TW202325691A - Diamine compound and manufacturing method thereof, and polymer formed from diamine compound and use thereof - Google Patents

Abstract

A diamine compound is provided. The diamine compound is represented by formula (I). In formula (I), A is a C7-C30 alicyclic hydrocarbon group having norbornane ring, and Y is *-COO-* or *-CONH-*.

Description

Diamine compound and preparation method thereof, polymer formed from diamine compound and use thereof

The present disclosure relates to a diamine compound, in particular to a diamine compound containing a norbornane ring.

Diamine compounds can be used to synthesize various polymers, such as polyimide, polyamide acid, epoxy resin, polyamide, polyurea, and polyimine; and used in various applications such as insulating tapes, wire varnishes, protective coatings, alignment films, transparent substrates, or films.

Generally, diamine compounds with a rod-like structure have a better filling factor, which can reduce the thermal expansion coefficient of the material formed therefrom. However, most rod-shaped diamine compounds contain aromatic groups, for example, 4-aminophenyl-4-aminobenzoate, which have a conjugated system, resulting in the formation of materials that are not Yellowing may occur during processing. Therefore, there is a need for diamine compounds that can impart good optical properties and lower thermal expansion coefficients to materials.

According to an embodiment of the present disclosure, a diamine compound represented by formula I is provided. (I)

In Formula I, A is an alicyclic hydrocarbon group containing a norbornane ring and having a carbon number ranging from 7 to 30, and Y is *-COO-* or *-CONH-*.

According to an embodiment of the present disclosure, a method for preparing a diamine compound is provided, comprising: performing a hydrogenation reaction on a compound represented by formula III to form a diamine compound represented by formula I. (I) (III)

In formulas I and III, A is an alicyclic hydrocarbon group containing a norbornane ring and having a carbon number of 7 to 30, and B is an alicyclic group containing a norbornane ring or a norbornene ring and having a carbon number of 7 to 30. Hydrocarbyl, and Y is *-COO-* or *-CONH-*.

According to an embodiment of the present disclosure, a polymer derived from the diamine compound represented by Formula I is provided. (I)

In Formula I, A is an alicyclic hydrocarbon group containing a norbornane ring and having a carbon number ranging from 7 to 30, and Y is *-COO-* or *-CONH-*.

According to an embodiment of the present disclosure, an application of the above-mentioned polymer is provided, which is used in insulating tapes, wire varnishes, protective coatings, alignment films, transparent substrates, or films.

In order to make the features of the present disclosure clear and easy to understand, the following examples are specifically cited below, together with the accompanying drawings, for a detailed description as follows. For other precautions, please refer to the technical field.

The following is a detailed description of the diamine compound provided in this case and the polymer formed by it. It should be understood that the following descriptions provide many different embodiments or examples for implementing different aspects of some embodiments of the present disclosure. The specific components and arrangements described below are only for simple and clear description of some embodiments of the present disclosure. Of course, these are only examples rather than limitations of the present disclosure.

In the text, the terms "about", "approximately" and "substantially" usually mean within 5%, preferably within 3%, more preferably within 1%, or within 2% of a given value or range , or within 1%, or within 0.5%. The quantities given here are approximate quantities, that is, the terms "about", "approximately" and "substantially" can still be implied if there is no specific description of "about", "approximately" and "substantially". meaning.

The diamine compound and the preparation method thereof of the present disclosure will be described in detail below.

[Diamine compound]

According to an embodiment of the present disclosure, a diamine compound represented by formula I is provided. (I)

In Formula I, A is an alicyclic hydrocarbon group containing a norbornane ring and having a carbon number ranging from 7 to 30, and Y is *-COO-* or *-CONH-*.

In some embodiments, the disclosed diamine compound can be represented by formula II. (II)

In formula II, B is absent or *-CH ₂ -*, Y is *-COO-* or *-CONH-*, and n and m represent 0 or an integer of 1~2. Wherein, in formula II, at least one B is *-CH ₂ -*, so that the diamine compound contains a norbornane ring group.

In some embodiments, the diamine compound of the present disclosure may be, for example, the structure shown below, but not limited thereto: , , ,or .

In some embodiments, the diamine compound of the present disclosure may be, for example, the structure shown below, but not limited thereto: , , , , ,or .

[Preparation of diamine compound]

According to an embodiment of the present disclosure, a method for preparing a diamine compound is provided, comprising: performing a hydrogenation reaction on a compound represented by formula III to form a diamine compound represented by formula I. (I) (III)

In formulas I and III, A is an alicyclic hydrocarbon group containing a norbornane ring and having a carbon number of 7 to 30, and B is an alicyclic group containing a norbornane ring or a norbornene ring and having a carbon number of 7 to 30. Hydrocarbyl, and Y is *-COO-* or *-CONH-*.

In some embodiments, the compound represented by formula III can be formed by reacting the diol compound represented by formula IV with nitrobenzoyl chloride. B-(OH) ₂ (IV)

In Formula IV, B is an alicyclic hydrocarbon group containing a norbornane ring or a norbornene ring and having 7 to 30 carbon atoms.

In some embodiments, the compound represented by formula III can be formed by reacting the diamine compound represented by formula V with nitrobenzoyl chloride. B-(NH ₂ ) ₂ (V)

In Formula V, B is an alicyclic hydrocarbon group containing a norbornane ring or a norbornene ring and having 7 to 30 carbon atoms.

The following table lists specific examples and corresponding chemical names of diamine compounds disclosed in the present disclosure. Diamine compound Chemical Name Tetradecahydro-1,4:5,8-dimethylanthracene-9,10-diyl-bis(4-aminobenzoate) (tetradecahydro-1,4:5,8-dimethanoanthracene-9,10 -diyl bis(4-aminobenzoate)) Tetradecahydro-1,4:5,8-dimethylanthracene-9,10-diyl-bis(3-aminobenzoate) (tetradecahydro-1,4:5,8-dimethanoanthracene-9,10 -diyl bis(3-aminobenzoate)) Bicyclo[2.2.1]heptane-2,5-diyl bis(4-aminobenzoate) (bicyclo[2.2.1]heptane-2,5-diyl bis(4-aminobenzoate)) N,N'-(tetradecahydro-1,4:5,8-dimethylanthracene-9,10-diyl)-bis(4-aminobenzamide)(N,N'-(tetradecahydro- 1,4:5,8-dimethanoanthracene-9,10-diyl)bis(4-aminobenzamide)) N,N'-(tetradecahydro-1,4:5,8-dimethylanthracene-9,10-diyl)-bis(3-aminobenzamide)(N,N'-(tetradecahydro- 1,4:5,8-dimethanoanthracene-9,10-diyl)bis(3-aminobenzamide)) N,N'-(bicyclo[2.2.1]heptane-2,5-diyl)-bis(4-aminobenzamide)(N,N'-(bicyclo[2.2.1]heptane-2, 5-diyl)bis(4-aminobenzamide))

As mentioned above, the diamine compounds of the present disclosure can be used to form various polymers (for example, polyimide, polyamic acid, epoxy resin, polyamide, polyurea, and polyimine), and these Polymers are used for various purposes. Examples of these polymers and their preparation methods are described below, but it should be noted that the types of polymers and their preparation methods are not limited thereto.

According to an embodiment of the present disclosure, there is provided a polymer formed from a diamine compound represented by formula I. (I)

In Formula I, A is an alicyclic hydrocarbon group containing a norbornane ring and having a carbon number ranging from 7 to 30, and Y is *-COO-* or *-CONH-*.

[Polyamide]

In some embodiments, the polymer of the present disclosure can be polyamic acid, which includes repeating units of the following general formula.

In the above general formula, X is a tetravalent organic group derived from a tetracarboxylic dianhydride compound. In some embodiments, the tetracarboxylic dianhydride compound can be 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA), bicyclo[3,3,0]octane-2,4 , 6,8-tetracarboxylic dianhydride (BODA), pyromellitic dianhydride (PMDA) or 2,3,5-tricarboxycyclopentylacetic dianhydride (TCA), but not limited thereto. In addition, one tetracarboxylic dianhydride compound may be used alone, or two or more tetracarboxylic dianhydride compounds may be used in combination to react with the diamine compound represented by Formula I of the present disclosure to form polyamic acid. In the above general formula, Y ₁ is a residue derived from the diamine compound represented by formula I of the present disclosure.

[Manufacturing method of polyamide acid]

In some embodiments, the polyamic acid of the present disclosure is formed by the following method: mixing a tetracarboxylic dianhydride compound and a diamine compound represented by Formula I of the present disclosure in a solvent for condensation polymerization to form a polyamide Amino acid. In some embodiments, the condensation polymerization reaction can be stirred at room temperature at 200-400 rpm for 3-12 hours under a nitrogen atmosphere, for example, at room temperature at room temperature at 300 rpm for 4 hours. After the reaction is completed, it is cooled to obtain polyamic acid.

[Polyimide]

In some embodiments, the polymer of the present disclosure may be polyimide, which includes repeating units of the following general formula.

In the above general formula, X is a tetravalent organic group derived from a tetracarboxylic dianhydride compound, and Y ₁ is a residue derived from a diamine compound represented by Formula I of the present disclosure. The types of the tetracarboxylic dianhydride compounds are as described above, and will not be repeated here. In addition, one tetracarboxylic dianhydride compound may be used alone, or two or more tetracarboxylic dianhydride compounds may be used in combination to react with the diamine compound represented by Formula I of the present disclosure to form polyimide.

[Manufacturing method of polyimide]

In some embodiments, the polyimide of the present disclosure is formed by the following method: performing polymerization (polymerization) on a tetracarboxylic dianhydride compound and a diamine compound represented by formula I of the present disclosure in a solvent to obtain a polyimide amino acid, and then imidize the polyamic acid to form polyimide. The following two synthesis methods for imidizing polyamic acid are listed, but not limited thereto. The first method is divided into two stages. First, the tetracarboxylic dianhydride compound and the diamine compound shown in Formula I of the present disclosure are reacted in a polar solvent to form a polyimide precursor ( precursor) polyamide acid. After that, the imidization reaction is carried out by high temperature method (300°C~500°C) or chemical method, so that the polyamic acid is dehydrated and ring-closed to form polyimide. In some embodiments, the high-temperature method is carried out at a temperature of 300-500° C. for 4-8 hours, for example, at a temperature of 400° C. for 6 hours. In some embodiments, the chemical method is to add acetic anhydride and a catalyst at room temperature to 120° C. to react for 3 to 24 hours, for example, to react at 90° C. for 16 hours. The second method is to synthesize polyimide in one stage, place the tetracarboxylic dianhydride compound and the diamine compound represented by the formula I of the present disclosure in a polar aprotic solvent, and heat up to reflux temperature for the reaction , which forms polyimide. After the reaction is completed, it is cooled, and recrystallized, purified and dried to obtain a polyimide solid.

[epoxy resin]

In some embodiments, the polymer of the present disclosure can be an epoxy resin, which includes structural units of the following general formula. or

In the above general formula, Y ₁ is a residue derived from the diamine compound shown in Formula I of the present disclosure, R ₁ is a divalent organic group, and n and m represent integers ranging from 2 to 1000.

[Preparation method of epoxy resin]

In some embodiments, the epoxy resin of the present disclosure is formed by the following method: an epoxy compound of the following general formula is reacted with a diamine compound represented by formula I of the present disclosure to form an epoxy resin:

In the above general formula, R1 is a p-valent organic group, and p represents an integer of 2-6, such as 3, 4 or 5. It should be understood that the epoxy compound may be any epoxy compound having more than two epoxy groups known in the art, which will not be listed here. In addition, one epoxy compound may be used alone, or two or more epoxy compounds may be used in combination to react with the diamine compound represented by formula I of the present disclosure to form an epoxy resin.

[Polyamide]

In some embodiments, the disclosed polymer can be polyamide, which includes repeating units of the following general formula.

In the above general formula, R ₂ is a divalent organic group derived from a diacid compound or a diacid halide compound, and Y ₁ is a residue derived from a diamine compound represented by formula I of the present disclosure. The diacid compound and diacid halide compound can be any diacid compound and diacid halide compound known in the art, which are not listed here. In addition, one kind of diacid compound or diacid halide compound can be used alone, and two or more diacid compounds and/or diacid halide compounds can be used in combination to react with the diamine compound represented by formula I of the present disclosure to form poly Amide.

[Manufacturing method of polyamide]

In some embodiments, the polyamide of the present disclosure is formed by reacting a diacid compound and/or a diacid halide compound with a diamine compound represented by formula I of the present disclosure to form a polyamide.

[polyurea]

In some embodiments, the disclosed polymer can be polyurea, which includes repeating units of the following general formula.

In the above general formula, R ₄ is a divalent organic group derived from a diisocyanate compound, and Y ₁ is a residue derived from a diamine compound represented by formula I of the present disclosure. The diisocyanate compound may be any diisocyanate compound known in the art, which will not be listed here. In addition, one diisocyanate compound may be used alone, or two or more diisocyanate compounds may be used in combination to react with the diamine compound represented by formula I of the present disclosure to form polyurea.

[Preparation method of polyurea]

In some embodiments, the polyurea of the present disclosure is formed by reacting a diisocyanate compound with a diamine compound represented by Formula I of the present disclosure to form a polyurea.

[Polyimide]

In some embodiments, the disclosed polymer can be polyimine, which includes repeating units of the following general formula.

In the above general formula, R ₃ is a divalent organic group derived from a dialdehyde compound, and Y ₁ is a residue derived from a diamine compound represented by formula I of the present disclosure. The dialdehyde compound may be any dialdehyde compound known in the art, which will not be listed here. In addition, one dialdehyde compound may be used alone, or two or more dialdehyde compounds may be used in combination to react with the diamine compound represented by Formula I of the present disclosure to form polyimine.

[Manufacturing method of polyimine]

In some embodiments, the polyimine of the present disclosure is formed by reacting a dialdehyde compound with a diamine compound represented by formula I of the present disclosure to form a polyimine.

[This disclosure discloses the optical properties of polymers]

In some embodiments, the polymers of the present disclosure have a total light transmittance (T.T) greater than 80%, for example, 82%, 85%, 88%, 91%, 94%, 97% or 99%.

In some embodiments, the polymer of the present disclosure has a yellowness index (YI) of less than 5, preferably less than 3, more preferably less than 2. For example, 4.5, 4, 3.5, 3, 2.5, 2, 1.5, 1, or 0.5.

In some embodiments, b* of the disclosed polymer is less than 3, preferably less than 2, more preferably less than 1.5. For example, 2.8, 2.5, 2.3, 1.8, 1.4, 1 or 0.5.

In some embodiments, the haze of the disclosed polymer is less than 2.5%, preferably less than 2%, more preferably less than 1%, for example, 2.2%, 1.8%, 1.5%, 1.2%, 0.8%, 0.5%, 0.3%, 0.2% or 0.1%.

[This disclosure discloses the physical and chemical properties of polymers]

In some embodiments, the polymers of the present disclosure have a glass transition temperature (Tg) greater than 200°C, preferably greater than 230°C, more preferably greater than 250°C. For example, 210°C, 215°C, 220°C, 225°C, 235°C, 240°C, 245°C, 255°C, 260°C, 265°C, 270°C, 275°C, or 280°C.

In some embodiments, the coefficient of thermal expansion (CTE) of the disclosed polymer is less than 55 ppm/°C, preferably less than 50 ppm/°C, more preferably less than 45 ppm/°C, for example, 53 ppm/°C, 48 ppm/°C °C, 46 ppm/°C, 43 ppm/°C, 41 ppm/°C, 39 ppm/°C, 36 ppm/°C, or 33 ppm/°C.

[Use of polymer disclosed in this disclosure]

According to an embodiment of the present disclosure, an application of a polymer containing a diamine compound is provided, which is used in insulating tapes, wire varnishes, protective coatings, alignment films, transparent substrates, or films, but not limited thereto.

In some embodiments, the polymers containing diamine compounds disclosed herein can be applied to components in electronic devices. In some embodiments, the "element" may be an optical element, for example, a transparent film, a transparent substrate, a transparent sheet, or a transparent layer, but not limited thereto. In some embodiments, the "element" may also be a non-optical element, such as a semiconductor element, but not limited thereto.

In this disclosure, the term "electronic device" means a device including one or more organic semiconductor layers or materials. In some embodiments, electronic devices include, but are not limited to: (1) devices that convert electrical energy into radiation (e.g., light emitting diodes, light emitting diode displays, diode lasers, or lighting panels) , (2) Devices that use electronic processing to detect signals (for example, photodetectors, photoconductive cells, photoresistors, photoswitches, phototransistors, photocells, infrared (IR) detectors, or biosensors), ( 3) devices that convert radiation into electrical energy (for example, photovoltaic devices or solar cells), (4) devices (for example, transistors or diodes) that contain one or more electronic components that include one or more organic semiconductor layers, or any combination of devices in (1) to (4).

In some embodiments, the polymers of the present disclosure can be applied to components in liquid crystal displays (LCDs). In some embodiments, the disclosed polymers can be applied to alignment layers in display devices. In some embodiments, the disclosed polymers can be applied to components in organic electronic devices (eg, organic light-emitting diodes (OLEDs)). In some embodiments, the polymers of the present disclosure can be applied to a transparent protective filter of a camera.

Hereinafter, the present disclosure will provide several examples to more specifically illustrate the achievable effects of the polymers according to the embodiments of the present disclosure, as well as the properties of the polymers prepared by applying the present disclosure. However, the following examples are for illustrative purposes only, and should not be construed as limitations on the implementation of the present disclosure.

[Preparation Example 1] Diamine compound (tetradecylhydro-1,4:5,8-dimethylanthracene-9,10-diyl-bis(4-aminobenzoate))

For the synthesis of diol compound 4, refer to the relevant synthesis steps disclosed in the patent document (WO2017209199 A1), and diol is synthesized from compound 1 (1,4-benzoquinone) and compound 2 (dicyclopentadiene) Compound 4.

step 3

4-Nitrobenzoyl chloride (1.5 g, 8.2 mmol) was added to a solution of diol compound 4 (0.5 g, 2.0 mmol) in 21 mL of pyridine. The solution was stirred at room temperature. After 16 hours, the white solid was filtered and washed with methanol (20 mL) to give a white solid product (0.7 g, 63.1%), namely diester compound 5. The NMR spectrum data of diester compound 5 is as follows: ¹ H NMR (400 MHz, CDCl ₃ , 298 K): δ=1.18 (d, J=8.4 Hz, 1H), 1.30 (d, J=8.4 Hz, 1H), 1.49-1.56 (m, 2H), 2.19-2.30 (m, 2H), 2.69-2.78 (m, 2H), 2.89-2.98 (m, 4H), 4.73-4.85 (m, 2H), 6.29-6.32 (m , 2H), 6.33-6.37 (m, 2H), 8.21-8.27 (m, 4H), 8.28-8.34 (m, 4H). MS: cald for C ₃₀ H ₂₇ N ₂ O ₈ : m/z 543.2; found : 543.2 [M+H] ⁺ .

step 4

Diester compound 5 (0.6 g, 1.10 mmol) was dissolved in 24 mL methanol and 72 mL dichloromethane, and 5% Pd/C (0.06 g) was added. The mixture was stirred at room temperature under hydrogen atmosphere for 16 hours. The solution was filtered and concentrated to give a white solid product (0.5 g, 93.2%), which was the diamine compound 6 (tetrahydro-1,4:5,8-dimethylanthracene-9,10-diyl-bis (4-aminobenzoate)). The NMR spectral data of diamine compound 6 are as follows: ¹ H NMR (400 MHz, CDCl ₃ , 298 K): δ=1.20-1.42 (m, 6H), 1.46-1.54 (m, 2H), 1.63-1.75 (m, 2H), 1.98-2.09 (m, 2H), 2.17-2.24 (m, 2H), 2.31-2.38 (m, 2H), 2.67-2.81 (m, 4H), 4.02 (brs, 4H), 5.32-5.50 (m, 2H), 6.59-6.66 (m, 4H), 7.80-7.89 (m, 4H). MS: cald for C ₃₀ H ₃₄ N ₂ O ₄ Na: m/z 509.2; found: 509.6 [M+Na ] ⁺ .

[Preparation Example 2] Diamine compound (tetradecylhydro-1,4:5,8-dimethylanthracene-9,10-diyl-bis(3-aminobenzoate))

For the synthesis of diol compound 4, refer to the relevant synthesis steps disclosed in the patent document (WO2017209199 A1). Diol compound 4 was synthesized from 1,4-benzoquinone and dicyclopentadiene.

3-Nitrobenzoyl chloride (1.86 g, 10.0 mmol) was added to diol-containing compound 4 (1.0 g, 4.0 mmol), 4-dimethylaminopyridine (4-DMAP) (0.05 g, 0.04 mmol) and 40 mL of pyridine solution. The solution was stirred at room temperature. After 16 hours, 200 mL of water was added to the reaction mixture. The white solid was filtered and washed with methanol to give a white solid product (1.5 g, 69%), which was diester compound 5'.

The diester compound 5' (0.5 g, 1.0 mmol) was dissolved in 7.5 mL of methanol and 15 mL of dichloromethane, and 10% Pd/C (0.05 g) was added. The mixture was stirred at room temperature under hydrogen atmosphere for 24 hours. The solution was filtered and concentrated to give a white solid product (0.5 g, 92%), which was the diamine compound 6' (tetradecylhydro-1,4:5,8-dimethylanthracene-9,10-diyl- bis(3-aminobenzoate)). The NMR spectral data of diamine compound 6' are as follows: ¹ H NMR (400 MHz, CDCl ₃ , 298 K): δ=1.26-1.45 (m, 6H), 1.49-1.59 (m, 2H), 1.64-1.72 (m , 2 H), 2.01-2.09 (m, 2H), 2.18-2.28 (m, 2H), 2.32-2.42 (m, 2H), 2.71-2.85 (m, 4H), 3.80 (brs, 4H), 5.39- 5.51 (m, 2H), 6.82-6.90 (m, 2H), 7.18-7.25 (m, 2H), 7.32-7.37 (m, 2H), 7.40-7.49 (m, 2H). MS: cald for C ₃₀ H ₃₅ N ₂ O ₄ : m/z 487.3; found: 487.3 [M+H] ⁺ .

[Preparation Example 3] Diamine compound (bicyclo[2.2.1]heptane-2,5-diyl-bis(4-aminobenzoate))

step 1

In a 1 L round bottom flask, compound 7 (2,5-norbornadiene) (100 g, 1.08 mol) and 97% formic acid (600 mL) were added under an argon atmosphere. The reaction was refluxed at 120 °C for 24 hours, after which the formic acid was distilled off, and a transparent liquid of the diformate was obtained by vacuum distillation (120~130 °C, 10 mmHg/13.3 mbar). The crude dicarboxylate (198.7 g, 1.07 mol) was placed in a 3 L round bottom flask and dissolved in THF (1.5 L). The solution was cooled to 0 °C and a solution containing NaOH (424 g) and water (600 mL) was added via dropping funnel over 30 minutes. After the reaction mixture was stirred at room temperature for 10 hours, it was extracted with ethyl acetate. The aqueous layer was saturated with sodium chloride, and then extracted with ethyl acetate. The combined organics were dried over magnesium sulfate and concentrated to give the product (100 g) as the diol compound 8 as a colorless solid. The NMR spectrum data of diol compound 8 is as follows: ¹ H NMR (400 MHz, CDCl ₃ , 298 K): δ= 0.93-1.09 (m, 1H), 1.17-1.25 (m, 1H), 1.44-1.85 (m, 4H), 1.96-2.29 (m, 4H), 3.63-4.52 (m, 4H). GC/MS: [MH]=127.

step 2

In a 100 mL round bottom flask, diol compound 8 (1.0 g, 5.43 mmol) was dissolved in dichloromethane (10 mL) and trimethylamine (1.65 g, 16.29 mmol) at 0-10 °C. Under nitrogen atmosphere, compound 9 (4-nitrobenzoyl chloride) (2.22 g, 11.94 mmol) was added dropwise for 1 hour and left at room temperature. The solution was stirred at room temperature for 16 hours. After the reaction was completed, the solution was washed three times with 100 mL of water, and the organic layer was dried by rotary evaporation to obtain a yellow solid (1.5 g, 69%), namely dinitro compound 10. The NMR spectral data of dinitro compound 10 are as follows: ¹ H NMR (400 MHz, d6-DMSO, 298 K): δ= 1.03-1.25 (m, 1H), 1.32-1.44 (m, 1H), 1.55-1.88 ( m, 4H), 1.93-2.61 (m, 4H), 4.66-5.02 (m, 2H), 8.14-8.37 (m, 8H); LC/MS: [M+Na]=449.

step 3

Dinitro compound 10 (1.0 g, 5.43 mmol) was dissolved in 6 mL methanol and 24 mL dichloromethane, and 10% Pd/C (0.1 g) was added. The mixture was stirred at room temperature under hydrogen atmosphere for 24 hours. The solution was filtered and concentrated to give a white solid product (0.73 g, 85%), which was diamine compound 11 (bicyclo[2.2.1]heptane-2,5-diyl-bis(4-aminobenzoate )). The NMR spectral data of diamine compound 11 are as follows: ¹ H NMR (400 MHz, d6-DMSO, 298 K): δ= 1.29-1.35 (m, 1H), 1.47-1.54 (m, 1H), 1.58-1.98 (m , 4H), 2.01-2.54 (m, 4H), 4.53-4.82 (m, 2H), 5.95-6.00 (NH ₂ , m, 4H), 6.53-6.58 (m, 4H), 7.59-7.66 (m, 4H ); LC/MS: [M+H]=367.

[Preparation Example 4] Polyimide

The diamine compound 6 (1.0852 g, 0.0022 mole) and TFMB (0.7143 g, 0.0022 mole) of the aforementioned Preparation Example 1 were placed in a 100 mL three-necked flask containing 5 g GBL, while maintaining a slow nitrogen flow. TCA (1.0000 g, 0.0044 mole) was added to the solution, after which 5 g GBL was added again. The above mixture was mechanically stirred at room temperature under nitrogen flow for 24 hours, resulting in a clear viscous solution. Add 5 g of GBL to the viscous solution for dilution. 3.6434 g (0.03571 mole) of acetic anhydride (Ac ₂ O) and 3.8371 g (0.02678 mole) of TPA were slowly dropped into the solution and heated to 60° C. for 12 hours. After the reaction was completed, the solution was dropped into methanol and washed 3 times with methanol. Afterwards, the solid was filtered and dried in a vacuum oven to obtain pure polyimide powder.

Each of the above components represents the following compounds:

GBL: γ-butyrolactone (γ-butyrolactone) (purchased from Shengyi Chemical Co., Ltd.)

TFMB: 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl (2,2'-bis(trifluoromethyl)benzidine) (purchased from Shifeng Technology Co., Ltd.)

TCA: 2,3,5-tricarboxycyclopentyl acetic acid dianhydride (3-(carboxymethyl)-1,2,4-cyclopentanetricarboxylic acid 1,4:2,3-dianhydride) (Li Changrong Chemical Industry Co., Ltd. manufacture)

TPA: triphenylamine (purchased from TCI)

[Preparation Example 5] Polyimide varnish

The white polyimide powder prepared in Preparation Example 4 was dissolved in GBL (15 wt %) and degassed under vacuum to form a varnish.

[Preparation Example 6] Polyimide film

The polyimide varnish was coated on the glass substrate by a knife coater to form a wet film. The wet film was dried in an oven by heating at 50° C. for 1 hour, 150° C. for 1 hour, and 200° C. for 2 hours to remove the solvent and form a polyimide film. Afterwards, the polyimide film was peeled off from the substrate by immersion in deionized water. Various properties of the polyimide film were measured by the following test methods.

[Example 1] Glass transition temperature test

Using a thermomechanical analyzer "TMA/Q400" manufactured by TA Instruments, the glass transition temperature (glass transition temperature, Tg) analysis was performed using a tensile film clamp. Cut the sample into 16 mm X 5 mm, clamp both ends of the test piece with a film clamp and place it in TMA, pass nitrogen gas with a flow rate of 100 ml/min as a protective atmosphere, and apply a fixed load of 0.05N , from 50°C to 350°C at a heating rate of 10°C/min, then cooled back to 50°C by natural cooling, and then to 500°C at a rate of 10°C/min. The inflection point of the slope change in the TMA measurement data is the glass transition temperature (Tg).

[Example 2] Coefficient of thermal expansion test

Using a thermomechanical analyzer "TMA/Q400" manufactured by TA Instruments, the coefficient of thermal expansion (coefficient of thermal expansion, CTE) analysis was performed using a tensile film fixture. Cut the sample into 16 mm X 5 mm, clamp both ends of the test piece with a film clamp and place it in TMA, pass nitrogen gas with a flow rate of 100 ml/min as a protective atmosphere, and apply a fixed load of 0.05N , from 50°C to 350°C at a heating rate of 10°C/min, then cooled back to 50°C by natural cooling, and then to 500°C at a rate of 10°C/min. The coefficient of thermal expansion (CTE) value can be obtained by extracting the slope of 50~200°C from the TMA measurement data.

[Example 3] Total light transmittance test

According to ASTM D1003, the total light transmittance (total transmittance, T.T) was measured using a colorimetric and turbidity simultaneous measuring instrument "CSP-001" manufactured by Nippon Denshoku Kogyo Co., Ltd.

[Example 4] Yellowness index test

According to ASTM D1925, the yellowness index (yellowness index, YI) was measured using a chromaticity and turbidity simultaneous measuring instrument "CSP-001" manufactured by Nippon Denshoku Kogyo Co., Ltd.

[Example 5] b value (b*) test

In accordance with ASTM D1925, the CIE L*a*b* coordinates were measured using a chromaticity and turbidity simultaneous measuring instrument "CSP-001" manufactured by Nippon Denshoku Kogyo Co., Ltd.

[Example 6] Haze test

According to ASTM D1003, the haze (haze) was measured using a color and turbidity simultaneous measuring instrument "CSP-001" manufactured by Nippon Denshoku Kogyo Co., Ltd.

The physical and chemical properties of the polyimide film prepared in Preparation Example 6 were tested by the above test method. The test results are as follows: the glass transition temperature is 283°C, the thermal expansion coefficient is 35 ppm/°C, the total light transmittance is 90.4%, the haze is 0.2%, the yellowness index is 1.65, and the b value (b*) is 0.85.

The present disclosure provides a novel diamine compound comprising a non-conjugated norbornane ring structure. Since this novel diamine compound has a non-conjugated norbornane ring structure, the optical properties (such as total light transmittance, yellowness index, b value, and haze) of the synthesized polymer can be improved. In addition, the huge ring structure fused with cyclohexyl and norbornyl can make the compound molecule more rigid, and the structure is not easy to flip, which further improves the dimensional stability of polymer materials and reduces the coefficient of thermal expansion (CTE) . Therefore, the diamine compounds containing alicyclic hydrocarbon groups disclosed in the present disclosure can be used as key components of soft materials in electronic devices, so that the synthesized polymers have good heat resistance and optical properties. In addition, since the diamine compound of the present disclosure can be synthesized into a wide variety of polymer materials, for example, polyimide, polyamic acid, epoxy resin, polyamide, polyurea or polyimide, the present disclosure can be It is widely used in various industrial fields that require many materials such as heat resistance and optical properties.

Several embodiments are summarized above so that those skilled in the art of the present invention can better understand the viewpoints of the embodiments of the present invention. Those with ordinary knowledge in the technical field of the present invention should understand that they can design or modify other processes and structures based on the embodiments of the present invention, so as to achieve the same purpose and/or advantages as the embodiments introduced here. Those skilled in the technical field of the present invention should also understand that such equivalent processes and structures do not deviate from the spirit and scope of the present invention, and they can, without departing from the spirit and scope of the present invention, Make all sorts of changes, substitutions, and substitutions.

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Claims (15)

A diamine compound, represented by formula I: (I) wherein A is an alicyclic hydrocarbon group containing a norbornane ring (norbornane ring) and the carbon number is between 7 and 30, and Y is *-COO-* or *-CONH-*. The diamine compound as described in Claim 1, wherein the diamine compound is represented by formula II: (II) wherein B is absent or *-CH ₂ -*, Y is *-COO-* or *-CONH-*, and n and m represent 0 or an integer of 1~2. The diamine compound as described in claim 1, wherein the diamine compound is: , , ,or . The diamine compound as described in claim 1, wherein the diamine compound is: , , , , ,or . A method for preparing a diamine compound, comprising: performing a hydrogenation reaction on a compound shown in formula III to form a diamine compound shown in formula I, (I) (III) wherein A is an alicyclic hydrocarbon group containing a norbornane ring and having a carbon number of 7 to 30, B is an alicyclic hydrocarbon group containing a norbornane ring or a norbornene ring and having a carbon number of 7 to 30, and Y is *-COO-* or *-CONH-*. The preparation method of diamine compound as described in claim item 5, wherein the compound shown in formula III is formed by the reaction of diol compound shown in formula IV and nitrobenzoyl chloride, B-(OH) ₂ (IV ) wherein B is an alicyclic hydrocarbon group containing a norbornane ring or a norbornene ring and a carbon number between 7 and 30. The preparation method of the diamine compound as described in claim item 5, wherein the compound shown in formula III is formed by reacting the diamine compound shown in formula V with nitrobenzoyl chloride, B-(NH ₂ ) ₂ ( V) wherein B is an alicyclic hydrocarbon group containing a norbornane ring or a norbornene ring and a carbon number between 7 and 30. A polymer derived from a diamine compound shown in formula I: (I) wherein A is an alicyclic hydrocarbon group containing a norbornane ring and the carbon number is between 7 and 30, and Y is *-COO-* or *-CONH-*. The macromolecule as claimed in item 8, wherein the macromolecule comprises repeating units of the following general formula: Wherein X is a 4-valent organic group, and _Y is a residue derived from a diamine compound shown in formula I. The macromolecule as claimed in item 8, wherein the macromolecule comprises repeating units of the following general formula: Wherein X is a 4-valent organic group, and _Y is a residue derived from a diamine compound shown in formula I. The macromolecule as claimed in item 8, wherein the macromolecule comprises structural units of the following general formula: or Wherein Y ₁ is a residue derived from a diamine compound shown in formula I, R ₁ is a divalent organic group, and n and m represent an integer of 2-1000. The macromolecule as claimed in item 8, wherein the macromolecule comprises repeating units of the following general formula: wherein R ₂ is a divalent organic group, and Y ₁ is a residue derived from a diamine compound shown in formula I. The macromolecule as claimed in item 8, wherein the macromolecule comprises repeating units of the following general formula: Wherein R ₄ is a divalent organic group, and Y ₁ is a residue derived from a diamine compound shown in formula I. The macromolecule as claimed in item 8, wherein the macromolecule comprises repeating units of the following general formula: wherein R ₃ is a divalent organic group, and Y ₁ is a residue derived from a diamine compound shown in formula I. A use of the polymer as described in Claim 8, which is used in insulating tapes, wire varnishes, protective coatings, alignment films, transparent substrates, or films.