KR20190031187A - Diamine compound and method of preparing the same - Google Patents

Abstract

The present invention relates to a diamine compound represented by chemical formula 1 and a method for manufacturing the same. In the chemical formula 1, each of R^1 and R^2 is independently selected from a group consisting of F, Cl, Br, I, CF_3, CN, COOH, COOR^3, and CHO, each of n and m is independently an integer of 1 to 4, and R^3 is an alkyl group or an aryl group having 1 to 12 carbon atoms. An object of the present invention is to provide the method for manufacturing the diamine compound having excellent efficiency.

Description

DIAMINE COMPOUND AND METHOD OF PREPARING THE SAME [0002]

The present invention relates to a diamine compound, a process for producing the same, and a process for producing the same. More specifically, the present invention relates to a diamine compound having two amine groups at both terminals of a molecular structure and a method for producing the same.

The diamine compound can be used for various purposes, for example, as a monomer of polyamide or polyimide. Specifically, a polyamide may be produced by a condensation reaction of a diamine compound and a dicarboxylic acid compound, or a polyimide may be produced by a condensation reaction of a diamine compound and a tetracarboxylic dianhydride compound.

The polyimide resin can replace, for example, a glass substrate of a display device and is required to have excellent physical properties in terms of heat resistance, dimensional stability, strength, insulation and flexibility.

For example, Korean Patent Laid-Open Publication No. 2003-0027769 discloses a polyimide copolymer, but further development of monomers to complement the above-mentioned physical properties is required.

Korean Patent Publication No. 2003-0027769

An object of the present invention is to provide a diamine compound having two amine groups at both terminals of a molecular structure.

An object of the present invention is to provide a process for producing a diamine compound having excellent efficiency.

1. A diamine compound represented by the formula (1): < EMI ID =

[Chemical Formula 1]

Wherein R ¹ and R ² are each independently selected from the group consisting of F, Cl, Br, I, CF ₃ , CN, COOH, COOR ³ and CHO; n and m are each independently 1 And R ³ is an alkyl group or an aryl group having 1 to 12 carbon atoms.

2. The diamine compound according to item ¹ above, wherein R ¹ and R ² are symmetrically located in the biphenylene group.

3. The diamine compound according to item 1 above, wherein n and m are 1, and R ¹ and R ² are CF ₃ and are each substituted at the 2, 2'-position of the biphenylene group.

4. A process for preparing a compound represented by the formula (4), comprising: reacting a compound represented by the formula (2) with a compound represented by the formula (3) to produce a compound represented by the formula (4); And hydrolyzing an amide group located at both ends of the compound represented by the formula (4).

[Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

Wherein R ¹ and R ² are each independently selected from the group consisting of F, Cl, Br, I, CF ₃ , CN, COOH, COOR ³ and CHO, Each independently an integer of 1 to 4, and R ³ is an alkyl group or an aryl group having 1 to 12 carbon atoms.

According to some embodiments, a diamine compound is provided that is capable of forming a polyamide or polyimide by an amidation reaction.

In some embodiments, the polyimide prepared from the diamine compound may have transparency as the halogen group, the electron-withdrawing group of CF ₃ , CHO, COOH and COOR is substituted for the biphenylene group of the diamine compound.

According to some embodiments, the polyimide prepared from the diamine compound according to embodiments of the present invention exhibits a linear shape and may have a high Tg.

In some embodiments, as the sulfonamide group of the diamine compound undergoes a hydrogen bond with the electron withdrawing group, the polyimide prepared comprising the diamine compound may have a high hardness and a Tg.

According to exemplary embodiments of the present invention, diamine compounds of specific formula and methods for their preparation are provided. The diamine compound can be prepared at a high yield, and the polyimide can be improved in physical properties.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, It will be obvious to those skilled in the art that such modifications and variations are within the scope of the appended claims.

According to some embodiments, a diamine compound represented by formula (1) is provided.

[Chemical Formula 1]

Wherein R ¹ and R ² are each independently selected from the group consisting of F, Cl, Br, I, CF ₃ , CN, COOH, COOR ³ and CHO; n and m are each independently 1 And R ³ is an alkyl group or an aryl group having 1 to 12 carbon atoms.

In some embodiments, R < ¹ > and R < ² > of the diamine compound represented by formula (1) may be located symmetrically to the biphenylene group. Due to the symmetry of R ¹ and R ² , the molecular structure of the compound of formula (1) can be more stabilized.

According to one embodiment, n and m of the diamine compound represented by the formula (1) are 1, and R ¹ and R ² are CF ₃ , and each may be substituted at the 2, 2'-position of the biphenylene group. R ¹ and R ² can increase the transparency of the polyimide prepared from CF ₃ by drawing the electron density of the diamine compound of the formula (1).

The compound of Formula 1 may include, for example, a compound of Formula 1-1.

[Formula 1-1]

The compound of Formula 1-1 is a trifluoromethyl group may be separated from the non-phenyl group both sides sulfonamide groups (sulfonamide group, -SO ₂ NH-) in the (CF _3). Therefore, the intramolecular interaction can be suppressed and the intermolecular interaction can be relatively increased, so that the physical properties such as Tg can be improved.

Hereinafter, the processes of the diol production method according to the embodiments of the present invention will be described in detail with reference to specific experimental examples. It should be noted that the embodiments and the comparative examples included in the experimental examples are illustrative of the present invention but are not intended to limit the scope of the appended claims and various changes and modifications may be made to the embodiments within the scope and spirit of the present invention It is obvious to those skilled in the art that such variations and modifications are within the scope of the appended claims.

The diamine compound of formula (1) according to exemplary embodiments of the present invention can be prepared by the following method.

According to some embodiments, a compound represented by the following formula (2) can be produced by reacting a compound represented by the following formula (2) with a compound represented by the formula (3).

(2)

(3)

[Chemical Formula 4]

Wherein R ¹ and R ² are each independently selected from the group consisting of F, Cl, Br, I, CF ₃ , CN, COOH, COOR ³ and CHO, Each independently an integer of 1 to 4, and R ³ is an alkyl group or an aryl group having 1 to 12 carbon atoms.

For example, the compound of Formula 2 may be dissolved in a solvent. The solvent may include, for example, tetrahydrofuran.

The compound of Formula 3 may be added to the reaction solution in which the compound of Formula 2 is dissolved. In addition, sodium carbonate may be added to the reaction solution. The sodium carbonate can adjust the pH of the reaction solution, for example.

The reaction solution may be allowed to stand at room temperature to allow the reaction to proceed. Further, by further performing stirring at room temperature, the reaction rate can be improved.

The reaction solution after completion of the reaction is filtered, and the solvent can be concentrated by evaporation under reduced pressure. The concentrated solution can be reacted with caustic soda. The solution reacted with the caustic soda can be separated.

For example, the organic layer of the layered solution may contain the compound of Formula 4 above. The solution of the organic layer may be separated, washed with water and dried. The drying can be carried out through anhydrous mortar.

The solid content of the dried solution is filtered, and the filtrate is concentrated under reduced pressure to precipitate crystals.

The precipitated crystals may contain the compound of the formula (4).

The compound of Formula 4 may be reacted with water and caustic soda. The caustic soda can be decomposed into an amine group by, for example, basic hydrolysis reaction of the amide group of the compound of formula (4). The basic hydrolysis reaction may be carried out with heating or stirring to improve the reaction rate.

Hydrochloric acid may be added to the solution in which the basic hydrolysis reaction has been completed. The hydrochloric acid may neutralize the reaction-terminated solution.

The neutralized solution can be extracted with ethyl acetate. The organic layer may be washed with distilled water. The washed organic layer can be dried with an inorganic brine. The dried solution can be concentrated by heating. The above-mentioned heat condensation can be carried out at normal pressure. A dichloromethane solvent may be added to the heated and concentrated solution and the mixture may be cooled by stirring. The compound of formula (1) may be precipitated by cooling. The precipitated solid may be filtered to obtain the compound of formula (1).

The polyimide of the exemplary embodiments of the present invention can be prepared by including the diamine compound of the above formula (1). The polyimide may be formed by a condensation polymerization reaction of the diamine compound of Formula 1 with a dianhydride compound. The condensation polymerization reaction may include a step of reacting the diamine compound with the dianhydride compound to form a polyimide, for example, to form a polyimide acid, and then forming a polyimide by a second reaction.

In exemplary embodiments, the polyimide may be prepared by reacting the compound of Formula 1 and the dianhydride compound in a substantially 1: 1 molar ratio. The molar ratio may include, for example, 1: 0.8 to 1: 1.2.

In some embodiments, the dianhydride compound may comprise two 4-phthalic anhydride groups. The 4-phthalic anhydride may be represented by the following general formula (12).

[Chemical Formula 12]

According to exemplary embodiments, the dianhydride compound may be represented by the following formula (11).

(11)

In the compound of Formula 11, the trifluoromethyl group is substituted with two carbon atoms at the center of the molecule, so that the electron density of the polyimide can be strongly attracted to the trifluoromethyl group. Therefore, the transparency of the polyimide can be increased as the electron density decreases in the carbon skeleton forming the aromatic resonance structure. For example, the yellowish color of the polyimide film can be reduced.

In some embodiments, the polyimide may be prepared by reacting the compound of Formula 1, the dianhydride compound, and the compound of Formula 2 below.

In some embodiments, the sum of the moles of the compound of Formula 1 and the compound of Formula 2 and the molar ratio of the dianhydride compound may be substantially 1: 1. For example, the sum of the mole number of the compound of Formula 1 and the compound of Formula 2 and the mole number of the dianhydride compound may be 1: 0.8 to 1: 1.2.

According to exemplary embodiments, the compound of Formula 1, the compound of Formula 2, and the compound of Formula 11 may be reacted at a molar ratio of substantially 0.9: 0.1: 1. The polyimide prepared at the above-mentioned molar ratio can further improve Tg and transmittance characteristics.

According to exemplary embodiments, the polyimide film can be used as an optical film having various functions in an optical display device.

Manufacturing example

N, N '- Di (4- acetamidobenzenesulfonyl ) -2,2'- bis (trifluoromethyl) benzidine  synthesis

24 g of 2,2'-bis (trifluoromethyl) benzidine was dissolved in 170 ml of tetrahydrofuran (THF), and 38.5 g of N-acetamidobenzenesulfonyl chloride and 23.8 g of sodium carbonate were added to the reaction solution. After stirring at room temperature, And the reaction solution was filtered. The filtrate was concentrated under reduced pressure, and 240 ml of water and 15 g of 50% sodium hydroxide (NaOH) were added. The mixture was stirred for 30 minutes and then layered. The water layer was washed three times with 100 ml of ethyl acetate, acidified (pH = 4) with aqueous hydrochloric acid solution and then extracted with 700 ml of ethyl acetate. The separated organic layer was washed three times with 100 ml of water, and the separated organic layer was dried with anhydrous sodium sulfate (Na ₂ SO ₄ ). The solid was filtered, and the filtrate was concentrated when the crystals were precipitated so as to be filtered. This was heated and dried to obtain 28 g of white crystalline N, N'-Di (4-acetamidobenzenesulfonyl) -2,2'-bis (trifluoromethyl) benzidine having an HPLC purity of 99.6%.

Example

N, N '- Di (4- aminobenzenesulfonyl ) -2,2'- bis (trifluoromethyl) benzidine  synthesis

25 g of N, N'-Di (4-acetamidobenzenesulfonyl) -2,2'-bis (trifluoromethyl) benzidine obtained in the above Preparation Example was added to 125 ml of water and 27.7 g of 50% caustic soda aqueous solution, The decomposition reaction was completed. After making pH = 5 with 10% hydrochloric acid aqueous solution, 150 ml of ethyl acetate was added, and the organic layer was washed five times with 150 ml of distilled water. The organic layer was dried over anhydrous magnesium sulfate and then subjected to silica gel short column. The solvent was concentrated by heating at normal pressure, and 80 ml of dichloromethane was added thereto, followed by cooling with stirring. The precipitated solid was filtered and dried to obtain 18.9 g of white solid N, N'-Di (4-aminobenzenesulfonyl) -2,2'-bis (trifluoromethyl) benzidine having an HPLC purity of 99.98%.

N, N'-Di (4-aminobenzenesulfonyl) -2,2'-bis (trifluoromethyl) benzidine obtained according to Synthesis Example 2 has the following H-NMR peak:

1 H-NMR (DMSO d6): 6.08 ppm 4H (s), 6.54-6.57 ppm 4H (d), 7.15-7.43 ppm 10H (m), 10.41 ppm 2H (s).

Claims (4)

A diamine compound represented by the formula (1):
[Chemical Formula 1]

Wherein R ¹ and R ² are each independently selected from the group consisting of F, Cl, Br, I, CF ₃ , CN, COOH, COOR ³ and CHO; n and m are each independently 1 And R ³ is an alkyl or aryl group having 1 to 12 carbon atoms.
^{2. The} diamine compound of claim 1, wherein R < ¹ > and R < ² > are symmetrically located in the biphenylene group.
The diamine compound according to claim 1, wherein n and m are 1, and R ¹ and R ² are CF ₃ , and each is substituted at the 2, 2'-position of the biphenylene group.
Reacting a compound represented by the formula (2) with a compound represented by the formula (3) to produce a compound represented by the formula (4); And
A process for producing a diamine compound represented by the general formula (1), which comprises hydrolyzing an amide group located at both ends of the compound represented by the general formula (4).
[Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

Wherein R ¹ and R ² are each independently selected from the group consisting of F, Cl, Br, I, CF ₃ , CN, COOH, COOR ³ and CHO, Each independently an integer of 1 to 4, and R ³ is an alkyl group or an aryl group having 1 to 12 carbon atoms.