Diamine compounds, polyimide acids, polyimides, methods for preparing the same, and their use

Abstract

The present application provides a diamine compound, a polyimide acid, a polyimide, and a method for preparing and using the same. The diamine compound has a chemical structure represented by formula (I): [Formula 1] JPEG2025526974000068.jpg40131 (wherein R1 and R2 are independently selected from a single bond, substituted or unsubstituted alkylene, substituted or unsubstituted alkenylene, substituted or unsubstituted alkynylene, substituted or unsubstituted arylene, substituted or unsubstituted arylene alkyl, substituted or unsubstituted heteroarylene, substituted or unsubstituted heteroarylene alkyl, or substituted or unsubstituted alicylidene).

Description

[Technical Field]

[0001] Cross-references to related applications This disclosure claims priority to Chinese Patent Application No. 202211212701.2, filed on 30 September 2022, titled "Diamine Compounds, Polyimide Acids, Polyimides, Methods for Preparing the Same, and Uses thereof," which is incorporated herein by reference in its entirety.

[0002] field This disclosure relates to the technical field of materials, more particularly to diamine compounds, polyimide acids, polyimides, methods for preparing the same, and the use thereof. [Background technology]

[0003] With the continuous development of electronic devices, polyimide films, possessing various advantages, have become an important material attracting considerable interest from manufacturers. However, currently, the bonding strength between polyimide and metal components is poor, which limits the use and development of polyimide. Therefore, there is a need to improve the performance of polyimide. [Overview of the project]

[0004] In view of this, the present disclosure provides diamine compounds, polyimide acids, polyimides, methods for preparing the same, and their uses. The diamine compounds, polyimide acids, and polyimides have a 1,10-phenanthrolinyl group, which can coordinate to a metal atom to form a strong coordination bond, thus improving the bonding strength between the polyimide and the metal component and promoting the use of polyimides.

[0005] In a first embodiment, the present disclosure provides a diamine compound having a chemical structure represented by formula (I). [ka] (In the formula, R1 and R2 are independently selected from single bonds, substituted or unsubstituted alkylenes, substituted or unsubstituted alkenylenes, substituted or unsubstituted alkynylenes, substituted or unsubstituted arylenes, substituted or unsubstituted arylenealkyls, substituted or unsubstituted heteroarylenes, substituted or unsubstituted heteroarylenealkyls, or substituted or unsubstituted alicylidenes.)

[0006] The diamine compounds provided in this disclosure have a 1,10-phenanthrolinyl group, and the diamine compounds can be used as raw materials for preparing polyimides, so that the polyimides also have a 1,10-phenanthrolinyl group to ensure bonding strength between the polyimides and the metal members.

[0007] In one embodiment of this disclosure, the substituted or unsubstituted alkylene is a substituted or unsubstituted C1-C8 alkylene. Substituted or unsubstituted alkenylenes are C2-C8 alkenylenes, Substituted or unsubstituted alkynylenes are substituted or unsubstituted C2-C8 alkynylenes. Substituted or unsubstituted arylenes are substituted or unsubstituted C6~C 30 It is arrine, Substituted or unsubstituted arylenes are substituted or unsubstituted C7~C 40 It is an arylene alkyl, Substituted or unsubstituted heteroarylenes are substituted or unsubstituted C2-C 30 It is a heteroarylene, Substituted or unsubstituted arylenes are substituted or unsubstituted C3-C 40 It is a heteroarylenealkyl, Substituted or unsubstituted alicylidene is substituted or unsubstituted C3~C 30 It is Alisiliden.

[0008] In one embodiment of this disclosure, R1 and R2 are independently single bonds, substituted or unsubstituted C6-C6 bonds. 30Arylene, or substituted or unsubstituted C7-C 40 Selected from arylene alkyl.

[0009] In one embodiment of this disclosure, the diamine compound is of formula (I-1) to (I-4): [ka] It contains one of the compounds represented by [formula].

[0010] In a second embodiment, the present disclosure provides a method for preparing diamine compounds. The method includes the following steps:

[0011] The first reactant is prepared. The first reactant has a chemical structure represented by formula (II). [ka] (In the formula, R3 and R4 are independently selected from a chlorine atom, a bromine atom, an iodine atom, or an astatine atom.)

[0012] A second reactant is prepared. The second reactant has a chemical structure represented by formula (III). H2N-R5(III) (In the formula, R5 is selected from hydrogen, an alkyl substituted with boric acid or a boric acid ester, an alkenyl substituted with boric acid or a boric acid ester, an alkynyl substituted with boric acid or a boric acid ester, an aryl substituted with boric acid or a boric acid ester, an aralkyl substituted with boric acid or a boric acid ester, a heteroaryl substituted with boric acid or a boric acid ester, a heteroarylalkyl substituted with boric acid or a boric acid ester, or an alicyyl substituted with boric acid or a boric acid ester).

[0013] The first reactant and the second reactant are mixed under basic conditions to form a reaction solution, which is then reacted to obtain a diamine compound. The diamine compound has a chemical structure represented by formula (I). [Chemical formula] (wherein, R1 and R2 are independently selected from a single bond, substituted or unsubstituted alkylene, substituted or unsubstituted alkenylene, substituted or unsubstituted alkynylene, substituted or unsubstituted arylene, substituted or unsubstituted arylenealkyl, substituted or unsubstituted heteroarylene, substituted or unsubstituted heteroarylenealkyl, or substituted or unsubstituted arysilylidene).

[0014] The method for preparing the diamine compound of the present disclosure is simple and convenient to operate, whereby large-scale production of the diamine compound can be achieved, and the production and use of polyimide can be promoted.

[0015] In one embodiment of the present disclosure, the reaction solution further contains a catalyst and a catalyst ligand.

[0016] The catalyst includes a copper-based catalyst and a palladium-based catalyst. The copper-based catalyst contains cuprous oxide, and the palladium-based catalyst contains at least one of bis(3,5,3',5'-dimethoxydibenzylideneacetone)palladium, bis(tri-tert-butyl)palladium, tris(dibenzylideneacetone)palladium, palladium chloride, palladium acetate, tetrakis(triphenylphosphine)palladium, and bis(tri-tert-butylphosphine)palladium.

[0017] [[ID=二十二]]The catalyst ligand contains at least one of N,N'-dimethylethylenediamine, triphenylphosphine, 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl, 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene, triphenylphosphine oxide, and tris(o-methylphenyl)phosphine.

[0018] The molar ratio of the first reactant, the second reactant, the catalyst, and the catalyst ligand is 1:(2 - 50):(0.005 - 0.2):(0.005 - 0.5).

[0019] The reaction solution further contains an alkaline substance, the alkaline substance comprising at least one of potassium carbonate, sodium carbonate, cesium fluoride, sodium hydroxide, potassium hydroxide, and barium hydroxide.

[0020] The molar ratio of the first reactant, the second reactant, and the alkaline substance is 1:(2~50):(0.05~10).

[0021] The reaction temperature is between 25°C and 180°C, and the reaction time is between 2 hours and 72 hours.

[0022] In one embodiment of the present disclosure, the reaction solution further comprises a solvent, the solvent comprising water, ethylene glycol, or 1,4-dioxane, wherein the volume ratio of 1,4-dioxane to water is 2 to 10.

[0023] In one embodiment of this disclosure, the reaction is carried out under an inert atmosphere.

[0024] In a third embodiment, the disclosure provides a polyimide acid comprising a repeating unit represented by formula (IV). [ka] (In the formula, R1 and R2 are independently selected from single bonds, substituted or unsubstituted alkylenes, substituted or unsubstituted alkenylenes, substituted or unsubstituted alkynylenes, substituted or unsubstituted arylenes, substituted or unsubstituted arylenealkyls, substituted or unsubstituted heteroarylenes, substituted or unsubstituted heteroarylenealkyls, or substituted or unsubstituted alisylidenes, and R7 is selected from substituted or unsubstituted arylenes or substituted or unsubstituted heteroarylenes).

[0025] The polyimide acid provided in this disclosure has a 1,10-phenanthrolinyl group, which can form a chemical bond with a metal component to improve adhesion to the metal component, thus facilitating the preparation of polyimide and improving the bonding strength between the polyimide and the metal component.

[0026] In one embodiment of the present disclosure, the polyimide acid has a chemical structure represented by formula (V). [ka] (In the formula, R8 is selected from substituted or unsubstituted alkylenes, substituted or unsubstituted arylenes, or substituted or unsubstituted heteroarylenes, where n is 5 to 2000 and m is 0 to 1000).

[0027] In a fourth embodiment, the disclosure provides a method for preparing a polyimide acid, comprising the following steps: A first diamine compound is mixed with a dianhydride to form a mixed solution, which is reacted to obtain a polyimide acid. The first diamine compound is a diamine compound according to the first embodiment, or a diamine compound prepared by the preparation method according to the second embodiment. The polyimide acid contains repeating units represented by formula (IV). [ka] (In the formula, R1 and R2 are independently selected from single bonds, substituted or unsubstituted alkylenes, substituted or unsubstituted alkenylenes, substituted or unsubstituted alkynylenes, substituted or unsubstituted arylenes, substituted or unsubstituted arylenealkyls, substituted or unsubstituted heteroarylenes, substituted or unsubstituted heteroarylenealkyls, or substituted or unsubstituted alisylidenes, and R7 is selected from substituted or unsubstituted arylenes or substituted or unsubstituted heteroarylenes).

[0028] The method for preparing polyimide acids provided in this disclosure is simple and easy to operate, which enables the large-scale production of polyimide acids and facilitates the preparation of polyimide acids.

[0029] In one embodiment of the present disclosure, the molar ratio of the first diamine compound to the dianhydride is 0.9 to 1.1.

[0030] The dianhydride comprises at least one of the following: pyromellitic acid dianhydride, 2,3,3',4'-diphenyl ether tetracarboxylic acid dianhydride, 3,3',4,4'-benzophenone tetracarboxylic acid dianhydride, 3,3',4,4'-diphenyl sulfone tetracarboxylic acid dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl ether dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)benzophenone dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylmethane dianhydride, and 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfone dianhydride.

[0031] The mixed solution further comprises a second diamine compound, the second diamine compound comprising at least one of 4,4'-diaminodiphenyl ether, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenyl sulfone, 1,3-diamino-2-methylpropane, N,N-bis(4-aminophenyl)-1,4-phenylenediamine, 9,9-bis(4-aminophenyl)fluorene, 1,2-diaminocyclohexane, and ethylenediamine.

[0032] The mixed solution further contains a solvent, the solvent comprising at least one of dimethyl sulfoxide, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, and m-cresol.

[0033] The reaction temperature is between 0°C and 100°C, and the reaction time is between 2 and 12 hours.

[0034] In a fifth embodiment, the disclosure provides a polyimide having repeating units represented by formula (VI). [ka] (In the formula, R1 and R2 are independently selected from single bonds, substituted or unsubstituted alkylenes, substituted or unsubstituted alkenylenes, substituted or unsubstituted alkynylenes, substituted or unsubstituted arylenes, substituted or unsubstituted arylenealkyls, substituted or unsubstituted heteroarylenes, substituted or unsubstituted heteroarylenealkyls, or substituted or unsubstituted alisylidenes, and R7 is selected from substituted or unsubstituted arylenes or substituted or unsubstituted heteroarylenes).

[0035] The polyimides provided in this disclosure have 1,10-phenanthrolinyl groups, which can form chemical bonds with metal components to improve the adhesion of the polyimides to metal components and promote the use of polyimides.

[0036] In one embodiment of the present disclosure, the polyimide has a chemical structure represented by formula (VII). [ka] (In the formula, R8 is selected from substituted or unsubstituted alkylenes, substituted or unsubstituted arylenes, or substituted or unsubstituted heteroarylenes, where n is 5 to 2000 and m is 0 to 1000).

[0037] In a sixth embodiment, the disclosure provides a method for preparing a polyimide, comprising the following steps: A polyimide acid prepared by the third embodiment, or by the preparation method of the fourth embodiment, is imidized to obtain a polyimide. The polyimide has repeating units represented by formula (VI). [ka] (In the formula, R1 and R2 are independently selected from single bonds, substituted or unsubstituted alkylenes, substituted or unsubstituted alkenylenes, substituted or unsubstituted alkynylenes, substituted or unsubstituted arylenes, substituted or unsubstituted arylenealkyls, substituted or unsubstituted heteroarylenes, substituted or unsubstituted heteroarylenealkyls, or substituted or unsubstituted alisylidenes, and R7 is selected from substituted or unsubstituted arylenes or substituted or unsubstituted heteroarylenes).

[0038] The method for preparing polyimides provided in this disclosure is simple and easy to operate, enabling large-scale production of polyimides, and allowing for the preparation of polyimides with high bonding strength to metal components, thus promoting the use of polyimides.

[0039] In a seventh embodiment, the disclosure provides a battery assembly comprising a heat dissipation component, a polyimide film disposed on the surface of the heat dissipation component, and a battery core disposed on the surface of the polyimide film. The polyimide film is made of a polyimide according to the fifth embodiment or a polyimide prepared by the preparation method according to the sixth embodiment.

[0040] In the battery assembly provided in this disclosure, the heat dissipation component and the battery core are connected by a polyimide film. The polyimide film improves the bonding strength to the heat dissipation component, and the polyimide is insulating, further ensuring the safety of the battery assembly.

[0041] In an eighth aspect, the disclosure provides an electronic device including a battery assembly according to a seventh aspect.

[0042] The battery assemblies of electronic devices provided in this disclosure have high safety and therefore facilitate the use of electronic devices.

[0043] To better illustrate the embodiments of this disclosure or the technical solutions in the prior art, drawings required for use in the embodiments or the prior art are briefly described below. Specific embodiments described herein are used solely for illustrative purposes of this disclosure, and this disclosure is not limited thereto. [Brief explanation of the drawing]

[0044] [Figure 1] This figure schematically illustrates the bonding of a polyimide to a metal atom, as provided in one embodiment of the present disclosure. [Figure 2] This is a schematic cross-sectional view of a battery assembly provided in one embodiment of the present disclosure. [Figure 3] This figure schematically illustrates the bonding of a polyimide film provided in one embodiment of the present disclosure to a heat dissipation component. [Modes for carrying out the invention]

[0045] Technical solutions according to embodiments of this disclosure are described below clearly and fully with reference to the accompanying drawings of embodiments of this disclosure. Obviously, the embodiments described are only a part of, and not all, of embodiments of the present invention. All other embodiments that can be obtained by those skilled in the art without creative effort based on embodiments of this disclosure are within the scope of the present invention.

[0046] This disclosure provides diamine compounds. The diamine compounds have a chemical structure represented by formula (I). [ka] (wherein R1 and R2 are independently selected from single bonds, substituted or unsubstituted alkylenes, substituted or unsubstituted alkenylenes, substituted or unsubstituted alkynylenes, substituted or unsubstituted arylenes, substituted or unsubstituted arylenealkyls, substituted or unsubstituted heteroarylenes, substituted or unsubstituted heteroarylenealkyls, or substituted or unsubstituted alisylidenes). The diamine compounds provided in this disclosure have a 1,10-phenanthrolinyl group (i.e., [ka] ) has. Diamine compounds can be used as raw materials for preparing polyimides, and the polyimides prepared therein also have 1,10-phenanthrolinyl groups to ensure bonding strength between the polyimide and the metal member.

[0047] In this disclosure, R1 and R2 are independently selected from single bonds, substituted or unsubstituted alkylenes, substituted or unsubstituted alkenylenes, substituted or unsubstituted alkylenes, substituted or unsubstituted arylenes, substituted or unsubstituted arylenealkyls, substituted or unsubstituted heteroarylenes, substituted or unsubstituted heteroarylenealkyls, or substituted or unsubstituted alicylidenes. R1 is selected from single bonds, alkylenes, substituted alkylenes, alkenylenes, substituted alkenylenes, alkylenes, substituted alkylenes, arylenes, substituted arylenes, arylenealkyls, substituted arylenealkyls, heteroarylenes, substituted heteroarylenes, heteroarylenealkyls, substituted heteroarylenealkyls, alicylidenes, or substituted alicylidenes. R2 is selected from a single bond, alkylene, substituted alkylene, alkenylene, substituted alkenylene, alkylene, substituted alkylene, arylene, substituted arylene, arylenealkyl, substituted arylenealkyl, heteroarylene, substituted heteroarylene, heteroarylenealkyl, substituted heteroarylenealkyl, alicylidene, or substituted alicylidene.

[0048] In this disclosure, alkyl is a group obtained by removing one hydrogen atom from an alkane molecule, and may include linear alkyls and branched alkyls. In particular, alkyl may include, but is not limited to, at least one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, 2-methylbutyl, 3-methylbutyl, 4-methylbutyl, 2,2-dimethylpropyl, n-hexyl, heptyl, 2-methylhexyl, 3-methylhexyl, 4-methylpentyl, 5-methylpentyl, 2-ethylbutyl, 3-ethylbutyl, heptyl, octyl, nonyl, and decyl. In one embodiment of this disclosure, substituted or unsubstituted alkyl may be substituted or unsubstituted C1-C8 alkyls. That is, alkyl has 1 to 8 carbon atoms. In particular, alkyl may have 1, 2, 3, 4, 5, 6, 7, or 8 carbon atoms, but is not limited.

[0049] In this disclosure, alkylene is a divalent saturated group formed by removing one hydrogen atom from an alkyl group. In particular, alkylene may include, but is not limited to, at least one of -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2-, and -CH2CH2CH2CH2CH2CH2-. In one embodiment of this disclosure, substituted or unsubstituted alkylene is a substituted or unsubstituted C1-C8 alkylene. That is, alkylene has 1 to 8 carbon atoms. In particular, alkylene may have, but is not limited to, 1, 2, 3, 4, 5, 6, 7, or 8 carbon atoms.

[0050] In this disclosure, an alkenyl is a divalent unsaturated hydrocarbon chain containing at least one double bond, and may include linear or branched alkenyls. In particular, an alkenyl may include, but is not limited to, at least one of ethenyl, propenyl, isopropenyl, butenyl, butadienyl, pentenyl, pentadienyl, hexenyl, hexadienyl, heptenyl, octenyl, nonenyl, and decenyl. In one embodiment of this disclosure, a substituted or unsubstituted alkenyl is a substituted or unsubstituted C2-C8 alkenyl. That is, an alkenyl has 2 to 8 carbon atoms. In particular, an alkenyl has, but is not limited to, 2, 3, 4, 5, 6, 7, or 8 carbon atoms.

[0051] In this disclosure, an alkenylene is a divalent unsaturated group formed by removing one hydrogen atom from an alkenyl. In particular, an alkenylene may include, but is not limited to, at least one of -CH=CH-, -CH=CHCH2-, -CH2CH=CH-, -CH=CHCH2CH2CH2-, -CH2CH2CH=CH-, -CH2CH=CHCH2-, -CH=CH-CH=CH-, -CH=CHCH2CH2CH2-, -CH=CH-CH=CH2CH2-, and -CH=CH2CH2CH=CH-. In one embodiment of this disclosure, a substituted or unsubstituted alkenylene is a substituted or unsubstituted C2-C8 alkenylene. That is, an alkenylene has 2 to 8 carbon atoms. In particular, an alkenylene may have 2, 3, 4, 5, 6, 7, or 8 carbon atoms, but is not limited to these.

[0052] In this disclosure, alkynyl is a trivalent unsaturated hydrocarbon chain containing at least one triple bond, and may include linear or branched alkynyls. In particular, alkynyl may include, but is not limited to, at least one of ethynyl, propynyl, butynyl, pentynyl, and hexynyl. In one embodiment of this disclosure, substituted or unsubstituted alkynyl is a substituted or unsubstituted C2-C8 alkynyl. That is, alkynyl has 2 to 8 carbon atoms. In particular, alkynyl has, but is not limited to, 2, 3, 4, 5, 6, 7, or 8 carbon atoms.

[0053] In this disclosure, alkynylene is a divalent unsaturated group formed by removing one hydrogen atom from an alkynyl. In particular, alkynylene may include, but is not limited to, at least one of the following: -C≡C-, -C≡CCH2-, -CH2C≡C-, -C≡CCH2CH2-, -CH2C≡CCH2-, -CH2CH2C≡CCH2-, -CH2C≡CC≡C-, -C≡CCH2CH2CH2-, -CH2C≡CCH2CH2-, -CH2CH2C≡CC≡C-CH2-, -C≡CCH2CH2CH2CH2-, -CH2C≡CCH2CH2CH2-, -CH2CH2C≡CCH2CH2-, -CH2CH2CH2C≡CCH2-, and -CH2CH2CH2CH2C≡C-metamorphosis. In one embodiment of this disclosure, the substituted or unsubstituted alkynylene is a substituted or unsubstituted C2-C8 alkynylene. That is, the alkynylene has 2 to 8 carbon atoms. In particular, the alkynylene has, but is not limited to, 2, 3, 4, 5, 6, 7, or 8 carbon atoms.

[0054] In this disclosure, aryl is an aromatic group. In particular, aryl may include, but is not limited to, phenyl, naphthalenyl, anthracenyl, tetracenyl, pentacenyl, and tetrahydronaphthalenyl. In one embodiment of this disclosure, the substituted or unsubstituted aryl is a substituted or unsubstituted C6-C6 group. 30It is aryl. That is, aryl has 6 to 30 carbon atoms. In particular, aryl has, but is not limited to, 6, 10, 12, 14, 18, 22, 24, 26, or 30 carbon atoms.

[0055] In the present disclosure, arylene is a divalent aromatic group. In particular, arylene may include, but is not limited to, at least one of phenylene, naphthalenylene, anthracenylene, tetracenylene, pentacenylene, and tetrahydronaphthalenylene. In one embodiment of the present disclosure, substituted or unsubstituted arylene is substituted or unsubstituted C6-C 30 It is arylene. That is, arylene has 6 to 30 carbon atoms. In particular, arylene has, but is not limited to, 6, 10, 12, 14, 18, 22, 24, 26, or 30 carbon atoms.

[0056] In the present disclosure, arylenealkyl is a combined group formed by linking arylene to alkylene. In particular, arylenealkyl [Chemical formula] and [Chemical formula] may include, but is not limited to, at least one of. In one embodiment of the present disclosure, substituted or unsubstituted arylenealkyl is substituted or unsubstituted C7-C 40 It is arylenealkyl. That is, arylenealkyl has 7 to 40 carbon atoms. In particular, arylenealkyl has, but is not limited to, 7, 8, 9, 10, 15, 18, 20, 25, 26, 30, 32, 37, or 40 carbon atoms.

[0057] In this disclosure, a heteroaryl is an aryl having at least one oxygen, sulfur, or nitrogen atom. In particular, a heteroaryl may include, but is not limited to, at least one of pyridyl, furyl, thienyl, indolyl, quinolinyl, imidazolinyl, and thiazolyl. In one embodiment of this disclosure, a substituted or unsubstituted heteroaryl is a substituted or unsubstituted C2-C 30 It is a heteroaryl compound. That is, a heteroaryl compound has 2 to 30 carbon atoms. In particular, a heteroaryl compound may have, but is not limited to, 3, 5, 8, 12, 17, 20, 25, 28, or 30 carbon atoms.

[0058] In this disclosure, heteroarylene is a divalent heteroaryl. In particular, heteroarylene may include, but is not limited to, at least one of pyridylene, furylene, thienylene, indolylene, quinolinylene, imidazolinylene, and thiazolylen. In one embodiment of this disclosure, the substituted or unsubstituted heteroarylene is a substituted or unsubstituted C2-C 30 It is a heteroarylene. That is, a heteroarylene has 2 to 30 carbon atoms. In particular, a heteroarylene may have, but is not limited to, 3, 5, 8, 12, 17, 20, 25, 28, or 30 carbon atoms.

[0059] In this disclosure, heteroarylenealkyl is a combination group formed by linking heteroarylene to alkylene. In particular, heteroarylenealkyl is [ka] and [ka] It may include, but is not limited to, at least one of the following. In one embodiment of the present disclosure, the substituted or unsubstituted heteroarylenealkyl is a substituted or unsubstituted C3-C 40It is a heteroarylenealkyl. That is, a heteroarylenealkyl has 2 to 40 carbon atoms. In particular, a heteroarylenealkyl may have, but is not limited to, 5, 6, 10, 13, 18, 22, 27, 30, 33, or 39 carbon atoms.

[0060] In this disclosure, alisilyl is a carbocyclic group that does not have a phenyl ring. In particular, alisilyl may include, but is not limited to, at least one of cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclopentenyl. In one embodiment of this disclosure, a substituted or unsubstituted alisilyl is a substituted or unsubstituted C3-C 30 It is an alisilyl. That is, an alisilyl has 3 to 30 carbon atoms. In particular, an alisilyl has, but is not limited to, 3, 5, 9, 10, 13, 15, 18, 23, 26, or 30 carbon atoms.

[0061] In this disclosure, alisilidene is divalent alisilyl. In particular, alisilidene may include, but is not limited to, cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, and cyclopentenylene. In one embodiment of this disclosure, substituted or unsubstituted alisilidene is substituted or unsubstituted C3-C 30 It is alicylylene. That is, alicylylene has 3 to 30 carbon atoms. In particular, alicylylene has, but is not limited to, 3, 5, 9, 10, 13, 15, 18, 23, 26, or 30 carbon atoms.

[0062] In this disclosure, the substituted groups (e.g., alkyl, alkylene, alkenyl, alkenylene, alkynyl, alkynylene, aryl, arylene, arylenealkyl, heteroaryl, heteroarylene, heteroarylenealkyl, and alicylidene) are groups substituted with substituents. In one embodiment, the substituents include at least one of halo, nitrogen, oxygen, sulfur, hydroxyl, nitro, amino, mercapto, methoxy, and cyano.

[0063] In this disclosure, R1 and / or R2 may be single bonds, i.e., the amino group (-NH2) may be directly reacted with the phenanthrolinyl group. In one embodiment, both R1 and R2 are single bonds, and the diamine compound is of formula (I-1): [ka] It has the chemical structural formula represented by .

[0064] The diamine compound represented by formula (I-1) has a simple structure and very stable properties, facilitating the preparation of stable polyimides.

[0065] In one embodiment of this disclosure, R1 and R2 are independently single bonds, substituted or unsubstituted C6-C6 bonds. 30 Arylene, or substituted or unsubstituted C7-C 40 Selected from arylenealkyl groups. This further improves the structural stability of the diamine compound. In one embodiment, R1 and R2 are the same group. In another embodiment, R1 and R2 are different groups. In one embodiment of this disclosure, the diamine compound is of formula (I-1) to (I-4): [ka] It contains one of the compounds represented by . When R1 and R2 are both single bonds, the diamine compound has the chemical structure represented by formula (I-1); when R1 and R2 are both arylene, the diamine compound has the chemical structures represented by formulas (I-2) and (I-3); and when R1 and R2 are both arylene alkyl, the diamine compound has the chemical structure represented by formula (I-4).

[0066] This disclosure further provides a method for preparing diamine compounds, by which diamine compounds according to any one of the embodiments described above may be prepared. The method comprises the following steps:

[0067] The first reactant is prepared. The first reactant has a chemical structure represented by formula (II). [ka] (In the formula, R3 and R4 are independently selected from a chlorine atom, a bromine atom, an iodine atom, or an astatine atom.)

[0068] A second reactant is prepared. The second reactant has a chemical structure represented by formula (III). H2N-R5(III) (In the formula, R5 is selected from hydrogen, an alkyl substituted with boric acid or a boric acid ester, an alkenyl substituted with boric acid or a boric acid ester, an alkynyl substituted with boric acid or a boric acid ester, an aryl substituted with boric acid or a boric acid ester, an aralkyl substituted with boric acid or a boric acid ester, a heteroaryl substituted with boric acid or a boric acid ester, a heteroarylalkyl substituted with boric acid or a boric acid ester, or an alisilyl substituted with boric acid or a boric acid ester.)

[0069] The first reactant and the second reactant are mixed under basic conditions to form a reaction solution, which is then reacted to obtain a diamine compound. The diamine compound has a chemical structure represented by formula (I). [ka] (In the formula, R1 and R2 are independently selected from single bonds, substituted or unsubstituted alkylenes, substituted or unsubstituted alkenylenes, substituted or unsubstituted alkylenes, substituted or unsubstituted arylenes, substituted or unsubstituted arylenes, substituted or unsubstituted arylenealkyls, substituted or unsubstituted heteroarylenes, substituted or unsubstituted heteroarylenealkyls, or substituted or unsubstituted alisylidenes.)

[0070] The method for preparing the diamine compounds of this disclosure is simple and easy to operate, thereby enabling the large-scale production of diamine compounds and facilitating the production and use of polyimides.

[0071] In this disclosure, R3 and R4 in the first reactant may be the same group or different groups. In one embodiment, R3 and R4 are the same group, which facilitates the reaction. In particular, the first reactant is [ka] and [ka] This may be the case, but is not limited to these. In this disclosure, R5 in the second reactant is selected from hydrogen, an alkyl substituted with boric acid or a borate ester, an alkenyl substituted with boric acid or a borate ester, an alkynyl substituted with boric acid or a borate ester, an aryl substituted with boric acid or a borate ester, an aralkyl substituted with boric acid or a borate ester, a heteroaryl substituted with boric acid or a borate ester, a heteroarylalkyl substituted with boric acid or a borate ester, or an alisilyl substituted with boric acid or a borate ester. In particular, R5 is NH3, [ka] , [ka] , and [ka] This may be done, but is not limited to these. In this disclosure, a diamine compound is prepared by subjecting the first reactant and the second reactant to Suzuki coupling.

[0072] In one embodiment of the present disclosure, the reaction solution further comprises a catalyst and a catalytic ligand. The addition of the catalyst and catalytic ligand accelerates the progress of the reaction. In one embodiment of the present disclosure, the catalyst comprises a copper-based catalyst and a palladium-based catalyst. The copper-based catalyst comprises cuprous oxide, and the palladium (Pb)-based catalyst comprises at least one of bis(3,5,3',5'-dimethoxydibenzylideneacetone)palladium, bis(tri-tert-butyl)palladium, tris(dibenzylideneacetone)palladium, palladium chloride, palladium acetate, tetrakis(triphenylphosphine)palladium, and bis(tri-tert-butylphosphine)palladium. In one embodiment of the present disclosure, the catalyst ligand comprises at least one of N,N'-dimethylethylenediamine, triphenylphosphine, 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl, 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene, triphenylphosphine oxide, and tris(o-methylphenyl)phosphine. The catalyst and catalyst ligand can effectively promote the Suzuki coupling. In one embodiment of the present disclosure, the molar ratio of the first reactant to the second reactant to the catalyst and catalyst ligand is 1:(2~50):(0.005~0.2):(0.005~0.5). This facilitates the Suzuki coupling and improves the efficiency of preparing the diamine compound. In one embodiment, the molar ratio of the first reactant to the second reactant to the catalyst to the catalytic ligand is 1:(3~45):(0.01~0.18):(0.01~0.45). In another embodiment, the molar ratio of the first reactant to the second reactant to the catalyst to the catalytic ligand is 1:(8~37):(0.05~0.16):(0.1~0.4). In yet another embodiment, the molar ratio of the first reactant to the second reactant to the catalyst to the catalytic ligand is 1:(10~25):(0.05~0.1):(0.1~0.3). In yet another embodiment, the molar ratio of the first reactant to the second reactant to the catalyst to the catalytic ligand is 1:(30~50):(0.1~0.2):(0.3~0.5).

[0073] In one embodiment of the present disclosure, the reaction solution further contains an alkaline substance to facilitate the progress of the reaction under basic conditions. In one embodiment of the present disclosure, the alkaline substance includes at least one of potassium carbonate, sodium carbonate, cesium fluoride, sodium hydroxide, potassium hydroxide, and barium hydroxide. In one embodiment of the present disclosure, the molar ratio of the first reactant to the second reactant to the alkaline substance is 1:(2~50):(0.05~10). This can facilitate the progress of Suzuki coupling and improve the efficiency of preparing the diamine compound. In one embodiment, the molar ratio of the first reactant to the second reactant to the alkaline substance is 1:(3~45):(0.1~9). In another embodiment, the molar ratio of the first reactant to the second reactant to the alkaline substance is 1:(8~37):(2~8). In another embodiment, the molar ratio of the first reactant to the second reactant to the alkaline substance is 1:(10~25):(1~4). In another embodiment, the molar ratio of the first reactant, the second reactant, and the alkaline substance is 1:(30-50):(5-8).

[0074] In one embodiment of the present disclosure, the reaction solution further comprises a solvent used to dissolve and disperse the components in the reaction solution. In the present disclosure, the solvent may be, but is not limited to, water, ethylene glycol, or 1,4-dioxane. In one embodiment, the solvent may be a mixture of water and 1,4-dioxane. In particular, the volume ratio of 1,4-dioxane to water may be, but is not limited to, 2 to 10.

[0075] In one embodiment of this disclosure, the reaction temperature is 25°C to 180°C, and the reaction time is 2 hours to 72 hours. This ensures the progress of the reaction, improves the efficiency of preparing the diamine compound, and avoids the occurrence of side reactions. In particular, the reaction temperature in the preparation of the diamine compound may be, but is not limited to, 25°C, 30°C, 40°C, 45°C, 60°C, 80°C, 100°C, 115°C, 130°C, 145°C, or 180°C, and the reaction time may be, but is not limited to, 2 hours, 8 hours, 10 hours, 20 hours, 35 hours, 40 hours, 55 hours, 65 hours, or 70 hours. In one embodiment, the reaction temperature is 45°C to 90°C, and the reaction time is 35 hours to 72 hours. In another embodiment, the reaction temperature is 100°C to 180°C, and the reaction time is 2 hours to 30 hours. In one embodiment of this disclosure, the reaction may be carried out under an inert gas atmosphere to avoid the occurrence of side reactions. In particular, the inert gas may be argon, nitrogen, or the like, but is not limited to these. Furthermore, the diamine compound may be obtained after the reaction by separation and purification.

[0076] In one embodiment of the present disclosure, the first reactant is reacted with NH3 to prepare a diamine compound represented by formula (I-1). In one embodiment, [ka] The mixture is mixed with aqueous ammonia and reacted to prepare the compound represented by formula (I-1). In particular, catalysts, catalytic ligands, alkaline substances, etc., may also be added. In one particular embodiment, under a nitrogen atmosphere, brominated 1,10-phenanthroline, 28% concentrated aqueous ammonia, a copper-based catalyst (cuprous oxide), N,N'-dimethylethylenediamine, and potassium carbonate are dissolved in ethylene glycol and stirred at 45°C to 180°C for 2 to 72 hours to obtain the diamine compound of formula (I-1). In particular, the molar ratio of brominated 1,10-phenanthroline, 28% concentrated aqueous ammonia, a copper-based catalyst (cuprous oxide), N,N'-dimethylethylenediamine, and potassium carbonate may be, but is not limited to, 1:(10~50):(0.01~0.1):(0.05~0.5):(0.05~0.5). The reaction scheme of the above reaction is shown below. [ka]

[0077] In one embodiment of this disclosure, [ka] but [ka] It is mixed and reacted to prepare a compound represented by formula (I-2). In particular, catalysts, catalytic ligands, alkaline substances, etc. may also be added. In one specific embodiment, under a nitrogen atmosphere, [ka] , [ka] The palladium-based catalyst, catalyst ligand, and alkaline substance were dissolved in a solvent and stirred at 45°C to 120°C for 2 to 72 hours to obtain the diamine compound of formula (I-2). In particular, [ka] and, [ka] The molar ratio of the palladium-based catalyst, the catalytic ligand, and the alkaline substance may be, but is not limited to, 1:(2~4):(0.01~0.1):(0.01~0.5):(2~10). The reaction scheme for the above reaction is shown below. [ka]

[0078] In one embodiment of this disclosure, [ka] but [ka] It is mixed and reacted to prepare a compound represented by formula (I-3). In particular, catalysts, catalytic ligands, alkaline substances, etc. may also be added. In one specific embodiment, under a nitrogen atmosphere, [ka] , [ka] The palladium-based catalyst, catalyst ligand, and alkaline substance were dissolved in a solvent and stirred at 45°C to 120°C for 2 to 72 hours to obtain the diamine compound of formula (I-3). In particular, [ka] and, [ka] The molar ratio of the palladium-based catalyst, the catalytic ligand, and the alkaline substance may be, but is not limited to, 1:(2~4):(0.01~0.1):(0.01~0.5):(2~10). The reaction scheme for the above reaction is shown below. [ka]

[0079] In one embodiment of this disclosure, [ka] but [ka] It is mixed and reacted to prepare a compound represented by formula (I-4). In particular, catalysts, catalytic ligands, alkaline substances, etc. may also be added. In one specific embodiment, under a nitrogen atmosphere, [ka] , [ka] The palladium-based catalyst, catalyst ligand, and alkaline substance were dissolved in a solvent and stirred at 45°C to 120°C for 2 to 72 hours to obtain the diamine compound of formula (I-4). In particular, [ka] and, [ka] The molar ratio of the palladium-based catalyst, the catalytic ligand, and the alkaline substance may be, but is not limited to, 1:(2~4):(0.01~0.1):(0.01~0.5):(2~10). The reaction scheme for the above reaction is shown below. [ka]

[0080] This disclosure provides a method for preparing a polyimide acid, comprising the following steps: A first diamine compound according to any of the above embodiments is mixed with a dianhydride to form a mixed solution, which is reacted to obtain a polyimide acid. The polyimide acid comprises repeating units represented by formula (IV). [ka] (In the formula, R1 and R2 are independently selected from single bonds, substituted or unsubstituted alkylenes, substituted or unsubstituted alkenylenes, substituted or unsubstituted alkynylenes, substituted or unsubstituted arylenes, substituted or unsubstituted arylenealkyls, substituted or unsubstituted heteroarylenes, substituted or unsubstituted heteroarylenealkyls, or substituted or unsubstituted alisylidenes, and R7 is selected from substituted or unsubstituted arylenes or substituted or unsubstituted heteroarylenes).

[0081] The method for preparing polyimide acids provided in this disclosure is simple and convenient to operate, thereby enabling the large-scale production of polyimide acids. The prepared polyimide acids have 1,10-phenanthrolinyl groups, which can form chemical bonds with metal components to improve adhesion to metal components, thus facilitating the preparation of polyimides and improving the bonding strength between polyimides and metal components. It can be understood that R1 and R2 in the diamine compound represented by formula (I) are the same as the repeating units in the polyimide acid represented by formula (IV).

[0082] In this disclosure, R7 is selected from substituted or unsubstituted arylene or substituted or unsubstituted heteroarylene, and the R7 group shares two carbon atoms with the group on either side of the R7 group. For example, when R7 is phenyl, the repeating unit represented by formula (IV) is: [ka] In one embodiment of the present disclosure, the number of repeating units represented by formula (IV) in the polyimide acid may be 5 to 2000, but is not limited thereto. In one embodiment, the number of repeating units represented by formula (IV) in the polyimide acid may be 20 to 2000. In another embodiment, the number of repeating units represented by formula (IV) in the polyimide acid may be 100 to 1800. In yet another embodiment, the number of repeating units represented by formula (IV) in the polyimide acid may be 300 to 1500.

[0083] In one embodiment of the present disclosure, the dianhydride includes at least one of pyromellitic dianhydride, 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfone tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl ether dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)benzophenone dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylmethane dianhydride, and 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfone dianhydride. The selection of the dianhydride determines the R7 group.

[0084] In one embodiment of this disclosure, the molar ratio of the first diamine compound to the dianhydride is 0.9 to 1.1. This facilitates the rapid preparation of polyimide acids. In particular, the molar ratio of the first diamine compound to the dianhydride may be, but is not limited to, 0.9, 0.95, 1, 1.05, or 1.1.

[0085] In one embodiment of the present disclosure, the mixed solution further comprises a solvent. The components in the mixed solution are mixed and dispersed in the solvent. In one embodiment of the present disclosure, the solvent may comprise at least one of dimethyl sulfoxide, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, and m-cresol.

[0086] In one embodiment of this disclosure, the reaction temperature is 0°C to 100°C and the reaction time is 2 to 12 hours. In particular, the reaction temperature in the preparation of polyimide acid may be 0°C, 5°C, 10°C, 15°C, 20°C, 25°C, 30°C, 40°C, 45°C, 50°C, 60°C, 70°C, 80°C, 90°C, or 100°C, but is not limited to these, and the reaction time may be 2 hours, 3 hours, 5 hours, 6 hours, 8 hours, 9 hours, or 12 hours, but is not limited to these. In one embodiment, the reaction temperature is 45°C to 60°C and the reaction time is 7 to 12 hours. In another embodiment, the reaction temperature is 60°C to 100°C and the reaction time is 2 to 7 hours. In yet another embodiment, the reaction temperature is 0°C to 50°C and the reaction time is 3 to 7 hours.

[0087] In one embodiment of the present disclosure, the mixed solution further comprises a second diamine compound. The addition of the second diamine compound improves the film-forming performance of the polyimide acid and polyimide. In one embodiment of the present disclosure, the second diamine compound comprises at least one of 4,4'-diaminodiphenyl ether, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenyl sulfone, 1,3-diamino-2-methylpropane, N,N-bis(4-aminophenyl)-1,4-phenylenediamine, 9,9-bis(4-aminophenyl)fluorene, 1,2-diaminocyclohexane, and ethylenediamine. The second diamine compound has rotational properties, such as sp3 hybrid oxygen, to improve the film-forming performance of the polyimide acid. In one embodiment, the content of the second diamine compound in the mixed solution is less than the content of the first diamine compound. In a particular embodiment, the mixed solution contains a second diamine compound, which ensures the film-forming performance of the polyimide film in the subsequent preparation of the polyimide film.

[0088] In one embodiment of the present disclosure, when the mixed solution contains a second diamine compound, the polyimide acid has a chemical structure represented by formula (V). [ka] (In the formula, R8 is selected from substituted or unsubstituted alkylene, substituted or unsubstituted arylene, or substituted or unsubstituted heteroarylene). The selection of the second diamine compound determines the R8 group.

[0089] In one embodiment of this disclosure, n may be 5 to 2000. In one embodiment, n is 20 to 2000. In another embodiment, n is 20 to 2000. In another embodiment, n is 100 to 1800. In another embodiment, n is 300 to 1500. In another embodiment, n is 500 to 1000. In another embodiment, n is 1000 to 1500.

[0090] In one embodiment of this disclosure, m is 1000 or less. In one embodiment, m is 0 to 1000. That is, the mixed solution does not contain the second diamine compound, and m is 0. In another embodiment, m is 10 to 900. In another embodiment, m is 100 to 850. In another embodiment, m is 200 to 700. In another embodiment, m is 200 to 500. In another embodiment, m is 500 to 800.

[0091] This disclosure provides polyimide acids, which include repeating units represented by formula (IV). [ka] (wherein R1 and R2 are independently selected from single-bonded, substituted or unsubstituted alkylene, substituted or unsubstituted alkenylene, substituted or unsubstituted alkylene, substituted or unsubstituted alkynylene, substituted or unsubstituted arylene, substituted or unsubstituted arylenealkyl, substituted or unsubstituted heteroarylene, substituted or unsubstituted heteroarylenealkyl, or substituted or unsubstituted alisylidene, and R7 is selected from substituted or unsubstituted arylene or substituted or unsubstituted heteroarylene). The polyimide acids provided in this disclosure have a 1,10-phenanthrolinyl group, which can form a chemical bond with a metal component to improve adhesion to the metal component, thus facilitating the preparation of the polyimide and improving the bonding strength between the polyimide and the metal component. In this disclosure, the polyimide acid may be prepared according to any embodiment of the method for preparing the polyimide acid.

[0092] This disclosure provides a method for preparing polyimides. The method comprises the following steps: A polyimide acid according to any one of the above embodiments is imidized to obtain a polyimide. The polyimide comprises repeating units represented by formula (VI). [ka] (In the formula, R1, R2, and R7 are the same as those in polyimide acids.)

[0093] The method for preparing polyimides provided in this disclosure is simple and convenient to operate, thereby enabling large-scale production of polyimides. The prepared polyimides have 1,10-phenanthrolinyl groups, which can form chemical bonds with metal components to improve the adhesion of the polyimides to metal components, and thus promote the use of polyimides.

[0094] In this disclosure, imidation may be performed by heat treatment, but is not limited thereto. The polyimide acid is converted to polyimide after heat treatment. In one embodiment of this disclosure, when the second diamine compound is used in the process of preparing the polyimide acid, the polyimide has a chemical structure represented by formula (VII). [ka] (In the formula, R8 is the same as in polyimide acid.)

[0095] If the second diamine compound is not used in the preparation process of the polyimide acid, then m is 0 in the chemical structure of the polyimide represented by formula (VII).

[0096] This disclosure provides polyimides, which include repeating units represented by formula (VI). [ka] (wherein R1 and R2 are independently selected from single-bonded, substituted or unsubstituted alkylene, substituted or unsubstituted alkenylene, substituted or unsubstituted alkylene, substituted or unsubstituted alkynylene, substituted or unsubstituted arylenealkyl, substituted or unsubstituted heteroarylene, substituted or unsubstituted heteroarylenealkyl, or substituted or unsubstituted alisylidene, and R7 is selected from substituted or unsubstituted arylene or substituted or unsubstituted heteroarylene). The polyimides provided in this disclosure have a 1,10-phenanthrolinyl group, which can form a chemical bond with a metal component to improve the adhesion of the polyimide to the metal component, thus promoting the use of the polyimide. In this disclosure, the polyimide may be prepared according to any embodiment of the method for preparing the polyimide. The polyimides provided in this disclosure have good thermal stability and can still maintain a rigid structure at high temperatures, which is beneficial for their use. In one embodiment, the polyimide can still maintain good stability at temperatures above 500°C.

[0097] Figure 1 schematically shows the bonding of a polyimide provided in one embodiment of the present disclosure to a metal atom, where m is the metal element and the dotted line represents the coordination bond formed between the polyimide and the metal. The polyimide provided in the present disclosure can form a coordination compound having a five-membered ring with the metal element, thereby increasing the bonding force between the polyimide film and the metal surface when the polyimide is used. In particular, the metal element may be, but is not limited to, aluminum, copper, iron, zinc, titanium, etc.

[0098] This disclosure provides a method for preparing a polyimide film, further comprising the following steps: a polyimide acid is coated and then imidized to obtain a polyimide film. In one embodiment, the imidization includes a heat treatment at 80°C to 400°C for 1 to 10 hours. In particular, the imidization temperature may be, but is not limited to, 120°C, 150°C, 180°C, 200°C, 230°C, 250°C, 290°C, 310°C, or 370°C. The imidization time may be, but is not limited to, 1 hour, 3 hours, 7 hours, 9 hours, or 10 hours. In another embodiment, the imidization includes a heat treatment at 80°C to 200°C for 1 to 6 hours, followed by heating to 200°C to 400°C, and a heat treatment for 1 to 4 hours. Heat treatment at high temperatures can improve the imidization efficiency. Furthermore, the heating rate may be 1°C / min to 7°C / min. In particular, the heating rate may be, but is not limited to, 2°C / min, 3°C / min, 4°C / min, 5°C / min, or 6°C / min. In one particular embodiment, the imidation includes a heat treatment at 120°C for 1 hour, followed by heating to 250°C for 1 hour, and heating to 350°C for 1 hour, with a heating rate of 2°C / min. In another particular embodiment, the imidation includes a heat treatment at 80°C for 2 hours, followed by heating to 120°C for 1 hour, heating to 160°C for 1 hour, heating to 180°C for 1 hour, heating to 240°C for 1 hour, heating to 280°C for 1 hour, and heating to 350°C for 1 hour, with a heating rate of 2°C / min.

[0099] In this disclosure, the inventors have found through research that when R1 and R2 in formula (I) are independently selected from single-bonded, substituted or unsubstituted arylene, substituted or unsubstituted heteroarylene, or substituted or unsubstituted alicylidene, the film-forming performance of the polyimide acid and polyimide is reduced if a second diamine compound is not added during the preparation of the polyimide acid and polyimide. Therefore, when R1 and R2 are independently selected from single-bonded, substituted or unsubstituted arylene, substituted or unsubstituted heteroarylene, or substituted or unsubstituted alicylidene, the film-forming performance of the polyimide acid and polyimide can be increased by adding a second diamine compound. In one embodiment, when the polyimide acid or polyimide is prepared using one of the compounds represented by formulas (I-1) to (I-4), a second diamine compound may be added to improve the film-forming performance of the polyimide acid or polyimide.

[0100] This disclosure provides a battery assembly comprising a polyimide film, wherein the polyimide film is made of polyimide according to any one of the embodiments described above. Figure 2 is a schematic cross-sectional view of a battery assembly provided in one embodiment of this disclosure. The battery assembly 10 includes a heat dissipation component 13, a polyimide film 12 disposed on the surface of the heat dissipation component 13, and a battery core 11 disposed on the surface of the polyimide film 12. In the related art, since the battery core 11 generates heat during use, the heat dissipation component 13 needs to be positioned to transfer the heat generated by the battery core 11, thereby lowering the temperature of the battery core 11 and ensuring the lifespan and safety of the battery core 11 during use. When the heat dissipation component 13 is positioned on the surface of the battery core 11, it is necessary to connect the heat dissipation component 13 and the battery core 11, ensuring a bonding force between them and ensuring that relative movement does not occur during use. When a connecting structure is used, the weight of the battery assembly 10 is excessively increased, and the connecting structure may also damage the surface of the heat dissipation component 13, thus reducing safety during use. In the battery assembly 10 provided in this disclosure, the battery core 11 and the heat dissipation component 13 are connected by a polyimide film 12. Because the polyimide used in the polyimide film 12 has a 1,10-phenanthrolinyl group, the bonding force between the polyimide film 12 and the heat dissipation component 13 is increased so that the polyimide film 12 used for insulation does not detach during use, thereby improving the safety and lifespan of the battery assembly 10. Furthermore, in related technologies, with increasing energy density of the battery core 11, insulation treatment between the battery core 11 and the heat dissipation component 13 is required to ensure the safety of the battery assembly 10. With the application and development of cell-to-body (CTB) technology for the battery core 11, the battery assembly 10 is located below the vehicle seat and needs to support the weight of passengers, raising the demands for higher safety of the battery assembly 10. The polyimide film 12 made from the polyimide provided in this disclosure is insulating and further improves the safety of the battery assembly 10 in use.

[0101] In one embodiment of this disclosure, the surface of the heat dissipation component 13 is made of a metallic material. This facilitates the formation of chemical bonds between the polyimide film 12 and the surface of the heat dissipation component 13, improving the bonding strength. In particular, the metallic material may be, but is not limited to, at least one of aluminum, copper, aluminum alloys, and copper alloys, or stainless steel. In this disclosure, the heat dissipation component 13 may be, but is not limited to, a liquid cooling plate. Figure 3 is a schematic diagram showing the bonding of the polyimide film 12 to the heat dissipation component 13 provided in one embodiment of this disclosure, where the surface of the heat dissipation component 13 is made of a metallic material, M is a metallic element, and the dotted lines represent coordination bonds formed between the polyimide of the polyimide film 12 and the metallic element of the heat dissipation component 13. In one embodiment of this disclosure, the surface of the battery core 11 is made of a metallic material. Chemical bonds are formed between the polyimide film 12 and the surface of the battery core 11, which improves the bonding strength. In particular, the metallic material may be, but is not limited to, at least one of aluminum, copper, aluminum alloys, and copper alloys, or stainless steel.

[0102] This disclosure provides an electronic device comprising a battery assembly 10 according to any one of the embodiments described above. The electronic device may be, but is not limited to, a vehicle, a mobile phone, a server, and a computer. The battery assembly 10 of the electronic device provided in this disclosure has high safety and therefore facilitates the use of the electronic device.

[0103] The technical solutions of this disclosure are further illustrated by specific examples and comparative examples. [Examples]

[0104] The diamine compound was prepared by the following method.

[0105] Under a nitrogen atmosphere, cuprous oxide (catalyst), brominated 1,10-phenanthroline, 28% concentrated aqueous ammonia, potassium carbonate (alkaline substance), and N,N'-dimethylethylenediamine (catalyst ligand) (molar ratio 0.1:1:50:0.5:0.5) were dissolved in ethylene glycol and stirred at 180°C for 72 hours. After the reaction, the solution was cooled to room temperature, extracted with ethyl acetate, and purified by column chromatography to obtain the diamine compound of formula (I-1). [Examples]

[0106] The diamine compound was prepared by the following method.

[0107] Under a nitrogen atmosphere, palladium acetate (catalyst), triphenylphosphine (catalytic ligand), brominated 1,10-phenanthroline, aminophenylboron hydrochloride, and sodium hydroxide (alkaline substance) (molar ratio 0.02:0.05:1:2.1:8) were dissolved in 1,4-dioxane and stirred at 100°C for 18 hours. After the reaction, the solution was cooled to room temperature, filtered, and purified by column chromatography to obtain the diamine compound of formula (I-2). [Examples]

[0108] The diamine compound was prepared by the following method.

[0109] Under a nitrogen atmosphere, bis(3,5,3',5'-dimethoxydibenzylideneacetone)palladium (catalyst), triphenylphosphine (catalyst ligand), brominated 1,10-phenanthroline, aminophenylboron hydrochloride, and potassium carbonate (alkaline substance) (molar ratio 0.01:0.02:1:2.1:8) were dissolved in 1,4-dioxane and water (volume ratio 5:1) and stirred at 100°C for 18 hours. After the reaction, the solution was cooled to room temperature, filtered, and purified by column chromatography to obtain the diamine compound of formula (I-3). [Examples]

[0110] The diamine compound was prepared by the following method.

[0111] Under a nitrogen atmosphere, palladium acetate (catalyst), triphenylphosphine (catalytic ligand), brominated 1,10-phenanthroline, 4-(aminomethyl)phenyl)boric acid, and potassium carbonate (alkaline substance) (molar ratio 0.01:0.02:1:2.1:8) were dissolved in 1,4-dioxane and stirred at 100°C for 12 hours. After the reaction, the solution was cooled to room temperature, filtered, and purified by column chromatography to obtain the diamine compound of formula (I-4). [Examples]

[0112] Polyimide acid was prepared by the following method.

[0113] 10.5 g of the diamine compound prepared in Example 1, 10 g of 4,4'-diaminodiphenyl ether, and 160 g of N,N-dimethylformamide were sequentially added to the reactor, stirred, and the temperature was adjusted to 60°C. 21.8 g of pyromellitic anhydride was slowly added to the reactor, stirred for 6 hours, and then cooled to room temperature to obtain polyimide acid. [Examples]

[0114] Polyimide acid was prepared by the following method.

[0115] 18.1 g of the diamine compound prepared in Example 2, 10 g of 4,4'-diaminodiphenyl ether, and 180 g of N,N-dimethylformamide were sequentially added to the reactor and stirred, and the temperature was adjusted to 60°C. 21.8 g of pyromellitic anhydride was slowly added to the reactor and stirred for 12 hours, then cooled to room temperature to obtain polyimide acid. [Examples]

[0116] Polyimide acid was prepared by the following method.

[0117] 18.1 g of the diamine compound prepared in Example 3, 10 g of 4,4'-diaminodiphenyl ether, and 160 g of N,N-dimethylformamide were sequentially added to the reactor and stirred, and the temperature was adjusted to 45°C. 21.8 g of pyromellitic anhydride was slowly added to the reactor and stirred for 4 hours, then cooled to room temperature to obtain polyimide acid. [Examples]

[0118] Polyimide acid was prepared by the following method.

[0119] 39 g of the diamine compound prepared in Example 4 and 160 g of N,N-dimethylformamide were sequentially added to the reactor, stirred, and the temperature was adjusted to 0°C. 21.8 g of pyromellitic anhydride was slowly added to the reactor, stirred for 6 hours, and then cooled to room temperature to obtain polyimide acid.

[0120] (Comparative Example 1) Polyimide acid was prepared by the following method.

[0121] 20 g of 4,4'-diaminodiphenyl ether and 160 g of N,N-dimethylformamide were sequentially added to the reactor, stirred, and the temperature was adjusted to 45°C. 21.8 g of pyromellitic anhydride was slowly added to the reactor, stirred for 4 hours, and then cooled to room temperature to obtain polyimide acid.

[0122] Performance testing The structures of the diamine compounds obtained in Examples 1-4 were characterized by nuclear magnetic resonance spectroscopy. The 1H NMR results are as follows.

[0123] Equation (I-1): ¹H NMR (500 MHz, chloroform-d) δ 8.44 (d, ¹H), 7.49 (m, ²H), 4.51 (d, ¹H), 4.40 (d, ¹H); Formula (I-2): ¹H NMR (500MHz, Chroroholm-d) δ 8.88 (d, 2H), 8.38 (m, 2H), 7.87 (t, 2H), 7.63-7.57 (m, 2H), 6.67-6.1 (m, 2H), 4.20 (d, 1H), 4.13 (d, 1H); Equation (I-3): ¹H NMR (500MHz, Chroroholm-d) δ 8.89 (d, 2H), 8.46 (m, 2¹H), 7.87 (t, 2H), 7.29 (m, 2H), 7.28 (m, 2H), 6.98 (t, 2H), 6.68-6.62 (m, 2H), 4.38 (d, 2H), 4.29 (d, 2H); および Equation (I-4): 1H NMR (500MHz, Chroroholm-d) δ 8.95 (d, J=2.0Hz, 1H), 8.61 (q, J=1.4Hz, 1H), 7.87 (t, J=1.3Hz, 1H), 7.68-7.63 (m, 2H), 7.30 (dt, J=8.0, 1.1Hz, 2H), 4.05 (tt, J=6.2, 1.0Hz, 2H), 2.52 (dt, J=7.1, 6.2Hz, 1H), 2.36 (dt, J=7.0, 6.2Hz, 1H).

[0124] The polyimide acids prepared in Examples 5-8 and Comparative Example 1 were coated and cast onto the surface of aluminum plates, respectively, to prepare wet films of the corresponding solutions. The wet films were moved to an oven and imidization was carried out by heating according to the following heating procedure: 80°C / 2 hours, 120°C / 1 hour, 160°C / 1 hour, 180°C / 1 hour, 240°C / 1 hour, 280°C / 1 hour, and 350°C / 1 hour, with a heating rate of 2°C / min. Polyimide films were obtained formed on the surface of the aluminum plates. The bonding strength between the polyimide film and the aluminum plate was tested according to the ASTM D3359 Method B cross-cut tape test, and the bonding strength was obtained as shown in Table 1. Furthermore, the decomposition temperature of the formed polyimide film, 5% weight loss, was detected according to GB / T13464-2008. The results are shown in Table 1. The polyimide acids prepared in Examples 5-8 and Comparative Example 1 were coated and cast onto the surface of a glass plate, respectively, to prepare wet films of the corresponding solutions. The wet films were moved to an oven and imidization was carried out according to the same heating procedure as above. Polyimide films were obtained formed on the surface of the glass plate. After the glass plate cooled to room temperature, it was immersed in deionized water, and the polyimide film was peeled off to obtain the corresponding self-supporting polyimide film. Film formation performance was specifically evaluated as follows: If the film is formed on the glass as a single, cohesive piece of film material, and the film surface remains undamaged and intact after peeling, the film formation performance is considered very good. If the film is formed on the glass as a single, cohesive piece of film material, and the film surface remains undamaged but not intact after peeling, the film formation performance is considered normal. If the film is broken into pieces on the glass, the film formation performance is considered poor. Table 1 shows that, compared to Comparative Example 1, the polyimide film provided in this disclosure exhibits a higher decomposition temperature at 5% weight loss and thus much better thermal stability.Compared to Example 7, the diamine compound used in Example 6 and the amino group in the prepared polyimide are located on the axis of rotation of the phenyl ring, which improves linearity and further enhances thermal stability. The 1,10-phenanthrolinyl group in the polyimide film can form a coordination bond with aluminum, thus increasing the bonding strength between the polyimide film and the aluminum plate, and thus facilitating the use of polyimide. [Table 1]

[0125] The diamine compounds, polyimide acids, and polyimides provided in this disclosure have a 1,10-phenanthrolinyl group, which can form a chemical bond with a metal component to improve the bonding strength with the metal component, and thus facilitate their use in electronic devices.

[0126] The embodiments described above are only a few examples of the present application, and although they are described in detail, they are not intended to limit the scope of the disclosure. Several modifications and improvements can be made by those skilled in the art without departing from the ideas of the disclosure, and it will be understood by those skilled in the art that all such modifications and improvements are intended to be within the scope of the disclosure. Accordingly, the scope of the disclosure is defined by the appended claims. [Explanation of Symbols]

[0127] 10 Battery Assembly 11 Battery core 12 Polyimide film 13 Heat dissipation components

Claims

1. A diamine compound having the chemical structure represented by formula (I-3). 【Chemistry 1】

2. Formula (I-4): 【Chemistry 2】 A diamine compound having the chemical structural formula represented by the formula shown.

3. A method for preparing a diamine compound, Prepare a first reactant having the chemical structure represented by formula (II). 【Transformation 3】 (In the formula, R ３ and R ４ (These atoms are independently selected from chlorine, bromine, iodine, or astatine atoms.) 【Chemistry 4】 Prepare a second reactant having the chemical structural formula represented by , The first reactant and the second reactant are mixed under basic conditions to form a reaction solution, which is then reacted to obtain a diamine compound having the chemical structure represented by formula (I-3). 【Transformation 5】 A method for providing this.

4. A method for preparing a diamine compound, Prepare a first reactant having the chemical structure represented by formula (II). 【Transformation 6】 (In the formula, R3 and R4 are independently selected from a chlorine atom, a bromine atom, an iodine atom, or an astatine atom.) 【Transformation 7】 Prepare a second reactant having the chemical structural formula represented by , The first reactant and the second reactant are mixed under basic conditions to form a reaction solution, which is then reacted to obtain a diamine compound having the chemical structure represented by formula (I-4). 【Transformation 8】 A method for providing this.

5. The reaction solution further comprises a catalyst and a catalytic ligand. The catalyst comprises a copper-based catalyst and a palladium-based catalyst, the copper-based catalyst comprises cuprous oxide, and the palladium-based catalyst comprises at least one of bis(3,5,3',5'-dimethoxydibenzylideneacetone)palladium, bis(tri-tert-butyl)palladium, tris(dibenzylideneacetone)palladium, palladium chloride, palladium acetate, tetrakis(triphenylphosphine)palladium, and bis(tri-tert-butylphosphine)palladium. The catalyst ligand comprises at least one of N,N'-dimethylethylenediamine, triphenylphosphine, 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl, 4,5-bis(diphenylphosphine)-9,9-dimethylxanthene, triphenylphosphine oxide, and tris(o-methylphenyl)phosphine. The molar ratio of the first reactant, the second reactant, the catalyst, and the catalyst ligand is 1:(2-50):(0.005-0.2):(0.005-0.5), The reaction solution further comprises an alkaline substance, the alkaline substance comprising at least one of potassium carbonate, sodium carbonate, cesium fluoride, sodium hydroxide, potassium hydroxide, and barium hydroxide. The molar ratio of the first reactant, the second reactant, and the alkaline substance is 1:(2-50):(0.05-10). The reaction temperature is between 25°C and 180°C, and the reaction time is between 2 hours and 72 hours. The preparation method according to claim 3 or 4.

6. The preparation method according to claim 3 or 4, wherein the reaction solution further comprises a solvent, the solvent comprising water, ethylene glycol, and 1,4-dioxane, and the volume ratio of 1,4-dioxane to water is 2 to 10.

7. The preparation method according to claim 3 or 4, wherein the reaction is carried out under an inert atmosphere.

8. Polyimide acid having repeating units represented by formula (IV) 【Chemistry 9】 (In the formula, R １ and R ２ R is independently selected from substituted or unsubstituted alkylene, substituted or unsubstituted alkenylene, substituted or unsubstituted alkynylene, substituted or unsubstituted arylenealkyl, substituted or unsubstituted heteroarylene, substituted or unsubstituted heteroarylenealkyl, or substituted or unsubstituted alisylidene, ７ (The element is selected from substituted or unsubstituted arylenes or substituted or unsubstituted heteroarylenes.)

9. The polyimide acid according to claim 8, having a chemical structural formula represented by formula (V). 【Chemistry 10】 (In the formula, R ８ (where n is selected from substituted or unsubstituted alkylenes, substituted or unsubstituted arylenes, or substituted or unsubstituted heteroarylenes, with n being 5 to 2000 and m being 0 to 1000).

10. A method for preparing polyimide acid, comprising mixing a first diamine compound and a dianhydride to form a mixed solution and reacting them to obtain polyimide acid, wherein the first diamine compound is the diamine compound described in claim 1 or 2, or a diamine compound prepared by the preparation method described in claim 3 or 4, and comprises a repeating unit represented by formula (IV). 【Chemistry 11】 (wherein, R １ and R ２ are each independently selected from substituted or unsubstituted alkylene, substituted or unsubstituted alkenylene, substituted or unsubstituted alkynylene, substituted or unsubstituted arylenealkyl, substituted or unsubstituted heteroarylene, substituted or unsubstituted heteroarylenealkyl, or substituted or unsubstituted alicyclidene, and R ７ is selected from substituted or unsubstituted arylene or substituted or unsubstituted heteroarylene).

11. The molar ratio of the first diamine compound to the dianhydride is 0.9 to 1.

1. The dianhydride comprises at least one of pyromellitic acid dianhydride, 2,3,3',4'-diphenyl ether tetracarboxylic acid dianhydride, 3,3',4,4'-benzophenone tetracarboxylic acid dianhydride, 3,3',4,4'-diphenyl sulfone tetracarboxylic acid dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl ether dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)benzophenone dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylmethane dianhydride, and 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfone dianhydride. The mixed solution further comprises a second diamine compound, the second diamine compound comprising at least one of 4,4'-diaminodiphenyl ether, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenyl sulfone, 1,3-diamino-2-methylpropane, N,N-bis(4-aminophenyl)-1,4-phenylenediamine, 9,9-bis(4-aminophenyl)fluorene, 1,2-diaminocyclohexane, and ethylenediamine. The mixed solution further comprises a solvent, the solvent comprising at least one of dimethyl sulfoxide, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, and m-cresol. The preparation method according to claim 10, wherein the reaction temperature is 0°C to 100°C and the time is 2 hours to 12 hours.

12. Polyimide having repeating units represented by formula (VI) 【Chemistry 12】 (In the formula, R １ and R ２ R is independently selected from substituted or unsubstituted alkylene, substituted or unsubstituted alkenylene, substituted or unsubstituted alkynylene, substituted or unsubstituted arylenealkyl, substituted or unsubstituted heteroarylene, substituted or unsubstituted heteroarylenealkyl, or substituted or unsubstituted alisylidene, ７ (The element is selected from substituted or unsubstituted arylenes or substituted or unsubstituted heteroarylenes.)

13. The polyimide according to claim 12, having a chemical structural formula represented by formula (VII). 【Chemistry 13】 (In the formula, R ８ (where n is selected from substituted or unsubstituted alkylenes, substituted or unsubstituted arylenes, or substituted or unsubstituted heteroarylenes, with n being 5 to 2000 and m being 0 to 1000).

14. A method for preparing polyimide, comprising imidizing a polyimide acid according to claim 8 to obtain a polyimide, wherein the polyimide comprises repeating units represented by formula (VI). 【Chemistry 14】 (In the formula, R １ and R ２ R is independently selected from substituted or unsubstituted alkylene, substituted or unsubstituted alkenylene, substituted or unsubstituted alkynylene, substituted or unsubstituted arylenealkyl, substituted or unsubstituted heteroarylene, substituted or unsubstituted heteroarylenealkyl, or substituted or unsubstituted alisylidene, ７ (The element is selected from substituted or unsubstituted arylenes or substituted or unsubstituted heteroarylenes.)

15. A battery assembly (10) comprising a heat dissipation component (13), a polyimide film (12) disposed on the surface of the heat dissipation component (13), and a battery core (11) disposed on the surface of the polyimide film (12), wherein the polyimide film (12) is made of the polyimide described in claim 12 or 13, or a polyimide prepared by the preparation method described in claim 14.

16. The battery assembly (10) according to claim 15, wherein the surface of the heat dissipation component (13) is made of a metal material, and the surface of the battery core (11) is made of a metal material.

17. An electronic device comprising the battery assembly (10) according to claim 15.

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