KR20120121677A - Novel diamine compound containing terpyridine or phenanthroline and method use the same - Google Patents

Abstract

PURPOSE: A diamine compound containing terpyridine or phenanthroline functional groups is provided to be used as a catalytic and dielectric material. CONSTITUTION: A diamine compound containing terpyridine or phenanthroline groups is denoted by chemical formula 1. A method for preparing the diamine compounds comprises: a step of reacting a compound of chemical formula 2 with a compound of chemical formula 3 to prepare a compound of chemical formula 4; a step of reducing the compound of chemical formula 4 to prepare a compound of chemical formula 1a.

Description

Preparation and Application of Novel Diamine Compound Containing Terpyridine or phenanthroline and Method Use the Same

The present invention relates to a diamine comprising a terpyridine and a phenanthrosine functional group and a preparation method thereof.

 The most important intermolecular interaction, used in macromolecular chemistry, is the coordination of metals and organic ligands. The coordination bond between the metal and the organic ligand can be applied to various fields by introducing various properties and properties of the metal into the unique properties of the organic molecules by using the interaction of the metal and the organic ligand.

In order to take advantage of this interaction, ligands such as terpyridine and phenanthrosine are commonly used as functional groups of organic ligands. Various ligands have been introduced into various fields by preparing various metals and metal complex compounds using ligands having functional groups such as terpyridine and phenanthrosine. For example, a dye consisting of a ruthenium metal complex is applied to a nanodevice and applied as a molecular switch, and a terpyridine metal complex is made of spherical or cyclic to form a terpyridine metal complex of a fullerene, which has recently been attracting attention as a material for solar cells. A lot of researches have been reported.

By introducing terpyridine into the polymer side chain, a polymer design and manufacture capable of introducing a metal complex have also been reported.

In addition, the metal complex using terpyridine can design macromolecular structure in molecular design. In other words, using such a structural design, a document has been reported to produce dendrimers, micelles, resins, etc. in a nano reactor, using them as a new catalyst.

As such, there is a need for the synthesis of new diamine compounds that can be used as organic ligands capable of coordinating metals and can also be used as monomers having terpyridine and phenanthrosine as functional groups in polymer synthesis.

The present invention provides a novel diamine compound comprising a terpyridine and a phenanthrosine functional group and a method for preparing the same.

The present invention also provides a copolymer prepared by using a new diamine compound containing a terpyridine and a phenanthrosine functional group as a monomer.

The present invention provides a diamine compound comprising a terpyridine or phenanthrosine functional group capable of reacting with monomers such as dianhydride, dicarboxylic acid, diester, and the like to form a polymer and effectively coordinating with metals or metal oxides. do. The diamine compound including the terpyridine or phenanthrosine functional group of the present invention is represented by the following formula (1).

[Formula 1]

[In Formula 1,

R is an amine group or -O-Ar-NH ₂ , and Ar is C ₆ -C ₁₂ aryl;

n is a constant from 0 to 2;

A is any one selected from the following structural formulas.]

In Formula 1, aryl of C ₆ to C ₁₂ aryl is not particularly limited, but may be one selected from phenyl, naphthyl, biphenyl, anthracenyl, and fluorenyl, and phenyl is preferable.

In addition, one aspect of the synthesis of the diamine compound containing a terpyridine or phenanthrosine functional group of the present invention is as follows.

The diamine compound containing a terpyridine or phenanthrosine functional group represented by the formula (1a),

Preparing a compound of Chemical Formula 4 by reacting a compound of Chemical Formula 2 with a compound of Chemical Formula 3;

To prepare a compound of formula 1a by reducing the compound of formula (4).

[Formula 1a]

[Formula 2]

(3)

    A-X

[Formula 4]

[Formula 1a, Formula 2 to Formula 4,

n is a constant from 0 to 2;

X is halogen;

A is any one selected from the following structural formulas.]

The compound of Formula 2 is prepared by the following formula (7) to the compound of formula (6);

It may be prepared to include a terpyridine group or a phenanthrosine group prepared by the following;

[Formula 6]

[Formula 7]

[In Formula 6 or 7, X is a halogen.]

Another aspect of the synthesis of the diamine compound containing a terpyridine or phenanthrosine functional group of the present invention is as follows.

That is, the diamine compound containing a terpyridine or phenanthrosine functional group represented by the general formula (1b),

Preparing a compound of Chemical Formula 9 by reacting the compound of Chemical Formula 3 with the compound of Chemical Formula 8;

Preparing a compound of Chemical Formula 10 by oxidizing Chemical Formula 9;

Preparing a compound of Chemical Formula 12 by reacting a compound of Chemical Formula 10 with a compound of Chemical Formula 11;

It comprises; reducing the compound of Formula 12 to produce a compound of Formula 1b.

[Chemical Formula 1b]

(3)

   A-X

[Formula 8]

[Chemical Formula 9]

[Formula 10]

[Formula 11]

[Chemical Formula 12]

In Chemical Formula 1b, Chemical Formula 3, and Chemical Formulas 8 to 12,

X is halogen; A or Ar is the same as defined in formula 1 of claim 1.]

In another aspect, the present invention provides a polymer prepared by reacting a diamine compound comprising a terpyridine group or a phenanthrosine group represented by Formula 1 with a mixture of one or two or more selected from dianhydrides, dicarboxylic acids and diesters.

The present invention provides novel diamine compounds comprising terpyridine and phenanthrosine functional groups.

In addition, the novel diamine compound including the terpyridine and phenanthrosine functional groups according to the present invention can react with monomers such as dianhydride, dicarboxylic acid, diester, and the like to form a polymer.

In addition, the diamine compound containing a terpyridine or phenanthrosine functional group according to the present invention imides a terpyridine and phenanthrosine functional group to a polyimide excellent in thermal and electrical properties when the polyimide is prepared by reaction with dianhydride By introducing into the side chain there is an advantage that can effectively introduce the coordination bond with the metal or metal oxide.

1 shows the ¹ H NMR of the compound of Example 1.
2 shows ¹ H NMR of the compound 4-1 of Example 4. FIG.
Figure 3 shows the mass spectrum of the 4-1 compound of Example 4.
Figure 4 shows the FT-IR of PAA and PI obtained by polymerizing Example 1 of the present invention with PMDA.

  Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to those skilled in the art.

Example 1 Compound 1 (4 ′-(3,5-Diaminophenyl) -2,2 ′: 6 ′, 2 ′ ′-terpyridine (4 ′-(3,5-Diaminophenyl) -2,2 ′: 6 ′, 2 ′ ′-terpyridine)

Compound 1-1  Preparation of (2,6-Dibromo-4-nitropyridine)

2,6-Dibromo-4-nitropyridine was prepared using 2,6-dibromopyridine as a starting material using the same method as described in the following patent (WO 2005/026164, PTC / EP 2004). / 052229).

¹ H NMR (CDCl ₃ ): 8.19 (s, 2H)

Compound 1-2 Preparation of (2- (Tributylstannyl) pyridine)

2-Bromopyridine was used as starting material and prepared using the same method set forth in the following literature (R. Shetty et. Al., Tetrahedron Lett. , 2007 , 48 , 113-117).

¹ H NMR (CDCl ₃ ): 8.75-8.72 (m, 1H), 7.51-7.38 (m, 2H), 7.13-7.08 (m, 1H), 1.88 (t, 6H), 1.67-1.45 (m, 6H) , 1.25-1.08 (m, 6H), 0.94 (t, 9H)

Compound 1-3  Preparation of (4'-Nitro-2,2 ': 6', 2 ''-terpyridine)

2,6-dibromo-4-nitropyridine (5.64 g, 0.02 mol) and 2- (tributylstenyl) pyridine (14.7 g, 0.04 mol) were added to the flask under nitrogen atmosphere at room temperature using anhydrous toluene. Melt while stirring. After addition of tetrakis (triphenylphosphine) palladium (0) (0.23 g, 0.2 mol), nitrogen was maintained at 120 ^° C. for 24 hours while maintaining the atmosphere. After completion of the reaction, the reaction mixture was cooled to room temperature, 20 ml of ammonium chloride solution was added, followed by extraction three times using toluene, and the extracted organic solvent was dried using MgSO ₄ . after removal under reduced pressure, and after the acid treatment using an addition of water, and hydrochloric acid, again, makes it stirred for 30 min. to give extracted with dichloromethane gives was neutralized using a 2N-NaOH aqueous solution. the neutralized organic solvent MgSO ₄ After drying using, the solvent was removed under reduced pressure, and hexane was added thereto to obtain white solid crystals.

¹ H NMR (CDCl ₃ ): δ 9.16 (s, 2H), 8.77-8.75 (m, 2H), 8.64-8.60 (m, 2H), 7.94-7.88 (m, 2H), 7.44-7.39 (m, 2H )

Compound 1-4 Preparation of (4'-Amino-2,2 ': 6', 2 ''-terpyridine)

4'-nitro-2,2 ', 6', 2 ''-terpyridine (2.7 g, 0.01 mol) and 40 ml of ethanol were added to the flask under nitrogen flow and stirred for about 10 minutes, followed by 5% Pd / C ( Add 0.5 g). Thereafter, 10 ml of hydrazine hydrate is slowly added dropwise for 30 minutes, and then it is checked whether hydrogen gas is generated. The temperature is raised to 80 ^° C. and stirred at reflux for 24 hours. After the reaction is complete, the catalyst is removed by filtration. The solvent is concentrated under pressure and extracted with ethyl acetate. The extracted solution was washed with brine, dried using MgSO ₄ , filtered, and the solvent was removed by further removing the solvent under reduced pressure and drying.

¹ H NMR (CDCl ₃ ): δ 8.68-8.59 (m, 4H), 7.86-7.80 (m, 2H), 7.74 (s, 2H), 7.32-7.28 (m, 2H), 4.35 (bs, 2H)

Compound 1-5 Preparation of (4'-Bromo-2,2 ': 6', 2 ''-terpyridine)

Add 4'-amino-2,2 ': 6', 2 ''-terpyridine (2.36 g, 0.01 mol), 48% HBr (20 ml), cool the internal temperature to 5 ^o C with ice water, Br ₂ Slowly add 3 ml (0.05 mol) dropwise. NaNO ₂ is dissolved in 10 ml of distilled water and added and stirred for 24 h. At the end of the reaction, the mixture is poured into 200 ml of distilled water and neutralized with 10% NaOH solution. Extract with ethyl acetate and wash several times with brine. The organic layer was dried over MgSO ₄ and distilled under reduced pressure to prepare a solvent.

¹ H NMR (CDCl ₃ ): δ 8.75-8.69 (m, 2H), 8.65 (s, 2H), 8.60-8.57 (m, 2H), 7.89-7.83 (m, 2H), 7.38-7.33 (m, 2H )

Compound 1-6 Preparation of (1-Bromo-3,5-dinitrobenzene)

1,3-dinitrobenzene (1,3-Dinitrobenzene) (10 g , 0.06 mol) while maintaining the dissolved in 60 mL concentrated sulfuric acid and then 80 C ^o N - bromosuccinimide (N -Bromosuccinimide) (15 g , 0.083 mol) was added dropwise nine times for 10 minutes, and the reaction mixture was heated to 95 ^° C. for 24 hours. After completion of the reaction, the resultant was poured into iced water and the resulting precipitate was filtered, washed several times with distilled water and prepared by recrystallization with methanol (Methanol).

¹ H NMR (CDCl ₃ ): δ 9.00 (s, 1H), 8.71 (s, 2H)

Compound 1-7 Preparation of (3,5-dinitrophenylboronic acid, pinacol ester)

1-bromo-3,5-dinitrobenzene (1 g, 4 mmol), bis (pinacolato) diborane (Bis (pinacolato) diboran (1.23 g, 4.9 mmol), dichloro [1,1'-bis Dichloro [1,1'-bis (diphenylphosphino) ferrocene] palladium (II) dichloromethane) (0.17 g, 0.2 mmol) and potassium acetate (photassium acetate) (dichlorophosphino) ferrocene] palladium (II) dichloromethane) 1.2 g, 12 mmol) is added to the flask in a glove box. Anhydrous DMF (50 ml) is added under nitrogen and reacted at 80 ^° C. for 24 hours. After completion of the reaction, the catalyst portion was removed by filtration and the solvent was removed under reduced pressure. Prepared by recrystallization using acetonitrile.

¹ H NMR (CDCl ₃ ): δ 9.06 (t, 1H), 8.88 (d, 2H), 1.35 (s, 12H)

Compound 1-8 Preparation of (4 ′-(3,5-Dinitrophenyl) -2,2 ′: 6 ′, 2 ′ ′-terpyridine)

Dissolve 4'-bromo-2,2 ': 6', 2 ''-terpyridine (624 mg, 2 mmol) with 15 ml of 1,2-dimethoxyethane. Stir at room temperature for 30 minutes to bring the inside of the reactor into nitrogen atmosphere, 3,5-dinitrophenylboronic acid, pinacol ester (617 mg, 2.1 mmol) and tetrakis (triphenylphosphine) palladium (0) (Tetrakis 2 ml of (triphenylphosphine) palladium (0)) (60 mg, 5 mmol%) and 2M-Na ₂ CO ₃ solution were added and reacted for 24 hours while maintaining at 85 ^° C. After the completion of the reaction, the reaction mixture was cooled to room temperature and 50 mL of distilled water was added to the reaction mass to terminate the reaction, and slightly acidified (PH = 5) with 2N-HCl. Filtration under reduced pressure, washing with distilled water several times, and prepared by recrystallization with methanol.

¹ H NMR (CDCl ₃ ): δ 9.14 (t, 1H), 9.06 (d, 2H), 8.82 (s, 2H), 8.72 (d, 2H), 8.69 (d, 2H), 7.92 (t, 2H) , 7.42 (q, 2 H)

Compound 1 Preparation of (4 ′-(3,5-Diaminophenyl) -2,2 ′: 6 ′, 2 ′ ′-terpyridine)

20 ml of 4 '-(3,5-dianinophenyl) -2,2': 6 ', 2''-terpyridine (400 mg, 1 mmol) Ethanol is added to the reactor. After addition of 5% Pd / C (53 mg, 5 mol%), 0.2 ml (4 mmol) of Hydrazine hydrate was injected. After confirming that the hydrogen gas is generated, it was reacted for 24 hours by raising the temperature to 80 ^° C. After the reaction was completed, the mixture was cooled to room temperature, and the catalyst was filtered off. Extraction was performed using dichloromethane, the solvent was removed under reduced pressure, and recrystallized with ethanol.

¹ H NMR (CDCl ₃ ): δ 8.73-8.64 (m, 6H), 7.88-7.85 (m, 2H), 7.24-7.18 (m, 2H), 6.66 (s, 2H), 6.23 (s, 1H), 3.71 (bs, 4H)

Example 2 4 '-(3,5-diaminobiphenyl) -2,2': 6 ', 2' '-terpyridine (4'-(3,5-dinitrobiphenyl) -2,2 ': 6 ', 2' '-terpyridine)

Compound 2-1 (4'-( p Preparation of -Bromophenyl) -2,2 ': 6', 2 ''-terpyridine)

4-bromobenzaldehyde (2 g, 4.9 mmol), 2-acetylpyridine (1.18 g, 9.8 mmol) and NaOH (0.4 g, 9.8 mmol) were placed in a mortar Put and mix well. Go well until a yellow solid is formed. The resulting solid is washed with water and ethanol to give a white solid. After drying, the obtained white solid was transferred to a flask, and stirred and refluxed for 2 hours by adding ammonium acetate (3 g, excess) and acetic acid (30 ml). After the reaction was completed, water was added to form a precipitate, and the obtained precipitate was filtered and washed with water and ethanol to prepare.

¹ H NMR (CDCl ₃ ): δ 8.82-8.59 (m, 6H), 7.88 (td, 2H), 7.75 (d, 2H), 7.61 (d, 2H), 7.36 (t, 2H)

Compound 2-2 Preparation of (4 '-(3,5-dinitrobiphenyl) -2,2': 6 ', 2' '-terpyridine)

4 '-( p -bromophenyl) -2,2': 6 ', 2''-terpyridine instead of 4'-bromo-2,2': 6 ', 2''-terpyridine , Except that toluene was used as the solvent was prepared in the same manner as in compound 1-8 .

¹ H NMR (CDCl ₃ ): δ 8.83 (t, 1H), 8.77 (d, 2H), 8.68 (s, 2H), 8.65 (d, 2H), 8.63 (d, 2H), 8.02 (t, 2H) , 7.91 (d, 2H), 7.87 (d, 2H), 7.52 (q, 2H)

Compound 2 ( Preparation of 4 '-(3,5-dinitrobiphenyl) -2,2': 6 ', 2' '-terpyridine)

4 '-(3,5-diaminophenyl) -2,2': 6 ', 2''-terpyridine instead of 4'-(3,5-dinitrobiphenyl) -2,2 ': 6' Prepared by the same method as the compound 1 except using 2,2 ''-terpyridine.

¹ H NMR (CDCl ₃ ): δ 8.74-8.66 (m, 9H), 7.91-7.85 (m, 2H), 7.79 (d, 2H), 7.65 (d, 2H), 7.38-7.34 (m, 2H), 3.21 (bs, 4H)

Example 3 Preparation of 5- (3,5-diaminophenyl) -1,10-phenanthrosine (5- (3,5-dinitrophenyl) -1,10-phenanthroline)

Compound 3-1 Preparation of (5-Bromophenanthroline)

Phenanthroline (1.2 g, 6.7 mmol) is placed in a reactor designed for pressure. 5 ml of oleum (15%) and 0.2 ml (4 mmol) of Br ₂ are added dropwise under an ice bath. Cover with a Teflon screw stopper with a Viton O-ring, slowly raise the temperature to 135 ^° C and stir for 24 hours. After the reaction is completed, the mixture is cooled to room temperature, poured into ice water, and neutralized with ammonia water (NH ₄ OH). Extracted with chloroform (CHCl ₃ ), treated with activated charcoal, and dried over Na ₂ SO ₄ . The organic solvent was removed under reduced pressure, and recrystallized using hot diethlether and a small amount of dichloromethane (CH ₂ Cl ₂ ).

¹ H NMR (CDCl ₃ ): δ 9.17 (m, 2H), 8.64 (dd, 1H), 8.15 (dd, 1H), 8.12 (s, 1H), 7.72 (dd, 1H), 7.61 (dd, 1H)

Compound 3-2 Preparation of (5- (3,5-dinitrophenyl) -1,10-phenanthroline)

It was prepared in the same manner as in Compound 1-8 , except that 5-bromophenanthrosine was used instead of 4'-bromo-2,2 ': 6', 2 ''-terpyridine.

¹ H NMR (CDCl ₃ ): δ 9.17 (m, 2H), 9.14 (t, 1H), 9.02 (d, 2H), 8.64 (dd, 1H), 8.15 (dd, 1H), 8.12 (s, 1H) , 7.72 (dd, 1H), 7.61 (dd, 1H)

Compound 3 Preparation of (5- (3,5-dinitrophenyl) -1,10-phenanthroline)

 5- (3,5-dinitrophenyl) -1,10-phenanthrosine in place of 4 '-(3,5-dinitrophenyl) -2,2': 6 ', 2' '-terpyridine Except that, it was prepared in the same manner as in compound 1.

¹ H NMR (CDCl ₃ ): δ 9.12 (m, 2H), 8.62 (dd, 1H), 8.12 (dd, 1H), 8.10 (s, 1H), 7.70 (dd, 1H), 7.57 (dd, 1H) , 6.72 (d, 2H), 5.83 (t, 1H), 4.21 (bs, 4H)

Example 4 Preparation of 4 '-[4- (Bis-3,5-diaminophenoxy) phenyl] -2,2': 6 ', 2' '-terpyridine

Compound 4-1 (4 '-[4- (3,5- dimethoxyphenyl ] -2,2 ': 6', 2 ''- terpyridine Manufacturing

Compound 2-1 4 '-( p -Bromophenyl) -2,2': 6 ', 2''-terpyridine (3.8 g, 0.01 mol) was added to 1,2-dimethoxyethane in a 100 ml three-necked flask reactor in a nitrogen atmosphere. Dissolve in 20 ml and add 3,5-dimethoxyphenylboronic acid, pinacol ester (3.2 g 0.012 mol) and prepare in the same manner as Compound 1-8 Compound 4-1 was obtained in 75% yield.

Chemical Formula: C ₂₉ H ₂₃ N ₃ O ₂

Molecular Weight: 445.51

GC-MS (m / z): 445 (M ⁺¹ , 100), 414 (23), 381 (21), 223 (48)

Elemental Analysis (%): C, 78.18; H, 5.20; N, 9.43; O, 7.18

Compound 4-2 Preparation of (4 '-[4- (3,5-dihydroxyphenyl] -2,2': 6 ', 2' '-terpyridine)

Compound 4-1 (2.2 g, 5 mmol) was dissolved in 20 ml of dichloromethane, and 4 ml of hydrobromic acid was slowly added dropwise over 30 minutes in an ice-cold state, followed by stirring at room temperature for 24 hours, to obtain Compound 4-2 (4- (3 , 5-dihydroxyphenyl) -2,2 ': 6', 2 ''-terpyridine) was obtained in 80% yield.

Chemical Formula: C ₂₇ H ₁₉ N ₃ O ₂

Molecular Weight: 417.46

GC-MS (m / z): 417 (M ⁺¹ , 100), 400 (53), 383 (41)

Elemental Analysis: C, 77.68; H, 4.59; N, 10.07; O, 7.67

¹ H NMR (DMSO): δ 9.35-9.11 (m, 4H), 8.61-8.54 (m, 2H), 7.91-7.89 (m, 2H), 7.32-7.12 (m, 6H), 6.89 (s, 2H) , 6.23 (s, 1H), 5.38 (bs, 2H)

Compound 4-3 (4 '-[4- (Bis-3,5-dinitrophenoxy) phenyl] -2,2': 6 ', 2' '

- terpyridine Manufacturing

Compound 4-2 (4.17 g, 0.01 mol) and 1-bromo-4-nitrobenzene (4.6 g, 0.023 mol) were added to a 100 ml three-necked flask with nitrogen atmosphere and dissolved in 50 ml of DMSO. Thereafter, potassium hydroxide (1.3 g 0.023 mol) was added dropwise, and the reaction temperature was allowed to react at 95 ^° C. for 24 hours. After cooling to room temperature, 200 ml of distilled water was added to a beaker, and the reaction material was added thereto to obtain a white solid. This was filtered, washed 2-3 times with distilled water and washed several times with ethanol to dry the crystals to give compound 4-3 (5.27 g 80%) as a white crystals.

Chemical Formula: C ₃₉ H ₂₅ N ₅ O ₆

Molecular Weight: 659.65

GC-MS (m / z): 659 (M ⁺¹ , 64), 613 (48), 567 (38), 521 (100)

Elemental Analysis: C, 70.10; H, 3.63; N, 10.82; O, 15.45

¹ H NMR (DMSO): δ 9.26-9.12 (m, 4H), 8.52 (d, 2H), 8.23 (d, 4H), 7.94-7.88 (m, 2H), 7.23-7.01 (m, 12H), 6.81 (s, 1H)

Compound 4 (4 '-[4- (Bis-3,5-diaminophenoxy) phenyl] -2,2': 6 ', 2' '

- terpyridine Manufacturing

Compound 4-3 (5 g, 7.5 mmol) was dissolved in 40 ml of ethanol and 40 ml of DMF in a hydrogenation reactor, and 5% Pd / C (0.01 g) was added dropwise and stirred for 24 hours to oxidize with TLC and KMnO ₄ solution. Upon completion of the identification, the catalyst was filtered off and the filtrate was concentrated to obtain crystals. Recrystallization with ethanol afforded 3.4 g 75% of compound 4 as white crystals.

Chemical Formula: C ₃₉ H ₂₉ N ₅ O ₂

Molecular Weight: 599.68

GC-MS (m / z): 599 (M ⁺¹ , 100), 491 (78), 383 (54)

Elemental Analysis: C, 78.11; H, 4.87; N, 11.68; O, 5.34

¹ H NMR (DMSO): δ 9.35-9.11 (m, 4H), 8.54 (d, 2H), 7.89 (d, 4H), 7.32-7.12 (m, 6H), 6.89-6.65 (m, 8H), 6.83 (s, 1H), 6.23 (bs, 4H)

[Example 5] Terpyridine groups Function  Preparation of polyimide containing

Compound 1 (diamine (4 ′-(3,5-diaminophenyl) -2,2 ′: 6 ′, 2 ′ ′-terpyridine)) containing terpyridine structure in a 250 ml three neck flask (3.39 g, 0.01 mol) was dissolved in 81 g of dimethylacetylamide, and then the reaction temperature was controlled to 5 degrees or less with ice water. Then, PMDA (1,2,4,5-benzenetetracarboxylic dianhydride; pyromellitic dianhydride) (5.56 g, 0.01 mol) was slowly added to the ice water. The polyamic acid (PAA), a polyimide precursor having a solid content of 10%, was prepared through a 1: 1 solution polymerization process which was maintained at room temperature according to this recording and reacted for 12 hours.

The polyamic acid thus prepared was subjected to film casting using a film applicator, followed by heat treatment in a convection oven at 80 degrees 30 minutes, 200 degrees 30 minutes, and 370 degrees 30 minutes to prepare a polyimide (PI) film having a thickness of 50 μm.

As shown above, the diamine containing terpyridine according to the present invention can synthesize a polymer by a condensation polymerization method by reacting with dianhydride, and the synthesized polymer contains a functional group capable of coordinating with a metal. Coordination bond with metal is possible.

In view of the above results, by introducing a terpyridine structure into the polymer matrix through the method proposed in the present invention, the coordination property is improved, and thus it may be applicable to various fields.

Claims (5)

Diamine compound containing a terpyridine group or a phenanthrosine group represented by the following formula (1).
[Formula 1]

[In the above formula (1)
R is an amine group or -O-Ar-NH ₂ , and Ar is C ₆ -C ₁₂ aryl;
n is a constant from 0 to 2;
A is any one selected from the following structural formulas.]

Preparing a compound of Chemical Formula 4 by reacting a compound of Chemical Formula 2 with a compound of Chemical Formula 3;
A method for preparing a diamine compound comprising a terpyridine group or a phenanthrosine group, the method comprising: reducing a compound of Formula 4 to produce a compound of Formula 1a.
[Formula 1a]

(2)

(3)
AX
[Chemical Formula 4]

[Formula 1a, Formula 2 to Formula 4,
n is a constant from 0 to 2;
X is halogen;
A is any one selected from the following structural formulas.]

The method of claim 2,
The compound of Formula 2 is prepared by the following formula (7) to the compound of formula (6);
A method for preparing a diamine compound comprising a terpyridine group or a phenanthrosine group prepared by the following Formula 7;
[Chemical Formula 6]

(7)

[In Formula 6 or 7, X is a halogen.] Preparing a compound of Chemical Formula 9 by reacting the compound of Chemical Formula 3 with the compound of Chemical Formula 8;
Preparing a compound of Chemical Formula 10 by oxidizing Chemical Formula 9;
Preparing a compound of Chemical Formula 12 by reacting a compound of Chemical Formula 10 with a compound of Chemical Formula 11;
A method for preparing a diamine compound comprising a terpyridine group or a phenanthrosine group, the method comprising: reducing a compound of Formula 12 to produce a compound of Formula 1b.
[Chemical Formula 1b]

(3)
AX
[Chemical Formula 8]

[Chemical Formula 9]

[Formula 10]

(11)

[Chemical Formula 12]

In Chemical Formula 1b, Chemical Formula 3, and Chemical Formulas 8 to 12,
X is halogen; A or Ar is the same as defined in formula 1 of claim 1.] A polymer prepared by reacting a diamine compound comprising a terpyridine group or a phenanthrosine group represented by Formula 1 with one or more mixtures selected from dianhydrides, dicarboxylic acids and diesters.
[Formula 1]

[In the above formula (1)
R is an amine group or -O-Ar-NH ₂ , and Ar is C ₆ -C ₁₂ aryl;
n is a constant from 0 to 2;
A is one selected from the following structural formulas.]

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