Diamine monomer compound and preparation method, resin, flexible film and electronic device

Abstract

The present application provides a diamine monomer compound, the general structural formula of which is: The present application also provides a preparation method of the diamine monomer compound, a polyimide resin prepared using the diamine monomer compound, and a flexible film and electronic device using the polyimide resin. The diamine monomer compound introduces a large volume sterically hindered fluorene structure into its structure, which can effectively hinder the close stacking of molecular chains, thereby imparting good transparency; the diamine monomer compound introduces an amide bond structure on the side group, which can form a hydrogen bond between the molecular side chains, thereby effectively reducing the thermal expansion coefficient.

Description

Technical Field

[0001] The present application relates to a diamine monomer compound and a preparation method thereof, a polyimide resin prepared by using the diamine monomer compound, and a flexible film and electronic equipment using the polyimide resin. Background Art

[0002] Polyimide is a type of heterocyclic macromolecular polymer with an imide ring structure in the main chain, and has the characteristics of corrosion resistance, impact resistance, high and low temperature resistance, good mechanical properties, excellent film-forming properties and good dielectric properties. Polyimide is one of the engineering plastics that has been industrially produced and is widely used in organic electronic devices such as organic electrical storage, nonlinear optical materials, liquid crystal display alignment film materials, liquid crystal display phase difference compensation film materials, and electroluminescent diodes.

[0003] Since the birth of the first commercial polyimide Kapton film, polyimide has been promoted and applied to various fields of industrialization, such as microelectronics, optics, aerospace and military fields. With the expansion of the application field of polyimide, higher requirements have been placed on the performance of polyimide materials. Traditional polyimide contains a large number of rigid aromatic heterocycles in the molecule, which makes the interaction between the molecule and the molecular chain strong, and thus gives the material excellent comprehensive performance; however, the large number of charge transfer complexes produced at the same time also makes the transparency of the material poor, and the polyimide film often appears dark yellow or brown. This limits the application of polyimide in optics. In order to improve the transparency of polyimide materials, the commonly used solutions currently include introducing fluorine-containing groups, aliphatic or alicyclic structures and large steric groups into the molecular structure of polyimide to weaken the charge transfer effect within the molecule and between the molecular chains, but this inevitably causes a decrease in the overall performance of the material, especially an increase in the thermal expansion coefficient, which reaches between 40-60ppm / K. However, this also causes the polyimide film to have a mismatch in thermal expansion with other materials under high temperature conditions during the preparation of flexible transparent devices, which in turn causes problems such as peeling, cracking, and warping of the polyimide film. Summary of the invention

[0004] In a first aspect, an embodiment of the present application provides a diamine monomer compound, the general structural formula of which is:

[0005]

[0006] Wherein, Ar1 is selected from one of the following:

[0007]

[0008] Ar2 is selected from one of the following:

[0009]

[0010] Ar3 is selected from one of the following:

[0011]

[0012] The diamine monomer compound introduces a large volume sterically hindered fluorene structure into the structure, which can effectively hinder the close stacking of molecular chains, thereby having good transparency; the diamine monomer compound introduces an amide bond structure on the side group, which can form a hydrogen bond between the molecular side chains, thereby effectively reducing the thermal expansion coefficient and improving dimensional stability.

[0013] In the embodiment of the present application, the structural formula of the diamine monomer compound is at least one of the following:

[0014]

[0015] The second aspect of the embodiment of the present application provides a polyimide resin, the general structural formula of which is:

[0016]

[0017] wherein X is an aromatic dianhydride residue or an alicyclic dianhydride residue, R is an aromatic diamine residue or an alicyclic diamine residue, m1 is an integer > 1, m2 is an integer > 1, and n is an integer > 1.

[0018] The structural formula of Y is:

[0019]

[0020] Wherein, Ar1 is selected from one of the following:

[0021]

[0022] Ar2 is selected from one of the following:

[0023]

[0024] Ar3 is selected from one of the following:

[0025]

[0026] The polyimide resin introduces a large volume sterically hindered fluorene structure into its structure, which can effectively hinder the close stacking of molecular chains, thereby giving the polyimide resin good transparency; the polyimide resin introduces an amide bond structure on the side group, which can form a hydrogen bond between the molecular side chains, thereby effectively reducing the thermal expansion coefficient of the polyimide resin and improving dimensional stability.

[0027] In the embodiment of the present application, the aromatic dianhydride residue or alicyclic dianhydride residue X is derived from one or more of the following compounds: pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, anhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, cyclobutane-1,2,3,4-tetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride , cyclohexane-1,2,4,5-tetracarboxylic dianhydride, norbornane-2,3,5,6-tetracarboxylic dianhydride, bicyclo[2.2.2]oct-7-ene-3,4,8,9-tetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 2,2',3 ,3'-diphenylsulfone tetracarboxylic dianhydride, 2,3,3',4'-diphenylsulfone tetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 2,2',3,3'-diphenyl ether tetracarboxylic dianhydride, 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride, 2,2-[bis(3,4-dicarboxyphenyl)]hexafluoropropane dianhydride, 5-(2,5-dioxotetrahydro)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride.

[0028] In the embodiment of the present application, the aromatic diamine residue or the alicyclic diamine residue R is derived from one or more of the following compounds: 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 1,4-bis(4-aminophenoxy)benzene, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis(4-aminophenoxyphenyl)sulfone, bis(3-aminophenoxyphenyl)sulfone, bis(4-aminophenoxy)biphenyl, bis{4-(4-aminophenoxy)phenyl}ether, 4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2',3,3'-tetramethyl 4,4'-diaminobiphenyl, 3,3',4,4'-tetramethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)benzidine, 2,6,2',6'-tetrakis(trifluoromethyl)benzidine, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-anilino)hexafluoropropane Fluoropropane, 2,2-bis(3-anilino)hexafluoropropane and 2,2-bis(3-amino-4-toluoyl)hexafluoropropane, 1,6-hexanediamine, 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane, 4,4'-diaminodicyclohexylmethane and 4,4'-diamino-3,3'-dimethylcyclohexylmethane.

[0029] In the embodiment of the present application, the polyimide resin is a diamine monomer compound. It is formed by polymerization with an aromatic diamine monomer or an alicyclic diamine monomer and an aromatic dianhydride monomer or an alicyclic dianhydride monomer.

[0030] A third aspect of the present application provides a method for preparing a diamine monomer compound, comprising:

[0031] Preparation of nitro compounds Wherein, X1 is halogen, and Ar1 is selected from one of the following:

[0032]

[0033] The nitro compound (B-1) is subjected to a coupling reaction to obtain a dinitro compound Wherein Ar2 is selected from one of the following:

[0034]

[0035] The dinitro compound (B-2) is reacted with an acyl chloride compound to obtain a dinitro compound Wherein Ar3 is selected from one of the following:

[0036]

[0037] The dinitro compound (B-3) is reduced to give

[0038] A fourth aspect of the embodiments of the present application provides a flexible film, comprising the polyimide resin described in the second aspect of the embodiments of the present application.

[0039] A fifth aspect of the embodiments of the present application provides an electronic device, comprising the flexible film described in the fourth aspect of the embodiments of the present application.

[0040] In an embodiment of the present application, the electronic device is an organic light-emitting display panel, and the electronic device further comprises a thin film transistor array layer and an organic light-emitting layer located on the flexible film, wherein the thin film transistor array layer is located between the flexible film and the organic light-emitting layer.

[0041] Since the polyimide resin has high transparency, it will not affect the light transmission of the organic light-emitting display panel, and the polyimide resin has a low thermal expansion coefficient, so when preparing the organic light-emitting display panel, the flexible film will not have problems such as peeling, cracking, and warping.

[0042] In the embodiment of the present application, when the electronic device is a foldable mobile phone, the flexible film is a base film located at the bottom of the foldable mobile phone and used to carry other elements of the foldable mobile phone, or a transparent cover film located on the front of the foldable mobile phone. BRIEF DESCRIPTION OF THE DRAWINGS

[0043] Figure 1 It is a preparation flow chart of an organic light-emitting display panel. DETAILED DESCRIPTION

[0044] The embodiments of the present application are described below in conjunction with the drawings in the embodiments of the present application.

[0045] In order to prepare polyimide with excellent comprehensive performance, rigid aromatic dianhydride and diamine structures are generally used for preparation to enhance the interaction between molecules and molecules. However, this also makes the transparency of polyimide film poor, usually showing a darker yellow or brown, thus limiting the application of polyimide in optics. In order to obtain transparent polyimide, it is usually necessary to introduce a large number of fluorine-containing groups, aliphatic or alicyclic structures and large volume steric structures into the molecular structure to weaken the charge transfer effect within the molecule and between molecular chains. However, at the same time, it will inevitably cause the decline of the heat resistance and mechanical properties of the film, especially the increase of the thermal expansion coefficient, which will cause the thermal expansion coefficient of the polyimide film to be mismatched with other materials (such as copper wire or materials of other layers in the organic light-emitting display panel), thereby causing damage such as warping and peeling.

[0046] Flexible organic light-emitting display panels usually use polyimide as a flexible substrate. Figure 1 As shown in the figure, the preparation process of the organic light-emitting display panel includes: providing optical glass, forming a polyimide film on the optical glass, forming a barrier layer for isolating water vapor and gas on the polyimide film, forming a thin film transistor (TFT) layer on the barrier layer, forming a light-emitting layer on the TFT layer, forming another barrier layer for isolating water vapor and gas on the light-emitting layer, and finally peeling off the optical glass from the polyimide film. However, when making the TFT layer (which can be a low-temperature polysilicon TFT or an oxide TFT), it usually undergoes a high-temperature treatment process. If the thermal expansion degree of the polyimide film does not match that of other materials, problems such as peeling, cracking, and warping may occur.

[0047] The embodiment of the present application provides a diamine monomer compound, which can be used to prepare a polyimide resin with high transparency and low thermal expansion coefficient.

[0048] The general structural formula of the diamine monomer compound is:

[0049]

[0050] Wherein, Ar1 is selected from one of the following:

[0051]

[0052] Ar2 is selected from one of the following:

[0053]

[0054] Ar3 is selected from one of the following:

[0055]

[0056] The diamine monomer compound is A side group having an amide bond structure is connected to each of the two benzene rings

[0057] In some embodiments, the structural formula of the diamine monomer compound is at least one of the following, but not limited thereto:

[0058]

[0059]

[0060] In the general structural formulas (I), (II), (III) and (IV) of the diamine monomer compounds described above, the two side groups In order to symmetrically connect to the two benzene rings of the fluorenyl group, in other embodiments, the two side groups may also be asymmetrically connected to the two benzene rings of the fluorenyl group.

[0061] The structure of the diamine monomer compound introduces a large volume steric hindrance fluorene structure, which can effectively hinder the close stacking of molecular chains, thereby having good transparency; the amide bond structure is introduced on the side group of the diamine monomer compound, which can form hydrogen bonds between the molecular side chains, thereby effectively reducing the thermal expansion coefficient and improving dimensional stability. Steric hindrance, also known as spatial steric hindrance, refers to the mutual repulsion caused by the spatial arrangement of groups inside the molecule.

[0062] The embodiment of the present application provides a polyimide resin, which is obtained by polymerizing the above-mentioned diamine monomer compound with other aromatic or alicyclic diamine monomers different from the above-mentioned diamine monomer compound, and aromatic or alicyclic dianhydride monomers.

[0063] The general structural formula of the polyimide resin includes:

[0064]

[0065] Wherein, X is an aromatic dianhydride residue or an alicyclic dianhydride residue, R is an aromatic diamine residue or an alicyclic diamine residue, and the structural formula of Y is m1 is an integer > 1, m2 is an integer > 1, and n is an integer > 1. In the present application, the aromatic or alicyclic dianhydride monomer, the aromatic or alicyclic diamine monomer, and the diamine monomer compound are monomers that are polymerized to form the polyimide resin. The aromatic or alicyclic dianhydride monomer and the aromatic or alicyclic diamine monomer are no longer a monomer compound but a group in the structural formula of the polyimide resin formed after polymerization, which is defined as a residue.

[0066] The polyimide resin comprises n repeating units, each of which comprises m1 and m2 The m1 number described in this application and m2 The polyimide resin is randomly arranged on the main chain.

[0067] The aromatic dianhydride residue or alicyclic dianhydride residue X is selected from one or more of the following compounds: pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1 ,4,5,8-tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, cyclobutane-1,2,3,4-tetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride Acid dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, norbornane-2,3,5,6-tetracarboxylic dianhydride, bicyclo[2.2.2]oct-7-ene-3,4,8,9-tetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 2,2', 3,3'-diphenylsulfone tetracarboxylic dianhydride, 2,3,3',4'-diphenylsulfone tetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 2,2',3,3'-diphenyl ether tetracarboxylic dianhydride, 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride, 2,2-[bis(3,4-dicarboxyphenyl)]hexafluoropropane dianhydride, 5-(2,5-dioxotetrahydro)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, and the like.

[0068] The aromatic diamine residue or alicyclic diamine residue R is derived from one or more of the following compounds: 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 1,4-bis(4-aminophenoxy)benzene, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis(4-aminophenoxyphenyl)sulfone, bis(3-aminophenoxyphenyl)sulfone, bis(4-aminophenoxy)biphenyl, bis{4-(4-aminophenoxy)phenyl}ether, 4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2',3,3'-tetramethyl-4,4 '-Diaminobiphenyl, 3,3',4,4'-tetramethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)benzidine, 2,6,2',6'-tetrakis(trifluoromethyl)benzidine, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-anilino)hexafluoropropane , 2,2-bis(3-anilino)hexafluoropropane and 2,2-bis(3-amino-4-toluoyl)hexafluoropropane, 1,6-hexanediamine, 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane, 4,4'-diaminodicyclohexylmethane and 4,4'-diamino-3,3'-dimethylcyclohexylmethane, etc.

[0069] The polyimide resin introduces a large volume sterically hindered fluorene structure into its structure, which can effectively hinder the close stacking of molecular chains, thereby giving the polyimide resin good transparency; the polyimide resin introduces an amide bond structure on the side group, which can form a hydrogen bond between the molecular side chains, thereby effectively reducing the thermal expansion coefficient of the polyimide resin and improving dimensional stability.

[0070] The present application also provides a flexible film, comprising the above-mentioned polyimide resin.

[0071] The present application also provides an electronic device, comprising the flexible film. The flexible film can be applied to a variety of electronic devices.

[0072] When the electronic device is a flexible organic light-emitting display panel, the electronic device further comprises a thin film transistor array layer and an organic light-emitting layer located on the flexible film, wherein the thin film transistor array layer is located between the flexible film and the organic light-emitting layer. Since the polyimide resin has high transparency, it will not affect the light transmission of the organic light-emitting display panel, and the polyimide resin has a low thermal expansion coefficient, so when preparing the organic light-emitting display panel, the flexible film will not have problems such as peeling, cracking, and warping.

[0073] When the electronic device is a foldable mobile phone, the flexible film may be a base film located at the bottom of the foldable mobile phone and used to carry other elements of the foldable mobile phone, or a transparent cover film located on the front of the foldable mobile phone.

[0074] The present application also provides a method for preparing the above diamine monomer compound, comprising:

[0075] Preparation of nitro compounds containing dihalogenated fluorene structure and Ar1 X1 is a halogen; the nitro compound (B-1) is subjected to a coupling reaction to obtain a dinitro compound containing an amino group and an Ar2 structure

[0076]

[0077] The dinitro compound (B-2) is reacted with an acyl chloride compound (e.g., benzoyl chloride) to prepare a dinitro compound containing an amide bond structure and an Ar3 structure.

[0078] The dinitro compound (B-3) is subjected to a reduction reaction to obtain

[0079] The preparation method of the polyimide resin comprises:

[0080] Prepare a diamine monomer, the diamine monomer has the general structural formula of

[0081] The diamine monomer is polymerized with other aromatic diamine monomers or alicyclic diamine monomers, and aromatic dianhydride monomers or alicyclic dianhydride monomers.

[0082] The embodiments of the present application are further described below through specific examples.

[0083] Monomer Example 1

[0084] Preparation of monomers:

[0085] 2,7-Dibromofluorene (32.4 g, 0.1 mol) and p-fluoronitrobenzene (42.3 g, 0.3 mol) were added with 100 ml of dimethyl sulfoxide (DMSO) solvent, stirred and dissolved, and then cesium fluoride (45.57 g, 0.3 mol, acid binding agent) was slowly added. At this time, the reaction solvent turned ink black. After evacuating and replacing the air with nitrogen, the mixture was heated to 150°C and reacted for 24 hours. After cooling to room temperature, the mixture was poured into ice water to obtain a yellow-gray solid. The solid was washed with water, filtered, and extracted with dichloromethane. The solvent was removed by rotary evaporation. The product was purified by recrystallization from dichloromethane / n-hexane to obtain a light yellow solid intermediate product I.

[0086]

[0087] Take the intermediate product I (113.24g, 0.2mol), p-aminophenylboronic acid (68.5g, 0.5mol), tetrakistriphenylphosphine palladium (2g, catalyst) and add it into a 2L reaction kettle, add tetrahydrofuran (THF, 800ml) and a saturated solution of potassium carbonate (69g, 0.5mol), evacuate at low temperature and fill with nitrogen, then heat under reflux to react for 24h, extract and remove the solvent by rotary evaporation, wash with ethanol, filter and recrystallize with toluene to obtain an orange-yellow solid intermediate product II.

[0088]

[0089] Take the intermediate product II (59g, 0.1mol), add THF (300ml) and triethylamine (Et3N, 30ml), wherein triethylamine is an acid binding agent, which absorbs the by-product hydrochloric acid to facilitate the reaction; slowly add benzoyl chloride (27.5ml, 0.24mol), stir the reaction at 65℃ for 3h, pour into water after the reaction, filter, wash with ethanol, and recrystallize from toluene to obtain an orange intermediate product III.

[0090]

[0091] Take the intermediate product III (79.8 g, 0.1 mol), add DMF (100 ml) and 10% palladium carbon (2 g), evacuate to remove air and then fill with hydrogen, stir at room temperature until the theoretical volume (13.44 L, 0.6 mol) of hydrogen is absorbed, pour into a large amount of water to precipitate after the reaction, filter and dissolve the filter cake with THF, filter the organic phase, spin dry and recrystallize from toluene to obtain a light yellow diamine monomer A.

[0092]

[0093] Monomer Example 2

[0094] Preparation of monomer (structure different from that of Example 1):

[0095] 3,6-dibromofluorene (32.4 g, 0.1 mol) and 2-fluoro-5-nitropyridine (42.87 g, 0.3 mol) were added with 100 ml of DMSO solvent, stirred and dissolved, and then cesium fluoride (45.57 g, 0.3 mol) was slowly added. At this time, the reaction solvent turned ink black. After evacuating and replacing the air with nitrogen, the mixture was heated to 150°C and reacted for 24 hours. After cooling to room temperature, the mixture was poured into ice water to obtain a yellow-gray solid. The solid was washed with water, filtered, and extracted with dichloromethane. The solvent was removed by rotary evaporation. The product was purified by recrystallization from dichloromethane / n-hexane to obtain a light yellow solid intermediate product I'.

[0096]

[0097] Take the intermediate product I' (113.18 g, 0.2 mol), (5-aminopyridin-2-yl)boric acid (68.97 g, 0.5 mol), tetrakistriphenylphosphine palladium (2 g) and add them into a 2L reaction kettle, add THF (800 ml) and a saturated solution of potassium carbonate (69 g, 0.5 mol), evacuate at low temperature and fill with nitrogen, then heat under reflux to react for 24 hours, extract and remove the solvent by rotary evaporation, wash with ethanol, filter and recrystallize with toluene to obtain an orange-yellow solid intermediate product II'.

[0098]

[0099] Take the intermediate product II' (59.42 g, 0.1 mol), add THF (300 ml) and Et3N (30 ml), slowly add benzoyl chloride (27.5 ml, 0.24 mol), stir and react at 65°C for 3 hours. After the reaction is completed, spin dry to remove the solvent and dissolve and filter with THF. After filtration, wash with ethanol and recrystallize with toluene to obtain an orange intermediate product III'.

[0100]

[0101] Take the intermediate product III' (80.0 g, 0.1 mol), add DMF (100 ml) and 10% palladium carbon (2 g), evacuate to remove air and then fill with hydrogen, stir at room temperature until the theoretical volume (13.44 L, 0.6 mol) of hydrogen is absorbed, pour into a large amount of water to precipitate after the reaction, filter and dissolve the filter cake with THF, filter the organic phase, spin dry and recrystallize from toluene to obtain a light yellow diamine monomer B.

[0102]

[0103] Polymer Example 1

[0104] Under nitrogen protection, diamine A (7.3889 g, 10 mmol) and monomer 4,4'-diaminotriphenylmethane (5.4872, 20 mmol) were added to the reaction bottle, and the solvent N,N-dimethylacetamide (DMAc, 92.64 ml) was added and stirred at room temperature until dissolved, and then the monomer 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA, 8.8266 g, 30 mmol) was slowly added, and stirred at room temperature overnight. Acetic anhydride (120 ml, dehydrating agent) and pyridine (60 ml, catalyst) were added and stirred at room temperature for 12 h, and then slowly poured into high-speed stirring ethanol to obtain a fibrous polyimide precipitate, which was dried to obtain polyimide. The obtained polyimide was dissolved in DMAc to prepare a glue solution with a solid content of 10%. After vacuuming to remove bubbles, it was scraped on a glass plate and placed in a vacuum oven and heated at a certain rate (80°C, 1h; 160°C, 1h; 250°C, 1h; 350°C, 0.5h). After cooling to room temperature, it was immersed in hot water to remove the film. The polyimide film with a thickness of about 30μm was measured by a step profiler.

[0105] Polymer Example 2 (Dianhydride is selected as pyromellitic dianhydride)

[0106] Under nitrogen protection, diamine A (7.3889 g, 10 mmol) and monomer 4,4'-diaminotriphenylmethane (5.4872, 20 mmol) were added to a reaction flask, solvent DMAc (82.90 ml) was added and stirred at room temperature until dissolved, then monomer pyromellitic dianhydride (PMDA, 6.5436 g, 30 mmol) was slowly added, stirred at room temperature overnight, acetic anhydride (120 ml, dehydrating agent) and pyridine (60 ml, catalyst) were added and stirred at room temperature for 12 h, and then slowly poured into high-speed stirring ethanol to obtain a fibrous polyimide precipitate, which was dried to obtain polyimide. The obtained polyimide was dissolved in DMAc to prepare a glue solution with a solid content of 10%. After vacuuming to remove bubbles, it was scraped on a glass plate and placed in a vacuum oven and heated at a certain rate (80°C, 1h; 160°C, 1h; 250°C, 1h; 350°C, 0.5h.). After cooling to room temperature, it was immersed in hot water to remove the film. The polyimide film with a thickness of about 30 μm was measured by a step profiler.

[0107] Polymer Example 3 (dianhydride selected as 4,4-hexafluoroisopropylphthalic anhydride)

[0108] Under nitrogen protection, diamine A (7.3889 g, 10 mmol) and monomer 4,4'-diaminotriphenylmethane (5.4872, 20 mmol) were added to a reaction flask, DMAc (111.86 ml) was added and stirred at room temperature until dissolved, then monomer 4,4-hexafluoroisopropylphthalic anhydride (6FDA, 13.3272 g, 30 mmol) was slowly added, stirred at room temperature overnight, acetic anhydride (120 ml, dehydrating agent) and pyridine (60 ml, catalyst) were added and stirred at room temperature for 12 h, and then slowly poured into high-speed stirring ethanol to obtain a fibrous polyimide precipitate, which was dried to obtain polyimide. The obtained polyimide was dissolved in DMAc to prepare a glue solution with a solid content of 10%. After vacuuming to remove bubbles, it was scraped on a glass plate and placed in a vacuum oven and heated at a certain rate (80°C, 1h; 160°C, 1h; 250°C, 1h; 350°C, 0.5h). After cooling to room temperature, it was immersed in hot water to remove the film. The polyimide film with a thickness of about 30μm was measured by a step profiler.

[0109] Polymer Comparative Example 1

[0110] Under nitrogen protection, add 4,4'-diaminotriphenylmethane (8.2310g, 30mmol) to the reaction bottle, add DMAc (92.64ml) and stir at room temperature until dissolved, then slowly add BPDA (8.8266g, 30mmol), stir at room temperature overnight, add acetic anhydride (120ml) and pyridine (6ml) and stir at room temperature for 12h, slowly pour into high-speed stirring ethanol to obtain fibrous polyimide precipitation, and dry to obtain polyimide. The obtained polyimide is dissolved in DMAc to prepare a glue solution with a solid content of 10%, vacuumed to remove bubbles, and then scraped on a glass plate, placed in a vacuum oven and heated at a certain program (80℃, 1h; 160℃, 1h; 250℃, 1h; 350℃, 0.5h.), cooled to room temperature, immersed in hot water to remove the film, and measured with a step profiler to obtain a polyimide film with a film thickness of about 30μm.

[0111] Polymer Comparative Example 2

[0112] Under nitrogen protection, add 4,4'-diaminotriphenylmethane (8.2310g, 30mmol) to the reaction bottle, add DMAc (82.90ml) and stir at room temperature until dissolved, then slowly add PMDA (6.5436g, 30mmol), stir at room temperature overnight, add acetic anhydride (120ml) and pyridine (60ml) and stir at room temperature for 12h, slowly pour into high-speed stirring ethanol to obtain fibrous polyimide precipitation, and dry to obtain polyimide. The obtained polyimide is dissolved in DMAc to prepare a glue solution with a solid content of 10%, vacuumed to remove bubbles, and then scraped on a glass plate, placed in a vacuum oven and heated at a certain program (80℃, 1h; 160℃, 1h; 250℃, 1h; 350℃, 0.5h.), cooled to room temperature, immersed in hot water to remove the film, and measured with a step profiler to obtain a polyimide film with a film thickness of about 30μm.

[0113] Polymer Comparative Example 3

[0114] Under nitrogen protection, add 4,4'-diaminotriphenylmethane (8.2310g, 30mmol) to the reaction bottle, add DMAc (111.86ml) and stir at room temperature until dissolved, then slowly add 6FDA (13.3272g, 30mmol), stir at room temperature overnight, add acetic anhydride (120ml) and pyridine (60ml) and stir at room temperature for 12h, slowly pour into high-speed stirring ethanol to obtain fibrous polyimide precipitation, and dry to obtain polyimide. The obtained polyimide is dissolved in DMAc to prepare a glue solution with a solid content of 10%, vacuumed to remove bubbles, and then scraped on a glass plate, placed in a vacuum oven and heated at a certain program (80℃, 1h; 160℃, 1h; 250℃, 1h; 350℃, 0.5h.), cooled to room temperature, soaked in hot water to remove the film, and measured with a step profiler to obtain a polyimide film with a film thickness of about 30μm.

[0115] Table 1

[0116]

[0117] From the data in Table 1, it can be seen that after the introduction of the sterically hindered fluorene group and the amide bond in Examples 1 to 3, the thermal expansion coefficient is significantly reduced compared with Comparative Examples 1 to 3, and the film also has good transparency.

[0118] It should be noted that the above are only specific implementations of the present application, but the protection scope of the present application is not limited thereto. Any technician familiar with the technical field can easily think of changes or substitutions within the technical scope disclosed in the present application, which should be included in the protection scope of the present application; the implementation methods of the present application and the features in the implementation methods can be combined with each other without conflict. Therefore, the protection scope of the present application shall be based on the protection scope of the claims.

Claims

1. A diamine monomer compound, characterized in that The general structural formula of the diamine monomer compound is: Wherein, Ar1 is selected from one of the following: Ar2 is selected from one of the following: Ar3 is selected from one of the following:

2. The diamine monomer compound according to claim 1, characterized in that The structural formula of the diamine monomer compound is at least one of the following:

3. A polyimide resin, characterized in that: The general structural formula of the polyimide resin is: wherein X is an aromatic dianhydride residue or an alicyclic dianhydride residue, R is an aromatic diamine residue or an alicyclic diamine residue, m1 is an integer > 1, m2 is an integer > 1, and n is an integer > 1. The structural formula of Y is: Wherein, Ar1 is selected from one of the following: Ar2 is selected from one of the following: Ar3 is selected from one of the following:

4. The polyimide resin according to claim 3, characterized in that The aromatic dianhydride residue or alicyclic dianhydride residue X is selected from one or more of the following compounds: pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, Chloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, cyclobutane-1,2,3,4-tetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, cyclohexane- 1,2,4,5-tetracarboxylic dianhydride, norbornane-2,3,5,6-tetracarboxylic dianhydride, bicyclo[2.2.2]oct-7-ene-3,4,8,9-tetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 2,2',3,3' -diphenyl sulfone tetracarboxylic dianhydride, 2,3,3',4'-diphenyl sulfone tetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 2,2',3,3'-diphenyl ether tetracarboxylic dianhydride, 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride, 2,2-[bis(3,4-dicarboxyphenyl)]hexafluoropropane dianhydride, 5-(2,5-dioxotetrahydro)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride.

5. The polyimide resin according to claim 3, characterized in that: The aromatic diamine residue or alicyclic diamine residue R is derived from one or more of the following compounds: 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 1,4-bis(4-aminophenoxy)benzene, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis(4-aminophenoxyphenyl)sulfone, bis(3-aminophenoxyphenyl)sulfone, bis(4-aminophenoxy)biphenyl, bis{4-(4-aminophenoxy)phenyl}ether, 4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2',3,3'-tetramethyl-4,4 '-Diaminobiphenyl, 3,3',4,4'-tetramethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)benzidine, 2,6,2',6'-tetrakis(trifluoromethyl)benzidine, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-anilino)hexafluoropropane , 2,2-bis(3-anilino)hexafluoropropane and 2,2-bis(3-amino-4-toluoyl)hexafluoropropane, 1,6-hexanediamine, 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane, 4,4'-diaminodicyclohexylmethane and 4,4'-diamino-3,3'-dimethylcyclohexylmethane.

6. The polyimide resin according to claim 3, characterized in that The polyimide resin is a diamine monomer compound It is formed by polymerization with an aromatic diamine monomer or an alicyclic diamine monomer and an aromatic dianhydride monomer or an alicyclic dianhydride monomer.

7. A method for preparing a diamine monomer compound, characterized in that: include: Preparation of nitro compounds Wherein, X1 is halogen, and Ar1 is selected from one of the following: The nitro compound (B-1) is subjected to a coupling reaction to obtain a dinitro compound Wherein Ar2 is selected from one of the following: The dinitro compound (B-2) is reacted with an acyl chloride compound to obtain a dinitro compound Wherein Ar3 is selected from one of the following: The dinitro compound (B-3) is reduced to give 8. A flexible film, characterized in that: The polyimide resin comprises the polyimide resin according to any one of claims 3 to 6.

9. An electronic device, characterized in that: It comprises the flexible film as claimed in claim 8.

10. The electronic device according to claim 9, characterized in that: The electronic device is an organic light emitting display panel, and further comprises a thin film transistor array layer and an organic light emitting layer located on the flexible film, wherein the thin film transistor array layer is located between the flexible film and the organic light emitting layer.

11. The electronic device according to claim 9, characterized in that: When the electronic device is a foldable mobile phone, the flexible film is a base film located at the bottom of the foldable mobile phone and used to support other elements of the foldable mobile phone, or a transparent cover film located on the front of the foldable mobile phone.

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