round flask was added 9- (4-butoxyphenyl) -3,6-dibromo-9H-carbazole (2 g, 4.23 mmole), 2- (tributylstynyl) (0.59 g, 0.85 mmole) of bis (triphenylphosphine) palladium (II) chloride (4.37 g, 10.14 mmol) and 30 mL of DMF were added and dissolved under nitrogen reflux. And the mixture was refluxed and stirred. After completion of the washing, the organic layer was dried over anhydrous magnesium sulfate, the solvent was removed under reduced pressure, and the product was isolated by column chromatography.

_{^{1 H NMR (300MHz, CDCl 3}} ) 1.83-1.94 (t, -CH 3, 3H), (m, -CH 2, 2H), 1.44-1.50 (m, -CH 2, 2H), 3.28-3.32 (t _{, -CH 2, 2H), 3.88} (s, -OCH3, 6H), 7.09-7.12 (d, Ar-H), 7.29-7.32 (d, Ar-H, 2H), 7.41-7.44 (d, -Ar , 2H), 7.74-7.77 (d, -Ar, 2H), 8.44 (s, -Ar, 2H)

Example 7 : 9- (4- Butoxy -3,5- Dimethylphenyl ) -3,6- Bis (4- Methoxyphenyl ) -9H- Carbazole  synthesis

7-1: 4- Methoxyphenylboronic acid  synthesis

1-Bromo-4-methoxybenzene (15.0 g, 80.2 mmole) is added to a 250 mL round-bottomed flask, and 150 mL of anhydrous tetrahydrofuran is added to dissolve and then the temperature is cooled to -78 ° C. When the cooling was completed, butyl lithium (5.65 g, 88.2 mmole) was slowly added dropwise while keeping the temperature low, followed by stirring for 1 hour. Trimethylborate (16.7 g, 160.4 mmole) was slowly added dropwise at the same temperature, stirred for an additional 1 hour, then warmed to room temperature and stirred for 12 hours. After the reaction was completed, the pH was adjusted to 2 by adding a 6M aqueous hydrochloric acid solution, extracted with ethyl acetate, and washed several times with distilled water. Upon completion of the washing, the organic layer was dried with anhydrous magnesium sulfate and filtered. The organic solvent was evaporated, the residue was dissolved in a small amount of tetrahydrofuran, and then n-hexane was added at 0 ° C to precipitate crystals, followed by filtration and drying.

_{^{1 H NMR (300MHz, CDCl 3}} ) δ 3.81 (s, 3H, -OCH 3), 6.89-6.91 (d, -Ar, 2H), 7.72-7.74 (d, -Ar, 2H)

7-2: 9- (4- Methoxy -3,5- Dimethylphenyl ) -9H- Carbazole  synthesis

To a round-bottom flask was added carbazole (7 g, 41.86 mmole), 5-iodo-2-methoxy-1,3-dimethylbenzene (14.26 g, 54.42 mmole), copper iodide (1.99 g, 10.47 mmol) (1.11 g, 4.19 mmol) was added to the solution, and 30 mL of 1,2-dichlorobenzene was added thereto to dissolve. After stirring at 180 ° C for 24 hours, copper And the salts were extracted with ethyl acetate and washed several times with distilled water. Upon completion of washing, the organic layer was dried over anhydrous magnesium sulfate, the solvent was removed under reduced pressure, and the product was isolated by column chromatography.

¹ H NMR (300 MHz, CDCl ₃ )? 3.90 (s, -OMe, 3H), 8.13 (d, Ar-H, 2H), 7.44 2H), 7.32 (d, Ar-H, 2H), 7.10

7-3: 3,6- Dibromo -9- (4- Methoxy -3,5- Dimethylphenyl ) -9H- Carbazole  synthesis

9- (4-methoxy-3,5-dimethylphenyl) -9H-carbazole (3.38 g, 11.22 mmole) was added to a 250 mL round-bottomed flask, and 30 mL of dichloromethane was added to dissolve the solution. N-Bromosuccine (3.39 g, 22.44 mmole) was added thereto, and the mixture was stirred at room temperature for 4 hours. After completion of the reaction, the reaction mixture was extracted with ethyl acetate and washed several times with distilled water. Upon completion of washing, the organic layer was dried over anhydrous magnesium sulfate, the solvent was removed under reduced pressure, and the product was isolated by column chromatography.

_{^{1 H NMR (300MHz, CDCl 3}} ) δ2.35 (s, CH, 6H), 3.90 (s, -OMe, 3H), 8.13 (s, Ar-H, 2H), 7.65 (d, Ar-H, 2H ), 7.36 (d, Ar-H, 2H), 7.06 (d,

7-4: 4- (3,6- Dibromo -9H- Carbazole -9-yl) -2,6-dimethylphenol

To a 250 mL round flask was added 3,6-dibromo-9- (4-methoxy-3,5-dimethylphenyl) -9H-carbazole (3.2 g, 6.96 mmole) and 30 mL of dichloromethane was added to dissolve Gt; 0 C < / RTI > When cooling is completed, BBr ₃ (1.65 mL, 17.40 mmol) is slowly added dropwise and stirred for 3 hours, and then the reaction is terminated by adding distilled water in an amount corresponding to 3 equivalents of BBr ₃ used in the reaction. After completion of the reaction, the reaction mixture is extracted with ethyl acetate and washed several times with distilled water. Upon completion of washing, the organic layer was dried over anhydrous magnesium sulfate, the solvent was removed under reduced pressure, and the product was isolated by column chromatography.

_{^{1 H NMR (300MHz, CDCl 3}} ) 2.35 (s, CH, 6H), 8.13 (s, Ar-H, 2H), 7.65 (d, Ar-H, 2H), 7.36 (d, Ar-H, 2H) , 7.06 (d, Ar-H, 2H)

7-5: 4- (3,6- Bis (4- Methoxyphenyl ) -9H- Carbazole -9-yl) -2,6-dimethylphenol

To a 250 mL round flask was added 4- (3,6-dibromo-9H-carbazol-9-yl) -2,6-dimethylphenol (2.13 g, 4.80 mmole), 4- methoxyphenylboronic acid Ethanol / H ₂ O (3: 1, 1: 1) was added under nitrogen reflux under nitrogen atmosphere, and potassium carbonate (1.99 g, 14.39 mmole) and tetrakis (triphenylphosphorine) palladium : 1) 60 mL was added to dissolve. Followed by reflux agitation at 80 ° C for 48 hours. After completion of the reaction, the reaction mixture is extracted with ethyl acetate and washed several times with distilled water. Upon completion of washing, the organic layer was dried over anhydrous magnesium sulfate, the solvent was removed under reduced pressure, and the product was isolated by column chromatography.

_{^{1 H NMR (300MHz, CDCl 3}} ) 2.35 (s, CH, 6H), 3.88 (s, -OCH3, 6H), 7.01-7.03 (d, -Ar, 4H), 7.06 (d, Ar-H, 2H) , 7.48-7.51 (d, -Ar, 2H), 7.63-7.65 (m, -Ar, 6H), 8.27

7-6: 9- (4- Butoxy -3,5- Dimethylphenyl ) -3,6- Bis (4- Methoxyphenyl ) -9H- Carbazole  synthesis

To a 250 mL round flask was added 4- (3,6-bis (4-methoxyphenyl) -9H-carbazol-9-yl) -2,6-dimethylphenol (1.89 g, 3.79 mmole) and anhydrous tetrahydrofuran 20 mL was added to dissolve and the reaction vessel was cooled to 0 ° C. After cooling, sodium hydride (0.17 g, 5.7 mmole) was added. After stirring at room temperature for 1 hour, 2-iodobutanol (1.7 g, 5.8 mmole) was slowly added dropwise. After stirring at room temperature for 12 hours, water was added to the reaction vessel to terminate the reaction. After the reaction was completed, the solvent was removed, and the reaction mixture was extracted with ethyl acetate and washed several times with distilled water. Upon completion of washing, the organic layer was dried over anhydrous magnesium sulfate, the solvent was removed under reduced pressure, and the product was isolated by column chromatography.

_{^{1 H NMR (300MHz, CDCl 3}} ) 1.83-1.94 (t, -CH 3, 3H), (m, -CH 2, 2H), 1.44-1.50 (m, -CH 2, 2H), 2.35 (s, CH , 6H), 3.28-3.32 (t, -CH 2, 2H), 3.88 (s, -OCH3, 6H), 7.01-7.03 (d, -Ar, 4H), 7.06 (d, Ar-H, 2H), 7.48-7.51 (d, -Ar, 2H), 7.63-7.65 (m, -Ar, 6H), 8.27

Example 8 : 9- Hexyl -3,6- Bis (4- Methoxyphenyl ) -9H- Carbazole  synthesis

8-1: 4- Methoxyphenylboronic acid  synthesis

1-Bromo-4-methoxybenzene (15.0 g, 80.2 mmole) was added to a 250 mL round-bottomed flask, and 150 mL of anhydrous tetrahydrofuran was added to dissolve and then cooled to -78 ° C. When the cooling was completed, butyl lithium (5.65 g, 88.2 mmole) was slowly added dropwise while keeping the temperature low, followed by stirring for 1 hour. Trimethylborate (16.7 g, 160.4 mmole) was slowly added dropwise at the same temperature, and the mixture was further stirred for 1 hour. After the temperature was elevated to room temperature, the mixture was stirred at room temperature for 12 hours. After the reaction was completed, the pH was adjusted to 2 with 6M hydrochloric acid, extracted with ethyl acetate, and washed several times with distilled water. Upon completion of the washing, the organic layer was dried over anhydrous magnesium sulfate and filtered. The organic solvent was evaporated and the residue was dissolved in a small amount of tetrahydrofuran, and then n-hexane was added at 0 ° C to precipitate crystals, which were then filtered and dried.

_{^{1 H NMR (300MHz, CDCl 3}} ) δ 3.81 (s, 3H, -OCH 3), 6.89-6.91 (d, -Ar, 2H), 7.72-7.74 (d, -Ar, 2H)

8-2: 9- Hexyl - Carbazole  synthesis

(5 g, 29.9 mmole), 1-bromohexane (4.84 g, 29.3 mmole), copper iodide (0.57 g, 2.99 mmol) and potassium carbonate (12.4 g, 89.71 mmol) were added to a 250 mL round- , 18-crown-6 (0.79 g, 2.99 mmol) were added, and 20 mL of 1,2-dichlorobenzene was added thereto under nitrogen reflux and dissolved, followed by stirring at 180 ° C for 24 hours. The copper and salts were filtered with filter paper, extracted with ethyl acetate, and washed several times with distilled water. After the washing was completed, the organic layer was dried over anhydrous magnesium sulfate, the solvent was removed under reduced pressure, and the product was isolated by column chromatography.

_{^{1 H NMR (300MHz, CDCl 3}} ) δ 0.86-1.90 (t, -CH 3, 3H), 1.31-1.43 (m, -CH 2, 6H), 1.89-1.92 (m, -CH 2, 2H), 4.31 _{-4.36 (t, -CH 2, 2H} ), 7.22-7.28 (m, -Ar, 2H), 7.41-7.49 (m, -Ar, 4H), 8.10-8.13 (d, -Ar, 2H)

8-3: 3, 6- Dibromo -9- Hexyl -9H- Carbazole  synthesis

In a 250 mL round flask, 9- (4-hexyl-9H-carbazole (6.2 g, 24.66 mmole) was added and 30 mL of THF was added to dissolve. N-Bromosuccinimide (9 g, 50.56 mmole) The organic layer was dried over anhydrous magnesium sulfate, and the solvent was removed under reduced pressure, and the residue was purified by column chromatography The product was isolated.

_{^{1 H NMR (300MHz, CDCl 3}} ) δ 0.86-1.90 (t, -CH 3, 3H), 1.31-1.43 (m, -CH 2, 6H), 1.89-1.92 (m, -CH 2, 2H), 4.31 _{-4.36 (t, -CH 2, 2H} ), 7.36 (d, Ar-H, 2H), 7.10 (m, Ar-H, 2H), 7.06 (d, Ar-H, 2H)

8-4: 9- Hexyl -3,6- Bis (4- Methoxyphenyl ) -9H- Carbazole  synthesis

Except that 3,6-dibromo-9-4-hexyl-9H-carbazole was used instead of 4- (3,6-bis (4-methoxyphenyl) -9H-carbazol- Was prepared in the same manner as in Example 6-5.

_{^{1 H NMR (300MHz, CDCl 3}} ) δ 0.86-1.90 (t, -CH 3, 3H), 1.31-1.43 (m, -CH 2, 6H), 1.89-1.92 (m, -CH 2, 2H), 4.31 _{-4.36 (t, -CH 2, 2H} ), 7.01-7.05 (d, Ar-H, 4H), 7.43-7.46 (d, Ar-H, 2H), 7.63-7.69 (d, Ar-H, 6H) , 8.29 (s, Ar-H, 2H)

8-5: 9- Hexyl -3,6-di (1H- Imidazole -1-yl) -9H- Carbazole  synthesis

The procedure of Example 6-7 was repeated except that 3,6-dibromo-9-hexyl-9H-carbazole was used in place of 9- (4-butoxyphenyl) -3,6-dibromo-9H- . ≪ / RTI >

_{^{1 H NMR (300MHz, CDCl 3}} ) 0.86-0.90 (t, -CH 3, 3H), 1.32-1.43 (m, -CH 2, 6H), 1.90-1.92 (t, -CH 2, 2H), 4.36- _{4.4 (t, N-CH 2} , 2H), 7.26 (s, Ar-H, 2H), 7.36 (s, Ar-H, 2H), 7.53 (s, -Ar, 4H), 7.90 (s, -Ar , 2H), 8.09 (s, -Ar, 2H)

8-6: 3,6- Bis (2,3- Dihydrothiethano [3,4-b] [1,4] dioxin Yl) -9- Hexyl -9H-carbazole < / RTI >

The procedure of Example 6-8 was repeated except that 3,6-dibromo-9-hexyl-9H-carbazole was used instead of 9- (4-butoxyphenyl) -3,6-dibromo-9H- Were prepared in the same manner.

_{^{1 H NMR (300MHz, CDCl 3}} ) 0.86-0.90 (t, -CH 3, 3H), 1.32-1.43 (m, -CH 2, 6H), 1.90-1.92 (t, -CH 2, 2H), 3.28- _{3.32 (t, -CH 2, 2H} ), 3.88 (s, -OCH 3, 6H), 4.36-4.4 (t, N-CH 2, 2H), 7.09-7.12 (d, Ar-H), 7.29-7.32 (d, -Ar, 2H), 7.41-7.44 (d, -Ar, 2H), 7.74-7.77

Example 9 : The hole transport material (HTM)  Containing ionic Quasi-solid  Polymer Electrolyte E3 )

An ionic liquid electrolyte was prepared by mixing the following materials in the acetonitrile solvent to the molar concentrations described below:

DMP II (1,2-dimethyl-3-propylimidazolium iodide): 0.6 mol (M),

LiI: 0.1 mol (M)

I ₂ : 0.05 mol (M)

tBP (tetrabutylammonium hexafluorophosphate): 0.5 mol (M)

A polyelectrolyte (PEO) having a molecular weight (M _n ) of 1,000,000 and a PPG [poly (propylene glycol)] having a molecular weight (M _n ) of 725 were added to the liquid electrolyte based on 100 parts by weight of the liquid electrolyte, 6 parts by weight and 4 parts by weight were mixed, and 9 parts by weight of 9- (2-butoxyethyl) -3,6-bis (4-methylphenyl) Hydroxyphenyl) -9H-carbazole (BMPC) were mixed in an amount of 20 parts by weight to prepare a quasi-solid polymer electrolyte containing a hole transporting material (HTM).

Example 10 ~ 13: The hole transport material (HTM)  Containing ionic Quasi-solid  Preparation of Polymer Electrolyte

9- (2-butoxyethyl) -3,6-bis (4-methoxyphenyl) -9H-carbazole (BMPC), which is a hole transport material of the present invention, (Example 10), 10 parts by weight (Example 11), 15 parts by weight (Example 12) and 30 parts by weight (Example 13) were prepared in the same manner as in Example 9, Quasi - solid polymer electrolyte containing the substance (HTM) was prepared.

Comparative Example 1 : PEO  Polymer Electrolyte E1 )

10 parts by weight of PEO [Poly (ethylene oxide)] having a molecular weight (M _n ) of 1,000,000 based on 100 parts by weight of the liquid electrolyte was mixed with the liquid electrolyte prepared in Example 8 to prepare a PEO polymer electrolyte.

Comparative Example 2 : PEO / PPG  Polymer Electrolyte E2 )

The liquid electrolyte prepared in Example 9, wherein the liquid electrolyte is 100 weight by parts based on molecular weight (M _n) is 1,000,000, the PEO [Poly (ethylene oxide)] 6 parts by weight and a molecular weight (M _n) 725 of PPG [Poly (propylene glycol)] were mixed to prepare a PEO / PPG polymer electrolyte.

Example  14: Manufacture of dye-sensitized solar cell

A dye-sensitized solar cell was prepared according to the following process.

1. FTTO glass substrate was put into a sodium hydroxide cleaning solution and ultrasonically washed for 1 hour, washed with distilled water and ethanol, and dried using nitrogen gas.

2. The washed FTO glass substrate was immersed in a 40 mM aqueous solution of TiCl ₄ and heated in an oven at 70 ° C for 30 minutes.

3.TiCl ₄ The treated FTO glass substrate was washed with distilled water and ethanol, dried using nitrogen gas, and heated in an oven at 80 ° C for 10 minutes.

4. Next, a 13 nm particle size TiO ₂ paste was coated on the TiCl ₄ -treated FTO glass substrate by a doctor blade method and dried at room temperature (20 ° C) for 2 hours.

5. The FTO glass substrate coated with TiO ₂ was dried in an oven at 80 ° C for 2 hours.

6. Then, the FTO glass substrate coated with TiO ₂ was fired at 500 ° C for 30 minutes while gradually raising the temperature using a heating furnace.

7. The fired FTO glass substrate was coated with a TiO ₂ paste having a particle size of 400 nm by a doctor blade method. After drying at room temperature (20 ° C) for 2 hours, the mixture was calcined at 500 ° C for 30 minutes while gradually raising the temperature using a heating furnace.

8. Subsequently, the fired FTO glass substrate was immersed in an aqueous 40 mM TiCl ₄ solution for 30 minutes, washed with distilled water and ethanol, dried using nitrogen gas, and dried in an oven at 80 ° C for 10 minutes.

9. The dried FTO glass substrate was then sintered for 30 minutes using a heating gun, dipped in a N719 dye slution (EtOH) diluted to 0.3 mM, and dried for 12 hours The dye was adsorbed.

10. The FTO glass substrate on which the dye was adsorbed was washed with ethanol and then dried using nitrogen gas.

11. Two holes with a diameter of 0.6 mm were drilled through the FFT glass substrate (for the counter electrode) to inject the electrolyte.

12. Next, the FTO glass substrate was immersed in an aqueous solution of H ₂ O / acetone / HCl (4: 4: 2, v / v / v%) for 1 hour and washed with an ultrasonic cleaner and dried in a 70 ° C. oven for 30 minutes .

13. Next, the FTO glass substrate was spin-coated with a Pt solution (2 mg of H ₂ PtCl ₆ dissolved in 1 mL of ethanol solution) and heated at 400 ° C. for 15 minutes using a heating gun.

14. The oxidation electrode and the reducing electrode prepared above were combined using a polymer sealing film using a hot press heated to 80 ° C.

15. The ionic quasi-solid polymer electrolyte (E3) containing HTM prepared in Example 9 was injected into the combined cells using a vacuum pump line, and then the solvent was evaporated on a hot plate at 60 ° C free-standing semi-solid polymer electrolyte.

16. The two holes were sealed with a sealing film and a cover glass.

Example  15 ~ 18: Manufacture of dye-sensitized solar cell

The procedure of Example 14 was repeated except that the ionic quasi-solid polymer electrolyte (E3) prepared in Example 9 was replaced with the ionic quasi-solid polymer electrolyte prepared in each of Examples 10 to 13 above To prepare solar cells of Examples 15 to 18, respectively.

Comparative Example 3  : Preparation of dye-sensitized solar cell

A solar cell was prepared in the same manner as in Example 14 except that the PEO solid electrolyte (E1) prepared in Comparative Example 1 was used as the electrolyte.

Comparative Example 4  : Preparation of dye-sensitized solar cell

A solar cell was prepared in the same manner as in Example 14 except that the PEO / PPG solid electrolyte (E2) prepared in Comparative Example 2 was used as the electrolyte.

Test Example  1: Measurement of ion conductivity of electrolyte

In order to measure the ionic conductivity of the polymer electrolyte prepared in Example 9 (E3), Comparative Example 1 (E1) and Comparative Example 2 (E2), the FTO | electrolyte | Pt cell was manufactured and the AC impedance was measured. , And the results are shown in Table 1 below. ≪ tb > < TABLE >

As can be seen from the above Table 1, the ionic conductivity of the electrolyte (E3) of Example 9, that is, BMPC (9- (2-butoxyethyl) -3,6-bis Phenyl) -9H-carbazole) in 20 parts by weight of the quasi-solid polymer electrolyte of the present invention exhibited the highest ionic conductivity.

Test Example  2: Performance evaluation of dye-sensitized solar cell

The photocurrent-voltage was measured under the illumination conditions of 1 sun (100 mW / cm ² ) using the dye-sensitized solar cell prepared in Example 14 and Comparative Examples 3 and 4, and the results are shown in Table 2 below . The current-voltage curves of the dye-sensitized solar cells of Example 14 and Comparative Examples 3 and 4 are shown in FIG. The photoelectric conversion efficiency (IPCE) is shown in Fig.

1 and 2, in the case of the solar cell using the electrolyte E3 including the hole transporting material (BMPC) of the present invention, V _oc was 0.78 V at 1 sun (100 mW / cm ² ) , J _{sc of} 15.22 mA / cm ² , the fill factor of 0.74%, and η of 8.64%.

Test Example  3: Of hole transport material (HTM)  Performance evaluation of dye-sensitized solar cell with concentration variation

In order to evaluate the performance of the dye-sensitized solar cells of Examples 14 to 18 prepared by including the quasi-solid polymer electrolyte (manufactured by Examples 10 to 13) containing different concentrations of hole transport materials (BMPC), AM 1.5 (100 mW / cm < ² >).

As a result of the measurement, the current-voltage curve was as shown in FIG.

The best performance of the solar cell of Example 14 using the electrolyte of Example 9 including 20 parts by weight of BMPC compared to the other concentrations in the current-voltage curve of FIG. 3 is that the quasi-solid polymer electrolyte at such a concentration is in a suitable gel state And the interaction between TiO ₂ and the electrolyte at the working electrode is facilitated, so that the movement of the electrons becomes active.

Test Example  4: Internal charge transfer resistance of dye-sensitized solar cells

In order to measure the charge transfer resistance of the electrolyte prepared in Example 9 (E3), Comparative Example 1 (E1) and Comparative Example 2 (E2) in a dye-sensitized solar cell, 1 sun (100 mW / cm ² shows the Nyquist plot obtained by measuring the AC impedance under the condition shown in FIG. At this time, an equivalent circuit set to obtain the internal resistance is shown in Fig. The internal resistance of the interface was determined by impedance fitting, and the results are shown in Table 3.

As can be seen from the above Table 3, the electrolyte E3 of Example 9 including the hole transporting material (BMPC) of the present invention showed a low resistance at the TiO ₂ / dye / electrolyte interface. These low resistances enable fast transfer of electrons to improve the efficiency of the dye-sensitized solar cell.

compare Test Example 1 : PEO  Characteristics and Cell Efficiency of Polymer Electrolyte

PEO polymer electrolyte is prepared by mixing (PEO) _N KI (or LiI) -I _2. When KI is 1 mole, N of PEO is 5, 8, 10, 12, 20, 30, , [PEO 5 mole: KI 1 mole], [PEO 8 mole: KI 1 mole], and [PEO 10 mole: KI 1 mole], as follows. And KI 1 mole of I ₂ time mole is _{[KI: I 2] = 1} : 0.1 in a molar ratio may be mixed and put in an acetonitrile solvent, Table 4 [PEO: KI = 12: 1 ] when each KI-I ₂ molar ratio and temperature.

Table 5 below shows the cell efficiency when the PEO / KI (or LiI) / I ₂ polymer electrolyte was used in the dye-sensitized solar cell.

compare Test Example 2 : PVdF - HFP / PS  Characteristics and Cell Efficiency of Polymer Electrolyte

The current-voltage curve of the dye-sensitized solar cell fabricated using the PVdF-HFP / PS polymer electrolyte is shown in FIG. The efficiency of the dye-sensitized solar cell is shown in Table 6 below.

Claims (12)

A quasi-solid polymer electrolyte comprising a hole transporting material (HTM), a polymer for a solid electrolyte, and a liquid electrolyte,
Wherein the hole transporting material is at least one selected from the group consisting of compounds represented by the following Chemical Formulas 2 to 10:
(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

In the above formulas 2 to 10
X is a C3 to C10 alkyl group, a C1 to C4 alkyl group substituted with a C2 to C6 alkoxy, or a C1 to C6 alkoxy group;
R2 and R3 are each independently hydrogen, a C1-C5 alkoxy group, a C3-C10 alkoxy group substituted with C1-C5 alkyl, a phenyl group, an imidazole group, or EDOT (3,4-ethylenedioxythiophene);
R4, R5, R6 and R7 are each independently hydrogen or a C1-C5 alkyl group;
m is 0 or 1; [5] The HTM according to claim 1, wherein the hole transport material (HTM) is contained in an amount of 5 to 30 parts by weight based on 100 parts by weight of the polymer for a solid electrolyte, and the polymer for a solid electrolyte is contained in an amount of 5 to 60 parts by weight Wherein the polymer electrolyte is a polymer electrolyte. The solid polymer electrolyte of claim 1, wherein the solid electrolyte polymer is selected from the group consisting of polyethylene oxide (PPO), polyvinylidene fluoride (PVdF), polyvinyl chloride (PVC), poly (methyl methacrylate) polyvinylidene fluoride-co-hexafluoropropylene (PVdF-HFP), and poly (epichlorohydrin-co-ethylene oxide) co-ethylene oxide). < / RTI > The method according to claim 1, wherein the liquid electrolyte is characterized in that it comprises an iodide (DMPII), and 4-tert- butyl-pyridine (tBP) is acetonitrile, LiI, I _2, 1,2- dimethyl-3-propyl imidazolium As a semi-solid polymer electrolyte. delete A compound selected from the group consisting of compounds represented by the following formulas (2) to (10):
(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

In the above formulas 2 to 10
X is a C3 to C10 alkyl group, a C1 to C4 alkyl group substituted with a C2 to C6 alkoxy, or a C1 to C6 alkoxy group;
R2 and R3 are each independently hydrogen, a C1-C5 alkoxy group, a C3-C10 alkoxy group substituted with C1-C5 alkyl, a phenyl group, an imidazole group, or EDOT (3,4-ethylenedioxythiophene);
R4, R5, R6 and R7 are each independently hydrogen or a C1-C5 alkyl group;
m is 0 or 1; delete delete The compound according to claim 6, wherein the compound represented by any of formulas (2) to (10)
9- (2-butoxyethyl) -3,6-bis (4-methoxyphenyl) -9H-carbazole,
4- [N, N-di (4- (2-ethyl) hexyloxyphenyl) amino] -1-butoxymethylbenzene,
4- [N, N-di (4- (2-ethyl) hexyloxyphenyl) amino] -3,5-dimethyl- 1-butoxymethylbenzene,
N, N-bis (4- (2-ethylhexyloxy) phenyl) naphthalen-1-
N- (4- (2-butoxyethyl) phenyl) -7- (2- ethylhexyloxy) -N- (7- (2- ethylhexyloxy) -9,9-dimethyl- Yl) -9,9-dimethyl-9H-fluoren-2-amine,
9- (4-butoxyphenyl) -3,6-bis (4-methoxyphenyl) -9H-carbazole,
9- (4-butoxy-3,5-dimethylphenyl) -3,6-bis (4-methoxyphenyl)
9-hexyl-3,6-bis (4-methoxyphenyl) -9H-carbazole,
9-hexyl-3,6-di (1H-imidazol-1-yl) -9H-carbazole, and
3,6-bis (2,3-dihydrosothieno [3,4-b] [1,4] dioxin-5-yl) -9-hexyl-9H-carbazole. A hole-transporting material comprising at least one compound represented by the general formulas (2) to (10) of claim 6. A first electrode comprising a conductive transparent substrate;
A light absorbing layer formed on one surface of the first electrode;
A second electrode disposed opposite to the first electrode on which the light absorbing layer is formed; And
And the quasi-solid polymer electrolyte according to claim 1, which is located in a space between the first electrode and the second electrode. delete

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