CN115703718B - Diamine monomer compound, preparation method thereof, resin, flexible film and electronic equipment - Google Patents
Diamine monomer compound, preparation method thereof, resin, flexible film and electronic equipment Download PDFInfo
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- CN115703718B CN115703718B CN202110909978.XA CN202110909978A CN115703718B CN 115703718 B CN115703718 B CN 115703718B CN 202110909978 A CN202110909978 A CN 202110909978A CN 115703718 B CN115703718 B CN 115703718B
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Abstract
本申请提供一种二胺单体化合物，结构通式为：本申请还提供该二胺单体化合物的制备方法、应用该二胺单体化合物制得的聚酰亚胺树脂、以及应用该聚酰亚胺树脂的柔性薄膜和电子设备。所述二胺单体化合物的结构中引入了大体积位阻的芴结构，可有效的阻碍分子链的紧密堆积，从而赋予良好的透明性；所述二胺单体化合物的侧基上引入酰胺键结构，可在分子侧链间形成氢键作用，从而有效降低热膨胀系数。
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, 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
The application relates to a diamine monomer compound and a preparation method thereof, polyimide resin prepared by using the diamine monomer compound, and a flexible film and electronic equipment using the polyimide resin.
Background
Polyimide is a 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 property, excellent film forming property, good dielectric property and the like. Polyimide is one of engineering plastics which has been industrially produced, and is widely applied to the fields of organic electronic devices such as organic electronic storage, nonlinear optical materials, liquid crystal display alignment film materials, liquid crystal display phase difference compensation film materials, electroluminescent diodes and the like.
Since the advent of the first commercialized polyimide Kapton film, polyimide has been popularized and applied to various industrial fields such as microelectronics, optics, aerospace, and military fields. Along with the expansion of polyimide application fields, higher requirements are also provided for the performance of polyimide materials. The traditional polyimide has strong interaction force between the intramolecular and the intermolecular chains due to the fact that a large amount of rigid aromatic heterocycle is contained in the molecule, so that the material has excellent comprehensive performance, however, the transparency of the material is poor due to the fact that a large amount of charge transfer complex is generated at the same time, and the polyimide film tends to be dark yellow or brown. This limits the application of polyimide in optics. In order to improve the transparency of polyimide materials, the current common proposal mainly comprises the introduction of fluorine-containing groups, aliphatic or alicyclic structures and groups with large steric hindrance into the polyimide molecular structure, so as to weaken the charge transfer effect in molecules and between molecular chains, but the charge transfer effect inevitably causes the reduction of the overall performance of the materials, particularly the increase of the thermal expansion coefficient, which reaches between 40 and 60 ppm/K. However, this also makes the polyimide film not matched with the thermal expansion degree of other materials under the high temperature condition in the preparation process of the flexible transparent device, and further causes the problems of stripping, cracking, warping and the like of the polyimide film.
Disclosure of Invention
The first aspect of the embodiment of the application provides a diamine monomer compound, which has the structural general formula:
Wherein Ar 1 is selected from one of the following:
ar 2 is selected from one of the following:
Ar 3 is selected from one of the following:
The diamine monomer compound has the advantages that a large-volume sterically hindered fluorene structure is introduced into the structure of the diamine monomer compound, so that the close packing of molecular chains can be effectively hindered, and the diamine monomer compound has good transparency, and the amide bond structure is introduced into the side group of the diamine monomer compound, so that hydrogen bonding effect can be formed between molecular side chains, thereby effectively reducing the thermal expansion coefficient and improving the dimensional stability.
In an embodiment of the present application, the diamine monomer compound has at least one of the following structural formulas:
the second aspect of the embodiment of the application provides polyimide resin, which has the following structural general formula:
Wherein X is an aromatic dianhydride residue or a cycloaliphatic dianhydride residue, R is an aromatic diamine residue or a cycloaliphatic diamine residue, m 1 is an integer >1, m 2 is an integer >1, n is an integer >1,
The structural formula of Y is as follows:
Wherein Ar 1 is selected from one of the following:
ar 2 is selected from one of the following:
Ar 3 is selected from one of the following:
The polyimide resin has the advantages that the structure of the polyimide resin is introduced with a fluorene structure with large volume steric hindrance, so that the close packing of molecular chains can be effectively blocked, and the polyimide resin is endowed with good transparency, and the side group of the polyimide resin is introduced with an amide bond structure, so that hydrogen bonding effect can be formed between molecular side chains, and the thermal expansion coefficient of the polyimide resin can be effectively reduced, and the dimensional stability is improved.
In an embodiment of the application, the aromatic dianhydride residue or the cycloaliphatic dianhydride residue X is derived from one or more of the following compounds: pyromellitic dianhydride, 3',4' -biphenyl tetracarboxylic dianhydride, 2, 3',4' -biphenyltetracarboxylic acid dianhydride, 2,3,5, 6-naphthalene tetracarboxylic acid dianhydride, 2,3,6, 7-naphthalene tetracarboxylic acid dianhydride, 1,4,5, 8-naphthalene tetracarboxylic acid dianhydride, 2, 6-dichloro naphthalene-1, 4,5, 8-tetracarboxylic acid dianhydride, 2, 7-dichloro naphthalene-1, 4,5, 8-tetracarboxylic acid dianhydride, 2,3,6, 7-tetrachloronaphthalene-1, 4,5, 8-tetracarboxylic acid dianhydride, 3,4,9, 10-perylene tetracarboxylic acid dianhydride, pyrazine-2, 3,5, 6-tetracarboxylic acid dianhydride, thiophene-2, 3,4, 5-tetracarboxylic acid dianhydride, 1,2,3, 4-cyclopentane tetracarboxylic acid dianhydride, cyclobutane-1, 2,3, 4-tetracarboxylic acid dianhydride, cyclopentane-1, 2,3, 4-tetracarboxylic acid dianhydride, cyclohexane-1, 2,4, 5-tetracarboxylic acid dianhydride, norbornane-2, 3, 6-tetracarboxylic acid dianhydride, 3, 4-tetracarboxylic acid dianhydride, 3-bicyclo [2, 3,4, 3-tetracarboxylic acid dianhydride, 3-bicyclo [2, 3, 4-tetracarboxylic acid dianhydride, 3-bicyclo [2, 3, 4-octa-dicarboxylic acid dianhydride; 4 '-Biphenyltetracarboxylic acid dianhydride, 2,3,5, 6-naphthalene tetracarboxylic acid dianhydride, 2,3,6, 7-naphthalene tetracarboxylic acid dianhydride, 1,4,5, 8-naphthalene tetracarboxylic acid dianhydride, 2, 6-dichloronaphthalene-1, 4,5, 8-tetracarboxylic acid dianhydride, 2, 7-dichloronaphthalene-1, 4,5, 8-tetracarboxylic acid dianhydride, 2,3,6, 7-tetrachloronaphthalene-1, 4,5, 8-tetracarboxylic acid dianhydride, 3,4,9, 10-perylene tetracarboxylic acid dianhydride, pyrazine-2, 3,5, 6-tetracarboxylic acid dianhydride thiophene-2, 3,4, 5-tetracarboxylic dianhydride, 1,2,3, 4-cyclopentane tetracarboxylic 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', 5- (2, 5-dioxotetrahydro) -3-methyl-3-cyclohexene-1, 2-dicarboxylic anhydride.
In an embodiment of the application, the aromatic diamine residue or the cycloaliphatic 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, p-phenylenediamine, 4-phenylenediamine, p-phenylenediamine, 4 bis {4- (4-aminophenoxy) phenyl } ether, 4 '-diaminobiphenyl, 2' -dimethyl-4, 4 '-diaminobiphenyl, 2' -diethyl-4, 4 '-diaminobiphenyl, 3' -dimethyl-4, 4 '-diaminobiphenyl, 3' -diethyl-4, 4 '-diaminobiphenyl, 2', bis {4- (4-aminophenoxy) phenyl } ether, 4 '-diaminobiphenyl, 2' -dimethyl-4, 4 '-diaminobiphenyl 2,2' -diethyl-4, 4 '-diaminobiphenyl, 3' -dimethyl-4, 4 '-diaminobiphenyl, 3' -diethyl-4, 4 '-diaminobiphenyl, 2', 2, 2-bis (3-anilino) hexafluoropropane and 2, 2-bis (3-amino-4-toluoyl) hexafluoropropane, 1, 6-hexamethylenediamine, 1, 4-cyclohexanediamine, 1, 3-cyclohexanediamine, 1, 4-bis (aminomethyl) cyclohexane, 1, 3-bis (aminomethyl) cyclohexane, 4' -diaminodicyclohexylmethane and 4,4' -diamino-3, 3' -dimethylcyclohexylmethane.
In an embodiment of the present application, the polyimide resin is a diamine monomer compoundIs polymerized with an aromatic diamine monomer or a cycloaliphatic diamine monomer, and an aromatic dianhydride monomer or a cycloaliphatic dianhydride monomer.
In a third aspect, the present embodiment provides a method for preparing a diamine monomer compound, including:
Preparation of nitro compounds Wherein X1 is halogen, ar 1 is selected from one of the following:
The nitro compound (B-1) is subjected to a coupling reaction to prepare a dinitro compound Wherein Ar 2 is selected from one of the following:
reacting a dinitro compound (B-2) with an acyl chloride compound to obtain a dinitro compound Wherein Ar 3 is selected from one of the following:
the dinitro compound (B-3) is obtained by reduction
According to a fourth aspect of the embodiment of the application, there is provided a flexible film comprising the polyimide resin according to the second aspect of the embodiment of the application.
A fifth aspect of the embodiment of the present application provides an electronic device, including the flexible film according to the fourth aspect of the embodiment of the present application.
In an embodiment of the 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 which are positioned on the flexible film, wherein the thin film transistor array layer is positioned between the flexible film and the organic light-emitting layer.
Since the polyimide resin has high transparency, it does not affect light transmission of the organic light emitting display panel, and the polyimide resin has low thermal expansion coefficient, the flexible film does not have problems of peeling, cracking, warping, etc. when the organic light emitting display panel is manufactured.
In an embodiment of the application, when the electronic device is a foldable mobile phone, the flexible film is a base film positioned at the bottom of the foldable mobile phone and used for carrying other elements of the foldable mobile phone or a transparent cover film positioned at the front of the foldable mobile phone.
Drawings
Fig. 1 is a flowchart of the preparation of an organic light emitting display panel.
Detailed Description
Embodiments of the present application will be described below with reference to the accompanying drawings in the embodiments of the present application.
In order to produce polyimide with excellent combination of properties, rigid aromatic dianhydride and diamine structures are generally used to enhance intramolecular and intermolecular interactions. However, this also makes polyimide films less transparent and often appear darker yellow or brown, thereby limiting the use of polyimide in optics. In order to obtain transparent polyimide, it is generally necessary to introduce a large amount of fluorine-containing groups, aliphatic or alicyclic structures and a structure with large steric hindrance into the molecular structure, and to weaken the charge transfer effects in and between the molecules. However, at the same time, the heat resistance, mechanical properties and the like of the film are inevitably reduced, and particularly the rise of the thermal expansion coefficient can cause the mismatch of the thermal expansion coefficient of the polyimide film and other materials (such as copper wires or materials of other layers in the organic light-emitting display panel) and further cause damages such as warping, peeling and the like.
Flexible organic light emitting display panels generally employ polyimide as a flexible substrate. As shown in fig. 1, the organic light emitting display panel is prepared by providing an optical glass, forming a polyimide film on the optical glass, forming a barrier layer for isolating moisture 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 moisture and gas on the light emitting layer, and finally peeling off the optical glass from the polyimide film. However, when a TFT (which may be a low temperature polysilicon TFT or an oxide TFT) layer is fabricated, a high temperature process is generally performed, and if the polyimide film is not matched with the thermal expansion degree of other materials, problems such as peeling, cracking, warping and the like may occur.
The embodiment of the application provides a diamine monomer compound which can be used for preparing polyimide resin with high transparency and low thermal expansion coefficient.
The structural general formula of the diamine monomer compound is as follows:
Wherein Ar 1 is selected from one of the following:
ar 2 is selected from one of the following:
Ar 3 is selected from one of the following:
the diamine monomer compound is Respectively connected with a lateral group with an amide bond structure on two benzene rings
In some embodiments, the structural general formula of the diamine monomer compound is at least one of the following, but not limited thereto:
in the above-mentioned structural general formulae (I), (II), (III) and (IV) of the diamine monomer compound, two side groups In order to be symmetrically attached to the two benzene rings of the fluorenyl group, in other embodiments, the two pendant groups may also be asymmetrically attached to the two benzene rings of the fluorenyl group.
The diamine monomer compound has the advantages that a large-volume sterically hindered fluorene structure is introduced into the structure of the diamine monomer compound, so that the close packing of molecular chains can be effectively hindered, and the diamine monomer compound has good transparency, and the amide bond structure is introduced into the side group of the diamine monomer compound, so that hydrogen bonding effect can be formed between molecular side chains, thereby effectively reducing the thermal expansion coefficient and improving the dimensional stability. Steric hindrance, also known as steric hindrance, refers to the mutual repulsion of the internal groups of a molecule in a steric arrangement.
The embodiment of the application provides a polyimide resin, which is polymerized by the diamine monomer compound, other aromatic or alicyclic diamine monomers different from the diamine monomer compound and aromatic or alicyclic dianhydride monomers.
The structural general formula of the polyimide resin comprises:
Wherein X is an aromatic dianhydride residue or a cycloaliphatic dianhydride residue, R is an aromatic diamine residue or a cycloaliphatic diamine residue, and Y has the structural formula M 1 is an integer >1, m 2 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 polymerized to form the polyimide resin, and the presence of the aromatic or alicyclic dianhydride monomer, the aromatic or alicyclic diamine monomer, and the like in the structural formula of the polyimide resin formed after polymerization is not a single monomer compound but a single group, and is defined as a residue.
The polyimide resin comprises n repeating units, each repeating unit comprising m 1 And m 2 M 1 of the applicationAnd m 2 Is randomly arranged on the main chain of the polyimide resin.
The aromatic dianhydride residue or the cycloaliphatic dianhydride residue X is derived from one or more of the following compounds: pyromellitic dianhydride, 3',4' -biphenyl tetracarboxylic dianhydride, 2, 3',4' -biphenyltetracarboxylic acid dianhydride, 2,3,5, 6-naphthalene tetracarboxylic acid dianhydride, 2,3,6, 7-naphthalene tetracarboxylic acid dianhydride, 1,4,5, 8-naphthalene tetracarboxylic acid dianhydride, 2, 6-dichloro naphthalene-1, 4,5, 8-tetracarboxylic acid dianhydride, 2, 7-dichloro naphthalene-1, 4,5, 8-tetracarboxylic acid dianhydride, 2,3,6, 7-tetrachloronaphthalene-1, 4,5, 8-tetracarboxylic acid dianhydride, 3,4,9, 10-perylene tetracarboxylic acid dianhydride, pyrazine-2, 3,5, 6-tetracarboxylic acid dianhydride, thiophene-2, 3,4, 5-tetracarboxylic acid dianhydride, 2,3,5, 6-pyridine tetracarboxylic acid dianhydride, 1,2,3, 4-cyclopentane tetracarboxylic acid dianhydride, cyclobutane-1, 2,3, 4-tetracarboxylic acid dianhydride, cyclopentane-1, 2,3, 4-tetracarboxylic acid dianhydride, cyclohexane-1, 2,4, 5-tetracarboxylic acid dianhydride, 2,3, 6-tetracarboxylic acid dianhydride, 3, 4-bicyclo [2, 3,4,5, 3-tetracarboxylic acid dianhydride, 3-bicyclo [2, 3,4, 5-tetracarboxylic acid dianhydride, 3-bicyclo [2, 3,5, 6-tetracarboxylic acid dianhydride, 3-octa-2, 3-bicyclo [ 2.5, 3, 6-tetracarboxylic acid dianhydride; 4 '-Biphenyltetracarboxylic acid dianhydride, 2,3,5, 6-naphthalene tetracarboxylic acid dianhydride, 2,3,6, 7-naphthalene tetracarboxylic acid dianhydride, 1,4,5, 8-naphthalene tetracarboxylic acid dianhydride, 2, 6-dichloronaphthalene-1, 4,5, 8-tetracarboxylic acid dianhydride, 2, 7-dichloronaphthalene-1, 4,5, 8-tetracarboxylic acid dianhydride, 2,3,6, 7-tetrachloronaphthalene-1, 4,5, 8-tetracarboxylic acid dianhydride, 3,4,9, 10-perylene tetracarboxylic acid dianhydride, pyrazine-2, 3,5, 6-tetracarboxylic acid dianhydride thiophene-2, 3,4, 5-tetracarboxylic dianhydride, 2,3,5, 6-pyridine tetracarboxylic dianhydride, 1,2,3, 4-cyclopentane tetracarboxylic 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', 5- (2, 5-dioxotetrahydro) -3-methyl-3-cyclohexene-1, 2-dicarboxylic anhydride, and the like.
The aromatic diamine residue or the cycloaliphatic 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, p-phenylenediamine, 4-phenylenediamine, p-phenylenediamine, 4 bis {4- (4-aminophenoxy) phenyl } ether, 4 '-diaminobiphenyl, 2' -dimethyl-4, 4 '-diaminobiphenyl, 2' -diethyl-4, 4 '-diaminobiphenyl, 3' -dimethyl-4, 4 '-diaminobiphenyl, 3' -diethyl-4, 4 '-diaminobiphenyl, 2', bis {4- (4-aminophenoxy) phenyl } ether, 4 '-diaminobiphenyl, 2' -dimethyl-4, 4 '-diaminobiphenyl 2,2' -diethyl-4, 4 '-diaminobiphenyl, 3' -dimethyl-4, 4 '-diaminobiphenyl, 3' -diethyl-4, 4 '-diaminobiphenyl, 2', 2, 2-bis (3-anilino) hexafluoropropane and 2, 2-bis (3-amino-4-toluoyl) hexafluoropropane, 1, 6-hexamethylenediamine, 1, 4-cyclohexanediamine, 1, 3-cyclohexanediamine, 1, 4-bis (aminomethyl) cyclohexane, 1, 3-bis (aminomethyl) cyclohexane, 4' -diaminodicyclohexylmethane, 4' -diamino-3, 3' -dimethylcyclohexylmethane, and the like.
The polyimide resin has the advantages that the structure of the polyimide resin is introduced with a fluorene structure with large volume steric hindrance, so that the close packing of molecular chains can be effectively blocked, and the polyimide resin is endowed with good transparency, and the side group of the polyimide resin is introduced with an amide bond structure, so that hydrogen bonding effect can be formed between molecular side chains, and the thermal expansion coefficient of the polyimide resin can be effectively reduced, and the dimensional stability is improved.
The application also provides a flexible film which comprises the polyimide resin.
The application also provides electronic equipment comprising the flexible film. The flexible film can be applied to various electronic devices.
When the electronic device is a flexible organic light emitting display panel, the electronic device further includes a thin film transistor array layer and an organic light emitting layer 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 does not affect light transmission of the organic light emitting display panel, and the polyimide resin has low thermal expansion coefficient, the flexible film does not have problems of peeling, cracking, warping, etc. when the organic light emitting display panel is manufactured.
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 at the front of the foldable mobile phone.
The application also provides a preparation method of the diamine monomer compound, which comprises the following steps:
preparation of nitro Compounds containing Dihalofluorene Structure and Ar 1 X1 is halogen, and the nitro compound (B-1) is subjected to a coupling reaction to prepare the dinitro compound containing amino and Ar 2 structure
Preparation of dinitro compound containing amide bond structure and Ar 3 structure by reacting dinitro compound (B-2) with acyl chloride compound (e.g. benzoyl chloride)
The dinitro compound (B-3) is obtained by reduction reaction
The preparation method of the polyimide resin comprises the following steps:
Preparing diamine monomer, wherein the structural general formula of the diamine monomer is
And polymerizing the diamine monomer with other aromatic diamine monomer or alicyclic diamine monomer, and aromatic dianhydride monomer or alicyclic dianhydride monomer.
The embodiments of the present application will be further described with reference to the following examples.
Monomer example one
Preparation of the monomer:
2, 7-dibromofluorene (32.4 g,0.1 mol) and p-fluoronitrobenzene (42.3 g,0.3 mol) are added with 100ml of dimethyl sulfoxide (DMSO) solvent, cesium fluoride (45.57 g,0.3mol and acid-binding agent) is slowly added after stirring and dissolving, at this time, the reaction solvent turns black, the reaction is heated to 150 ℃ after vacuumizing and nitrogen gas is introduced to displace air, the reaction is carried out for 24 hours, the reaction is cooled to room temperature and then poured into ice water, huang Huise solid is obtained, the dichloromethane is extracted after washing and filtering by water, the solvent is removed by rotary evaporation, and the product dichloromethane/n-hexane is recrystallized and purified to obtain a pale yellow solid intermediate product I.
The intermediate I (113.24 g,0.2 mol), para-aminophenylboric acid (68.5 g,0.5 mol) and tetraphenylphosphine palladium (2 g, catalyst) are taken and added into a 2L reaction kettle, a saturated solution of tetrahydrofuran (THF, 800 ml) and potassium carbonate (69 g,0.5 mol) is added, the mixture is vacuumized at a low temperature, nitrogen is filled, then the mixture is heated and refluxed for reaction for 24 hours, the solvent is removed by rotary evaporation after extraction, and toluene is recrystallized after ethanol washing and filtration, thus obtaining an orange solid intermediate II.
Intermediate II (59 g,0.1 mol) was taken, THF (300 ml) and triethylamine (Et 3 N,30 ml) were added, wherein triethylamine was an acid-binding agent, which was used to absorb by-product hydrochloric acid to facilitate the reaction, benzoyl chloride (27.5 ml,0.24 mol) was slowly added, the reaction was stirred at 65℃for 3 hours, poured into water after the reaction was completed, filtered, washed with ethanol, and toluene was recrystallized to give orange intermediate III.
Intermediate III (79.8 g,0.1 mol) was taken, DMF (100 ml) and 10% palladium on carbon (2 g) were added, the air was evacuated and then hydrogen was charged, the reaction was stirred at room temperature until the theoretical volume (13.44L, 0.6 mol) of hydrogen was absorbed, after the reaction was completed, a large amount of water was poured into the reaction vessel to precipitate, the filter cake was dissolved in THF after filtration, the toluene was recrystallized after the filtration of the organic phase and the spin-drying to give pale yellow diamine monomer A.
Monomer example two
Preparation of monomers (monomers structurally different from example one):
3, 6-dibromofluorene (32.4 g,0.1 mol) and 2-fluoro-5-nitropyridine (42.87 g,0.3 mol) are added with 100ml of DMSO solvent, cesium fluoride (45.57 g,0.3 mol) is slowly added after stirring and dissolving, at this time, the reaction solvent turns black, the reaction solvent is vacuumized, nitrogen is pumped to displace air, then heated to 150 ℃ for reaction for 24 hours, cooled to room temperature, poured into ice water, and then Huang Huise solid is obtained, dichloromethane is used for extraction after washing and filtering, solvent is removed by rotary evaporation, and the product dichloromethane/n-hexane is recrystallized and purified to obtain a pale yellow solid intermediate product I'.
Intermediate I '(113.18 g,0.2 mol), (5-aminopyridin-2-yl) boric acid (68.97 g,0.5 mol) and tetraphenylphosphine palladium (2 g) are taken and added into a 2L reaction kettle, a saturated solution of THF (800 ml) and potassium carbonate (69 g,0.5 mol) is added, vacuum pumping and nitrogen charging are carried out at low temperature, heating reflux reaction is carried out for 24h, solvent is removed by rotary evaporation after extraction, toluene is recrystallized after ethanol washing and filtration, and orange solid intermediate II' is obtained.
Intermediate II '(59.42 g,0.1 mol) was taken, THF (300 ml) and Et 3 N (30 ml) were added, benzoyl chloride (27.5 ml,0.24 mol) was slowly added, the reaction was stirred at 65℃for 3h, after the reaction was completed, the solvent was removed by spin-drying, then dissolved in THF and filtered, washed with ethanol after filtration, and toluene was recrystallized to give orange intermediate III'.
Taking intermediate product III' (80.0 g,0.1 mol), adding DMF (100 ml) and 10% palladium-carbon (2 g), vacuumizing, filling hydrogen, stirring at room temperature until the theoretical volume (13.44L, 0.6 mol) of hydrogen is absorbed, pouring a large amount of water after the reaction is finished for precipitation, filtering, dissolving a filter cake by THF, filtering an organic phase, spin-drying, and recrystallizing toluene to obtain light yellow diamine monomer B.
Polymer example one
Diamine A (7.3889 g,10 mmol) and monomer 4,4' -diaminotriphenylmethane (5.4872, 20 mmol) were added to a reaction flask under nitrogen protection, solvent N, N-dimethylacetamide (DMAc, 92.64 ml) was added and stirred at room temperature until dissolved, monomer 3,3', 4' -biphenyltetracarboxylic dianhydride (BPDA, 8.8266g,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 12h, and the mixture was slowly poured into ethanol stirred at high speed to obtain fibrous polyimide precipitate, which was dried to obtain polyimide. The polyimide obtained was dissolved in DMAc to prepare a glue solution with a solid content of 10%, the glue solution was drawn out to remove air bubbles, then the glue solution was blade-coated on a glass plate, and the glass plate was placed in a vacuum oven to be heated up (80 ℃,1h;160 ℃,1h;250 ℃,1h;350 ℃ and 0.5 h.) with a certain program, cooled to room temperature, immersed in hot water to be taken off the film, and the polyimide film with a film thickness of about 30 μm was obtained by measurement with a step meter.
Polymer example two (dianhydride selected as pyromellitic dianhydride)
Diamine A (7.3889 g,10 mmol) and monomer 4,4' -diaminotriphenylmethane (5.4872, 20 mmol) were added to a reaction flask under nitrogen protection, DMAc (82.90 ml) was added and stirred at room temperature until dissolved, then monomer pyromellitic dianhydride (PMDA, 6.5436g,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 12h, then the mixture was slowly poured into ethanol stirred at high speed to obtain fibrous polyimide precipitate, and the polyimide was obtained after drying. The polyimide obtained is dissolved in DMAc to prepare glue solution with the solid content of 10 percent, the glue solution is coated on a glass plate after vacuumizing and removing bubbles, the glass plate is placed in a vacuum oven to be heated up (80 ℃ for 1h, 160 ℃ for 1h, 250 ℃ for 1h, 350 ℃ for 0.5 h.) with a certain program, and the polyimide film with the film thickness of about 30m is obtained by immersing the polyimide film in hot water for demoulding after cooling to room temperature.
Polymer example three (dianhydride selected as 4, 4-hexafluoroisopropyl phthalic anhydride)
Diamine A (7.3889 g,10 mmol) and monomer 4,4' -diaminotriphenylmethane (5.4872, 20 mmol) were added to a reaction flask under nitrogen protection, DMAc (111.86 ml) was added and stirred at room temperature until dissolved, then monomer 4, 4-hexafluoroisopropyl phthalic anhydride (6 FDA,13.3272g,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 12h, and then the mixture was slowly poured into ethanol stirred at high speed to obtain fibrous polyimide precipitate, which was dried to obtain polyimide. The polyimide obtained was dissolved in DMAc to prepare a glue solution with a solid content of 10%, the glue solution was drawn out to remove air bubbles, then the glue solution was blade-coated on a glass plate, and the glass plate was placed in a vacuum oven to be heated up (80 ℃,1h;160 ℃,1h;250 ℃,1h;350 ℃ and 0.5 h.) with a certain program, cooled to room temperature, immersed in hot water to be taken off the film, and the polyimide film with a film thickness of about 30 μm was obtained by measurement with a step meter.
Polymer comparative example one
4,4' -Diaminotriphenylmethane (8.2310 g,30 mmol) was added to the reaction flask under nitrogen protection, DMAc (92.64 ml) was added and stirred at room temperature until dissolved, then BPDA (8.8266 g,30 mmol) was slowly added, stirred at room temperature overnight, acetic anhydride (120 ml) and pyridine (6 ml) were added and stirred at room temperature for 12h, and then the mixture was slowly poured into ethanol stirred at high speed to obtain fibrous polyimide precipitate, which was dried to obtain polyimide. The polyimide obtained was dissolved in DMAc to prepare a glue solution with a solid content of 10%, the glue solution was drawn out to remove air bubbles, then the glue solution was blade-coated on a glass plate, and the glass plate was placed in a vacuum oven to be heated up (80 ℃,1h;160 ℃,1h;250 ℃,1h;350 ℃ and 0.5 h.) with a certain program, cooled to room temperature, immersed in hot water to be taken off the film, and the polyimide film with a film thickness of about 30 μm was obtained by measurement with a step meter.
Polymer comparative example two
4,4' -Diaminotriphenylmethane (8.2310 g,30 mmol) was added to the reaction flask under nitrogen protection, DMAc (82.90 ml) was added and stirred at room temperature until dissolved, then PMDA (6.5436 g,30 mmol) was slowly added, stirred at room temperature overnight, acetic anhydride (120 ml) and pyridine (60 ml) were added and stirred at room temperature for 12h, and the mixture was slowly poured into ethanol stirred at high speed to obtain fibrous polyimide precipitate, which was dried to obtain polyimide. The polyimide obtained was dissolved in DMAc to prepare a glue solution with a solid content of 10%, the glue solution was drawn out to remove air bubbles, then the glue solution was blade-coated on a glass plate, and the glass plate was placed in a vacuum oven to be heated up (80 ℃,1h;160 ℃,1h;250 ℃,1h;350 ℃ and 0.5 h.) with a certain program, cooled to room temperature, immersed in hot water to be taken off the film, and the polyimide film with a film thickness of about 30 μm was obtained by measurement with a step meter.
Polymer comparative example three
4,4' -Diaminotriphenylmethane (8.2310 g,30 mmol) was added to the reaction flask under nitrogen protection, DMAc (111.86 ml) was added and stirred at room temperature until dissolved, then 6FDA (13.3272 g,30 mmol) was slowly added, stirred at room temperature overnight, acetic anhydride (120 ml) and pyridine (60 ml) were added and stirred at room temperature for 12 hours, and the mixture was slowly poured into ethanol stirred at high speed to obtain fibrous polyimide precipitate, which was dried to obtain polyimide. The polyimide obtained was dissolved in DMAc to prepare a glue solution with a solid content of 10%, the glue solution was drawn out to remove air bubbles, then the glue solution was blade-coated on a glass plate, and the glass plate was placed in a vacuum oven to be heated up (80 ℃,1h;160 ℃,1h;250 ℃,1h;350 ℃ and 0.5 h.) with a certain program, cooled to room temperature, immersed in hot water to be taken off the film, and the polyimide film with a film thickness of about 30 μm was obtained by measurement with a step meter.
TABLE 1
As can be seen from the data in Table 1, after the fluorene group and the amide bond containing large steric hindrance are introduced in examples 1 to 3, the thermal expansion coefficient is significantly reduced compared with comparative examples 1 to 3, and the film has good transparency.
It should be noted that, the above is only a specific embodiment of the present application, but the scope of the present application is not limited thereto, and any person skilled in the art can easily think about changes or substitutions within the technical scope of the present application, and the embodiments and features of the embodiments of the present application can be combined with each other without conflict. Therefore, the protection scope of the application is subject to the protection scope of the claims.
Claims (11)
1. A diamine monomer compound characterized by having the structural formula:
Wherein Ar 1 is selected from one of the following:
ar 2 is selected from one of the following:
Ar 3 is selected from one of the following:
2. The diamine monomer compound of claim 1, wherein the diamine monomer compound has at least one of the following structural formulas:
3. A polyimide resin, characterized in that the polyimide resin has a structural general formula:
Wherein X is an aromatic dianhydride residue or a cycloaliphatic dianhydride residue, R is an aromatic diamine residue or a cycloaliphatic diamine residue, m 1 is an integer >1, m 2 is an integer >1, n is an integer >1,
The structural formula of Y is as follows:
Wherein Ar 1 is selected from one of the following:
ar 2 is selected from one of the following:
Ar 3 is selected from one of the following:
4. A polyimide resin according to claim 3, characterized in that the aromatic dianhydride residue or the alicyclic dianhydride residue X is derived from one or more of the following compounds: pyromellitic dianhydride, 3',4' -biphenyl tetracarboxylic dianhydride, 2, 3',4' -biphenyltetracarboxylic acid dianhydride, 2,3,5, 6-naphthalene tetracarboxylic acid dianhydride, 2,3,6, 7-naphthalene tetracarboxylic acid dianhydride, 1,4,5, 8-naphthalene tetracarboxylic acid dianhydride, 2, 6-dichloro naphthalene-1, 4,5, 8-tetracarboxylic acid dianhydride, 2, 7-dichloro naphthalene-1, 4,5, 8-tetracarboxylic acid dianhydride, 2,3,6, 7-tetrachloronaphthalene-1, 4,5, 8-tetracarboxylic acid dianhydride, 3,4,9, 10-perylene tetracarboxylic acid dianhydride, pyrazine-2, 3,5, 6-tetracarboxylic acid dianhydride, thiophene-2, 3,4, 5-tetracarboxylic acid dianhydride, 1,2,3, 4-cyclopentane tetracarboxylic acid dianhydride, cyclobutane-1, 2,3, 4-tetracarboxylic acid dianhydride, cyclopentane-1, 2,3, 4-tetracarboxylic acid dianhydride, cyclohexane-1, 2,4, 5-tetracarboxylic acid dianhydride, norbornane-2, 3, 6-tetracarboxylic acid dianhydride, 3, 4-tetracarboxylic acid dianhydride, 3-bicyclo [2, 3,4, 3-tetracarboxylic acid dianhydride, 3-bicyclo [2, 3, 4-tetracarboxylic acid dianhydride, 3-bicyclo [2, 3, 4-octa-dicarboxylic acid dianhydride; 4 '-Biphenyltetracarboxylic acid dianhydride, 2,3,5, 6-naphthalene tetracarboxylic acid dianhydride, 2,3,6, 7-naphthalene tetracarboxylic acid dianhydride, 1,4,5, 8-naphthalene tetracarboxylic acid dianhydride, 2, 6-dichloronaphthalene-1, 4,5, 8-tetracarboxylic acid dianhydride, 2, 7-dichloronaphthalene-1, 4,5, 8-tetracarboxylic acid dianhydride, 2,3,6, 7-tetrachloronaphthalene-1, 4,5, 8-tetracarboxylic acid dianhydride, 3,4,9, 10-perylene tetracarboxylic acid dianhydride, pyrazine-2, 3,5, 6-tetracarboxylic acid dianhydride thiophene-2, 3,4, 5-tetracarboxylic dianhydride, 1,2,3, 4-cyclopentane tetracarboxylic 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', 5- (2, 5-dioxotetrahydro) -3-methyl-3-cyclohexene-1, 2-dicarboxylic anhydride.
5. A polyimide resin according to claim 3, characterized in that 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, p-phenylenediamine, 4-phenylenediamine, p-phenylenediamine, 4 bis {4- (4-aminophenoxy) phenyl } ether, 4 '-diaminobiphenyl, 2' -dimethyl-4, 4 '-diaminobiphenyl, 2' -diethyl-4, 4 '-diaminobiphenyl, 3' -dimethyl-4, 4 '-diaminobiphenyl, 3' -diethyl-4, 4 '-diaminobiphenyl, 2', bis {4- (4-aminophenoxy) phenyl } ether, 4 '-diaminobiphenyl, 2' -dimethyl-4, 4 '-diaminobiphenyl 2,2' -diethyl-4, 4 '-diaminobiphenyl, 3' -dimethyl-4, 4 '-diaminobiphenyl, 3' -diethyl-4, 4 '-diaminobiphenyl, 2', 2, 2-bis (3-anilino) hexafluoropropane and 2, 2-bis (3-amino-4-toluoyl) hexafluoropropane, 1, 6-hexamethylenediamine, 1, 4-cyclohexanediamine, 1, 3-cyclohexanediamine, 1, 4-bis (aminomethyl) cyclohexane, 1, 3-bis (aminomethyl) cyclohexane, 4' -diaminodicyclohexylmethane and 4,4' -diamino-3, 3' -dimethylcyclohexylmethane.
6. The polyimide resin according to claim 3, which is a diamine monomer compoundIs polymerized with an aromatic diamine monomer or a cycloaliphatic diamine monomer, and an aromatic dianhydride monomer or a cycloaliphatic dianhydride monomer.
7. A process for producing a diamine monomer compound, comprising:
Preparation of nitro compounds Wherein X1 is halogen, ar 1 is selected from one of the following:
The nitro compound (B-1) is subjected to a coupling reaction to prepare a dinitro compound Wherein Ar 2 is selected from one of the following:
reacting a dinitro compound (B-2) with an acyl chloride compound to obtain a dinitro compound Wherein Ar 3 is selected from one of the following:
the dinitro compound (B-3) is obtained by reduction
8. A flexible film comprising the polyimide resin according to any one of claims 3 to 6.
9. An electronic device comprising the flexible film of claim 8.
10. The electronic device of claim 9, wherein the electronic device is an organic light emitting display panel, the electronic device further comprising a thin film transistor array layer and an organic light emitting layer 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 of claim 9, wherein when the electronic device is a foldable mobile phone, the flexible film is a base film positioned at a bottom of the foldable mobile phone and used to carry other elements of the foldable mobile phone or a transparent cover film positioned at a front surface of the foldable mobile phone.
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