TWI863059B - 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 by diamine compound and use thereof

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

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

Generally speaking, rod-like diamine compounds have a better filling factor and can reduce the thermal expansion coefficient of the material formed therefrom. However, most rod-like diamine compounds contain aromatic groups, such as 4-aminophenyl-4-aminobenzoate, which has a conjugated system, resulting in yellowing of the formed material after long-term use or high-temperature processing. Therefore, there is a need for diamine compounds that can impart good optical properties and a lower thermal expansion coefficient to the material.

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

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

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

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

According to an embodiment of the present disclosure, a use of the polymer as described above is provided, which is used for insulating tape, wire paint, protective coating, alignment film, transparent substrate, or film.

In order to make the features of the present disclosure clear and easy to understand, the following is a detailed description of the embodiments with the accompanying drawings. For other matters, please refer to the technical field.

The following is a detailed description of the diamine compound provided in this case and the polymer formed therefrom. It should be understood that the following description provides many different embodiments or examples for implementing different aspects of some embodiments of the present disclosure. The specific elements and arrangements described below are only for the purpose of simply and clearly describing some embodiments of the present disclosure. Of course, these are only used for exemplification and are not intended to limit the present disclosure.

In the text, the terms "about", "approximately", and "substantially" generally mean within 5%, preferably within 3%, more preferably within 1%, or within 2%, or within 1%, or within 0.5% of a given value or range. The quantities given here are approximate quantities, that is, in the absence of specific description of "about", "approximately", and "substantially", the meaning of "about", "approximately", and "substantially" can still be implied.

The diamine compound and its preparation method disclosed in the present invention are described in detail below.

[Diamine compound]

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

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

In some embodiments, the diamine compound disclosed herein 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 to 2. 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 disclosed herein may have a structure as shown below, but is not limited thereto: , , ,or .

In some embodiments, the diamine compound disclosed herein may have a structure as shown below, but is not limited thereto: , , , , ,or .

[Preparation of diamine compounds]

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

In some embodiments, the compound of formula III can be formed by reacting a diol compound of formula IV with nitrobenzyl 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 of formula III can be formed by reacting a diamine compound of formula V with nitrobenzyl 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 of the diamine compounds disclosed herein and their corresponding chemical names. Diamine compounds Chemical name Tetradecahydro-1,4:5,8-dimethanoanthracene-9,10-diyl bis(4-aminobenzoate) Tetradecahydro-1,4:5,8-dimethanoanthracene-9,10-diyl bis(3-aminobenzoate) Bicyclo[2.2.1]heptane-2,5-diyl bis(4-aminobenzoate) N,N'-(tetradecahydro-1,4:5,8-dimethanoanthracene-9,10-diyl)bis(4-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)

As mentioned above, the diamine compounds disclosed herein can be used to form various polymers (e.g., polyimide, polyamide, epoxy resin, polyamide, polyurea, and polyimide), and these polymers can be used for various purposes. The following examples introduce these polymers and their preparation methods, but it should be noted that the types of polymers and preparation methods are not limited to these.

According to an embodiment of the present disclosure, a polymer is provided, which is formed by a diamine compound shown in Formula I. (I)

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

[Polyamide]

In some embodiments, the polymer disclosed herein may be a poly(amino acid) comprising repeating units of the following general formula.

In the above general formula, X is a 4-valent organic group derived from a tetracarboxylic dianhydride compound. In some embodiments, the tetracarboxylic dianhydride compound may 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-tricarboxycyclopentaneacetic dianhydride (TCA), but is not limited thereto. In addition, a single tetracarboxylic dianhydride compound may be used, or two or more tetracarboxylic dianhydride compounds may be used in combination to react with the diamine compound shown in Formula I of the present disclosure to form polyamide. In the above general formula, Y ₁ is a residue derived from the diamine compound shown in Formula I of the present disclosure.

[Preparation method of polyamine]

In some embodiments, the polyamine disclosed herein is formed by the following method: a tetracarboxylic dianhydride compound and a diamine compound shown in Formula I disclosed herein are mixed in a solvent for condensation polymerization to form polyamine. In some embodiments, the condensation polymerization reaction can be stirred at a speed of 200-400 rpm at room temperature for 3-12 hours, for example, at a speed of 300 rpm at room temperature for 4 hours under a nitrogen environment. After the reaction is completed, it is cooled to obtain polyamine.

[Polyimide]

In some embodiments, the polymer disclosed herein may be a polyimide comprising 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 _Y1 is a residue derived from a diamine compound represented by Formula I disclosed herein. The types of the tetracarboxylic dianhydride compound are as described above and will not be described in detail. In addition, a single 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 disclosed herein to form a polyimide.

[Preparation method of polyimide]

In some embodiments, the polyimide disclosed herein is formed by the following method: a tetracarboxylic dianhydride compound and a diamine compound shown in Formula I disclosed herein are polymerized in a solvent to obtain polyamide, and then the polyamide is imidized to form polyimide. The following two methods are listed for the synthesis of imidization of polyamide, but are not limited to them. The first method is divided into two stages. First, a tetracarboxylic dianhydride compound and a diamine compound shown in Formula I disclosed herein are placed in a polar solvent for reaction to form a precursor of polyimide, polyamide. Afterwards, the imidization reaction is carried out by a high temperature method (300°C~500°C) or a chemical method to dehydrate the polyamine and close the ring 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~120°C for 3~24 hours, for example, at a temperature of 90°C for 16 hours. The second method is to synthesize polyimide by a stage, and place a tetracarboxylic dianhydride compound and a diamine compound shown in Formula I disclosed in the present invention in a polar aprotic solvent for reaction, and then heat to reflux temperature for reaction to form polyimide. After the reaction is completed, it is cooled, recrystallized, purified and dried to obtain a polyimide solid.

[Epoxy]

In some embodiments, the polymer disclosed herein may be an epoxy resin comprising a structural unit of the following general formula. or

In the above general formula, _Y1 is a residue derived from the diamine compound represented by Formula I of the present disclosure, _R1 is a divalent organic group, and n and m represent integers of 2 to 1000.

[Method for preparing epoxy resin]

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

In the above general formula, R1 is a p-valent organic group, and p represents an integer of 2 to 6, such as 3, 4 or 5. It should be understood that the epoxy compound can be any epoxy compound having two or more epoxy groups known in the art, and no enumeration is given here. In addition, one epoxy compound can be used alone, or two or more epoxy compounds can be used in combination to react with the diamine compound shown in Formula I of the present disclosure to form an epoxy resin.

[Polyamide]

In some embodiments, the polymer disclosed herein may be a polyamide comprising repeating units of the following general formula.

In the above general formula, _R2 is a divalent organic group derived from a diacid compound or a diacyl halide compound, and _Y1 is a residue derived from a diamine compound represented by Formula I disclosed herein. The diacid compound and the diacyl halide compound may be any diacid compound and diacyl halide compound known in the art, and are not listed here. In addition, a single diacid compound or diacyl halide compound may be used alone, or two or more diacid compounds and/or diacyl halide compounds may be used in combination to react with the diamine compound represented by Formula I disclosed herein to form a polyamide.

[Preparation method of polyamide]

In some embodiments, the polyamide disclosed herein is formed by the following method: a diacid compound and/or a diacyl halide compound is reacted with a diamine compound represented by Formula I disclosed herein to form a polyamide.

[Polyurea]

In some embodiments, the polymer disclosed herein may be a polyurea comprising repeating units of the following general formula.

In the above general formula, _R4 is a divalent organic group derived from a diisocyanate compound, and _Y1 is a residue derived from a diamine compound represented by Formula I disclosed herein. The diisocyanate compound may be any diisocyanate compound known in the art, and no enumeration is given here. In addition, a single 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 disclosed herein to form a polyurea.

[Preparation method of polyurea]

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

[Polyimide]

In some embodiments, the polymer disclosed herein may be a polyimide comprising repeating units of the following general formula.

In the above general formula, _R3 is a divalent organic group derived from a dialdehyde compound, and _Y1 is a residue derived from a diamine compound represented by Formula I disclosed herein. The dialdehyde compound may be any dialdehyde compound known in the art, and no enumeration is given here. In addition, a single 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 disclosed herein to form a polyimine.

[Preparation method of polyimine]

In some embodiments, the polyimine disclosed herein is formed by the following method: a dialdehyde compound is reacted with a diamine compound represented by Formula I disclosed herein to form the polyimine.

[Optical properties of polymers disclosed herein]

In some embodiments, the total light transmittance (T.T) of the polymer disclosed herein is greater than 80%, for example, 82%, 85%, 88%, 91%, 94%, 97% or 99%.

In some embodiments, the yellowness index (YI) of the polymer disclosed herein is less than 5, preferably less than 3, and 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, the b* of the polymer disclosed herein is less than 3, preferably less than 2, and 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 polymer disclosed herein is less than 2.5%, preferably less than 2%, and 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%.

[Physical and chemical properties of polymers disclosed in this paper]

In some embodiments, the glass transition temperature (Tg) of the polymer disclosed herein is greater than 200°C, preferably greater than 230°C, and 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 polymer disclosed herein is less than 55 ppm/°C, preferably less than 50 ppm/°C, and more preferably less than 45 ppm/°C, for example, 53 ppm/°C, 48 ppm/°C, 46 ppm/°C, 43 ppm/°C, 41 ppm/°C, 39 ppm/°C, 36 ppm/°C or 33 ppm/°C.

[Application of the polymer disclosed herein]

According to an embodiment of the present disclosure, a use of a polymer containing a diamine compound is provided, which is used for insulating tape, wire paint, protective coating, alignment film, transparent substrate, or film, but is not limited thereto.

In some embodiments, the polymer containing diamine compounds disclosed herein can be applied to components in electronic devices. In some embodiments, the "component" can be an optical component, such as a transparent film, a transparent substrate, a transparent plate (sheet), or a transparent layer, but not limited thereto. In some embodiments, the "component" can also be a non-optical component, such as a semiconductor component, but not limited thereto.

In this disclosure, the term "electronic device" is intended to include a device comprising one or more organic semiconductor layers or materials. In some embodiments, the electronic device includes, but is not limited to: (1) a device that converts electrical energy into radiation (e.g., a light-emitting diode, a light-emitting diode display, a diode laser, or a lighting panel), (2) a device that uses electronic processing to detect signals (e.g., a photodetector, a photoconductive cell, a photoresistor, a photoswitch, a phototransistor, a phototube, an infrared (IR) detector, or a biosensor), (3) a device that converts radiation into electrical energy (e.g., a photovoltaic device or a solar cell), (4) a device that includes one or more electronic elements (e.g., a transistor or a diode), wherein the electronic elements include one or more organic semiconductor layers, or any combination of the devices in (1) to (4).

In some embodiments, the polymer disclosed herein can be applied to components in a liquid crystal display (LCD). In some embodiments, the polymer disclosed herein can be applied to an alignment layer in a display device. In some embodiments, the polymer disclosed herein can be applied to components in an organic electronic device (e.g., an organic light-emitting diode (OLED)). In some embodiments, the polymer disclosed herein can be applied to a transparent protective filter for a camera.

Hereinafter, the present disclosure will provide several embodiments to more specifically illustrate the effects that can be achieved by 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 embodiments are only for illustrative purposes and should not be interpreted as limitations on the implementation of the present disclosure.

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

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

Step 3

4-Nitrobenzyl chloride (1.5 g, 8.2 mmol) was added to a solution containing the diol compound 4 (0.5 g, 2.0 mmol) and 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 obtain a white solid product (0.7 g, 63.1%), which was the diester compound 5. The NMR spectrum data of the diester compound 5 are 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

The diester compound 5 (0.6 g, 1.10 mmol) was dissolved in 24 mL of methanol and 72 mL of dichloromethane, and 5% Pd/C (0.06 g) was added. The mixture was stirred at room temperature for 16 hours under a hydrogen atmosphere. The solution was filtered and concentrated to obtain a white solid product (0.5 g, 93.2%), which was the diamine compound 6 (tetradecahydro-1,4:5,8-dimethylanthracene-9,10-diyl-bis(4-aminobenzoate)). The NMR spectrum 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, 2 H), 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 (tetradecahydro-1,4:5,8-dimethylanthracene-9,10-diyl-bis(3-aminobenzoate))

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

3-Nitrobenzyl chloride (1.86 g, 10.0 mmol) was added to a solution containing the diol compound 4 (1.0 g, 4.0 mmol), 4-dimethylaminopyridine (4-DMAP) (0.05 g, 0.04 mmol) and 40 mL of pyridine. 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 obtain a white solid product (1.5 g, 69%), which was the 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 for 24 hours under a hydrogen atmosphere. The solution was filtered and concentrated to obtain a white solid product (0.5 g, 92%), which was the diamine compound 6' (tetradecahydro-1,4:5,8-dimethylanthracene-9,10-diyl-bis(3-aminobenzoate)). The NMR spectrum 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 1L 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 formic acid was distilled off and a transparent liquid of diformate was obtained by vacuum distillation (120-130 °C, 10 mmHg/13.3 mbar). The crude diformate (198.7 g, 1.07 mol) was placed in a 3L 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 to the solution with a dropping funnel over 30 minutes. The reaction mixture was stirred at room temperature for 10 hours and then 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 obtain a colorless solid product (100 g), which was bisol compound 8. The NMR spectrum data of bisol compound 8 are 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. Compound 9 (4-nitrobenzyl chloride) (2.22 g, 11.94 mmol) was added dropwise under nitrogen atmosphere for 1 hour and allowed to stand at room temperature. The solution was stirred at room temperature for 16 hours. After the reaction was completed, the solution was washed 3 times with 100 mL of water, and the organic layer was dried by rotary evaporation to obtain a yellow solid (1.5 g, 69%), which was 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

The dinitro compound 10 (1.0 g, 5.43 mmol) was dissolved in 6 mL of methanol and 24 mL of dichloromethane, and 10% Pd/C (0.1 g) was added. The mixture was stirred at room temperature for 24 hours under a hydrogen atmosphere. The solution was filtered and concentrated to obtain a white solid product (0.73 g, 85%), which was the diamine compound 11 (bicyclo[2.2.1]heptane-2,5-diyl-bis(4-aminobenzoate)). The NMR spectrum 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

In a 100 mL three-necked flask containing 5 g of GBL, the diamine compound 6 (1.0852 g, 0.0022 mole) and TFMB (0.7143 g, 0.0022 mole) of the above Preparation Example 1 were placed while maintaining a slow nitrogen flow. TCA (1.0000 g, 0.0044 mole) was added to the solution, and then 5 g of GBL was added again. The above mixture was mechanically stirred at room temperature and in a nitrogen flow for 24 hours to make the mixture a clear viscous solution. 5 g of GBL was added 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 dripped into the solution and heated to 60°C for 12 hours. After the reaction was completed, the solution was dropped into methanol and washed with methanol 3 times. Afterwards, the solid was filtered and dried in a vacuum oven to obtain pure polyimide powder.

The above components represent the following compounds:

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

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

TCA: 2,3,5-Tricarboxycyclopentane acetic anhydride (3-(carboxymethyl)-1,2,4-cyclopentanetricarboxylic acid 1,4:2,3-dianhydride) (manufactured by Lee Chang Jung Chemical Industries, Ltd.)

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 a glass substrate by a doctor blade coater to form a wet film. The wet film was dried in an oven 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. Thereafter, the polyimide film was peeled off from the substrate by immersing in deionized water. Various properties of the polyimide film were measured by the following test methods.

[Example 1] Glass transition temperature test

The glass transition temperature (Tg) analysis was performed using a TA Instruments thermal mechanical analyzer "TMA/Q400" and a stretch film fixture. The sample was cut into 16 mm x 5 mm pieces, and the two ends of the sample were clamped and fixed in the TMA with a film fixture. Nitrogen with a flow rate of 100 ml/min was introduced as a protective atmosphere. A fixed load of 0.05N was applied, and the temperature was raised from 50°C at a rate of 10°C/min to 350°C, then naturally cooled back to 50°C, and then raised to 500°C at 10°C/min. The turning point of the slope change in the TMA measurement data is the glass transition temperature (Tg).

[Example 2] Thermal Expansion Coefficient Test

The coefficient of thermal expansion (CTE) analysis was performed using a TA Instruments thermal mechanical analyzer "TMA/Q400" and a tensile film clamp. The sample was cut into 16 mm x 5 mm pieces, and the two ends of the sample were clamped and fixed in the TMA with a film clamp. Nitrogen with a flow rate of 100 ml/min was introduced as a protective atmosphere. A fixed load of 0.05N was applied, and the temperature was raised from 50°C at a rate of 10°C/min to 350°C, then naturally cooled back to 50°C, and then raised to 500°C at 10°C/min. The slope of 50~200°C from the TMA measurement data can be used to obtain the coefficient of thermal expansion (CTE) value.

[Example 3] Full light transmittance test

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

[Example 4] Yellowness Index Test

The yellowness index (YI) was measured in accordance with ASTM D1925 using the colorimetry and turbidity simultaneous tester "CSP-001" manufactured by Nippon Denshoku Industries Co., Ltd.

[Example 5] b value (b*) test

According to ASTM D1925, CIE L*a*b* coordinates were measured using the chromaticity and turbidity simultaneous tester "CSP-001" manufactured by Nippon Denshoku Industries Co., Ltd.

[Example 6] Fog test

Haze was measured in accordance with ASTM D1003 using the CSP-001 colorimetric and turbidity simultaneous tester manufactured by Nippon Denshoku Industries.

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

The present disclosure provides a novel diamine compound, which contains a non-conjugated norbornane ring structure. Since the novel diamine compound has a non-conjugated norbornane ring structure, the optical properties of the synthesized polymer (e.g., total light transmittance, yellowness index, b value, and haze) can be improved. In addition, the compound molecule can be made more rigid and the structure is not easy to flip, which further improves the dimensional stability of the polymer material and reduces the coefficient of thermal expansion (CTE). Therefore, the diamine compound containing alicyclic hydrocarbon groups disclosed in the present disclosure can be used as a key component of soft materials in electronic devices, so that the synthesized polymer has good heat resistance and optical properties. In addition, since the diamine compounds disclosed herein can be used to synthesize a wide variety of polymer materials, such as polyimide, polyamide, epoxy resin, polyamide, polyurea or polyimide, the present disclosure can be widely used in various industrial fields that require, for example, high heat resistance or optical properties of materials.

Several embodiments are summarized above so that those with ordinary knowledge in the art to which the present invention belongs can better understand the perspectives of the embodiments of the present invention. Those with ordinary knowledge in the art to which the present invention belongs should understand that they can design or modify other processes and structures based on the embodiments of the present invention to achieve the same purpose and/or advantages as the embodiments introduced herein. Those with ordinary knowledge in the art to which the present invention belongs should also understand that such equivalent processes and structures do not deviate from the spirit and scope of the present invention, and they can make various changes, substitutions and replacements without violating the spirit and scope of the present invention.

without.

without.

without.

Claims (11)

A diamine compound represented by Formula II:

wherein at least one B is *-CH ₂ -*, the remaining Bs are absent or *-CH ₂ -*, Y is *-COO-* or *-CONH-*, and n and m are both 0 or both 1. 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 polymer derived from a diamine compound represented by formula II:

wherein at least one B is *-CH ₂ -*, the remaining Bs are absent or *-CH ₂ -*, Y is *-COO-* or *-CONH-*, and n and m are both 0 or both 1. The polymer as claimed in claim 4, wherein the polymer comprises repeating units of the following general formula:

Wherein X is a tetravalent organic group, and _Y1 is a residue derived from the diamine compound represented by Formula II. The polymer as claimed in claim 4, wherein the polymer comprises repeating units of the following general formula:

Wherein X is a tetravalent organic group, and _Y1 is a residue derived from the diamine compound represented by Formula II. The polymer as claimed in claim 4, wherein the polymer comprises a structural unit of the following general formula:

or

wherein _Y1 is a residue derived from the diamine compound represented by formula II, _R1 is a divalent organic group, and n and m represent integers of 2 to 1000. The polymer as claimed in claim 4, wherein the polymer comprises repeating units of the following general formula:

Wherein R ₂ is a divalent organic group, and Y ₁ is a residue derived from the diamine compound represented by Formula II. The polymer as claimed in claim 4, wherein the polymer comprises repeating units of the following general formula:

Wherein R ₄ is a divalent organic group, and Y ₁ is a residue derived from the diamine compound represented by Formula II. The polymer as claimed in claim 4, wherein the polymer comprises repeating units of the following general formula:

Wherein R ₃ is a divalent organic group, and Y ₁ is a residue derived from the diamine compound represented by Formula II. A use of the polymer as described in claim 4, which is used for insulating tape, wire paint, protective coating, alignment film, transparent substrate, or film.