Diamine compounds and their preparation methods, polymers formed from diamine compounds and their applications

Abstract

This invention provides a diamine compound represented by Formula I. In Formula I, A is an alicyclic hydrocarbon group containing a norbornene ring and having 7 to 30 carbon atoms, and Y is *-COO-* or *-C ON H-*.

Description

Technical Field

[0001] This invention relates to a diamine compound, and more particularly to a diamine compound containing a norbornene ring. Background Technology

[0002] 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 for various applications, such as insulating tapes, wire coatings, protective coatings, alignment films, transparent substrates, or films.

[0003] Generally, rod-like diamine compounds have a better filling factor, which can reduce the coefficient of thermal expansion of the materials formed from them. However, most rod-like diamine compounds contain aromatic groups, such as 4-aminophenyl-4-aminobenzoate, which have a conjugated system, potentially causing yellowing of the materials formed during prolonged use or high-temperature processing. Therefore, there is a need for diamine compounds that can impart good optical properties and a low coefficient of thermal expansion to materials. Summary of the Invention

[0004] According to an embodiment of the present invention, a diamine compound is provided, represented by formula I.

[0005]

[0006] In Formula I, A is an alicyclic hydrocarbon group containing a norbornane ring and having between 7 and 30 carbon atoms, and Y is *-COO-* or *-CONH-*.

[0007] According to an embodiment of the present invention, a method for preparing a diamine compound is provided, comprising: hydrogenating a compound represented by Formula III to form a diamine compound represented by Formula I.

[0008]

[0009] In Formulas I and III, A is an alicyclic hydrocarbon group containing a norbornene ring and having between 7 and 30 carbon atoms, B is an alicyclic hydrocarbon group containing a norbornene ring or a norbornene ring and having between 7 and 30 carbon atoms, and Y is *-CO O-* or *-C ONH-*.

[0010] According to an embodiment of the present invention, a polymer is provided, which is derived from a diamine compound of formula I.

[0011]

[0012] In Formula I, A is an alicyclic hydrocarbon group containing a norbornene ring with a carbon number between 7 and 30, and Y is *-CO O-* or *-C ON H-*.

[0013] According to embodiments of the present invention, a use of the polymer as described above is provided, which is for use in insulating tapes, wire coatings, protective coatings, alignment films, transparent substrates, or films.

[0014] To make the features of the present invention clear and easy to understand, embodiments are provided below in conjunction with the accompanying drawings for detailed description. For other precautions, please refer to the technical field. Detailed Implementation

[0015] The following provides a detailed description of the diamine compound provided in this application and the polymer formed therefrom. It should be understood that the following description provides many different embodiments or examples to implement different variations of some embodiments of the present invention. The specific components and arrangements described below are merely for simple and clear description of some embodiments of the present invention. Of course, these are merely examples and not limitations of the present invention.

[0016] In this text, the terms "about," "approximately," and "substantially" generally indicate within 5% of a given value or range, preferably within 3%, more preferably within 1%, or within 2%, or within 1%, or within 0.5%. The given quantity is an approximate quantity, meaning that the meaning of "about," "approximately," or "substantially" may be implied even without specific mention of these terms.

[0017] The diamine compound of the present invention and its preparation method will be described in detail below.

[0018] [Diamine compounds]

[0019] According to an embodiment of the present invention, a diamine compound is provided, represented by formula I.

[0020]

[0021] In Formula I, A is an alicyclic hydrocarbon group containing a norbornane ring and having between 7 and 30 carbon atoms, and Y is *-COO-* or *-CONH-*.

[0022] In some embodiments, the diamine compound of the present invention may be represented by Formula II.

[0023]

[0024] In Formula II, B is absent or *-CH2-*, Y is *-COO-* or *-CONH-*, and n and m represent 0 or integers from 1 to 2. In Formula II, at least one B is *-CH2-*, thus the diamine compound contains a norbornene cyclogroup.

[0025] In some embodiments, the diamine compounds of the present invention may have, for example, the structures shown below, but are not limited thereto:

[0026]

[0027]

[0028] In some embodiments, the diamine compounds of the present invention may have, for example, the structures shown below, but are not limited thereto:

[0029]

[0030]

[0031] [Preparation of diamine compounds]

[0032] According to an embodiment of the present invention, a method for preparing a diamine compound is provided, comprising: hydrogenating a compound represented by Formula III to form a diamine compound represented by Formula I.

[0033]

[0034] In Formulas I and III, A is an alicyclic hydrocarbon group containing a norbornene ring and having between 7 and 30 carbon atoms, B is an alicyclic hydrocarbon group containing a norbornene ring or a norbornene ring and having between 7 and 30 carbon atoms, and Y is *-CO O-* or *-C ONH-*.

[0035] In some embodiments, the compound represented by Formula III may be formed by reacting the diol compound represented by Formula IV with nitrobenzyl chloride.

[0036] B-(OH)2(IV)

[0037] In Formula IV, B is an alicyclic hydrocarbon group containing a norbornene ring or a norbornene ring and having between 7 and 30 carbon atoms.

[0038] In some embodiments, the compound represented by Formula III may be formed by reacting the diamine compound represented by Formula V with nitrobenzyl chloride.

[0039] B-(NH2)2(V)

[0040] In formula V, B is an alicyclic hydrocarbon group containing a norbornene ring or a norbornene ring and having between 7 and 30 carbon atoms.

[0041] The table below lists specific examples of the diamine compounds of this invention and their corresponding chemical names.

[0042]

[0043]

[0044] As previously described, the diamine compounds of the present invention can be used to form various polymers (e.g., polyimides, polyamic acids, epoxy resins, polyamides, polyureas, and polyimides) and to use these polymers for various applications. Examples of these polymers and their preparation methods are given below, but it should be noted that the types of polymers and preparation methods are not limited thereto.

[0045] According to an embodiment of the present invention, a polymer is provided, which is formed from a diamine compound represented by Formula I.

[0046]

[0047] In Formula I, A is an alicyclic hydrocarbon group containing a norbornene ring with a carbon number between 7 and 30, and Y is *-CO O-* or *-C ONH-*.

[0048] [Polyamic acid]

[0049] In some embodiments, the polymer of the present invention may be polyamic acid, which comprises repeating units of the following general formula.

[0050]

[0051] In the above general formula, X is a tetravalent 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-tricarboxycyclopentylacetic dianhydride (TCA), but is not limited thereto. Furthermore, 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 of formula I of the present invention to form polyamic acid. In the above general formula, Y1 is a residue derived from the diamine compound of formula I of the present invention.

[0052] [Preparation method of polyamic acid]

[0053] In some embodiments, the polyamic acid of the present invention is formed by the following method: condensation polymerization of a tetracarboxylic acid dianhydride compound and a diamine compound of formula I of the present invention in a solvent to form polyamic acid. In some embodiments, the condensation polymerization reaction can be carried out under nitrogen atmosphere at room temperature with stirring at a speed of 200-400 rpm for 3-12 hours, for example, at room temperature with stirring at a speed of 300 rpm for 4 hours. After the reaction is completed, it is cooled to obtain polyamic acid.

[0054] [Polyimide]

[0055] In some embodiments, the polymer of the present invention may be a polyimide, which comprises repeating units of the following general formula.

[0056]

[0057] In the above general formula, X is a tetravalent organic group derived from a tetracarboxylic dianhydride compound, and Y1 is a residue derived from the diamine compound of formula I of the present invention. The types of tetracarboxylic dianhydride compounds have been described above and will not be repeated here. Furthermore, a single tetracarboxylic dianhydride compound can be used alone, or two or more tetracarboxylic dianhydride compounds can be combined and reacted with the diamine compound of formula I of the present invention to form polyimides.

[0058] [Preparation method of polyimide]

[0059] In some embodiments, the polyimide of the present invention is formed by the following method: polymerizing a tetracarboxylic dianhydride compound with a diamine compound of formula I of the present invention in a solvent to obtain polyamic acid, and then imidizing the polyamic acid to form a polyimide. Two synthetic methods for imidizing polyamic acid are listed below, but are not limited thereto. The first method is carried out in two stages. First, the tetracarboxylic dianhydride compound and the diamine compound of formula I of the present invention are reacted in a polar solvent to form a precursor of polyimide, polyamic acid. Then, an imidization reaction is carried out by a high-temperature method (300°C to 500°C) or a chemical method to dehydrate and close the ring of the polyamic acid to form a polyimide. In some embodiments, the high-temperature method is carried out at a temperature of 300°C to 500°C for 4 to 8 hours, for example, at a temperature of 400°C for 6 hours. In some embodiments, the chemical method is carried out at room temperature.

[0060] Acetic anhydride and catalyst are added at ~120°C and reacted for 3 to 24 hours, for example, at 90°C for 16 hours. A second method involves synthesizing polyimide in a single stage. A tetracarboxylic dianhydride compound is reacted with a diamine compound of formula I in a polar aprotic solvent, and the reaction is carried out at reflux temperature to form polyimide. After the reaction is complete, the mixture is cooled, recrystallized, purified, and dried to obtain solid polyimide.

[0061] [Epoxy Resin]

[0062] In some embodiments, the polymer of the present invention may be an epoxy resin, which comprises structural units of the following general formula.

[0063]

[0064] In the above general formula, Y1 is a residue of the diamine compound derived from Formula I of the present invention, R1 is a divalent organic group, and n and m represent integers from 2 to 1000.

[0065] [Preparation methods of epoxy resin]

[0066] In some embodiments, the epoxy resin of the present invention is formed by reacting an epoxy compound of the following general formula with a diamine compound of formula I of the present invention to form an epoxy resin:

[0067]

[0068] In the above general formula, R1 is a p-valent organic group, and p represents an integer from 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 will not be listed here. Furthermore, an epoxy compound can be used alone, or two or more epoxy compounds can be used in combination to react with the diamine compound of formula I of the present invention to form an epoxy resin.

[0069] [Polyamide]

[0070] In some embodiments, the polymer of the present invention may be a polyamide, which comprises repeating units of the following general formula.

[0071]

[0072] 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 the diamine compound of formula I of the present invention. The diacid compound and diacyl halide compound can be any diacid compound and diacyl halide compound known in the art, and are not listed here. Furthermore, a single diacid compound or diacyl halide compound can be used alone, or two or more diacid compounds and / or diacyl halide compounds can be used in combination to react with the diamine compound of formula I of the present invention to form a polyamide.

[0073] [Preparation methods of polyamides]

[0074] In some embodiments, the polyamide of the present invention is formed by reacting a diacid compound and / or a diacyl halide compound with a diamine compound of formula I of the present invention to form a polyamide.

[0075] Polyurea

[0076] In some embodiments, the polymer of the present invention may be a polyurea, which comprises repeating units of the following general formula.

[0077]

[0078] In the above general formula, R4 is a divalent organic group derived from a diisocyanate compound, and Y1 is a residue derived from the diamine compound of formula I of the present invention. The diisocyanate compound can be any diisocyanate compound known in the art, and will not be listed here. Furthermore, a single diisocyanate compound can be used alone, or two or more diisocyanate compounds can be combined and reacted with the diamine compound of formula I of the present invention to form a polyurea.

[0079] [Preparation method of polyurea]

[0080] In some embodiments, the polyurea of ​​the present invention is formed by reacting a diisocyanate compound with a diamine compound of formula I of the present invention to form a polyurea.

[0081] [Polyimide]

[0082] In some embodiments, the polymer of the present invention may be polyimide, which comprises repeating units of the following general formula.

[0083]

[0084] In the above general formula, R3 is a divalent organic group derived from a dialdehyde compound, and Y1 is a residue derived from the diamine compound of formula I of the present invention. The dialdehyde compound can be any dialdehyde compound known in the art, and will not be listed here. Furthermore, a single dialdehyde compound can be used alone, or two or more dialdehyde compounds can be used in combination to react with the diamine compound of formula I of the present invention to form a polyimide.

[0085] [Preparation method of polyimide]

[0086] In some embodiments, the polyimide of the present invention is formed by reacting a dialdehyde compound with a diamine compound of formula I of the present invention to form a polyimide.

[0087] [Optical properties of the polymer in this invention]

[0088] In some embodiments, the total light transmittance (TT) of the polymer of the present invention is greater than 80%, for example, 82%, 85%, 88%, 91%, 94%, 97%, or 99%.

[0089] In some embodiments, the yellowness index (YI) of the polymer of the present invention 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.

[0090] In some embodiments, the b* of the polymer of the present invention 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.

[0091] In some embodiments, the haze of the polymer of the present invention 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%.

[0092] [Physicochemical Properties of the Polymer in This Invention]

[0093] In some embodiments, the glass transition temperature (Tg) of the polymer of the present invention 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.

[0094] In some embodiments, the coefficient of thermal expansion (CTE) of the polymer of the present invention is less than 55 ppm / ℃, preferably less than 50 ppm / ℃, more preferably less than 45 ppm / ℃, for example, 53 ppm / ℃, 48 ppm / ℃, 46 ppm / ℃, 43 ppm / ℃, 41 ppm / ℃, 39 ppm / ℃, 36 ppm / ℃ or 33 ppm / ℃.

[0095] [Applications of the polymer in this invention]

[0096] According to embodiments of the present invention, a use is provided for a polymer containing a diamine compound, which is used in insulating tapes, wire coatings, protective coatings, alignment films, transparent substrates, or films, but is not limited thereto.

[0097] In some embodiments, the polymer containing the diamine compound of the present invention can be applied to components in electronic devices. In some embodiments, a "component" may be an optical component, such as a transparent film, a transparent substrate, a transparent sheet, or a transparent layer, but is not limited thereto. In some embodiments, a "component" may also be a non-optical component, such as a semiconductor component, but is not limited thereto.

[0098] In this invention, the term "electronic device" means a device comprising one or more organic semiconductor layers or materials. In some embodiments, the electronic device includes, but is not limited to:

[0099] (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 photoconductor, 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 components (e.g., a transistor or a diode), wherein the electronic components include one or more organic semiconductor layers, or any combination of the devices in (1) to (4).

[0100] In some embodiments, the polymer of the present invention can be applied to components in liquid crystal displays (LCDs). In some embodiments, the polymer of the present invention can be applied to alignment layers in display devices. In some embodiments, the polymer of the present invention can be applied to components in organic electronic devices (e.g., organic light-emitting diodes, OLEDs). In some embodiments, the polymer of the present invention can be applied to transparent protective filters for cameras.

[0101] The following embodiments will provide several examples to illustrate more specifically the effects achievable by polymers according to the embodiments of the present invention, and the properties of polymers prepared using the present invention. However, the following embodiments are for illustrative purposes only and should not be construed as limiting the implementation of the present invention.

[0102] [Preparation Example 1] Diamine compound (tetradecanohydro-1,4:5,8-dimethylanthracene-9,10-diyl-bis(4-aminobenzoate))

[0103]

[0104] For the synthesis of diol compound 4, please refer to the relevant synthetic steps disclosed in patent document (WO2017209199 A 1), in which diol compound 4 is synthesized from compound 1 (1,4-benzoquinone) and compound 2 (dicyclopentadiene).

[0105] Step 3

[0106]

[0107] 4-Nitrobenzoyl chloride (1.5 g, 8.2 mmol) was added to a solution containing 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 off and washed with methanol (20 mL) to give a white solid product (0.7 g, 63.1%), which was diester compound 5. The NMR spectra of diester compound 5 are as follows: 1 H NMR(400MHz,CD Cl3,298K): δ=1.18(d,J=8.4Hz,1H),1.30(d,J=8.4Hz,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:c ald for C 30 H 27 N2O8:m / z 543.2; found:543.2[M+H] + .

[0108] Step 4

[0109]

[0110] 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 give a white solid product (0.5 g, 93.2%), which was diamine compound 6 (tetradecano-1,4:5,8-dimethylanthracene-9,10-diyl-bis(4-aminobenzoate)). The NMR spectra of diamine compound 6 are as follows: 1 H NMR(400MHz,CD Cl3,298K): 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:c ald for C 30 H 34 N2 O4N a:m / z 509.2; found:509.6[M+N a] + .

[0111] [Preparation Example 2] Diamine compound (tetradecanohydro-1,4:5,8-dimethylanthracene-9,10-diyl-bis(3-aminobenzoate))

[0112]

[0113] For the synthesis of diol compound 4, please refer to the relevant synthetic steps disclosed in patent document (WO2017209199A 1), in which diol compound 4 is synthesized from 1,4-benzoquinone and dicyclopentadiene.

[0114] 3-Nitrobenzoyl chloride (1.86 g, 10.0 mmol) was added to a solution containing 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 give a white solid product (1.5 g, 69%), which was diester compound 5'.

[0115] 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 give a white solid product (0.5 g, 92%), which was diamine compound 6' (tetradecano-1,4:5,8-dimethylanthracene-9,10-diyl-bis(3-aminobenzoate)). The NMR spectra of diamine compound 6' are as follows: 1 H NMR(400MHz,CD Cl3,298K): δ=1.26-1.45(m,6H),1.49-1.59(m,2H),1.64-1.72(m,2H),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:c ald for C 30 H 35 N₂O₄: m / z 487.3; found: 487.3

[0116] [M+H] + .

[0117] [Preparation Example 3] Diamine compound (bicyclo[2.2.1]heptane-2,5-diyl-bis(4-aminobenzoate))

[0118]

[0119] Step 1

[0120]

[0121] 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. Afterward, the formic acid was removed by distillation, and a clear liquid dicarboxylate was obtained by vacuum distillation (120–130 °C, 10 mmHg / 13.3 mb ar). 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 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 again with ethyl acetate. The combined organic compounds were dried over magnesium sulfate and concentrated to give a colorless solid product (100 g), which was the diol compound 8. The NMR spectra of diol compound 8 are as follows: 1 H NMR (400MHz, CD Cl3, 298K): 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.

[0122] Step 2

[0123]

[0124] 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 over 1 hour under a nitrogen atmosphere and allowed to stand at room temperature. The solution was stirred at room temperature for 16 hours. After the reaction was complete, the solution was washed three times with 100 mL of water, and the organic layer was dried by rotary evaporation to give a yellow solid (1.5 g, 69%), which was dinitro compound 10. The NMR spectra of dinitro compound 10 are as follows: 1 H NMR(400MHz,d6-DM SO,298K): δ=1.03-1.25(m,1H),1.32-1.44(m,1H),1.55-1.88(m,4H),1.9 3-2.61(m,4H), 4.66-5.02(m,2H), 8.14-8.37(m,8H); LC / MS: [M+Na]=449.

[0125] Step 3

[0126]

[0127] 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 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 spectra of diamine compound 11 are as follows: 1 H NMR(400MHz,d6-DM SO,298K): 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(NH2,m,4H),6.53-6.58(m,4H),7.59-7.66(m,4H); LC / MS: [M+H]=367.

[0128] [Preparation Example 4] Polyimide

[0129] In a 100 mL three-necked flask containing 5 g GBL, the diamine compound 6 (1.0852 g, 0.0022 mol e) and TFMB (0.7143 g, 0.0022 mol e) from Preparation Example 1 were placed under a slow nitrogen flow. TCA (1.0000 g, 0.0044 mol e) was added to the solution, followed by another 5 g GBL. The mixture was mechanically stirred at room temperature under a nitrogen flow for 24 hours until a clear, viscous solution was obtained. 5 g GBL was added to the viscous solution for dilution. 3.6434 g (0.03571 mol e) of acetic anhydride (Ac₂O) and 3.8371 g (0.02678 mol e) of TPA were slowly added dropwise to the solution, and the mixture was heated to 60°C and maintained for 12 hours. After the reaction was complete, the solution was added dropwise to methanol and washed three times with methanol. The solid was then filtered and dried in a vacuum oven to obtain pure polyimide powder.

[0130] The above components represent the following compounds:

[0131] GB L: γ-butyrolactone (purchased from Sheng Yi Chemical Co., Ltd.)

[0132] TFMB: 2,2'-bis(trifluoromethyl)benzidine (purchased from Shifeng Technology Co., Ltd.)

[0133] TCA: 2,3,5-Tricarboxycyclopentylacetic dianhydride (3-(carboxymethyl)-1,2,4-cyclopentanetricarboxylic acid 1,4:2,3-dianhydride) (manufactured by Lee Chang Yung Chemical Industry Co., Ltd.)

[0134] TPA: Triphenylamine (purchased from TCI)

[0135] [Preparation Example 5] Polyimide Varnish

[0136] The white polyimide powder prepared in Preparation Example 4 was dissolved in GBL (15 wt%) and degassed under vacuum to form a varnish.

[0137] [Preparation Example 6] Polyimide Film

[0138] Polyimide varnish was applied to a glass substrate using a doctor blade coater to form a wet film. The wet film was then 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. The polyimide film was then peeled off the substrate by immersion in deionized water. Various properties of the polyimide film were measured using the following test methods.

[0139] [Example 1] Glass Transfer Temperature Test

[0140] Glass transition temperature (Tg) was analyzed using a TA Instruments Thermomechanical Analyzer "TMA / Q400" with a stretching film clamp. Samples were cut into 16mm x 5mm pieces, and the ends of the sample were clamped and fixed in the TMA using the film clamp. Nitrogen gas was introduced at a flow rate of 100 ml / min as a protective atmosphere, and a fixed load of 0.05 N was applied. The temperature was increased from 50°C to 350°C at a rate of 10°C / min, then allowed to cool naturally back to 50°C, and finally increased to 500°C at a rate of 10°C / min. The inflection point of the slope change in the TMA measurement data was taken as the glass transition temperature (Tg).

[0141] [Example 2] Thermal Expansion Coefficient Test

[0142] The coefficient of thermal expansion (CTE) was analyzed using a TA Instruments Thermomechanical Analyzer "TMA / Q400" with a stretching film fixture. The sample was cut into 16mm x 5mm pieces, and the two ends were clamped and fixed in the TMA using the film fixture. Nitrogen gas was introduced at a flow rate of 100 ml / min as a protective atmosphere, and a fixed load of 0.05 N was applied. The temperature was increased from 50°C to 350°C at a rate of 10°C / min, then allowed to cool naturally back to 50°C. The temperature was then increased again to 500°C at a rate of 10°C / min. The CTE value was obtained by extracting the slope from the TMA measurement data between 50 and 200°C.

[0143] [Example 3] Full Light Transmittance Test

[0144] Following AS TM D 1003, the total transmittance (TT) was measured using the "CSP-001" colorimetric and turbidity simultaneous measuring instrument manufactured by Nippon Denshoku Kogyo Co., Ltd.

[0145] [Example 4] Yellow Index Test

[0146] Following AS TM D 1925, the yellowness index (YI) was measured using the "CSP-001" color and turbidity simultaneous measuring instrument manufactured by Nippon Denshoku Kogyo Co., Ltd.

[0147] [Example 5] b-value (b*) test

[0148] Following AS TM D 1925, the CIE L*a*b* coordinates were measured using the "CSP-001" colorimetric and turbidity simultaneous measuring instrument manufactured by Nippon Denshoku Kogyo Co., Ltd.

[0149] [Example 6] Haze Test

[0150] Following AS TM D 1003, haze was measured using the "CSP-001" color and turbidity simultaneous measuring instrument manufactured by Nippon Denshoku Kogyo Co., Ltd.

[0151] The physicochemical properties of the polyimide film prepared in Preparation Example 6 were tested using the above-described test method. The test results are as follows: glass transition temperature is 283℃, coefficient of thermal expansion is 35ppm / ℃, total light transmittance is 90.4%, haze is 0.2%, yellow index is 1.65, and b-value (b*) is 0.85.

[0152] This invention provides a novel diamine compound comprising a non-conjugated norbornane ring structure. Due to the non-conjugated norbornane ring structure of this novel diamine compound, the optical properties of the synthesized polymer can be improved (e.g., total light transmittance, yellow index, b-value, and haze). Furthermore, the giant cyclic structure, for example, through the fusion of cyclohexyl and norbornane groups, makes the compound molecule more rigid and less prone to structural inversion, further improving the dimensional stability of the polymer material and reducing the coefficient of thermal expansion (CTE). Therefore, the diamine compound comprising alicyclic hydrocarbon groups of this invention can serve as a key component of flexible materials in electronic devices, giving the synthesized polymer excellent heat resistance and optical properties. Moreover, since the diamine compound of this invention can be used to synthesize a wide variety of polymer materials, such as polyimides, polyamic acids, epoxy resins, polyamides, polyureas, or polyimides, this invention can be widely applied in various industrial fields with requirements for materials with high heat resistance or optical properties.

[0153] The above outlines several embodiments to enable those skilled in the art to better understand the viewpoints of the embodiments of the present invention. Those skilled in the art 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 described herein. Those skilled in the art should also understand that such equivalent processes and structures do not depart from the spirit and scope of the present invention, and that various changes, substitutions, and replacements can be made without departing from the spirit and scope of the present invention.

Claims

1. A diamine compound, represented by formula II: (II) At least one of B is -CH2- The remaining B values ​​are either non-existent or... -CH2- Y is -COO- , and n and m represent 1 or 2.

2. The diamine compound of claim 1, wherein the diamine compound is: or .

3. The diamine compound of claim 1, wherein the diamine compound is: , or .

4. A method for preparing a diamine compound, comprising: The compound shown in Formula III is subjected to hydrogenation to form the diamine compound shown in Formula II. (II) (III) Where at least one B of the compound represented by formula II is -CH2- The remaining B values ​​are either non-existent or... -CH2- Y is -COO- , and n and m represent 1 or 2; In the compound represented by Formula III, B is an alicyclic hydrocarbon group containing a norbornene ring or a norbornene ring and having between 7 and 30 carbon atoms, and Y is... -COO- .

5. The method for preparing the diamine compound according to claim 4, wherein the compound represented by formula III is formed by reacting the diol compound represented by formula IV with nitrobenzyl chloride. B-(OH)2 (IV) Where B is an alicyclic hydrocarbon group containing a norbornene ring or a norbornene ring and having between 7 and 30 carbon atoms.

6. A polymer derived from a diamine compound of formula II: (II) At least one of B is -CH2- The remaining B values ​​are either non-existent or... -CH2- Y is -COO- , and n and m represent 1 or 2.

7. The polymer of claim 6, wherein the polymer comprises repeating units of the following general formula: Where X is a tetravalent organic group, and Y1 is a residue derived from the diamine compound shown in Formula II.

8. The polymer of claim 6, wherein the polymer comprises repeating units of the following general formula: Where X is a tetravalent organic group, and Y1 is a residue derived from the diamine compound shown in Formula II.

9. The polymer of claim 6, wherein the polymer comprises structural units of the following general formula: or Where Y1 is a residue derived from the diamine compound shown in formula II, R1 is a divalent organic group, and n and m represent integers from 2 to 1000.

10. The polymer of claim 6, wherein the polymer comprises repeating units of the following general formula: Where R2 is a divalent organic group, and Y1 is a residue derived from the diamine compound shown in Formula II.

11. The polymer of claim 6, wherein the polymer comprises repeating units of the following general formula: Where R4 is a divalent organic group, and Y1 is a residue derived from the diamine compound shown in Formula II.

12. The polymer of claim 6, wherein the polymer comprises repeating units of the following general formula: Where R3 is a divalent organic group, and Y1 is a residue derived from the diamine compound shown in Formula II.

13. Use of the polymer as described in claim 6, wherein it is used in insulating tapes, wire coatings, protective coatings, alignment films, transparent substrates, or films.

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