Diamine compounds, polyimide acid, polyimides, and methods of making and using the same

Abstract

The application provides a diamine compound, a polyimide acid, a polyimide and a preparation method and application thereof, a chemical structural formula of the diamine compound is shown as formula (I), wherein R1 and R2 are independently selected from a single bond, a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, a substituted or unsubstituted alkynylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted aralkylene group, a substituted or unsubstituted heteroarylene group, a substituted or unsubstituted heteroaralkylene group or a substituted or unsubstituted cycloalkylene group. The diamine compound contains a 1,10-phenanthroline group, can be used as a raw material for preparing a polyimide, and improves the binding performance of the polyimide.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of materials, in particular to a diamine compound, a polyimide acid, a polyimide and a preparation method and application thereof. BACKGROUND

[0002] With the continuous development of electronic equipment, polyimide film with various advantages has become the focus of manufacturers. However, the adhesion between the polyimide and the metal part is not good, which limits the use and development of the polyimide. Therefore, it is necessary to improve the performance of the polyimide. SUMMARY

[0003] Therefore, the present application provides a diamine compound, a polyimide acid, a polyimide and a preparation method and application thereof. The diamine compound, the polyimide acid and the polyimide have a 1,10-orthophenanthroline group, which can be coordinated with metal to form a strong coordination bond, thereby improving the adhesion between the polyimide and the metal part, and being conducive to the use of the polyimide.

[0004] In a first aspect, the present application provides a diamine compound, the chemical structural formula of the diamine compound is shown as formula (I),

[0005]

[0006] wherein R1, R2 are independently selected from a single bond, a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, a substituted or unsubstituted alkynylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted aralkylene group, a substituted or unsubstituted heteroarylene group, a substituted or unsubstituted heteroaralkylene group, or a substituted or unsubstituted cycloalkylene group.

[0007] The diamine compound provided by the present application contains a 1,10-orthophenanthroline group. The diamine compound can be used as a raw material for preparing a polyimide, so that the polyimide has a 1,10-orthophenanthroline group, and the adhesion between the polyimide and the metal part is ensured.

[0008] Optionally, the substituted or unsubstituted alkylene group is a substituted or unsubstituted C1-C8 alkylene group.

[0009] Optionally, the substituted or unsubstituted alkenylene group is a substituted or unsubstituted C2-C8 alkenylene group.

[0010] Optionally, the substituted or unsubstituted alkynylene group is a substituted or unsubstituted C2-C8 alkynylene group.

[0011] Optionally, the substituted or unsubstituted arylene group is a substituted or unsubstituted C6-C 30 ylene group.

[0012] Optionally, the substituted or unsubstituted aralkyl is a substituted or unsubstituted C7-C 40 aralkyl.

[0013] Optionally, the substituted or unsubstituted heteroaralkyl is a substituted or unsubstituted C2-C 30 heteroaralkyl.

[0014] Optionally, the substituted or unsubstituted aralkyl is a substituted or unsubstituted C7-C 40 heteroaralkyl.

[0015] Optionally, the substituted or unsubstituted cycloalkyl is a substituted or unsubstituted C3-C 30 cycloalkyl.

[0016] Optionally, the R1, the R2are independently selected from a single bond, a substituted or unsubstituted C6-C 30 aralkyl. 40 aralkyl.

[0017] Further, the diamine compound includes one of the compounds shown in the formula (I-1) to formula (I-4),

[0018]

[0019] In a second aspect, the present application provides a preparation method of a diamine compound, comprising:

[0020] providing a first reactant, the chemical structural formula of the first reactant is shown in formula (II), wherein R3, R4are independently selected from a chlorine atom, a bromine atom, an iodine atom or a stibine atom,

[0021]

[0022] providing a second reactant, the chemical structural formula of the second reactant is shown in formula (III), wherein R5is selected from hydrogen, a boronic acid or a boronic ester substituted alkyl, a boronic acid or a boronic ester substituted alkenyl, a boronic acid or a boronic ester substituted alkynyl, a boronic acid or a boronic ester substituted aryl, a boronic acid or a boronic ester substituted aralkyl, a boronic acid or a boronic ester substituted heteroaryl, a boronic acid or a boronic ester substituted heteroaralkyl, or a boronic acid or a boronic ester substituted cycloalkyl,

[0023] H2N-R5 (III);

[0024] mixing the first reactant and the second reactant under alkaline conditions to form a reaction solution, and reacting to obtain a diamine compound, wherein the diamine compound has a chemical structure as shown in formula (I), wherein R1 and R2 are independently selected from a single bond, a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, a substituted or unsubstituted alkynylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted aralkylene group, a substituted or unsubstituted heteroarylene group, a substituted or unsubstituted heteroaralkylene group, or a substituted or unsubstituted cycloalkylene group,

[0025]

[0026] The method for preparing the diamine compound in the present application is simple, convenient to operate, and can realize large-scale production of the diamine compound, which is beneficial to the generation and use of polyimide.

[0027] Optionally, the reaction solution further comprises a catalyst and a catalyst ligand.

[0028] Further, 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.

[0029] Further, the catalyst ligand comprises at least one of N,N'-dimethylethylenediamine, triphenylphosphine, 2-dicyclohexylphospho-2',4',6'-triisopropylbiphenyl, 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene, triphenylphosphine oxide, and tri(o-methylphenyl)phosphine.

[0030] Optionally, 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).

[0031] Optionally, the reaction solution further comprises an alkaline substance, and the alkaline substance comprises at least one of potassium carbonate, sodium carbonate, cesium fluoride, sodium hydroxide, potassium hydroxide, and barium hydroxide.

[0032] Further, the molar ratio of the first reactant, the second reactant, and the alkaline substance is 1:(2-50):(0.05-10).

[0033] Optionally, the reaction temperature is 25°C-180°C, and the reaction time is 2h-72h.

[0034] In a third aspect, the present application provides a polyimide acid, wherein the polyimide acid comprises a repeating unit as shown in formula (IV).

[0035]

[0036] wherein R1, 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 aralkylene, substituted or unsubstituted heteroarylene, substituted or unsubstituted heteroaralkylene, or substituted or unsubstituted cycloalkylene, and R7 is selected from substituted or unsubstituted arylene, or substituted or unsubstituted heteroarylene.

[0037] The polyimide acid provided by the application has a 1,10-phenanthroline group, which can form a chemical bond with a metal piece, thereby improving the adhesion between the polyimide acid and the metal piece, facilitating the preparation of the polyimide acid, and helping to improve the bonding force between the polyimide acid and the metal piece.

[0038] Optionally, the chemical structural formula of the polyimide acid is shown as formula (V),

[0039]

[0040] wherein R8 is selected from substituted or unsubstituted alkylene, substituted or unsubstituted arylene, or substituted or unsubstituted heteroarylene, n is 5-2000, and m is 0-1000.

[0041] In a fourth aspect, the application provides a preparation method of a polyimide acid, comprising mixing a diamine compound in the first aspect or a diamine compound prepared by the preparation method in the second aspect with a dianhydride to form a mixed solution, and obtaining the polyimide acid after reaction, wherein the polyimide acid comprises a repeating unit shown as formula (IV), wherein R1, 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 aralkylene, substituted or unsubstituted heteroarylene, substituted or unsubstituted heteroaralkylene, or substituted or unsubstituted cycloalkylene, and R7 is selected from substituted or unsubstituted arylene, or substituted or unsubstituted heteroarylene,

[0042]

[0043] The preparation method of the polyimide acid provided by the application is simple, convenient to operate, and can realize large-scale production of the polyimide acid, thereby facilitating the preparation of the polyimide.

[0044] Optionally, the molar ratio of the diamine compound to the dianhydride is 0.9-1.1.

[0045] Optionally, the dianhydride comprises at least one of pyromellitic dianhydride, 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-tetracarboxybenzophenone dianhydride, 3,3',4,4'-tetracarboxybiphenyl sulfone 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.

[0046] Optionally, the second diamine 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.

[0047] Optionally, the solvent comprises at least one of dimethyl sulfoxide, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, and m-cresol.

[0048] Optionally, the reaction is performed at a temperature of 0℃-100℃ for 2h-12h.

[0049] In a fifth aspect, the present application provides a polyimide comprising a repeating unit represented by formula (VI),

[0050]

[0051] wherein R1, 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 aralkylene, substituted or unsubstituted heteroarylene, substituted or unsubstituted heteroaralkylene, or substituted or unsubstituted cycloalkylene, and R7 is selected from substituted or unsubstituted arylene, or substituted or unsubstituted heteroarylene.

[0052] The polyimide provided by the present application contains 1,10-phenanthroline groups, which can form chemical bonds with metal parts, thereby improving the adhesion between the polyimide and the metal parts, and facilitating the use of the polyimide.

[0053] Optionally, the chemical structure of the polyimide is represented by formula (VII),

[0054]

[0055] wherein R8 is selected from substituted or unsubstituted alkylene, substituted or unsubstituted arylene, or substituted or unsubstituted heteroarylene, n is 5-2000, and m is 0-1000.

[0056] In a sixth aspect, the present application provides a method for preparing a polyimide, comprising imidizing the polyimide acid described in the third aspect or the polyimide acid described in the fourth aspect to obtain a polyimide, wherein the polyimide comprises a repeating unit represented by formula (VI), wherein R1 and R2 are independently selected from a single bond, a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, a substituted or unsubstituted alkynylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted arylene alkyl group, a substituted or unsubstituted heteroarylene group, a substituted or unsubstituted heteroarylene alkyl group, or a substituted or unsubstituted alicyclic group, and R7 is selected from a substituted or unsubstituted arylene group, or a substituted or unsubstituted heteroarylene group.

[0057]

[0058] The preparation method of the polyimide provided in the present application is simple and easy to operate, can realize large-scale production of polyimide, and can produce polyimide with strong bonding strength with metal parts, which is beneficial to the use of polyimide.

[0059] In the seventh aspect, the present application provides a battery module, including a heat dissipation component, a polyimide film arranged on the surface of the heat dissipation component, and a battery cell arranged on the surface of the polyimide film, wherein the material of the polyimide film includes the polyimide described in the fifth aspect or the polyimide obtained by the preparation method described in the sixth aspect.

[0060] In the battery module provided in the present application, the heat dissipation component and the battery cell are connected together by a polyimide film. The polyimide film improves the bonding strength with the heat dissipation component. At the same time, polyimide has insulating properties, further ensuring the safety of the battery module.

[0061] In an eighth aspect, the present application provides an electronic device comprising the battery module described in the seventh aspect.

[0062] The battery module in the electronic device provided in this application is safer and is beneficial to the use of the electronic device. BRIEF DESCRIPTION OF THE DRAWINGS

[0063] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for the embodiments or the description of the prior art. The specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.

[0064] Figure 1 A schematic diagram of the bonding between polyimide and metal provided in one embodiment of the present application.

[0065] Figure 2 A cross-sectional view of a battery module according to an embodiment of the present application.

[0066] Figure 3 A schematic view of the combination between a polyimide film and a heat dissipation assembly according to an embodiment of the present application.

[0067] Explanation of reference numerals:

[0068] Battery module-10, battery cell-11, polyimide film-12, heat dissipation assembly-13. DETAILED DESCRIPTION

[0069] The technical solutions in the embodiments of the present application will be described clearly and completely below with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are only some of the embodiments of the present application, but not all the embodiments. Based on the embodiments in the present application, all the other embodiments obtained by those skilled in the art without any creative work fall within the protection scope of the present application.

[0070] The present application provides a diamine compound, and the chemical structural formula of the diamine compound is shown as formula (I),

[0071]

[0072] wherein R1, 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 aralkylene, substituted or unsubstituted heteroarylene, substituted or unsubstituted heteroaralkylene, or substituted or unsubstituted cycloalkylene. The diamine compound provided by the present application contains a 1,10-phenanthroline group, and the diamine compound can be used as a raw material for preparing polyimide, so that the prepared polyimide has a 1,10-phenanthroline group, and the bonding force between the polyimide and the metal part is ensured.

[0073] In the present application, R1, R2independently selected from a single bond, substituted or unsubstituted alkylene, substituted or unsubstituted alkenylene, substituted or unsubstituted alkynylene, substituted or unsubstituted arylene, substituted or unsubstituted aralkylene, substituted or unsubstituted heteroarylene, substituted or unsubstituted heteroaralkylene, or substituted or unsubstituted aliphatic ring group means that R1is selected from a single bond, alkylene, substituted alkylene, alkenylene, substituted alkenylene, alkynylene, substituted alkynylene, arylene, substituted arylene, aralkylene, substituted aralkylene, heteroarylene, substituted heteroarylene, heteroaralkylene, substituted heteroaralkylene, aliphatic ring group, or substituted aliphatic ring group, and R2is selected from a single bond, alkylene, substituted alkylene, alkenylene, substituted alkenylene, alkynylene, substituted alkynylene, arylene, substituted arylene, aralkylene, substituted aralkylene, heteroarylene, substituted heteroarylene, heteroaralkylene, substituted heteroaralkylene, aliphatic ring group, or substituted aliphatic ring group.

[0074] In the present application, alkyl is an alkane molecule from which one hydrogen atom is removed, which can include straight-chain alkyl, branched-chain alkyl. Specifically, the alkyl group can include, but is not limited to, at least one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-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 the present embodiment, the substituted or unsubstituted alkyl group can be a substituted or unsubstituted C1-C8 alkyl group; that is, the number of carbon atoms of the alkyl group is 1-8. Specifically, the number of carbon atoms of the alkyl group can be, but is not limited to, 1, 2, 3, 4, 5, 6, 7, or 8.

[0075] In the present application, alkylene is a divalent saturated group formed by removing one hydrogen atom from an alkyl group. Specifically, the alkylene group can include, but is not limited to, at least one of -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2-, and -CH2CH2CH2CH2CH2CH2-. In the present embodiment, the substituted or unsubstituted alkylene group is a substituted or unsubstituted C1-C8 alkylene group; that is, the number of carbon atoms of the alkylene group is 1-8. Specifically, the number of carbon atoms of the alkylene group can be, but is not limited to, 1, 2, 3, 4, 5, 6, 7, or 8.

[0076] In the present application, alkenyl is a divalent unsaturated hydrocarbon chain containing at least one double bond, which can include straight chain alkenyl, branched chain alkenyl. Specifically, alkenyl can 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 the embodiments of the present application, substituted or unsubstituted alkenyl can be substituted or unsubstituted C2-C8 alkenyl; that is, the number of carbon atoms of alkenyl is 2-8. Specifically, the number of carbon atoms of alkenyl can be, but is not limited to, 2, 3, 4, 5, 6, 7, or 8.

[0077] In the present application, alkenylene is a divalent unsaturated group formed by removing one hydrogen atom from alkenyl. Specifically, alkenylene can include, but is not limited to, at least one of -CH=CH-, -CH=CHCH2-, -CH2CH=CH-, -CH=CHCH2CH2-, -CH2CH2CH=CH-, -CH2CH=CHCH2-, -CH=CH-CH=CH-, -CH=CHCH2CH2CH2-, -CH=CH-CH=CH2CH2-, and -CH=CH2CH2CH=CH-. In the embodiments of the present application, substituted or unsubstituted alkenylene is substituted or unsubstituted C2-C8 alkenylene; that is, the number of carbon atoms of alkenylene is 2-8. Specifically, the number of carbon atoms of alkenylene can be, but is not limited to, 2, 3, 4, 5, 6, 7, or 8.

[0078] In the present application, alkynyl is a divalent unsaturated hydrocarbon chain containing at least one triple bond, which can include straight chain alkynyl, branched chain alkynyl. Specifically, alkynyl can include, but is not limited to, at least one of ethynyl, propynyl, butynyl, pentynyl, and hexynyl. In the embodiments of the present application, substituted or unsubstituted alkynyl can be substituted or unsubstituted C2-C8 alkynyl; that is, the number of carbon atoms of alkynyl is 2-8. Specifically, the number of carbon atoms of alkynyl can be, but is not limited to, 2, 3, 4, 5, 6, 7, or 8.

[0079] In the present application, an alkynylene group is a divalent unsaturated group formed by removing a hydrogen atom from an alkynyl group. Specifically, the alkynylene group can include, but is not limited to, at least one of -C≡C-, -C≡CCH2-, -CH2C≡C-, -C≡CCH2CH2-, -CH2C≡CCH2-, -CH2CH2C≡C-, -C≡CC≡C-, -C≡CCH2CH2CH2-, -CH2C≡CCH2CH2-, -CH2CH2C≡CCH2-, -CH2C≡CC≡C-CH2-, -C≡CCH2CH2CH2CH2-, -CH2C≡CCH2CH2-, -CH2C≡CCH2CH2-, -CH2C≡CCH2CH2-, -CH2CH2C≡CCH2CH2-, -CH2CH2C≡CCH2CH2-, -CH2CH2C≡CCH2CH2-, -CH2CH2C≡CCH2CH2-, and -CH2CH2CH2CH2C≡C-. In an embodiment of the present application, the substituted or unsubstituted alkynylene group is a substituted or unsubstituted C2-C8 alkynylene group; that is, the number of carbon atoms in the alkynylene group is 2 to 8. Specifically, the number of carbon atoms in the alkynylene group can be, but is not limited to, 2, 3, 4, 5, 6, 7, or 8.

[0080] In the present application, aryl is an aromatic group. Specifically, aryl may include, but is not limited to, at least one of phenyl, naphthyl, anthracenyl, tetraphenyl, pentacene and tetrahydronaphthyl. In the embodiment of the present application, substituted or unsubstituted aryl is substituted or unsubstituted C6-C 30 that is, the number of carbon atoms in the aryl group is 6 to 30. Specifically, the number of carbon atoms in the aryl group can be, but is not limited to, 6, 10, 12, 14, 18, 22, 24, 26 or 30.

[0081] In the present application, an arylene group is a divalent aromatic group. Specifically, the arylene group may include, but is not limited to, at least one of phenylene, naphthylene, anthracene, tetraphenylene, pentacene and tetrahydronaphthylene. In the embodiment of the present application, the substituted or unsubstituted arylene group is a substituted or unsubstituted C6-C 30 that is, the number of carbon atoms in the arylene group is 6 to 30. Specifically, the number of carbon atoms in the arylene group can be, but is not limited to, 6, 10, 12, 14, 18, 22, 24, 26 or 30.

[0082] In this application, arylenealkyl is a composite group formed by linking arylene and alkylene. Specifically, arylenealkyl can include but is not limited to In the embodiment of the present application, the substituted or unsubstituted arylene alkyl group is a substituted or unsubstituted C7-C 40 that is, the number of carbon atoms in the arylene alkyl group is 7 to 40. Specifically, the number of carbon atoms in the arylene alkyl group can be, but is not limited to, 7, 8, 9, 10, 15, 18, 20, 25, 26, 30, 32, 37 or 40.

[0083] In the present application, heteroaryl is an aryl group having at least one oxygen, sulfur or nitrogen. Specifically, heteroaryl may include but is not limited to at least one of pyridyl, furyl, thienyl, indolyl, quinolyl, imidazolinyl and thiazolyl. In the embodiment of the present application, substituted or unsubstituted heteroaryl is substituted or unsubstituted C2-C 30 that is, the number of carbon atoms in the heteroaryl group is 2 to 30. Specifically, the number of carbon atoms in the heteroaryl group can be, but is not limited to, 3, 5, 8, 12, 17, 20, 25, 28 or 30.

[0084] In the present application, the heteroarylene group is a divalent heteroaryl group. Specifically, the heteroarylene group may include, but is not limited to, at least one of pyridylene, furylene, thienylene, indolylene, quinolylene, imidazolinylene and thiazolylene. In the embodiment of the present application, the substituted or unsubstituted heteroarylene group is a substituted or unsubstituted C2-C 30 that is, the number of carbon atoms in the heteroarylene group is 2 to 30. Specifically, the number of carbon atoms in the heteroarylene group can be, but is not limited to, 3, 5, 8, 12, 17, 20, 25, 28 or 30.

[0085] In the present application, heteroarylenealkyl is a composite group formed by linking heteroarylene and alkylene. Specifically, heteroarylenealkyl may include but is not limited to In the embodiment of the present application, the substituted or unsubstituted heteroarylalkylene group is a substituted or unsubstituted C3-C 40 that is, the number of carbon atoms in the heteroarylene alkyl group is 2 to 40. Specifically, the number of carbon atoms in the heteroarylene alkyl group can be, but is not limited to, 5, 6, 10, 13, 18, 22, 27, 30, 33 or 39.

[0086] In the present application, the alicyclic group is a carbocyclic group that does not contain a benzene ring. Specifically, the alicyclic group may include, but is not limited to, at least one of a cyclopropane group, a cyclobutane group, a cyclopentane group, a cyclohexane group, and a cyclopentenyl group. In the embodiment of the present application, the substituted or unsubstituted alicyclic group is a substituted or unsubstituted C3-C 30 that is, the number of carbon atoms in the alicyclic group is 3 to 30. Specifically, the number of carbon atoms in the alicyclic group can be, but is not limited to, 3, 5, 9, 10, 13, 15, 18, 23, 26, or 30.

[0087] In the present application, the alicyclic group is a divalent alicyclic group. Specifically, the alicyclic group may include, but is not limited to, at least one of cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene and cyclopentenylene. In the embodiment of the present application, the substituted or unsubstituted alicyclic group is a substituted or unsubstituted C3-C 30substituted or unsubstituted C3-C30 alkylenyl; that is, the number of carbon atoms of the alkylenyl is 3-30. Specifically, the number of carbon atoms of the alkylenyl can be, but is not limited to, 3, 5, 9, 10, 13, 15, 18, 23, 26, or 30.

[0088] In the present application, a substituted group (such as alkyl, alkylenyl, alkenyl, alkenylenyl, alkynyl, alkynylenyl, aryl, arylene, arylenealkyl, heteroaryl, heteroarylene, heteroarylenealkyl, aliphatic ring group, aliphatic ring groupalkyl) refers to a group substituted by a substituent. In an embodiment, the substituent includes at least one of halogen, nitrogen atom, oxygen atom, sulfur atom, hydroxyl, nitro, amine, mercapto, methoxy, and cyano.

[0089] In the present application, R1 and / or R2 can be a single bond, that is, the amino group (-NH2) can be directly connected to the phenanthroline group. In an embodiment, R1 and R2 are both single bonds, and the chemical structural formula of the diamine compound is shown in formula (I-1),

[0090]

[0091] The diamine compound shown in formula (I-1) has a simple structure and is more stable in performance, which is conducive to preparing a polyimide with stable performance.

[0092] In the embodiments of the present application, R1, R2 are independently selected from a single bond, a substituted or unsubstituted C6-C 30 arylene, or a substituted or unsubstituted C7-C 40 arylenealkyl. This is conducive to further improving the structural stability of the diamine compound. In an embodiment, R1 and R2 are the same group. In another embodiment, R1 and R2 are different groups. In an embodiment of the present application, the diamine compound includes one of the compounds shown in formula (I-1) to formula (I-4),

[0093] wherein, when R1 and R2 are both single bonds, the chemical structural formula of the diamine compound is shown in formula (I-1); when R1 and R2 are both arylene, the chemical structural formula of the diamine compound is shown in formula (I-2), formula (I-3); when R1 and R2 are both arylenealkyl, the chemical structural formula of the diamine compound is shown in formula (I-4).

[0094] The present application also provides a preparation method of a diamine compound, which can prepare the diamine compound in any of the above embodiments, including:

[0095] A first reactant is provided, and the chemical structural formula of the first reactant is shown in formula (II), wherein R3, R4 are independently selected from a chlorine atom, a bromine atom, an iodine atom, or a stibine atom,

[0096] A first reactant is provided, and the chemical structural formula of the first reactant is shown in formula (II), wherein R3, R4 are independently selected from a chlorine atom, a bromine atom, an iodine atom, or a stibine atom,

[0097] A second reactant is provided, and the chemical structure of the second reactant is shown in formula (III), wherein R5 is selected from hydrogen, boronic acid or boronic ester substituted alkyl, boronic acid or boronic ester substituted alkenyl, boronic acid or boronic ester substituted alkynyl, boronic acid or boronic ester substituted aryl, boronic acid or boronic ester substituted arylalkyl, boronic acid or boronic ester substituted heteroaryl, boronic acid or boronic ester substituted heteroarylalkyl, or boronic acid or boronic ester substituted alicyclic group,

[0098] H2N-R5 (III);

[0099] The first reactant and the second reactant are mixed under alkaline conditions to form a reaction solution, and a diamine compound is obtained through the reaction, and the chemical structure of the diamine compound is shown in formula (I), 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 arylalkylene, substituted or unsubstituted heteroarylene, substituted or unsubstituted heteroarylalkylene, or substituted or unsubstituted alicyclic group,

[0100]

[0101] The preparation method of the diamine compound in the present application is simple, convenient to operate, can realize large-scale production of the diamine compound, and is beneficial to the generation and use of polyimide.

[0102] In the present application, R3 and R4 in the first reactant can be the same group or different groups. In an embodiment, R3 and R4 are the same group, which is beneficial to the reaction. Specifically, the first reactant can be but is not limited to In the present application, R5 in the second reactant is selected from hydrogen, boronic acid or boronic ester substituted alkyl, boronic acid or boronic ester substituted alkenyl, boronic acid or boronic ester substituted alkynyl, boronic acid or boronic ester substituted aryl, boronic acid or boronic ester substituted arylalkyl, boronic acid or boronic ester substituted heteroaryl, boronic acid or boronic ester substituted heteroarylalkyl, or boronic acid or boronic ester substituted alicyclic group. Specifically, R5 can be but is not limited to NH3, In the present application, the first reactant and the second reactant are used to prepare the diamine compound through Suzuki reaction.

[0103] In the embodiments of the present application, the reaction solution further comprises a catalyst and a catalyst ligand. The addition of the catalyst and the catalyst ligand promotes the reaction. In an embodiment of the present application, the catalyst comprises at least one of 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. In an embodiment of the present application, the catalyst ligand comprises at least one of N,N'-dimethylethylenediamine, triphenylphosphine, 2-dicyclohexylphospho-2',4',6'-triisopropylbiphenyl, 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene, triphenylphosphine oxide, and tri(o-methylphenyl)phosphine. The catalyst and the catalyst ligand described above can effectively promote the Suzuki reaction. In an embodiment of the present application, 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). This is conducive to the Suzuki reaction and improves the preparation efficiency of the diamine compound. In an embodiment, the molar ratio of the first reactant, the second reactant, the catalyst, and the catalyst ligand is 1:(3-45):(0.01-0.18):(0.01-0.45). In another embodiment, the molar ratio of the first reactant, the second reactant, the catalyst, and the catalyst ligand is 1:(8-37):(0.05-0.16):(0.1-0.4). In yet another embodiment, the molar ratio of the first reactant, the second reactant, the catalyst, and the catalyst ligand is 1:(10-25):(0.05-0.1):(0.1-0.3). In yet another embodiment, the molar ratio of the first reactant, the second reactant, the catalyst, and the catalyst ligand is 1:(30-50):(0.1-0.2):(0.3-0.5).

[0104] In the embodiments of the present application, the reaction solution further comprises a basic substance. In this way, the reaction is carried out under basic conditions. In an embodiment of the present application, the basic substance can comprise at least one of potassium carbonate, sodium carbonate, cesium fluoride, sodium hydroxide, potassium hydroxide and barium hydroxide. In an embodiment of the present application, the molar ratio of the first reactant, the second reactant and the basic substance is 1:(2-50):(0.05-10). In this way, the Suzuki reaction is facilitated, and the preparation efficiency of the diamine compound is improved. In an embodiment, the molar ratio of the first reactant, the second reactant and the basic substance is 1:(3-45):(0.1-9). In another embodiment, the molar ratio of the first reactant, the second reactant and the basic substance is 1:(8-37):(2-8). In yet another embodiment, the molar ratio of the first reactant, the second reactant and the basic substance is 1:(10-25):(1-4). In yet another embodiment, the molar ratio of the first reactant, the second reactant and the basic substance is 1:(30-50):(5-8).

[0105] In the embodiments of the present application, the reaction solution further comprises a solvent, which is used to dissolve and disperse each component in the reaction solution. In the present application, the solvent can be, but is not limited to, water, ethylene glycol, 1,4 dioxane, etc. In an embodiment, the solvent can be a mixture of water and 1,4 dioxane. Specifically, the volume ratio of 1,4 dioxane to water can be, but is not limited to, 2-10.

[0106] In the embodiments of the present application, the reaction temperature is 25-180°C, and the reaction time is 2-72h. In this way, the reaction can be ensured to proceed, the preparation efficiency of the diamine compound is improved, and the occurrence of side reactions can be avoided. Specifically, in the preparation of the diamine compound, the reaction temperature can 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, etc., and the reaction time can be, but is not limited to, 2h, 8h, 10h, 20h, 35h, 40h, 55h, 65h or 70h, etc. In an embodiment, the reaction temperature is 45-90°C, and the reaction time is 35-72h. In another embodiment, the reaction temperature is 100-180°C, and the reaction time is 2-30h. In the embodiments of the present application, the reaction can be carried out under an inert gas, so that the occurrence of side reactions can be avoided. Specifically, the inert gas can be, but is not limited to, argon, nitrogen, etc. Specifically, after the reaction, the diamine compound can be obtained by separation and purification.

[0107] In an embodiment of the present application, the first reactant and NH3 can be reacted to prepare the diamine compound represented by formula (I-1). In an embodiment, the first reactant and NH3 can be reacted to prepare the diamine compound represented by formula (I-2). and ammonia, to obtain a compound represented by Formula (I-1). Specifically, a catalyst, a catalyst ligand, a basic substance, and the like can be further added. In one embodiment, brominated 1,10-phenanthroline, 28% concentrated ammonia, a copper catalyst (cuprous oxide), N,N'-dimethylethylenediamine, and potassium carbonate are dissolved in ethylene glycol under nitrogen protection, and stirred at 45°C to 180°C for 2 hours to 72 hours to obtain a diamine compound represented by Formula (I-1). Specifically, the molar ratio of brominated 1,10-phenanthroline, 28% concentrated ammonia, a copper catalyst (cuprous oxide), N,N'-dimethylethylenediamine, and potassium carbonate can be, but is not limited to, 1:(10-50):(0.01-0.1):(0.05-0.5):(0.05-0.5). The reaction formula of the above reaction is as follows:

[0108]

[0109] In one embodiment of the present application, a compound represented by Formula (I-2) can be obtained by mixing and reacting In one embodiment, a compound represented by Formula (I-2) can be obtained by mixing and reacting In one embodiment, a compound represented by Formula (I-2) can be obtained by mixing and reacting Specifically, the molar ratio of the palladium catalyst, the catalyst ligand, the basic substance, and the solvent can be, but is not limited to, 1:(2-4):(0.01-0.1):(0.01-0.5):(2-10). The reaction formula of the above reaction is as follows:

[0110]

[0111] In one embodiment of the present application, a compound represented by Formula (I-3) can be obtained by mixing and reacting In one embodiment, a compound represented by Formula (I-3) can be obtained by mixing and reacting In one embodiment, a compound represented by Formula (I-3) can be obtained by mixing and reacting Specifically, the molar ratio of the palladium catalyst, the catalyst ligand, the basic substance, and the solvent can be, but is not limited to, 1:(2-4):(0.01-0.1):(0.01-0.5):(2-10). The reaction formula of the above reaction is as follows:

[0112]

[0113] In one embodiment of the present application, Mix and react to obtain the compound represented by formula (I-4). Specifically, a catalyst, a catalyst ligand, an alkaline substance, etc. may also be added. In a specific embodiment, under nitrogen protection, The palladium catalyst, catalyst ligand, and alkaline substance are dissolved in a solvent and stirred at 45°C-120°C for 2h-72h to obtain a diamine compound represented by formula (I-4). Specifically, The molar ratio of the palladium catalyst, the catalyst ligand, and the alkaline substance can be, but is not limited to, 1:(2-4):(0.01-0.1):(0.01-0.5):(2-10). The reaction formula of the above reaction is as follows:

[0114]

[0115] The present application provides a method for preparing a polyimide acid, comprising mixing a diamine compound in any of the above embodiments with a dianhydride to form a mixed solution, and reacting to obtain a polyimide acid, wherein the polyimide acid comprises a repeating unit represented by formula (IV), wherein R1 and R2 are independently selected from a single bond, a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, a substituted or unsubstituted alkynylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted arylene alkyl group, a substituted or unsubstituted heteroarylene group, a substituted or unsubstituted heteroarylene alkyl group, or a substituted or unsubstituted alicyclic group, and R7 is selected from a substituted or unsubstituted arylene group, or a substituted or unsubstituted heteroarylene group.

[0116]

[0117] The preparation method of the polyimide acid provided in this application is simple and easy to operate, and can achieve large-scale production of polyimide acid; the prepared polyimide acid has a 1,10-phenanthroline group, which can form a chemical bond with the metal part, thereby improving the adhesion between the metal part and the metal part, which is beneficial to the preparation of polyimide and helps to improve the bonding strength between the polyimide and the metal part. It can be understood that the diamine compound shown in formula (I) and the polyimide acid repeating unit shown in formula (IV) have the same selection of R1 and R2.

[0118] In the present application, R7 is selected from substituted or unsubstituted arylene, or substituted or unsubstituted heteroarylene; R7 group and the groups on each side share two carbon atoms. For example, when R7 is a benzene ring, the repeating unit shown in formula (IV) is In embodiments of the present application, the number of repeating units represented by formula (IV) in the polyimide acid can be, but is not limited to, 5-2000. In an embodiment, the number of repeating units represented by formula (IV) in the polyimide acid can be 20-2000. In another embodiment, the number of repeating units represented by formula (IV) in the polyimide acid can be 100-1800. In yet another embodiment, the number of repeating units represented by formula (IV) in the polyimide acid can be 300-1500.

[0119] In embodiments of the present application, the dianhydride includes at least one of pyromellitic dianhydride, 2,3,3',4'-diphenyl ether tetra carboxylic dianhydride, 3,3',4,4'-tetracarboxybenzophenone dianhydride, 3,3',4,4'-tetracarboxybiphenyl sulfone 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) diphenyl methane dianhydride, and 4,4'-bis(3,4-dicarboxyphenoxy) diphenyl sulfone dianhydride. The selection of the dianhydride determines the R7group.

[0120] In embodiments of the present application, the molar ratio of the diamine compound and the dianhydride is 0.9-1.1. This is advantageous for the fast preparation of the polyimide acid. Specifically, the molar ratio of the diamine compound and the dianhydride can be, but is not limited to, 0.9, 0.95, 1, 1.05, or 1.1, etc.

[0121] In embodiments of the present application, the mixed solution further includes a solvent. The solvent disperses the components in the mixed solution. In an embodiment of the present application, the solvent can include at least one of dimethyl sulfoxide, N-methyl pyrrolidone, N,N-dimethyl formamide, N,N-dimethyl acetamide, and m-cresol.

[0122] In embodiments of the present application, the reaction temperature is 0°C-100°C, and the reaction time is 2h-12h. Specifically, the reaction temperature in the preparation of the polyimide acid can be, but is not limited to, 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, etc., and the reaction time can be, but is not limited to, 2h, 3h, 5h, 6h, 8h, 9h, or 12h, etc. In an embodiment, the reaction temperature is 45°C-60°C, and the reaction time is 7h-12h. In another embodiment, the reaction temperature is 60°C-100°C, and the reaction time is 2h-7h. In yet another embodiment, the reaction temperature is 0°C-50°C, and the reaction time is 3h-7h.

[0123] In an embodiment of the present application, the mixture further comprises a second diamine. The second diamine is added to improve the film-forming properties of the polyimide acid and the polyimide. In an embodiment of the present application, the second diamine 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 has rotatability, such as sp3 hybridization of oxygen, etc., to improve the film-forming properties of the polyimide acid. In an embodiment, the content of the second diamine in the mixture is less than the content of the diamine compound. In a specific embodiment, the mixture contains the second diamine, which can ensure the film-forming properties of the polyimide film when the polyimide film is subsequently prepared.

[0124] In an embodiment of the present application, when the mixture contains the second diamine, the chemical structure of the polyimide acid is shown in formula (V),

[0125]

[0126] wherein R8is selected from substituted or unsubstituted alkylene, substituted or unsubstituted arylene, or substituted or unsubstituted heteroarylene. The selection of the second diamine determines the R8group.

[0127] In an embodiment of the present application, n can be 5-2000. In an embodiment, n is 20-2000. In another embodiment, n is 20-2000. In yet another embodiment, n is 100-1800. In yet another embodiment, n is 300-1500. In yet another embodiment, n is 500-1000. In yet another embodiment, n is 1000-1500.

[0128] In an embodiment of the present application, m is less than or equal to 1000. In an embodiment, m is 0-1000. That is, when the mixture does not contain the second diamine, m is 0. In another embodiment, m is 10-900. In yet another embodiment, m is 100-850. In yet another embodiment, m is 200-700. In yet another embodiment, m is 200-500. In yet another embodiment, m is 500-800.

[0129] The present application provides a polyimide acid comprising a repeating unit shown in formula (IV),

[0130]

[0131] wherein R1, R2are 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 aralkylene, substituted or unsubstituted heteroarylene, substituted or unsubstituted heteroarylalkylene, or substituted or unsubstituted cycloalkylene, and R7is selected from substituted or unsubstituted arylene, or substituted or unsubstituted heteroarylene. The polyimide acid provided in the present application has a 1,10-phenanthroline group, which can form a chemical bond with a metal piece, thereby improving the adhesion between the polyimide and the metal piece, facilitating the preparation of the polyimide and helping to improve the bonding force between the polyimide and the metal piece. In the present application, the polyimide acid can be prepared by any one of the preparation methods of the polyimide acid.

[0132] The present application provides a preparation method of a polyimide, which comprises imidizing the polyimide acid in any one of the embodiments to obtain the polyimide, and the polyimide comprises a repeating unit represented by formula (VI), wherein R1, R2, and R7are the same as the selection in the polyimide acid,

[0133]

[0134] The preparation method of the polyimide provided in the present application is simple and convenient to operate, and can realize large-scale production of the polyimide; the prepared polyimide contains a 1,10-phenanthroline group, which can form a chemical bond with a metal piece, thereby improving the adhesion between the polyimide and the metal piece, facilitating the use of the polyimide.

[0135] In the present application, the imidization can be but is not limited to heat treatment; after the heat treatment, the polyimide acid becomes a polyimide. In the embodiments of the present application, when the polyimide acid contains a second diamine during the preparation process, the chemical structure of the polyimide is represented by formula (VII), wherein R8is the same as the selection in the polyimide acid,

[0136]

[0137] When the polyimide acid does not contain a second diamine during the preparation process, m in the chemical structure of the polyimide represented by formula (VII) is 0.

[0138] The present application provides a polyimide, which comprises a repeating unit represented by formula (VI),

[0139]

[0140] wherein R1, R2are 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 aralkylene, substituted or unsubstituted heteroarylene, substituted or unsubstituted heteroaralkylene, or substituted or unsubstituted cycloalkylene, and R7is selected from substituted or unsubstituted arylene, or substituted or unsubstituted heteroarylene. The polyimide provided in the present application contains 1,10-phenanthroline group, which can form chemical bond with metal element, thereby improving the adhesion between the polyimide and the metal element, and facilitating the use of the polyimide. In the present application, the polyimide can be prepared by any of the embodiments of the preparation method of the polyimide. The polyimide provided in the present application has good thermal stability, and can maintain good rigid structure at high temperature, thereby facilitating the use thereof. In an embodiment, the polyimide can maintain good stability at 500℃ or above.

[0141] Referring to Figure 1 The schematic diagram of the combination between the polyimide provided in an embodiment of the present application and metal is shown, wherein M is metal element, and the dotted line is the coordination bond formed between the polyimide and the metal. The polyimide provided in the present application can form five-membered ring coordination compound with metal element, thereby increasing the bonding force between the polyimide film and the metal surface during the use of the polyimide. Specifically, the metal element can be but is not limited to aluminum, copper, iron, zinc, titanium, etc.

[0142] The application also provides a method for preparing a polyimide film, comprising coating a polyimide acid and then imidizing to obtain the polyimide film. In an embodiment, the imidization comprises heating treatment at 80-400 ℃ for 1-10 h. Specifically, the temperature of the imidization can be, but is not limited to, 120 ℃, 150 ℃, 180 ℃, 200 ℃, 230 ℃, 250 ℃, 290 ℃, 310 ℃ or 370 ℃, etc.; and the time of the imidization can be, but is not limited to, 1 h, 3 h, 7 h, 9 h or 10 h, etc. In another embodiment, the imidization comprises heating treatment at 80-200 ℃ for 1-6 h, and then heating treatment at 200-400 ℃ for 1-4 h after temperature rising. The efficiency of the imidization can be improved by the temperature rising treatment. Further, the temperature rising speed can be 1-7 ℃ / min. Specifically, the temperature rising speed can be, but is not limited to, 2 ℃ / min, 3 ℃ / min, 4 ℃ / min, 5 ℃ / min or 6 ℃ / min, etc. In a specific embodiment, the imidization comprises heating at 120 ℃ for 1 h, heating at 250 ℃ for 1 h after temperature rising, and heating at 350 ℃ for 1 h after temperature rising, wherein the temperature rising speed is 2 ℃ / min. In another specific embodiment, the imidization comprises heating at 80 ℃ for 2 h, heating at 120 ℃ for 1 h after temperature rising, heating at 160 ℃ for 1 h after temperature rising, heating at 180 ℃ for 1 h after temperature rising, heating at 240 ℃ for 1 h after temperature rising, heating at 280 ℃ for 1 h after temperature rising, and heating at 350 ℃ for 1 h after temperature rising, wherein the temperature rising speed is 2 ℃ / min.

[0143] In the application, the inventors have found that when R1 and R2 in formula (I) are independently selected from a single bond, a substituted or unsubstituted arylene group, a substituted or unsubstituted heteroarylene group, or a substituted or unsubstituted cycloalkylene group, the addition of a second diamine can improve the film-forming property of the polyimide acid and the polyimide when preparing the polyimide acid and the polyimide. In an embodiment, when one of the compounds shown in formula (I-1) to formula (I-4) is used to prepare the polyimide acid or the polyimide, a second diamine can be added to improve the film-forming property of the polyimide acid or the polyimide.

[0144] The application provides a battery module comprising a polyimide film, and the material of the polyimide film comprises the polyimide in any of the above embodiments. Please refer to Figure 2A cross-sectional schematic view of a battery module according to an embodiment of the present application is provided, wherein the battery module 10 comprises a heat dissipation assembly 13, a polyimide film 12 arranged on the surface of the heat dissipation assembly 13, and a battery cell 11 arranged on the surface of the polyimide film 12. In the related art, since the battery cell 11 generates heat during use, the heat dissipation assembly 13 needs to be arranged to transfer the heat generated by the battery cell 11, so as to reduce the temperature of the battery cell 11 and ensure the service life and safety of the battery cell 11. When the heat dissipation assembly 13 is arranged on the surface of the battery cell 11, the heat dissipation assembly 13 and the battery cell 11 need to be connected together to ensure the bonding force therebetween, so as to ensure that no relative movement occurs during use. However, when a connecting structure is used, the weight of the battery module 10 is excessively increased, and the connecting structure can scratch the surface of the heat dissipation assembly 13, thereby reducing the safety. In the battery module 10 provided by the present application, the polyimide film 12 is used to connect the battery cell 11 and the heat dissipation assembly 13, and the polyimide used in the polyimide film 12 comprises a 1,10-phenanthroline group, which can increase the bonding force between the polyimide film 12 and the heat dissipation assembly 13, so as to ensure that the polyimide layer for insulation does not fall off during use, thereby improving the safety and service life of the battery module 10. Meanwhile, in the related art, as the energy density of the battery cell 11 increases, the battery cell 11 and the heat dissipation assembly 13 need to be insulated to ensure the safety of the battery module 10, and as the CTB technology is applied and developed, the battery module 10 is arranged under the seat of a vehicle and needs to bear the weight of passengers, so it is necessary to ensure the safety of the battery module 10. The polyimide film 12 made of polyimide provided by the present application has insulation, which further improves the safety of the battery module 10.

[0145] In the embodiment of the present application, the surface of the heat dissipation assembly 13 is made of metal. This is conducive to the formation of a chemical bond between the polyimide film 12 and the surface of the heat dissipation assembly 13, thereby improving the bonding force. Specifically, the metal material can be, but is not limited to, at least one of aluminum, copper, aluminum alloy, copper alloy, or stainless steel, etc. In the present application, the heat dissipation assembly 13 can be, but is not limited to, a liquid cooling plate, etc. Please refer to Figure 3 A bonding schematic view between the polyimide film 12 and the heat dissipation assembly 13 according to an embodiment of the present application is provided, wherein the surface of the heat dissipation assembly 13 is made of metal, M is a metal element, and the dotted line represents a coordination bond formed between the polyimide in the polyimide film 12 and the metal element in the heat dissipation assembly 13. In the embodiment of the present application, the surface of the battery cell 11 is made of metal. The polyimide film 12 can form a chemical bond with the surface of the battery cell 11, thereby improving the bonding force. Specifically, the metal material can be, but is not limited to, at least one of aluminum, copper, aluminum alloy, copper alloy, or stainless steel, etc.

[0146] The application provides an electronic device comprising the battery module 10 in any of the above embodiments. The electronic device can be, but is not limited to, a vehicle, a mobile phone, a server, a computer, etc. The battery module 10 in the electronic device provided by the application has higher safety, and is beneficial to use of the electronic device.

[0147] The technical solutions of the application are further described below through specific examples and comparative examples.

[0148] Example 1

[0149] A preparation method of a diamine compound comprises the following steps:

[0150] Cuprous oxide, brominated 1,10-phenanthroline, 28% concentrated ammonia, potassium carbonate and N,N'-dimethylethylenediamine (molar ratio of 0.1:1:50:0.5:0.5) are dissolved in ethylene glycol under nitrogen protection. After stirring at 180 DEG C for 72 hours, the solution is returned to room temperature, extracted with ethyl acetate, and then purified by column chromatography to obtain the diamine compound shown in formula (I-1).

[0151] Example 2

[0152] A preparation method of a diamine compound comprises the following steps:

[0153] Palladium acetate, triphenylphosphine, brominated 1,10-phenanthroline, aminobenzoic acid hydrochloride and sodium hydroxide (molar ratio of 0.02:0.05:1:2.1:8) are dissolved in 1,4-dioxane under nitrogen protection. After stirring at 100 DEG C for 18 hours, the solution is returned to room temperature, filtered, and then purified by column chromatography to obtain the diamine compound shown in formula (I-2).

[0154] Example 3

[0155] A preparation method of a diamine compound comprises the following steps:

[0156] Bis(3,5,3',5'-dimethoxydibenzylideneacetone)palladium, triphenylphosphine, brominated 1,10-phenanthroline, aminobenzoic acid hydrochloride and potassium carbonate (molar ratio of 0.01:0.02:1:2.1:8) are dissolved in 1,4-dioxane and water (volume ratio of 5:1) under nitrogen protection. After stirring at 100 DEG C for 18 hours, the solution is returned to room temperature, filtered, and then purified by column chromatography to obtain the diamine compound shown in formula (I-3).

[0157] Example 4

[0158] A preparation method of a diamine compound comprises the following steps:

[0159] Palladium acetate, triphenylphosphine, brominated 1,10-phenanthroline, 4- (aminomethyl)phenyl)boronic acid, potassium carbonate (molar ratio of 0.01:0.02:1:2.1:8) were dissolved in 1,4-dioxane under nitrogen protection. Stirring at 100°C for 12h, the solution was returned to room temperature after reaction, and then purified by column chromatography after filtration to obtain the diamine compound represented by formula (I-4).

[0160] Example 5

[0161] A preparation method of a polyimide acid, comprising:

[0162] The diamine compound prepared in Example 1, 4,4'-diaminodiphenyl ether and N,N-dimethylformamide were sequentially put into a reaction kettle, stirring was started, and the temperature was adjusted to 60°C; 21.8g of pyromellitic anhydride was slowly added into the kettle, and the stirring was continued for 6h before the temperature was lowered to room temperature to obtain the polyimide acid.

[0163] Example 6

[0164] A preparation method of a polyimide acid, comprising:

[0165] The diamine compound prepared in Example 2, 4,4'-diaminodiphenyl ether and N,N-dimethylformamide were sequentially put into a reaction kettle, stirring was started, and the temperature was adjusted to 60°C; 21.8g of pyromellitic anhydride was slowly added into the kettle, and the stirring was continued for 12h before the temperature was lowered to room temperature to obtain the polyimide acid.

[0166] Example 7

[0167] A preparation method of a polyimide acid, comprising:

[0168] The diamine compound prepared in Example 3, 4,4'-diaminodiphenyl ether and N,N-dimethylformamide were sequentially put into a reaction kettle, stirring was started, and the temperature was adjusted to 45°C; 21.8g of pyromellitic anhydride was slowly added into the kettle, and the stirring was continued for 4h before the temperature was lowered to room temperature to obtain the polyimide acid.

[0169] Example 8

[0170] A preparation method of a polyimide acid, comprising:

[0171] The diamine compound prepared in Example 4 and N,N-dimethylformamide were sequentially put into a reaction kettle, stirring was started, and the temperature was adjusted to 0°C; 21.8g of pyromellitic anhydride was slowly added into the kettle, and the stirring was continued for 6h before the temperature was lowered to room temperature to obtain the polyimide acid.

[0172] Comparative Example 1

[0173] A preparation method of a polyimide acid, comprising:

[0174] 20 g of 4,4'-diaminodiphenyl ether and 160 g of N,N-dimethylformamide were sequentially added into a reaction kettle, stirring was started, and the temperature was adjusted to 45°C; 21.8 g of pyromellitic anhydride was slowly added into the kettle, and after stirring for 4 h, the temperature was lowered to room temperature to obtain a polyimide acid.

[0175] Performance detection

[0176] The structures of the diamine compounds obtained in Examples 1-4 were characterized by nuclear magnetic resonance, and the obtained nuclear magnetic resonance hydrogen spectrum results were as follows:

[0177] Formula (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);

[0178] Formula (I-2): 1H NMR (500 MHz, Chloroform-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);

[0179] Formula (I-3): 1H NMR (500 MHz, Chloroform-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);

[0180] Formula (I-4): 1H NMR (500 MHz, Chloroform-d) δ 8.95 (d, J = 2.0 Hz, 1H), 8.61 (q, J = 1.4 Hz, 1H), 7.87 (t, J = 1.3 Hz, 1H), 7.68–7.63 (m, 2H), 7.30 (dt, J = 8.0, 1.1 Hz, 2H), 4.05 (tt, J = 6.2, 1.0 Hz, 2H), 2.52 (dt, J = 7.1, 6.2 Hz, 1H), 2.36 (dt, J = 7.0, 6.2 Hz, 1H).

[0181] The polyimide acids prepared in Examples 5-8 and Comparative Example 1 were coated onto the surface of an aluminum plate to prepare wet films of the corresponding solutions. The wet films were then transferred to an oven and subjected to imidization according to the following temperature ramp: 80°C / 2h, 120°C / 1h, 160°C / 1h, 180°C / 1h, 240°C / 1h, 280°C / 1h, and 350°C / 1h, at a ramp rate of 2°C / min, to obtain polyimide films formed on the surface of the aluminum plate. The bonding strength between the polyimide film and the aluminum plate was tested according to ASTM D3359 Method B Cross-cut Tape Test, and the bonding strength values ​​are shown in Table 1. The 5% decomposition temperature of the resulting polyimide film was also tested according to GB / T 13464-2008, with the results shown in Table 1. The polyimide acid obtained in Examples 5-8 and Comparative Example 1 was coated on the surface of a glass plate to prepare a corresponding solution wet film; the wet film was transferred to an oven and imidized according to the same heating program as above to obtain a polyimide film formed on the surface of the glass plate. After the glass plate was cooled to room temperature, it was immersed in deionized water to peel off the polyimide film to obtain the corresponding self-supporting polyimide film. The film-forming property evaluation is specifically as follows: if the film forms a whole piece of film material on the glass, the film surface is not broken and can remain intact after peeling, it is considered to be very good film forming. If the film forms a whole piece of film material on the glass, the film surface is not broken and cannot remain intact after peeling, it is considered to be average film forming. If the film is in pieces on the glass, it is considered to be unable to form a film. As can be seen from Table 1, compared with Comparative Example 1, the 5% decomposition temperature of the polyimide film provided in the present application is high, indicating that its thermal stability is very excellent; among them, compared with Example 7, the diamine compound used in Example 6 and the amino group in the obtained polyimide are on the rotation axis of the benzene ring, which enhances the linear properties and further improves its thermal stability; at the same time, the 1,10-phenanthroline group in the polyimide film can produce a coordination bond with aluminum, thereby making the bonding force between it and the aluminum plate high, which is conducive to the use of polyimide.

[0182] Table 1 Performance test results

[0183] Bonding force 5% decomposition temperature Film formability Example 5 5B 540℃ Very good Example 6 5B 550℃ Very good Example 7 5B 500℃ Very good Example 8 5B 515℃ Very good Comparative Example 1 0B 480℃ Very good

[0184] The diamine compound, polyimide acid and polyimide provided in the present application have 1,10-phenanthroline groups, which can form chemical bonds with metals, thereby improving the bonding strength between them and metal parts, which is beneficial for use in electronic devices.

[0185] The above-described embodiments are merely illustrative of several embodiments of the present application, which are described in more detail and in a specific and detailed manner, but should not be construed as limiting the scope of the patent of the present application. It should be noted that, for those of ordinary skill in the art, several modifications and improvements can be made without departing from the concept of the present application, and these all belong to the protection scope of the present application. Therefore, the protection scope of the patent of the present application should be subject to the appended claims.

Claims

1. A battery module, characterized in that: The invention comprises a heat dissipation component, a polyimide film arranged on the surface of the heat dissipation component, and a battery cell arranged on the surface of the polyimide film. The material of the polyimide film comprises polyimide, and the polyimide comprises a repeating unit represented by formula (VI). (WE), Wherein R1 and R2 are independently selected from a single bond, a phenylene group or a phenylenemethyl group, R7 is selected from a substituted or unsubstituted arylene group or a substituted or unsubstituted heteroarylene group, and the substituent is at least one of a halogen, a hydroxyl group, a nitro group, an amino group, a thiol group, a methoxy group and a cyano group.

2. The battery module according to claim 1, wherein: The chemical structure of the polyimide is shown in Formula (VII), (VII), Wherein R8 is selected from substituted or unsubstituted alkylene, substituted or unsubstituted arylene, or substituted or unsubstituted heteroarylene, the substituent is at least one of halogen, hydroxyl, nitro, amino, thiol, methoxy and cyano, n is 5-2000, and m is 0-1000.

3. The battery module according to claim 1, wherein: The polyimide is obtained by imidizing a polyimide acid, wherein the polyimide acid comprises a repeating unit represented by formula (IV). (IV)。 4. The battery module according to claim 3, wherein: The chemical structure of the polyimide acid is shown in Formula (V), （V）。 5. The battery module according to claim 3, wherein: The preparation method of the polyimide acid comprises: mixing a diamine compound and a dianhydride to form a mixed solution, and reacting the mixture to obtain the polyimide acid. The chemical structure of the diamine compound is shown in formula (I). （I）。 6. The battery module according to claim 5, wherein: The diamine compound includes one of the compounds represented by formula (I-1) to formula (I-4), (I-1)、 (I-2)、 (I-3)、 (I-4)。 7. The battery module according to claim 5, wherein: The molar ratio of the diamine compound to the dianhydride is 0.9-1.1; The dianhydride is at least one of pyromellitic anhydride, 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-tetracarboxybenzophenone dianhydride, 3,3',4,4'-tetracarboxydiphenylsulfone 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)diphenylsulfone dianhydride; The mixed solution also includes a second diamine, which is 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 liquid further includes a solvent, which is at least one of dimethyl sulfoxide, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide and m-cresol; The reaction temperature is 0°C-100°C, and the reaction time is 2h-12h.

8. The battery module according to claim 5, wherein: The preparation method of the diamine compound comprises: A first reactant is provided, wherein the chemical structure of the first reactant is shown in formula (II), wherein R3 and R4 are independently selected from a chlorine atom, a bromine atom, an iodine atom or an astatine atom, (II); A second reactant is provided, wherein the chemical structure of the second reactant is shown in Formula (III), wherein R5 is selected from hydrogen, an alkyl group substituted with boric acid or a borate ester, an aryl group substituted with boric acid or a borate ester, or an arylalkyl group substituted with boric acid or a borate ester, (III); The first reactant and the second reactant are mixed under alkaline conditions to form a reaction solution, and the diamine compound is obtained through reaction.

9. The battery module according to claim 8, wherein: The reaction solution also includes a catalyst and a catalyst ligand; The catalyst is selected from a copper-based catalyst and a palladium-based catalyst, the copper-based catalyst is cuprous oxide, and the palladium-based catalyst is at least one of bis(3,5,3',5'-dimethoxydibenzylideneacetone)palladium, di(tri-tert-butyl)palladium, trisdibenzylideneacetonepalladium, palladium chloride, palladium acetate, tetrakis(triphenylphosphine)palladium, and di(tri-tert-butylphosphine)palladium; The catalyst ligand is at least one of N,N'-dimethylethylenediamine, triphenylphosphine, 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl, 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene, triphenylphosphine oxide and tri(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 includes an alkaline substance, wherein the alkaline substance is 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 25°C-180°C, and the reaction time is 2h-72h.

10. An electronic device, characterized in that: A battery module comprising any one of claims 1 to 9.

Images