Diamine monomer with epoxy structure, preparation method thereof and polyimide resin

Abstract

The embodiment of the invention discloses a diamine monomer with an epoxy structure, a preparation method of the diamine monomer and polyimide resin. Wherein the molecular structural formula of the diamine monomer comprises one or more epoxy groups, and the molecular structural formula is specifically as follows: # imgabs0, A is a diamine residue and comprises a divalent aliphatic group, an alicyclic group or an aromatic group; p is any integer between 1 and 10.

Description

Technical Field

[0001] The present application belongs to the technical field of polymer materials, and more specifically, relates to a diamine monomer having an epoxy structure, a preparation method thereof, and a polyimide resin. Background Art

[0002] As an important component of polyimide resin, the molecular structure of diamine monomer has a crucial influence on the performance of polyimide film.

[0003] At present, in order to enhance the adhesion of polyimide film to substrates such as metal, glass, and silicon, the commonly used method is to introduce epoxy resin components into the film. However, epoxy resin and polyimide resin belong to two different types of polymers, and the molecular structures between them are quite different, which leads to the occurrence of phase separation. Phase separation not only reduces the adhesion between the polyimide film and the substrate, but may also cause adhesion failure. It can be seen that although traditional technical means attempt to solve the adhesion problem between the polyimide film and the substrate by adding epoxy resin, the phase separation problem caused by this method limits its effect in practical applications. Therefore, how to effectively improve the adhesion between the polyimide film and the substrate while ensuring the excellent performance of the polyimide film has become a technical problem that needs to be solved urgently. Summary of the invention

[0004] The purpose of the present application is to provide a new technical solution for a diamine monomer having an epoxy structure and a preparation method thereof and a polyimide resin.

[0005] According to the first aspect, an embodiment of the present application provides a diamine monomer having an epoxy structure, wherein the molecular structural formula of the diamine monomer includes one or more epoxy groups, and the molecular structural formula is as follows:

[0006]

[0007] Wherein, A is a diamine residue, which includes a divalent aliphatic group, alicyclic group or aromatic group; and p is any integer between 1 and 10.

[0008] Optionally, the diamine residue A includes the following substituted or unsubstituted groups:

[0009]

[0010] in, Indicates a connecting key; X 10 , X 11 , X 12 , X 13 , X 14 , X 15 , X 16 , X17 , X 18 , X 19 and X 20 Each independently selected from: a single bond, -O-, -S-, -C(CF3)2, -CO-, -SO2-, NR 11 R 12 or CR 13 R 14 , and R 11 , R 12 , R 13 and R 14 They are independently selected from: H or phenyl; n1 is any integer between 1 and 10.

[0011] Optionally, the substituent of the diamine residue A includes deuterium, a halogen group, a trifluoromethyl group, a cyano group, a heteroaryl group, an aryl group, an alkyl group, a deuterated alkyl group, a halogenated alkyl group, a cycloalkyl group, an alkoxy group or an aryloxy group;

[0012] The substituent of the diamine residue A includes one or more substituents.

[0013] Optionally, the aromatic group comprises an aryl group or a heteroaryl group;

[0014] The aryl group is a monocyclic aryl group or a condensed ring aryl group;

[0015] The heteroaryl group is a monocyclic heteroaryl group or a condensed-ring heteroaryl group.

[0016] Optionally, the aryl group includes phenyl, naphthyl, fluorenyl, anthracenyl, phenanthrenyl, biphenyl, terphenyl, benzo[9,10]phenanthrenyl, pyrenyl or benzofluoranthenyl;

[0017] The heteroaryl group includes thienyl, furanyl, pyrrolyl, imidazolyl, thiazolyl, oxazolyl, oxadiazolyl, triazolyl, pyridyl, triazinyl, acridinyl, pyridazinyl, pyrazinyl, quinolyl, quinazolinyl, quinoxalinyl, phenoxazinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, pyrazinopyrazinyl, isoquinolyl, indolyl, carbazolyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, benzocarbazolyl, benzothienyl, dibenzothienyl, thienothiphenyl, benzofuranyl, phenanthrolinyl, isoxazolyl, thiadiazolyl, phenothiazinyl, phenoxathiyl or dibenzo-p-dioxinyl.

[0018] Optionally, the aliphatic group includes a hydrocarbon group, a cycloalkyl group, an ether group or a keto group.

[0019] Alternatively, the alicyclic group is a non-aromatic hydrocarbon containing ring carbon atoms, including a monocyclic alkyl group, a spirocyclic alkyl group or a bridged cyclic alkyl group;

[0020] The carbon number of the alicyclic group is 3 to 10, and the alicyclic group includes one or more double bonds.

[0021] According to a second aspect, an embodiment of the present application provides a method for preparing a diamine monomer having an epoxy structure according to the first aspect, the preparation method comprising:

[0022] The hydroxyl-containing diamine is reacted with epichlorohydrin in a sodium hydroxide solution, and the hydroxyl group of the diamine can be replaced by the glycidyl ether to obtain a diamine monomer with an epoxy group.

[0023] Optionally, the synthesis formula of the diamine monomer is as follows:

[0024]

[0025] Wherein, A is a diamine residue, which includes a divalent aliphatic group, alicyclic group or aromatic group; and p is any integer between 1 and 10.

[0026] Optionally, the molar ratio of the hydroxyl-containing diamine to the epichlorohydrin is 1:1p to 3p.

[0027] In a third aspect, an embodiment of the present application provides a polyimide resin, wherein the polyimide resin is prepared by polymerization reaction of a diamine composite material and a dianhydride monomer;

[0028] Wherein, the diamine combination material at least includes the diamine monomer with an epoxy structure as described in the first aspect.

[0029] Optionally, the polyimide resin has a molecular structure as shown below:

[0030]

[0031] Wherein, X is an aromatic dianhydride residue or an alicyclic dianhydride residue, R is an aromatic diamine residue or an alicyclic diamine residue, which represents a tetracarboxylic acid residue having a tetravalent alicyclic or aromatic group, m is an integer between 50 and 200, and n is an integer between 0 and 100.

[0032] Optionally, the aromatic dianhydride residue comprises at least one of the following compounds:

[0033] Pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, cyclo-3-butane-1,2,3,4-tetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, Cyclohexane-1,2,4,5-tetracarboxylic dianhydride, norbornane-2,3,5,6-tetracarboxylic dianhydride, bicyclo[2.2.2]oct-7-ene-3,4,8,9-tetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 2,2',3,3'-diphenylsulfonetetracarboxylic dianhydride, 2,3,3',4'-diphenylsulfonetetracarboxylic dianhydride, 3,3',4,4'-diphenylethertetracarboxylic dianhydride, 2,2',3,3'-diphenylethertetracarboxylic dianhydride, 2,3,3',4'-diphenylethertetracarboxylic dianhydride;

[0034] The alicyclic dianhydride residue comprises at least one of the following compounds:

[0035] Pyrazine-2,3,5,6-tetracarboxylic dianhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride, 2,2-[bis(3,4-dicarboxyphenyl)]hexafluoropropane dianhydride, 5-(2,5-dioxotetrahydro)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride.

[0036] Optionally, the aromatic diamine residue comprises at least one of the following compounds:

[0037] 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 1,4-bis(4-aminophenoxy)benzene, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis(4-aminophenoxyphenyl)sulfone, bis(3-aminophenoxyphenyl)sulfone, bis(4-aminophenoxy)biphenyl, bis{4-(4-aminophenoxy)phenyl}ether, 4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-anilino)hexafluoropropane, 2,2-bis(3-anilino)hexafluoropropane and 2,2-bis(3-amino-4-toluoyl)hexafluoropropane;

[0038] The alicyclic diamine residue comprises at least one of the following compounds:

[0039] 1,6-hexanediamine, 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane, 4,4'-diaminodicyclohexylmethane and 4,4'-diamino-3,3'-dimethylcyclohexylmethane.

[0040] Optionally, the dianhydride monomer includes at least one of an aromatic dianhydride monomer and an alicyclic dianhydride monomer.

[0041] One beneficial effect of the embodiments of the present application is:

[0042] The technical solution provided in the embodiment of the present application forms a diamine monomer with an epoxy group by directly introducing an epoxy group into the molecular structure of a diamine, thereby avoiding the phase separation problem between the polyimide film and the epoxy resin caused by the separate introduction of epoxy resin in the traditional method. This new diamine monomer can not only improve the bonding performance of the polyimide film to the substrate, but also form a long-chain structure that is cross-linked with each other during the thermal curing process, which can enhance the mechanical properties of the polyimide. The diamine monomer with an epoxy structure proposed in the embodiment of the present application solves the phase separation problem in the traditional technology, and has important significance and practical application value in terms of improving the bonding performance of the polyimide film to the substrate and enhancing the mechanical properties of the film.

[0043] Other features and advantages of the present application will become apparent from the following detailed description of exemplary embodiments of the present application. DETAILED DESCRIPTION

[0044] Various exemplary embodiments of the present application are now described in detail. It should be noted that the relative arrangement of components and steps, numerical expressions and numerical values ​​set forth in these embodiments do not limit the scope of the present application unless otherwise specifically stated.

[0045] The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the present application, its application, or uses.

[0046] Techniques and equipment known to ordinary technicians in the relevant art may not be discussed in detail, but where appropriate, the techniques and equipment should be considered part of the specification.

[0047] In all examples shown and discussed herein, any specific values ​​should be interpreted as merely exemplary and not limiting. Therefore, other examples of the exemplary embodiments may have different values.

[0048] The following is a detailed description of the diamine monomer with an epoxy structure and its preparation method and the polyimide resin provided in the embodiments of the present application in conjunction with specific embodiments.

[0049] As an important component of polyimide resin, the molecular structure of diamine monomer has a crucial influence on the performance of polyimide film. In order to enhance the adhesion of polyimide film to substrates such as metal, glass, silicon and other substrates, epoxy resin components are generally introduced into polyimide film, and the epoxy groups on epoxy resin form chemical bonds with the substrate to enhance the adhesion between polyimide film and the substrate. However, since epoxy resin and polyimide belong to two different types of polymers, there are relatively large differences in molecular structure between them, which will cause large phase separation and lead to adhesion failure.

[0050] According to one embodiment of the present application, a diamine monomer having an epoxy structure is provided. The molecular structural formula of the diamine monomer includes one or more epoxy groups, and the molecular structural formula is as follows:

[0051]

[0052] Wherein, A is a diamine residue, which includes a divalent aliphatic group, alicyclic group or aromatic group; and p is any integer between 1 and 10.

[0053] According to the embodiment of the present application, the diamine monomer with an epoxy structure has a molecular structural formula as shown above, which contains two amino groups (-NH2), one or more epoxy groups and an unknown part A.

[0054] In the molecular formula of the above-mentioned diamine monomer having an epoxy structure, "H2N-" and "-NH2" composed of nitrogen atoms and hydrogen atoms indicate that this is a diamine monomer, because a diamine monomer generally has two amino (-NH2) groups.

[0055] In the molecular formula of the diamine monomer with an epoxy structure, "A" can be understood as a placeholder, which represents a diamine residue. The diamine residue A can be a divalent aliphatic group, an alicyclic group or an aromatic group. Aliphatic groups refer to chain structures mainly composed of carbon atoms and hydrogen atoms, which usually have high flexibility and easy processing characteristics. Alicyclic groups have a ring structure, which gives the material higher heat resistance and mechanical strength, while also enhancing its chemical stability. Aromatic groups refer to a class of cyclic structures with special stability, such as benzene rings, which can significantly improve the thermal and chemical stability of the material. In summary, these three groups each have unique chemical properties and functions.

[0056] In the embodiments of the present application, the epoxy group, a functional group with unique reactivity, is designed to be directly introduced into the diamine molecular structure. In the process of diamine polymerization to form polyimide resin, the problem of phase separation between epoxy resin and polyimide resin that may be caused by the introduction of epoxy resin alone is effectively avoided, thereby significantly improving the bonding performance of polyimide film to various substrates. It is worth mentioning that in the thermal curing process of polyimide film, these epoxy structures can form a strong and stable long-chain structure that is cross-linked with each other, thereby greatly enhancing the mechanical properties of polyimide film. This design has opened up a new path for improving the performance and application fields of polyimide film.

[0057] In the molecular structural formula of the diamine monomer with epoxy structure provided in the embodiment of the present application, A, as a diamine residue, shows its diversified chemical structure characteristics, which can be a divalent aliphatic group, alicyclic group or aromatic group. Specifically, the addition of aliphatic groups allows the formed diamine monomer to show excellent flexibility and processing performance, which provides convenience for the preparation of materials. The addition of alicyclic groups significantly improves the heat resistance and mechanical strength of the formed diamine monomer, so that the diamine monomer can also maintain excellent performance under general extreme environments. When the diamine residue A is an aromatic group, its unique cyclic structure gives the diamine monomer higher thermal stability and chemical stability, further enhancing its applicability in various application scenarios. According to the different needs of the actual application scenario, different types of diamine residues can be flexibly selected to adjust the performance of the formed diamine monomer, so as to meet the special requirements of different fields for material properties.

[0058] In the molecular structural formula of the diamine monomer with an epoxy structure provided in the embodiment of the present application, p is a key variable, and its value range is designed to be any integer between 1 and 10, which represents the number of epoxy groups in the molecular structural formula. By adjusting the value of p, the distribution density of the epoxy groups in the formed diamine monomer can be effectively controlled, thereby accurately regulating its reactivity with other compounds, and further optimizing the performance of the final diamine monomer.

[0059] As a preferred solution of the present application, the finally synthesized diamine monomer with epoxy structure should contain at least two epoxy groups. When such a diamine monomer containing two or more epoxy groups is used as the leading component of the polymerization reaction to prepare a film of polyimide resin material (referred to as polyimide film), its mechanical properties will be significantly improved. This design achieves a deep optimization of the performance of the polyimide film.

[0060] The diamine monomer with epoxy structure provided in the embodiment of the present application provides the possibility for preparing a new polymer material with excellent performance due to the presence of epoxy groups in its molecular structure and the adjustability of the diamine residue A and the number of epoxy groups (the value of p). Such a material may have better reactivity, processing performance, heat resistance, mechanical strength, thermal stability and chemical stability, and can be widely used in many fields.

[0061] In general, the diamine monomer with epoxy structure of the embodiment of the present application directly introduces epoxy groups ingeniously in its molecular structure. The polyimide resin formed by the polymerization of the diamine monomer shows excellent performance. It is particularly worth mentioning that the polyimide resin significantly enhances the bonding performance of polyimide film to various substrates such as metal, glass, silicon, etc., and interacts through a stable chemical bond to ensure that the film is tightly bonded to the substrate, thereby avoiding the problem of falling off. In addition, during the thermal curing process, these epoxy groups play a vital role, and they can form a strong and mutually cross-linked long chain structure, which not only effectively extends the chain, but also significantly enhances the mechanical properties of the film, such as tensile strength and impact resistance. This optimization not only improves the overall performance of the film, but also further expands its application field, thereby giving the polyimide film a higher application value.

[0062] In some examples of the present application, the diamine residue A includes the following substituted or unsubstituted groups:

[0063]

[0064] in, Indicates a connecting key; X 10 , X 11 , X 12 , X 13 , X 14 , X 15 , X 16 , X 17 , X 18 , X 19 and X 20 Each independently selected from: a single bond, -O-, -S-, -C(CF3)2, -CO-, -SO2-, NR 11 R 12 or CR 13 R 14 , and R 11 , R 12 , R 13 and R 14 They are independently selected from: H or phenyl; n1 is any integer between 1 and 10.

[0065] According to the examples provided in this application, a single bond generally refers to a covalent bond between two atoms that shares a pair of electrons. For example, in alkanes, carbon atoms are connected by single bonds to form a stable chemical bond.

[0066] -O-: This is a single bond formed by an oxygen atom and usually represents an ether bond. For example, in diethyl ether, two carbon atoms are connected by an oxygen atom.

[0067] -S-: This is a single bond formed by a sulfur atom, usually indicating a thioether bond. Thioethers are a class of organosulfur compounds in which a sulfur atom is attached to two carbon atoms or other organic groups.

[0068] -C(CF3)2-: This is a group formed by two trifluoromethyl (CF3) groups replacing a carbon atom. The trifluoromethyl (CF3) group is a highly electronegative group that can affect the physical and chemical properties of the molecule, such as polarity and hydrophobicity.

[0069] -CO-: This is a carbonyl group, a double bond formed by carbon and oxygen atoms. Carbonyl groups are widely present in organic compounds such as aldehydes, ketones, and carboxylic acids, and are important functional groups in organic synthesis.

[0070] -SO2-: This is a sulfoxide group, in which the sulfur atom forms two double bonds with two oxygen atoms. This group is commonly found in sulfoxide and sulfone compounds and has specific chemical properties and applications.

[0071] NR 11 R 12 : This is an amine group in which the nitrogen atom is bound to two groups R 11 and R 12 These groups can be hydrogen (forming a primary amine), a hydrogen and an organic group (forming a secondary amine), or two organic groups (forming a tertiary amine).

[0072] CR 13 R 14 : This is a carbon atom with two groups R 13 and R 14 The connected group. 13 and R 14 It can be hydrogen or other organic groups, which determine the chemical properties and reactivity of the carbon atom.

[0073] About R 11 , R 12 , R 13 and R 14 : These symbols represent substituents, i.e., other groups or atoms that can be attached to the above groups or atoms. 11 , R 12 , R 13 and R 14 Each is independently selected from H (hydrogen) or phenyl (C6H5, a ring structure consisting of six carbon atoms).

[0074] For example, in NR 11 R 12 In, R 11 and R 12They may be hydrogen (forming NH2, ie amino groups), or they may be phenyl groups (forming N(C6H5)2, ie diphenylamino groups).

[0075] In the examples of this application, the term "substituted or unsubstituted" has a specific meaning, which means that the functional group following it may or may not have a substituent. Taking "substituted or unsubstituted phenyl" as an example, it means that the phenyl group may be in its original form without any substitution or may have one or more substituents.

[0076] It should be noted that, in the examples of this application, It represents a connecting bond, and the non-positional connecting bond involved refers to one that extends from any site in the ring system and can connect to any position of another molecule in the ring system through which the bond passes.

[0077] In some examples of the present application, the substituents of the diamine residue A include deuterium, a halogen group, a trifluoromethyl group, a cyano group, a heteroaryl group, an aryl group, an alkyl group, a deuterated alkyl group, a halogenated alkyl group, a cycloalkyl group, an alkoxy group or an aryloxy group; the substituents of the diamine residue A include one or more.

[0078] According to the examples of the present application, the substituents of the diamine residue A are of various kinds.

[0079] Deuterium is an isotope of hydrogen with one neutron and one proton in its nucleus. In organic chemistry, the introduction of deuterium can change the physical and chemical properties of molecules.

[0080] Halogen groups, for example, include fluorine, chlorine, bromine and iodine. Halogen atoms have strong electronegativity and can affect the reactivity and polarity of molecules.

[0081] The trifluoromethyl group is a highly electronegative group that can enhance the stability and hydrophobicity of the molecule.

[0082] The cyano group is a highly reactive functional group that can participate in a variety of organic reactions.

[0083] Heteroaryl, an aromatic group containing at least one heteroatom (eg, nitrogen, oxygen, sulfur), has unique electronic properties and reactivity.

[0084] Aryl refers to a benzene ring and its derivatives, which have a stable conjugated structure.

[0085] An alkyl group is a saturated hydrocarbon group and may be a straight chain or a branched chain.

[0086] A deuterated alkyl group is an alkyl group containing a deuterium atom.

[0087] A haloalkyl group is an alkyl group containing a halogen atom.

[0088] A cycloalkyl group is a saturated cyclic hydrocarbon group.

[0089] Alkoxy groups are groups of the form RO-, wherein R is an alkyl group.

[0090] Aryloxy is a group of the form ArO-, wherein Ar is an aryl group.

[0091] The above-mentioned substituents may appear on the diamine residue A alone or in combination, and their number may be one, two or more. The presence of these substituents has a significant effect on the properties of the diamine residue A and the molecule in which it is located. For example, they can change the polarity, solubility, reactivity, stability, etc. of the molecule, thereby affecting the physicochemical properties and processing performance of the material.

[0092] Further, taking the substituted phenyl as an example, the influence of the substituents in the diamine residue A on the benzene ring is further explored. There are many types of these substituents, including but not limited to deuterium, halogen groups (such as chlorine, fluorine, bromine, iodine, etc.), each of which gives the benzene ring unique chemical properties and reactivity. For example, the introduction of halogen groups can change the electron distribution of the benzene ring, thereby regulating its interaction with other molecules and enhancing its activity in specific reactions.

[0093] Groups such as trifluoromethyl and cyano not only provide stability to the benzene ring, but also give it specific functionality. The introduction of these groups can improve the thermal stability, electrical properties or optical properties of the material.

[0094] When it comes to more complex substituents, such as heteroaryl, aryl, alkyl, deuterated alkyl, halogenated alkyl, cycloalkyl, alkoxy and aryloxy, they bring richer chemical properties and potential application value to the benzene ring. These substituents achieve precise control of the properties of the benzene ring by changing the electron cloud distribution of the benzene ring, the interaction between molecules and the spatial configuration of the molecule.

[0095] It is worth mentioning that the number of these substituents is not fixed, it can be one, two or more. They can appear on the benzene ring in different combinations, jointly determining the overall properties and potential applications of the benzene ring. This flexibility makes it possible to obtain compounds with specific functions and properties by designing the type and number of substituents to meet the needs of different fields.

[0096] In general, by rationally selecting the type and amount of substituents, the properties of the diamine residue A and the molecule in which it resides can be precisely controlled to meet the needs of different application scenarios.

[0097] In some examples of the present application, the aromatic group includes an aryl group or a heteroaryl group, wherein the aryl group is a monocyclic aryl group or a condensed-ring aryl group, and the heteroaryl group is a monocyclic heteroaryl group or a condensed-ring heteroaryl group.

[0098] In the examples of the present application, when the diamine residue A is an aromatic group, the aromatic group here includes two categories: aromatic group and heteroaryl group. Specifically:

[0099] The aryl group refers to a group derived from an aromatic carbocyclic ring, which includes not only monocyclic aryl groups such as phenyl, but also condensed aryl groups such as naphthyl. In addition, two or more monocyclic aryl groups (such as biphenyl) connected by conjugation of carbon-carbon bonds, a combination of a monocyclic aryl group and a condensed aryl group, and a connection form of two or more condensed aryl groups all belong to the category of aryl groups.

[0100] The heteroaryl group refers to an aromatic ring containing one, two or more heteroatoms in the ring, wherein the heteroatom may be at least one of B, O, N, P, Si, Se and S. These heteroaryl groups may be a single ring structure or a condensed ring structure.

[0101] In some examples of the present application, the aryl group includes phenyl, naphthyl, fluorenyl, anthracenyl, phenanthrenyl, biphenyl, terphenyl, benzo[9,10]phenanthrenyl, pyrenyl or benzofluoranthenyl;

[0102] The heteroaryl group includes thienyl, furanyl, pyrrolyl, imidazolyl, thiazolyl, oxazolyl, oxadiazolyl, triazolyl, pyridyl, triazinyl, acridinyl, pyridazinyl, pyrazinyl, quinolyl, quinazolinyl, quinoxalinyl, phenoxazinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, pyrazinopyrazinyl, isoquinolyl, indolyl, carbazolyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, benzocarbazolyl, benzothienyl, dibenzothienyl, thienothiphenyl, benzofuranyl, phenanthrolinyl, isoxazolyl, thiadiazolyl, phenothiazinyl, phenoxathiyl or dibenzo-p-dioxinyl.

[0103] The above-mentioned aromatic and heteroaromatic groups provide a rich material basis and technical support for the research and application in the fields of organic chemistry and materials science due to their unique properties and wide application fields.

[0104] In some examples of the present application, the aliphatic group includes a hydrocarbon group, a cyclic hydrocarbon group, an ether group or a keto group.

[0105] According to the example of the present application, another material of the diamine residue A is described, that is, it can be an aliphatic group. The aliphatic group is derived from aliphatic compounds, which are mainly composed of hydrocarbon chains and can be saturated or unsaturated. Here, aliphatic compounds include but are not limited to hydrocarbons, fatty ethers, and fatty ketones. When these compounds lose at least one hydrogen atom, an aliphatic group is formed.

[0106] The hydrocarbon group is a group formed by an open-chain hydrocarbon losing at least one hydrogen atom, including, for example, alkyl, alkylene, etc. The hydrocarbon group has good stability and hydrophobicity, which enables the diamine residue A containing the hydrocarbon group to have application value in the synthesis of hydrophobic polymer materials or interface materials.

[0107] The cycloalkyl group is a group formed by a cyclic hydrocarbon losing at least one hydrogen atom, such as cycloalkyl and cycloalkylene groups. The presence of the cycloalkyl group can enhance the rigidity and stability of the molecule and help improve the thermal stability and mechanical properties of the polymer.

[0108] When a fatty ether loses at least one hydrogen atom, it forms an ether group. An ether group is a group containing an oxygen atom connecting two hydrocarbon groups, in the form of RO-R'. The presence of an ether group can enhance the polarity of the molecule, affect the solubility of the molecule and its interaction with other molecules, thereby adjusting the physical and chemical properties of the material.

[0109] Ketones are formed when aliphatic ketones lose at least one hydrogen atom. Ketones are groups containing carbonyl groups, in the form of R-CO-R'. Ketones are highly active functional groups that can participate in a variety of organic reactions, making it possible to synthesize compounds with specific functions.

[0110] In the examples of the present application, the aliphatic group includes a hydrocarbon group, and the hydrocarbon group includes, for example, an alkyl group, the number of carbon atoms of the alkyl group is 1 to 10, and these alkyl groups have different carbon chain lengths, ranging from the simplest methyl group to the longer octyl group. The specific examples of these alkyl groups are rich and varied, including methyl, ethyl, n-propyl, isopropyl, and butyl, pentyl, and hexyl groups in various positions. These groups are not only structurally diverse, but also exhibit unique properties in practical applications.

[0111] In the examples of the present application, the alkyl group may be an alkyl group with a carbon number of 1 to 10, and the carbon number of the alkyl group is, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10. Further, the alkyl group may specifically include, but is not limited to, methyl, ethyl, n-propyl, isopropyl, 1-butyl (n-Bu, n-butyl, -CH2CH2CH2CH3), 2-methyl-1-propyl (i-Bu, i-butyl, -CH2CH(CH3)2), 2-butyl (s-Bu, s-butyl, -CH(CH3)CH2CH3), 2-methyl-2-propyl (t-Bu, t-butyl, -C(CH3)3), 1 -pentyl (n-pentyl, -CH2CH2CH2CH2CH3), 2-pentyl (-CH(CH3)CH2CH2CH3), 3-pentyl (-CH(CH2CH3)2), 2-methyl-2-butyl (-C(CH3)2CH2CH3), 3-methyl-2-butyl (-CH(CH3)CH(CH3)2), 3-methyl-1-butyl (-CH2CH2CH(CH3)2), 2-methyl-1-butyl (-CH2CH(CH3)CH2CH3), 1-hexyl (-CH2CH2CH2CH2CH2CH3), 2-hexyl (-CH(CH3)CH2CH2CH2CH3), 3-hexyl (-CH(CH2CH3)(CH2CH2CH3)), 2-methyl-2-pentyl (-C(CH3)2CH2CH2CH3), 3-methyl-2-pentyl (-CH(CH3)CH(CH3)CH 2CH3), 4-methyl-2-pentyl (-CH(CH3)CH2CH(CH3)2), 3-methyl-3-pentyl (-C(CH3)(CH2CH3)2), 2-methyl-3-pentyl (-CH(CH2CH3)CH(CH3)2), 2,3-dimethyl-2-butyl (-C(CH3)2CH(CH3)2), 3,3-dimethyl-2-butyl (-CH(CH3)C(CH3)3 and octyl.

[0112] The introduction of aliphatic groups brings great flexibility and adjustability to the design of the diamine monomer. By selecting different aliphatic groups, the physical and chemical properties of the diamine monomer formed can be precisely controlled. In addition, the introduction of the above-mentioned aliphatic groups can also significantly improve the mechanical properties, thermal stability and processing properties of the diamine monomer formed.

[0113] In some examples of the present application, the alicyclic group is a non-aromatic hydrocarbon containing ring carbon atoms, including a monocyclic alkyl group, a spirocyclic alkyl group or a bridged cycloalkyl group; wherein the number of carbon atoms of the alicyclic group is 3 to 10, and the alicyclic group includes one or more double bonds.

[0114] The alicyclic group is a special type of aliphatic group, which is characterized by containing ring carbon atoms and being a non-aromatic hydrocarbon.

[0115] The alicyclic group can be further divided into monocyclic alkyl, spirocyclic alkyl and bridged cyclic alkyl groups. These different types of ring structures give them their own unique physical and chemical properties.

[0116] In particular, it is mentioned in the examples of the present application that the alicyclic groups have 3 to 10 carbon atoms, which means that these groups are of moderate size, neither too large to affect the overall properties of the molecule nor too simple to lack sufficient structural diversity.

[0117] In addition, in the examples of this application, it is also pointed out that the alicyclic group can contain one, two or more double bonds. The presence of double bonds increases the reactivity of the group, allowing them to participate in more organic reactions, thereby synthesizing compounds with specific functions.

[0118] The introduction of the alicyclic group can significantly change the physical and chemical properties of the compound. For example, the ring structure can enhance the rigidity and stability of the molecule, so that the compound containing the alicyclic group can remain stable under high temperature or high pressure environment. At the same time, the presence of double bonds makes these compounds more reactive and can be used to synthesize materials with specific functional groups.

[0119] According to another embodiment of the present application, a method for preparing a diamine monomer having an epoxy structure as described above is provided, the preparation method comprising: reacting a hydroxyl-containing diamine with epichlorohydrin in a sodium hydroxide solution, wherein the hydroxyl group of the diamine can be replaced by the glycidyl ether to obtain a diamine monomer having an epoxy group.

[0120] In some examples of the present application, the synthesis formula of the diamine monomer is as follows:

[0121]

[0122] Wherein, A is a diamine residue, which includes a divalent aliphatic group, alicyclic group or aromatic group; and p is any integer between 1 and 10.

[0123] According to the method for preparing a diamine monomer having an epoxy structure provided in an embodiment of the present application, the preparation method utilizes the reaction between a hydroxyl-containing diamine and epichlorohydrin to obtain a diamine monomer having an epoxy group.

[0124] First, from the perspective of the main raw materials involved in the reaction, hydroxyl-containing diamine is used, which is an important starting material. Hydroxyl is a very active functional group that can participate in a variety of chemical reactions, especially reactions with halogenated hydrocarbons (such as epichlorohydrin). Among them, hydroxyl-containing diamines include, for example, 2,5-diaminophenol, 2,5-diaminoresorcinol or 3,3'-dihydroxybenzidine.

[0125] Next, the hydroxyl-containing diamine is placed in a sodium hydroxide solution. Sodium hydroxide plays two main roles here: first, as a base, it helps deprotonate the hydroxyl group of the diamine, making it easier to participate in the reaction; second, as a catalyst, it promotes the subsequent reaction process. Then, epichlorohydrin is added to this system. Epichlorohydrin is a compound containing an epoxy group and a chlorine atom. Under the action of sodium hydroxide, the chlorine atom can be replaced, and the epoxy group reacts with the hydroxyl group of the diamine to form an ether bond.

[0126] The key to the above reaction is that the hydroxyl group of the diamine can be replaced by glycidyl ether. This means that during the reaction, the epoxy group of epichlorohydrin will undergo an etherification reaction with the hydroxyl group of the diamine, thereby generating a diamine monomer with an epoxy group.

[0127] Furthermore, a diamine containing a hydroxyl group (-OH) reacts with epichlorohydrin in a sodium hydroxide solution, and the hydroxyl group is replaced by glycidyl ether to obtain a novel diamine monomer with an epoxy group.

[0128] Finally, through a series of subsequent steps, such as separation and purification, the final target product, a diamine monomer with an epoxy group, can be obtained.

[0129] This diamine monomer has a special epoxy structure, which gives it unique chemical properties and application potential. For example, the epoxy group is highly reactive and can further participate in a variety of chemical reactions to synthesize more compounds with specific functions.

[0130] In some examples of the present application, the molar ratio of the hydroxyl-containing diamine to the epichlorohydrin is 1:1p~3p.

[0131] In the examples of the present application, the molar ratio range between the hydroxyl-containing diamine and epichlorohydrin is described, and this molar ratio is set to 1:1p to 1:3p, which means that each mole of the hydroxyl-containing diamine reacts with 1p to 3p moles of epichlorohydrin.

[0132] In actual situations, due to factors such as reaction conditions, purity of reactants, and possible side reactions, it may not always be optimal to react completely according to a molar ratio of 1:1p. Therefore, this application also considers higher molar ratios such as 1:1.1p or 1:2.3p. This means that more epichlorohydrin participates in the reaction. One benefit of this design is that the conversion rate of hydroxyl-containing diamines can be increased, that is, more diamine molecules can participate in the reaction and be converted into the target product. In addition, increasing the amount of epichlorohydrin can also inhibit the occurrence of side reactions to a certain extent and improve the purity and yield of the product.

[0133] However, too high a molar ratio may also cause some problems. For example, too much epichlorohydrin may increase the complexity of the reaction system, making subsequent separation and purification steps more difficult. In addition, too much unreacted material may also have an adverse effect on the environment.

[0134] By setting the molar ratio between the hydroxyl-containing diamine and epichlorohydrin to 1:1p to 1:3p, the preparation method provided in the embodiment of the present application not only ensures the reaction efficiency, but also takes into account the purity and yield of the product, as well as environmental friendliness. The setting of this molar ratio helps to optimize the reaction process and improve the quality and yield of the target product.

[0135] According to another embodiment of the present application, a polyimide resin is provided, wherein the polyimide resin is prepared by polymerization reaction of a diamine combination material and a dianhydride monomer; wherein the diamine combination material at least includes the diamine monomer having an epoxy structure as described above.

[0136] Polyimide resin is a polymer material with excellent properties and is widely used in aerospace, electronics, automobile manufacturing and other fields.

[0137] The polyimide resin provided in this embodiment is prepared by a polymerization reaction between a diamine composite material and a dianhydride monomer.

[0138] In the description of the above embodiment, it is mentioned that the diamine composite material at least includes a diamine monomer having an epoxy structure. This means that in the process of preparing the polyimide resin, a diamine monomer having an epoxy group is used as a key component. The epoxy group is a highly active functional group that can react with other compounds to form a stable chemical bond.

[0139] The polyimide resin provided in the embodiment of the present application adopts a polymerization reaction between a diamine monomer having an epoxy group and a dianhydride monomer, and based on the epoxy group of the diamine monomer, the phase separation of the epoxy resin and the polyimide resin added alone is avoided. At the same time, the bonding performance and mechanical properties of the polyimide resin film are improved. This is because the introduction of the epoxy group can improve the bonding performance of the polyimide film and the substrate, and at the same time, a long chain of cross-linking can be formed during the thermal curing process to extend the chain, which is conducive to improving the mechanical properties of the polyimide film.

[0140] Due to the use of diamine monomers with epoxy structures, polyimide resin forms a highly cross-linked network structure during the polymerization process, which gives the resin excellent mechanical strength, hardness and wear resistance. The introduction of epoxy groups also enhances the thermal stability of polyimide resin. Polyimide resin has good resistance to a variety of chemical reagents and solvents and can maintain stable performance in various harsh chemical environments.

[0141] In addition, in the present application, by adjusting the type and proportion of the diamine combination material, customized regulation of the performance of the polyimide resin can be achieved to meet the special requirements of different application fields for material performance.

[0142] In general, the technical solution provided in the embodiments of the present application introduces epoxy groups into the molecular structure of diamine monomers to prepare a new type of diamine monomer, and uses this type of diamine monomer to carry out a polymerization reaction in combination with a dianhydride monomer. The obtained polyimide resin has stronger substrate adhesion performance, higher Young's modulus, greater elongation at break, lower thermal expansion coefficient and anti-warping performance after being prepared into a film, which is conducive to expanding its application in the field of high-strength and high-adhesion polyimide films.

[0143] In addition, the diamine combination material also includes other diamine monomers without epoxy structure, including hydrocarbon-containing diamines. Other diamine monomers without epoxy structure include, for example, 2,5-diaminophenol, 2,5-diaminoresorcinol or 3,3'-dihydroxybenzidine and other hydrocarbon-containing diamines.

[0144] Polyimide molecules are high-performance polymers whose performance depends largely on their molecular structure. In the above-mentioned diamine combination material, in addition to introducing diamine monomers with epoxy groups, other diamine monomers without epoxy structures can also be introduced.

[0145] The benefit of introducing other diamine monomers without epoxy structures is that the chemical structure of polyimide molecules can be adjusted, thereby affecting their physical and chemical properties. For example, these diamine monomers may have different properties such as flexibility, polarity, and reactivity. They work together with diamine monomers with epoxy groups to achieve comprehensive optimization of polyimide materials in terms of mechanical properties, thermal stability, and processability.

[0146] Of course, the diamine combination material for making the polyimide resin may only contain diamine monomers having an epoxy structure, that is, it does not contain other diamine monomers without an epoxy structure, which may make the polyimide material more specifically exhibit the characteristics imparted by the diamine monomers having epoxy groups.

[0147] In some examples of the present application, the polyimide resin has a molecular structure as shown below:

[0148]

[0149] Wherein, X is an aromatic dianhydride residue or an alicyclic dianhydride residue, R is an aromatic diamine residue or an alicyclic diamine residue, which represents a tetracarboxylic acid residue having a tetravalent alicyclic or aromatic group, m is an integer between 50 and 200, and n is an integer between 0 and 100.

[0150] According to the molecular structure of the polyimide resin shown in the above example of the present application, the dianhydride residue X comes from a diamine monomer having an epoxy structure, and the diamine residue R comes from other diamine monomers that may not have an epoxy structure. It should be noted that if only a diamine monomer having an epoxy structure is used in the diamine combination material, n is 0.

[0151] In the molecular structure of the polyimide resin, X represents an aromatic dianhydride residue or an alicyclic dianhydride residue. These residues provide stability and strength to the polyimide resin. Aromatic dianhydride residues generally have higher thermal and chemical stability, while alicyclic dianhydride residues may give the resin better processing properties and flexibility.

[0152] In the molecular structure of the polyimide resin, R represents an aromatic diamine residue or an alicyclic diamine residue. These residues also have a certain influence on the performance of the polyimide resin. Aromatic diamine residues help to enhance the strength and rigidity of the polymer, while alicyclic diamine residues may improve the toughness and impact resistance of the resin.

[0153] In addition, in the molecular structure of the polyimide resin, m and n represent an integer between 50 and 200 and an integer between 0 and 100, respectively. These two parameters represent the length and crosslinking degree of the polymer chain, and have a significant impact on the performance and processing properties of the polyimide resin.

[0154] In some examples of the present application, the aromatic dianhydride residue includes at least one of the following compounds:

[0155] Pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, cyclo-3-butane-1,2,3,4-tetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, Cyclohexane-1,2,4,5-tetracarboxylic dianhydride, norbornane-2,3,5,6-tetracarboxylic dianhydride, bicyclo[2.2.2]oct-7-ene-3,4,8,9-tetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 2,2',3,3'-diphenylsulfonetetracarboxylic dianhydride, 2,3,3',4'-diphenylsulfonetetracarboxylic dianhydride, 3,3',4,4'-diphenylethertetracarboxylic dianhydride, 2,2',3,3'-diphenylethertetracarboxylic dianhydride, 2,3,3',4'-diphenylethertetracarboxylic dianhydride;

[0156] The alicyclic dianhydride residue comprises at least one of the following compounds:

[0157] Pyrazine-2,3,5,6-tetracarboxylic dianhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride, 2,2-[bis(3,4-dicarboxyphenyl)]hexafluoropropane dianhydride, 5-(2,5-dioxotetrahydro)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride.

[0158] According to the above examples, the specific types of aromatic dianhydride residues and alicyclic dianhydride residues used in the process of preparing polyimide resins are described. Aromatic dianhydride residues and alicyclic dianhydride residues are both important components in the preparation of polyimide resins, and they can be used together with diamine monomers (including diamine monomers with epoxy structures and other diamine monomers without epoxy structures) to construct the molecular structure of polyimide through polymerization reaction.

[0159] Aromatic dianhydride residues are mainly derived from compounds with aromatic ring structures. Such compounds can introduce aromatic rings into polyimide to increase the rigidity and thermal stability of the polymer.

[0160] The alicyclic dianhydride residues are mainly derived from compounds with alicyclic structures. The alicyclic structure brings high flexibility and processability to polyimide while maintaining a certain thermal stability.

[0161] By using different types of aromatic and alicyclic dianhydride residues, polyimide resins with different properties can be prepared. These resins show diversity in mechanical properties, thermal stability, chemical stability, etc., and can adapt to different working environments and application requirements.

[0162] By adjusting the ratio and type of aromatic and alicyclic dianhydride residues, the comprehensive properties of polyimide resin can be optimized. For example, increasing the ratio of aromatic dianhydride can improve the thermal stability and rigidity of the resin; increasing the ratio of alicyclic dianhydride can improve the flexibility and processability of the resin.

[0163] In addition, since the properties of polyimide resins can be flexibly controlled by adjusting the type and proportion of dianhydride residues, their application range is further expanded.

[0164] In some examples of the present application, the aromatic diamine residue includes at least one of the following compounds:

[0165] 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 1,4-bis(4-aminophenoxy)benzene, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis(4-aminophenoxyphenyl)sulfone, bis(3-aminophenoxyphenyl)sulfone, bis(4-aminophenoxy)biphenyl, bis{4-(4-aminophenoxy)phenyl}ether, 4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-anilino)hexafluoropropane, 2,2-bis(3-anilino)hexafluoropropane and 2,2-bis(3-amino-4-toluoyl)hexafluoropropane;

[0166] The alicyclic diamine residue comprises at least one of the following compounds:

[0167] 1,6-hexanediamine, 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane, 4,4'-diaminodicyclohexylmethane and 4,4'-diamino-3,3'-dimethylcyclohexylmethane.

[0168] According to the examples of this application, the specific types of aromatic diamine residues and alicyclic diamine residues used in the preparation process of polyimide resin are described. These diamine residues and the above-mentioned dianhydride residues jointly construct the molecular structure of polyimide through polymerization reaction, thereby determining its performance and application characteristics.

[0169] Aromatic diamine residues are derived from diamine compounds containing aromatic rings. Such compounds generally impart excellent thermal stability, mechanical strength, and chemical stability to polyimide resins.

[0170] The alicyclic diamine residues are derived from diamine compounds containing alicyclic structures. Such compounds generally impart good flexibility and processability to polyimide resins while maintaining certain thermal stability.

[0171] By using different types of aromatic and alicyclic diamine residues, the properties of polyimide resins can be tuned. For example, increasing the proportion of aromatic diamines can improve the thermal stability and mechanical strength of the resin, while increasing the proportion of alicyclic diamines can improve its flexibility and processability.

[0172] By combining different diamine residues, polyimide resins with different performance characteristics can be prepared to meet the needs of different application fields.

[0173] By designing the type and ratio of diamine residues, it is possible to maintain certain key properties of polyimide resin while improving other properties. This balance and optimization makes polyimide resin a material with excellent comprehensive properties.

[0174] In some examples of the present application, the dianhydride monomer includes at least one of an aromatic dianhydride monomer and an alicyclic dianhydride monomer.

[0175] Aromatic dianhydride monomers refer to dianhydride compounds containing aromatic ring structures. Due to the rigid structure and stability of the aromatic ring, this type of dianhydride monomer gives polyimide resins high thermal stability, good insulation and mechanical strength.

[0176] Alicyclic dianhydride monomers are dianhydride compounds containing alicyclic structures. Alicyclic structures are more flexible than aromatic rings, so alicyclic dianhydride monomers can give polyimide resins better flexibility and processability. At the same time, they also have certain thermal stability, which allows polyimide resins to have a wider range of applications while maintaining certain performance.

[0177] By using at least one of an aromatic dianhydride monomer and an alicyclic dianhydride monomer, polyimide resins with different properties can be prepared. These resins can exhibit different properties in terms of thermal stability, mechanical strength, flexibility, etc. according to the requirements of specific application scenarios.

[0178] Due to the diversity of dianhydride monomer types, the application scope of polyimide resins has been further expanded. Whether it is the aerospace field that requires high performance, or the automotive manufacturing and construction materials fields that require good flexibility and processability, suitable polyimide resin materials can be found.

[0179] The embodiments of the present application are further described below through Examples 1 to 3 and Comparative Examples 1 to 4.

[0180] Example 1

[0181] (1) The synthesis equation of the diamine monomer having an epoxy structure is as follows:

[0182]

[0183] To a 500mL three-necked flask, add 12.4g (0.1mol) of 2,5-diaminophenol and 200mL of 5M sodium hydroxide aqueous solution, stir under nitrogen protection, add 10.18g (0.11mol) of epichlorohydrin, react at 65°C for 3h, filter and wash with water until neutral after the reaction, and recrystallize to obtain 10.82g of diamine monomer A with an epoxy structure, with a yield of 65.1%.

[0184] (2) The preparation of polyimide resin is as follows:

[0185] Take 7.44g (60mmol) of 2,5-diaminophenol and 6.31g (38mmol) of diamine monomer A with an epoxy structure in a 500mL three-necked flask, add 250mL of anhydrous N,N'-dimethylacetamide DMAC, stir at room temperature until dissolved, then add 21.38g (98mmol) of 1,2,4,5-pyromellitic dianhydride PMDA, stir and react for 3h to obtain polyimide resin glue A.

[0186] Example 2

[0187] (1) The synthesis equation of the diamine monomer having an epoxy structure is as follows:

[0188]

[0189] Add 14 g (0.1 mol) of 2,5-diaminoresorcin to a 500 mL three-necked flask, add 200 mL of 5M sodium hydroxide aqueous solution, stir under nitrogen protection, add 21.28 g (0.23 mol) of epichlorohydrin, react at 65 ° C for 3 h, filter and wash with water until neutral after the reaction, recrystallize to obtain 13.30 g of diamine monomer B with an epoxy structure, with a yield of 59.3%.

[0190] (2) The preparation of polyimide resin is as follows:

[0191] Take 8.4g (60mmol) of 2,5-diaminoresorcinol and 8.52g (38mmol) of diamine monomer B with an epoxy structure in a 500mL three-necked flask, add 250mL of anhydrous N,N'-dimethylacetamide DMAC, stir at room temperature until dissolved, then add 21.38g (98mmol) of 1,2,4,5-pyromellitic dianhydride PMDA, stir and react for 3h to obtain polyimide resin glue B.

[0192] Example 3

[0193] (1) The synthesis equation of the diamine monomer having an epoxy structure is as follows:

[0194]

[0195] Add 21.6 g (0.1 mol) of 3,3'-dihydroxybenzidine to a 500 mL three-necked flask, add 200 mL of 5M sodium hydroxide aqueous solution, stir under nitrogen protection, add 21.28 g (0.23 mol) of epichlorohydrin, react at 65 ° C for 3 h, filter and wash with water until neutral after the reaction, recrystallize to obtain 14.20 g of diamine monomer C with an epoxy structure, with a yield of 47.3%.

[0196] (2) The preparation of polyimide resin is as follows:

[0197] Take 12.96g (60mmol) of 3,3'-dihydroxybenzidine and 11.41g (38mmol) of diamine monomer C with an epoxy structure in a 500mL three-necked flask, add 250mL of anhydrous N,N'-dimethylacetamide DMAC, stir at room temperature until dissolved, then add 21.38g (98mmol) of 1,2,4,5-pyromellitic dianhydride PMDA, stir and react for 3h to obtain polyimide resin glue C.

[0198] Comparative Example 1

[0199] Take 12.15g (98mmol) of 2,5-diaminophenol in a 500mL three-necked flask, add 250mL of anhydrous N,N'-dimethylacetamide DMAC, stir at room temperature until dissolved, then add 21.38g (98mmol) of 1,2,4,5-pyromellitic dianhydride PMDA, stir and react for 3h to obtain polyimide resin glue A'.

[0200] Comparative Example 2

[0201] Take 13.72g (98mmol) of 2,5-diaminoresorcinol in a 500mL three-necked flask, add 250mL of anhydrous N,N'-dimethylacetamide DMAC, stir at room temperature until dissolved, then add 21.38g (98mmol) of 1,2,4,5-pyromellitic dianhydride PMDA, stir and react for 3h to obtain polyimide resin glue B'.

[0202] Comparative Example 3

[0203] Take 21.17g (98mmol) of 3,3'-dihydroxybenzidine in a 500mL three-necked flask, add 250mL of anhydrous N,N'-dimethylacetamide DMAC, stir at room temperature until dissolved, then add 21.38g (98mmol) of 1,2,4,5-pyromellitic dianhydride PMDA, stir and react for 3h to obtain polyimide resin glue C'.

[0204] Comparative Example 4

[0205] Take 13.72g (98mmol) of 2,5-diaminoresorcinol in a 500mL three-necked flask, add 250mL of anhydrous N,N'-dimethylacetamide DMAC, stir at room temperature until dissolved, then add 21.38g (98mmol) of 1,2,4,5-pyromellitic dianhydride PMDA, stir and react for 3h, then add 5g of polyethylene glycol diglycidyl ether to obtain polyimide resin glue D'.

[0206] According to the above-mentioned Examples 1 to 3 and Comparative Examples 1 to 4, the products were subjected to mechanical property tests and adhesive property tests, respectively.

[0207] (1) Mechanical properties test methods are as follows:

[0208] After the polyimide resin glue was vacuum-debubbled, it was evenly coated on a glass sheet by a flat plate coating method to make a wet film with a thickness of 200um. The wet film was placed in a vacuum oven, and the temperature was raised to 80℃, 120℃, 180℃, 250℃, 300℃ and 350℃ for 30 minutes, and then taken out after cooling to room temperature to obtain a polyimide cured film. The obtained polyimide cured film was cut into strips with a width of 10mm, and the Young's modulus (Et) and elongation at break (m) of the film were tested using a Zwick electronic universal testing machine according to the GB / T1843 standard. The test results are shown in Table 1.

[0209] Table 1 Mechanical properties of polyimide resin glue after film formation

[0210] serial number Resin glue Et / GPa m / ％ Example 1 A 2.31 25.3 Example 2 B 2.42 32.7 Example 3 C 2.56 38.3 Comparative Example 1 A' 2.13 11.6 Comparative Example 2 B' 2.19 12.1 Comparative Example 3 C' 2.10 12.3 Comparative Example 4 D' 2.36 21

[0211] It can be seen from the test results shown in Table 1 that the use of diamine monomers with epoxy groups in the synthesis of polyimide resins can effectively improve the Young's modulus and elongation at break of polyimide films, and its effect on enhancing mechanical properties is more effective than the traditional method of adding epoxy resin to polyimide resins.

[0212] (2) Adhesion performance test method, as follows:

[0213] After the polyimide resin glue is vacuum-debubbled, it is evenly coated on glass sheets, copper foils and silicon wafers using a flat blade coating method to produce a wet film with a thickness of 250 um. The wet film is placed in a vacuum oven and heated to 80°C, 120°C, 180°C, 250°C, 300°C and 350°C in sequence for 30 minutes. After cooling to room temperature, it is taken out to obtain a polyimide cured film with a thickness of about 30 um.

[0214] The polyimide resin glue solution was placed in a -18℃ refrigerator for 1 month, then taken out and warmed to room temperature, and the previous steps were repeated to make a film. The white grid knife test method was used to test the adhesion performance of the polyimide film to the substrate. The test method is as follows: (a) Place the sample on a flat and stable surface; (b) Hold the knife and evenly form a specified number of cuts at an appropriate spacing and cutting rate; (c) Cut at 90° to intersect the original tangent to form a grid pattern; (d) Use a soft brush to brush away debris along the diagonal direction; (e) Place the sample in a constant temperature and humidity chamber at 85℃ and 85% humidity for 100 hours, then take it out, wipe it dry and place it at room temperature; (f) Remove a 75mm long 3M adhesive tape, with the center of the tape located at the center of the grid, and press it flat on the surface with your fingers; (g) Within five minutes of sticking, tear off the tape steadily at an angle of 60° within 0.5s or 1s.

[0215] The grid morphology was compared according to the adhesion test standard and evaluated on a scale of 0-5.

[0216]

[0217] The test results of the above-mentioned bonding performance are shown in Table 2.

[0218] Table 2 Adhesive properties of polyimide resin glue after film formation

[0219]

[0220] In Table 2, the adhesive property a represents the adhesive property of the polyimide resin just prepared, and the adhesive property b represents the adhesive property of the polyimide resin after being stored for one month.

[0221] From the test results shown in Table 2, it can be seen that the use of diamines with epoxy groups to synthesize polyimide can effectively improve the adhesion of polyimide film to glass, copper foil and silicon wafer, and its storage stability is higher than the traditional method of adding epoxy resin to polyimide resin.

[0222] The above embodiments focus on the differences between the various embodiments. As long as the different optimization features between the various embodiments are not contradictory, they can be combined to form a better embodiment. Considering the simplicity of the text, they will not be repeated here.

[0223] Although some specific embodiments of the present application have been described in detail by way of example, it should be understood by those skilled in the art that the above examples are only for illustration, not for limiting the scope of the present application. It should be understood by those skilled in the art that the above embodiments may be modified without departing from the scope and spirit of the present application. The scope of the present application is defined by the appended claims.

Claims

1. A diamine monomer having an epoxy structure, characterized in that: The molecular structural formula of the diamine monomer includes one or more epoxy groups, and the molecular structural formula is as follows: Wherein, A is a diamine residue, which includes a divalent aliphatic group, alicyclic group or aromatic group; and p is any integer between 1 and 10.

2. The diamine monomer having an epoxy structure according to claim 1, characterized in that: The diamine residue A includes the following substituted or unsubstituted groups: in, Indicates a connecting key; X 10 , X 11 , X 12 , X 13 , X 14 , X 15 , X 16 , X 17 , X 18 , X 19 and X 20 Each independently selected from: a single bond, -O-, -S-, -C(CF3)2, -CO-, -SO2-, NR 11 R 12 or CR 13 R 14 , and R 11 , R 12 , R 13 and R 14 They are independently selected from: H or phenyl; n1 is any integer between 1 and 10.

3. The diamine monomer having an epoxy structure according to claim 2, characterized in that: The substituents of the diamine residue A include deuterium, a halogen group, a trifluoromethyl group, a cyano group, a heteroaryl group, an aryl group, an alkyl group, a deuterated alkyl group, a halogenated alkyl group, a cycloalkyl group, an alkoxy group or an aryloxy group; The substituent of the diamine residue A includes one or more substituents.

4. The diamine monomer having an epoxy structure according to claim 1, characterized in that: The aromatic group includes an aryl group or a heteroaryl group; The aryl group is a monocyclic aryl group or a condensed ring aryl group; The heteroaryl group is a monocyclic heteroaryl group or a condensed-ring heteroaryl group.

5. The diamine monomer having an epoxy structure according to claim 4, characterized in that: The aryl group includes phenyl, naphthyl, fluorenyl, anthracenyl, phenanthrenyl, biphenyl, terphenyl, benzo[9,10]phenanthrenyl, pyrenyl or benzofluoranthenyl; The heteroaryl group includes thienyl, furanyl, pyrrolyl, imidazolyl, thiazolyl, oxazolyl, oxadiazolyl, triazolyl, pyridyl, triazinyl, acridinyl, pyridazinyl, pyrazinyl, quinolyl, quinazolinyl, quinoxalinyl, phenoxazinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, pyrazinopyrazinyl, isoquinolyl, indolyl, carbazolyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, benzocarbazolyl, benzothienyl, dibenzothienyl, thienothiphenyl, benzofuranyl, phenanthrolinyl, isoxazolyl, thiadiazolyl, phenothiazinyl, phenoxathiyl or dibenzo-p-dioxinyl.

6. The diamine monomer having an epoxy structure according to claim 1, characterized in that: The aliphatic group includes a hydrocarbon group, a cyclic hydrocarbon group, an ether group or a keto group.

7. The diamine monomer having an epoxy structure according to claim 1, characterized in that: The alicyclic group is a non-aromatic hydrocarbon containing ring carbon atoms, including a monocyclic alkyl group, a spirocyclic alkyl group or a bridged cyclic alkyl group; The carbon number of the alicyclic group is 3 to 10, and the alicyclic group includes one or more double bonds.

8. A method for preparing a diamine monomer having an epoxy structure according to any one of claims 1 to 7, characterized in that: The preparation method comprises: The hydroxyl-containing diamine is reacted with epichlorohydrin in a sodium hydroxide solution, and the hydroxyl group of the diamine can be replaced by the glycidyl ether to obtain a diamine monomer with an epoxy group.

9. The method for preparing a diamine monomer having an epoxy structure according to claim 8, characterized in that: The synthesis equation of the diamine monomer is as follows: Wherein, A is a diamine residue, which includes a divalent aliphatic group, alicyclic group or aromatic group; and p is any integer between 1 and 10.

10. The method for preparing a diamine monomer having an epoxy structure according to claim 8, characterized in that: The molar ratio of the hydroxyl-containing diamine to the epichlorohydrin is 1:1p-3p.

11. A polyimide resin, characterized in that: The polyimide resin is prepared by polymerization reaction of a diamine composite material and a dianhydride monomer; Wherein, the diamine combination material at least includes the diamine monomer with an epoxy structure as described in any one of claims 1 to 7.

12. The polyimide resin according to claim 11, characterized in that The polyimide resin has a molecular structure as shown below: Wherein, X is an aromatic dianhydride residue or an alicyclic dianhydride residue, R is an aromatic diamine residue or an alicyclic diamine residue, which represents a tetracarboxylic acid residue having a tetravalent alicyclic or aromatic group, m is an integer between 50 and 200, and n is an integer between 0 and 100.

13. The polyimide resin according to claim 12, characterized in that The aromatic dianhydride residue comprises at least one of the following compounds: Pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, cyclo-3-butane-1,2,3,4-tetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, Cyclohexane-1,2,4,5-tetracarboxylic dianhydride, norbornane-2,3,5,6-tetracarboxylic dianhydride, bicyclo[2.2.2]oct-7-ene-3,4,8,9-tetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 2,2',3,3'-diphenylsulfonetetracarboxylic dianhydride, 2,3,3',4'-diphenylsulfonetetracarboxylic dianhydride, 3,3',4,4'-diphenylethertetracarboxylic dianhydride, 2,2',3,3'-diphenylethertetracarboxylic dianhydride, 2,3,3',4'-diphenylethertetracarboxylic dianhydride; The alicyclic dianhydride residue comprises at least one of the following compounds: Pyrazine-2,3,5,6-tetracarboxylic dianhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride, 2,2-[bis(3,4-dicarboxyphenyl)]hexafluoropropane dianhydride, 5-(2,5-dioxotetrahydro)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride.

14. The polyimide resin according to claim 12, characterized in that: The aromatic diamine residue comprises at least one of the following compounds: 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 1,4-bis(4-aminophenoxy)benzene, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis(4-aminophenoxyphenyl)sulfone, bis(3-aminophenoxyphenyl)sulfone, bis(4-aminophenoxy)biphenyl, bis{4-(4-aminophenoxy)phenyl}ether, 4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-anilino)hexafluoropropane, 2,2-bis(3-anilino)hexafluoropropane and 2,2-bis(3-amino-4-toluoyl)hexafluoropropane; The alicyclic diamine residue comprises at least one of the following compounds: 1,6-hexanediamine, 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane, 4,4'-diaminodicyclohexylmethane and 4,4'-diamino-3,3'-dimethylcyclohexylmethane.

15. The polyimide resin according to claim 11, characterized in that The dianhydride monomer includes at least one of an aromatic dianhydride monomer and an alicyclic dianhydride monomer.

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