Polyimide composition as well as preparation method and application thereof

Abstract

The invention discloses a polyimide composition, and particularly relates to a dual-curing (such as photocuring and thermocuring) polyimide composition, which comprises polyimide and amino-containing acrylate, the polyimide has a repeating unit of the following structure (I): # imgabs0 #, and the amino-containing acrylate is selected from one or more of the following structures: # imgabs1 # imgabs2 #. The acrylic acid is combined with the amine, and the acrylic acid is combined with the polyimide in an end group reaction manner, so that the acrylic acid and the polyimide are introduced into the composition; and finally, acrylic acid can play a photocuring effect as early-stage setting, and polyimide is used for curing and forming the composition in a thermocuring form, so that the overall solubility can be improved, and a material with excellent performance can be obtained.

Description

Technical Field

[0001] The present invention relates to a polyimide composition, and a preparation method and application thereof, and particularly relates to a dual-curing polyimide composition, a preparation method and an application thereof. Background Art

[0002] Dual curing, also known as double curing, refers to the realization of curing through the combined action of two or more curing methods. These curing methods are not independent of each other, but rather cooperate with each other to jointly promote the curing process of the adhesive. Common dual curing is the combination of photocuring and other curing methods, and other curing methods can be thermal curing, moisture curing, oxidation curing, anaerobic curing, etc.

[0003] Due to its advantages such as rapid curing, high production efficiency, energy saving, and environmental protection, photocuring has been widely used in the fields of printing, packaging, electronics, communication, aviation, aerospace, etc. However, single UV photocuring products still have disadvantages such as incomplete curing, inability to cure irregular or shaped products, and colored slurries interfering with absorbance and affecting curing efficiency. Therefore, the development of a dual-curing system that combines photocuring with other curing methods is of great significance for overcoming the weaknesses of photocuring adhesives and expanding their application scope.

[0004] In the prior art, many dual-curing systems use a combination of acrylate and epoxy resin. For example, the photo-thermal dual-curing systems disclosed in CN115449033A, CN108753228A, CN118580774A, and CN102010686B all include epoxy resin and acrylate active monomers. Epoxy resin has the characteristics of excellent mechanical properties, high adhesion, and strong processability, and is widely used in the fields of coatings, adhesives, and composite materials. However, the defect of this dual-curing system is that the epoxy resin has a relatively large coefficient of thermal expansion, and even if the acrylate is used to supplement its flexible properties, it still cannot reach a high level of heat resistance to expansion. Summary of the Invention

[0005] The present invention provides a polyimide, a composition, and a preparation method and application thereof to realize a dual-curing system.

[0006] The first aspect of the present application is to provide a polyimide composition, particularly a dual-curing (such as photocuring and thermal curing) polyimide composition, including a polyimide component and an amino-containing acrylate. Among them, the polyimide component is a polyimide having a repeating unit of the following structure (I), or a precursor of a polyimide having a repeating unit of the following structure (II), or a mixture of the polyimide and the polyimide precursor:

[0007]

[0008] Among them, at least one end of the polyimide component has an anhydride group;

[0009] The amino-containing acrylate is selected from one or more of the following structures:

[0010]

[0011] Among them, R1 is a tetravalent organic group, R2 is a divalent organic group, and m and n are both positive integers of ≥1.

[0012] The second aspect of the present invention provides an acrylate group-terminated polyimide, which is obtained by an amidation or imidization reaction of the terminal anhydride group of the polyimide component with the amino group in the amino-containing acrylate.

[0013] In a preferred embodiment, R1 may be one or more of aliphatic hydrocarbons and aromatic hydrocarbons, and is preferably a tetravalent organic group of C4-C60, more preferably a tetravalent organic group of C5-C50, more preferably a tetravalent organic group of C6-C30, and may be selected from the following structures:

[0014]

[0015]

[0016] One or more of them.

[0017] In a preferred embodiment, R2 may be one or more of a chain aliphatic hydrocarbon with or without a branched chain, a cyclic aliphatic ring, and an aromatic ring, more preferably a divalent organic group of C2-C60, more preferably a divalent organic group of C3-C50, more preferably a divalent organic group of C4-C40, more preferably a divalent organic group of C5-C30, more preferably a divalent organic group of C6-C25, more preferably a divalent organic group of C8-C20. R2 is preferably an aromatic ring, which may be one or more aromatic rings, or more than one aromatic ring is connected by M, and M may be one or more of NH, O, S, Si, CO, COO, and CONH.

[0018] Preferably, the branched chain may be an R group substituted with or without an X group, and the R group may be a single bond, or may also be a carbon chain containing or not containing heteroatoms. The carbon chain may be a C1-C10 carbon chain, more preferably a C1-C8 carbon chain, more preferably a C1-C6 carbon chain, more preferably a C1-C4 carbon chain, such as an alkyl group.

[0019] Among them, the carbon chain containing heteroatoms means that at least one C atom on the carbon chain is replaced by a heteroatom, and the heteroatom can be one or more of the following structures: -O-, -S-, -NH-, -CO-NH-, -CO-, -COO-.

[0020] Preferentially, X can be one or more of a halogen atom, a hydroxyl group, a nitro group, an amino group, an aldehyde group.

[0021] For example, R2 can be selected from:

[0022]

[0023] -CH2-CH2-, -CH2-CH(CH3)-, -CH2-CH2-CH2-, -CH2-CH(CH3)-CH2-, -CH2-C(CH3)2-CH2-, -CH2-(CH2)2-CH2-, -CH2-(CH2)3-CH2-, -CH2-(CH2)4-CH2-, or one or more of them.

[0024] In a preferred embodiment, n is preferably an integer selected from 1 to 10, more preferably an integer from 1 to 8, and even more preferably an integer from 1 to 6, such as 1, 2, 3, 4, 5.

[0025] In a preferred embodiment, m is preferably an integer selected from 1 to 50, preferably an integer from 2 to 45, more preferably an integer from 3 to 40, more preferably an integer from 4 to 30, more preferably an integer from 5 to 20, more preferably an integer from 6 to 15, and even more preferably an integer from 7 to 10.

[0026] In a preferred embodiment, by weight percentage, in the polyimide composition, the content of the polyimide component is preferably 10 - 90 wt%, more preferably 20 - 88 wt%, more preferably 30 - 85 wt%, more preferably 50 - 80 wt%, more preferably 60 - 75 wt%, and even more preferably 65 - 70 wt%.

[0027] In a preferred embodiment, by weight percentage, in the polyimide composition, the content of the amino acrylate is preferably 5 - 30 wt%, more preferably 8 - 25 wt%, more preferably 10 - 20 wt%, and even more preferably 12 - 18 wt%.

[0028] In a preferred embodiment, the viscosity of the polyimide component is 5 cp to 25000 cp, more preferably 10 - 20000 cp, more preferably 20 - 15000 cp, more preferably 50 - 10000 cp, more preferably 100 - 8000 cp, and even more preferably 500 - 5000 cp.

[0029] In a preferred embodiment, the polyimide composition may further include an acrylic active monomer. Preferably, based on weight percentage, in the polyimide composition, the content of the acrylic active monomer is 1-25 wt%, more preferably 2-20 wt%, more preferably 5-15 wt%, and more preferably 8-12 wt%.

[0030] In a preferred embodiment, the structure of the acrylic active monomer is wherein, R4 is H or methyl; R3 is one or more of a saturated carbon chain, an unsaturated carbon chain, and a cyclic structure. For example, a carbon chain of C1-C10, a cyclic structure of C3-C12, such as R3 being one or more of methyl, ethyl, propyl, ethylene, hexylene, and isobornylene.

[0031] And one or more of the saturated carbon chain, the unsaturated carbon chain, and the cyclic structure may contain a Y substituent, and the Y substituent may be a hydroxyl group, a halogen atom, a nitro group, an aldehyde group, etc.

[0032] wherein, p is a positive integer, preferably 1-4, more preferably 1-3, and more preferably 1-2.

[0033] More preferably, the acrylic active monomer may be one or more selected from methyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 1,6-hexanediol diacrylate, and isobornyl acrylate.

[0034] In a preferred embodiment, the polyimide composition may further include an initiator. Preferably, based on weight percentage, in the polyimide composition, the content of the initiator is 0.01-10 wt%, more preferably 0.05-8 wt%, more preferably 0.1-5 wt%, more preferably 0.12-3 wt%, and more preferably 0.15-1.5 wt%.

[0035] Among them, the initiator is preferably a photoinitiator. For example, the photoinitiator is selected from one or a combination of 4-phenyldibenzoyl ketone, benzoin diethyl ether, benzoin dimethyl ether, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone, 2-hydroxy-methylphenyl propane-1-one, 1-hydroxycyclohexyl phenyl ketone, phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide, 2-methyl-1-(4-methylthiophenyl)-2-morpholin-1-one, ethyl 4-(N,N-dimethylamino)benzoate, and isopropylthioxanthone.

[0036] In a preferred embodiment, the polyimide composition may further include a crosslinking agent. Preferably, based on weight percentage, in the polyimide composition, the content of the crosslinking agent is 0.01 - 5 wt%, more preferably 0.05 - 3 wt%, more preferably 0.1 - 2 wt%, more preferably 0.15 - 1.5 wt%, more preferably 0.2 - 1.2 wt%, more preferably 0.3 - 1 wt%, and more preferably 0.5 - 0.8 wt%.

[0037] In a preferred embodiment, the crosslinking agent may be one or more of polyol acrylate or polyol methacrylate, and the polyol refers to at least a diol, such as a diol, triol, tetrol, etc.

[0038] More preferably, the polyol may be one or more of ethylene glycol, 1,2 - propylene glycol, 1,4 - butanediol, neopentyl glycol, 1,6 - hexanediol, trimethylolpropane, pentaerythritol, dipropylene glycol, diethylene glycol, polyethylene glycol, polypropylene glycol, xylitol, and sorbitol.

[0039] For example, the crosslinking agent may be one or a combination of hexanediol diacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, polyethylene glycol dimethacrylate, etc.

[0040] In a preferred embodiment, the polyimide composition may further include an additive, especially a functional additive. Preferably, based on weight percentage, in the polyimide composition, the content of the additive is ≤5 wt%, more preferably ≤4 wt%, such as 0.01 - 3 wt%, more preferably 0.05 - 2.5 wt%, more preferably 0.1 - 2 wt%, and more preferably 0.5 - 1.5 wt%.

[0041] In a preferred embodiment, the additive may be one or more of an antifoaming agent, a leveling agent, and a tackifier.

[0042] In a preferred embodiment, based on weight percentage, in the polyimide composition, the content of the antifoaming agent is preferably 0.01 - 1 wt%.

[0043] In a preferred embodiment, based on weight percentage, in the polyimide composition, the content of the leveling agent is preferably 0.01 - 1 wt%.

[0044] In a preferred embodiment, based on weight percentage, in the polyimide composition, the content of the tackifier is preferably 0.01 - 1 wt%.

[0045] In a preferred embodiment, the defoamer can be one or a combination of more than one of BYK-021, BYK-024, BYK-028, BYK-051, BYK-A530, BYK-141, BYK-1795, SAG-4865, TSA-750SH, TEGO-810, and TEGO-805.

[0046] In a preferred embodiment, the leveling agent can be one or a combination of more than one of BYK-302, BYK-333, BYK-346, TEGO-410, TEGO-450, and DC-57.

[0047] In a preferred embodiment, the tackifier can be one or a combination of more than one of BYK-428, BYK-4511, and TT-935.

[0048] A method for preparing the dual-curing polyimide composition includes the steps of:

[0049] Under an inert gas environment, at a first preset temperature, the polyimide component and the amino acrylate are mixed. More preferably, the method for preparing the dual-curing polyimide composition includes the steps of:

[0050] Under an inert gas environment:

[0051] At a first preset temperature, the polyimide component and the amino acrylate are mixed to obtain mixture A; at a second preset temperature and a preset rotation speed, the acrylic monomer, the initiator, and the crosslinking agent are added to mixture A.

[0052] More preferably, the method for preparing the dual-curing polyimide composition includes the steps of:

[0053] Under an inert gas environment:

[0054] At a first preset temperature, the polyimide component and the amino acrylate are mixed to obtain mixture A; at a second preset temperature, the acrylic monomer, the initiator, and the crosslinking agent are added to mixture A to obtain mixture B;

[0055] Mixture B and the functional additives are mixed under a preset vacuum degree.

[0056] In a preferred embodiment, the first preset temperature is 20-50 °C, preferably 25-45 °C, and more preferably 30-40 °C.

[0057] In a preferred embodiment, the inert gas is a gas that does not react with the components in the dual-curing polyimide composition, such as nitrogen.

[0058] In a preferred embodiment, the polyimide component and the amino acrylate are mixed under stirring conditions. More preferably, the stirring speed is 100 - 1000 rpm, preferably 200 - 700 rpm, and more preferably 400 - 600 rpm.

[0059] In a preferred embodiment, the second preset temperature is 20 - 35 °C, preferably 23 - 23 °C, and more preferably 25 - 28 °C.

[0060] In a preferred embodiment, mixture B is obtained by mixing under stirring. More preferably, the stirring speed for obtaining mixture B is 300 - 1500 rpm, preferably 500 - 1000 rpm, and more preferably 600 - 900 rpm.

[0061] In a preferred embodiment, the preset vacuum degree (relative vacuum degree) is -0.01 to -0.08 MPa, preferably -0.01 to -0.07 MPa, and more preferably -0.01 to -0.05 MPa.

[0062] In a preferred embodiment, the method for obtaining the polyimide component includes: acid anhydride and diamine H2N-R2-NH2 monomers undergo a polycondensation reaction.

[0063] Preferably, the polycondensation reaction is carried out at 0 - 100 °C, more preferably at 20 - 90 °C, more preferably at 40 - 80 °C, and more preferably at 50 - 60 °C.

[0064] Preferably, the molar ratio of acid anhydride to diamine > 1, more preferably 1.1 - 2.5, more preferably 1.3 - 2.2, more preferably 1.5 - 2, and more preferably 1.6 - 1.8.

[0065] Preferably, the polycondensation reaction is carried out in an inert gas atmosphere, and the inert gas flux is more preferably ≥0.1 L / min, more preferably ≥0.5 L / min, more preferably 1 - 5 L / min, more preferably 1.5 - 4 L / min, and more preferably 2 - 3 L / min.

[0066] Preferably, the polycondensation reaction time is at least 30 min, more preferably at least 45 min, more preferably 1 - 4 h, and more preferably 2 - 3 h.

[0067] Preferably, the polycondensation reaction is carried out under stirring conditions, and the stirring rate is preferably 50 - 800 rpm, more preferably 80 - 700 rpm, more preferably 100 - 600 rpm, more preferably 150 - 500 rpm, more preferably 200 - 400 rpm, and more preferably 250 - 300 rpm.

[0068] The present invention combines acrylic acid with polyimide by using the end - group reaction method of acrylic acid, so as to introduce acrylic acid into the composition. Ultimately, acrylic acid can play the role of photocuring as a preliminary shaping, while polyimide cures and forms the composition through thermal curing. Compared with the prior art, the technical solution of the present invention has the following beneficial effects:

[0069] 1) By introducing acrylate structure into polyimide, the overall solubility can be improved.

[0070] 2) The present invention combines acrylic acid and polyimide through chemical reaction. Compared with the conventional technical solution of using the two as composite materials, the present invention can obtain materials with excellent performance. Specific Embodiments

[0071] The present invention provides a dual - curing polyimide system and its preparation method. To make the purpose, technical solution and effects of the present invention clearer and more definite, the following examples are given to further elaborate on the present invention in detail. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0072] It should be noted that the terms "first", "second", etc. in the specification and claims of the present invention are used to distinguish similar objects and do not necessarily need to describe a specific order or sequence. It should be understood that such used data can be interchanged under appropriate circumstances. In addition, the terms "comprising" and "having" and any variations thereof are intended to cover non - exclusive inclusion. For example, a process, method, system, product or device comprising a series of steps or units does not necessarily have to be limited to those steps or units clearly listed, but may include other steps or units not clearly listed or inherent to these processes, methods, products or devices.

[0073] Example 1:

[0074] Amino - containing acrylate (CAS No.7659 - 38 - 3): Polyimide component: And its precursor polyamic acid mixture, viscosity 10000 cp

[0075] Photoinitiator 907: 2 - Methyl - 1 - (4 - methylthiophenyl) - 2 - morpholinopropan - 1 - one

[0076] Photoinitiator 819: Phenylbis(2,4,6 - trimethylbenzoyl)phosphine oxide Functional additives: 0.05 kg defoamer BYK - 051, 0.05 kg leveling agent TEGO - 450, 0.01 kg tackifier TT - 935

[0077] Under the condition that the inert gas ventilation volume is 2 L / min, using N-methylpyrrolidone as the reaction medium, at a reaction temperature of 60 °C and a stirring rate of 300 rpm, pyromellitic dianhydride was added to 4,4'-diaminodiphenyl ether, with the molar ratio of anhydride / diamine = 1.8 / 1, and a polycondensation reaction was carried out for 2 h to obtain a polyimide component. The synthesized product is a mixture of polyimide and its polyamic acid precursor.

[0078] The reaction flask was purged with N2 for 10 min, and 79 kg of the polyimide component and 12 kg of the aminoacrylate were mixed at 40 °C and 500 rpm for 2 h to obtain mixture A-1. The FT-IR spectrum showed that the C=O absorption peak in the anhydride near 1793 cm -1 and 1845 cm -1 still existed, but the C-O-C absorption peak in the anhydride around 1065 cm -1 was significantly weakened. Moreover, the primary amine peak at 1635 cm -1 was significantly weakened, indicating that the terminal anhydride of the polyimide component reacted with the amino group in the aminoacrylate. Due to the low reaction temperature, the carboxyl group of the polyamic acid did not react with the amino group, and imidization did not occur.

[0079] At 25 °C and 800 rpm, 8 kg of isobornyl acrylate (IBOA), 0.79 kg of initiator (a mixture of 0.55 kg of photoinitiator 907 and 0.24 kg of photoinitiator 819), and 0.1 kg of trimethylolpropane triacrylate (TMPTA) were added to mixture A-1 to obtain mixture B-1.

[0080] The mixture B-1 and the functional additives were mixed with a gravity planetary mixer under a relative vacuum of -0.03 MP to obtain the final composition.

[0081] Example 2:

[0082] Aminoacrylate (CAS No. 7659-38-3):

[0083] Polyimide component: And its precursor polyamic acid mixture, viscosity 11200 cp

[0084] Photoinitiator TPO: 2,4,6-Trimethylbenzoyl-diphenylphosphine oxide Functional additives: 0.05 kg of defoamer BYK-051, 0.05 kg of leveling agent TEGO-450, 0.01 kg of tackifier TT-935

[0085] Under the condition that the inert gas ventilation volume is 2 L / min, using N-methylpyrrolidone as the reaction medium, at a reaction temperature of 70 °C and a stirring rate of 200 rpm, pyromellitic dianhydride was added to p,p'-diaminobiphenyl (benzidine) with a molar ratio of anhydride / diamine = 1.5 / 1, and a polycondensation reaction was carried out for 2 h to obtain a polyimide component. The synthesized product is a mixture of polyimide and its polyamic acid precursor.

[0086] The reaction flask was purged with N2 for 10 min, and 79 kg of the polyimide component and 12 kg of the amino group-containing acrylate were mixed at 40 °C and 500 rpm for 2 h to obtain mixture A-2.

[0087] 8 kg of isobornyl acrylate (IBOA), 0.79 kg of initiator TPO, and 0.1 kg of trimethylolpropane triacrylate (TMPTA) were added to mixture A-2 at 25 °C and 800 rpm to obtain mixture B-2.

[0088] The mixture B-2 and the functional additives were mixed using a gravity planetary mixer under a relative vacuum of -0.03 MP to obtain the final composition.

[0089] Example 3:

[0090] Amino group-containing acrylate (CAS No. 7659-38-3): Polyimide component: And its precursor polyamic acid, viscosity 10300 cp

[0091] Photoinitiator 2959: 2-Hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone

[0092] Photoinitiator ITX: Isopropyl thioxanthone

[0093] Photoinitiator EDB: Ethyl 4-(N,N-dimethylamino)benzoate Functional additives: 0.05 kg of defoamer BYK-051, 0.05 kg of leveling agent TEGO-450, 0.01 kg of tackifier TT-935

[0094] Under the condition that the inert gas ventilation volume is 2 L / min, using N-methylpyrrolidone as the reaction medium, at a reaction temperature of 50 °C and a stirring rate of 350 rpm, pyromellitic dianhydride was added to p-phenylenediamine with a molar ratio of anhydride / diamine = 2.1 / 1, and a polycondensation reaction was carried out for 2 h to obtain a polyimide component. The synthesized product is a mixture of polyimide and its polyamic acid precursor.

[0095] The reaction flask was purged with N2 for 10 min, and 79 kg of polyimide component and 12 kg of aminoacrylate were mixed at 40 °C and 500 rpm for 2 h to obtain mixture A-3.

[0096] At 25 °C and 800 rpm, 8 kg of isobornyl acrylate (IBOA), 0.79 kg of initiator (a mixture of 0.6 kg of photoinitiator 2959, 0.09 kg of photoinitiator ITX, and 0.1 kg of photoinitiator EDB), and 0.1 kg of trimethylolpropane triacrylate (TMPTA) were added to mixture A-3 to obtain mixture B-3.

[0097] The mixture B-3 and the functional additives were mixed using a gravity planetary mixer under a relative vacuum of -0.03 MPa to obtain the final composition.

[0098] Example 4:

[0099] Aminoacrylate (CAS No. 7659-38-3): Polyimide component:

[0100] And its precursor polyamic acid, viscosity 11000 cp

[0101] Photoinitiator 907: 2-methyl-1-(4-methylthiophenyl)-2-morpholin-1-one

[0102] Photoinitiator 819: Phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide Functional additives: 0.05 kg of defoamer BYK-051, 0.05 kg of leveling agent TEGO-450, 0.01 kg of tackifier TT-935

[0103] Under the condition that the inert gas ventilation rate was 2 L / min, using N-methylpyrrolidone as the reaction medium, at a reaction temperature of 80 °C and a stirring rate of 350 rpm, diphenyltetracarboxylic dianhydride was added to 4,4'-diaminodiphenyl ether, and the molar ratio of anhydride / diamine = 1.4 / 1. The polycondensation reaction was carried out for 2.5 h to obtain the polyimide component. The synthesized product was a mixture of polyimide and its polyamic acid precursor.

[0104] The reaction flask was purged with N2 for 10 min, and 79 kg of polyimide component and 12 kg of aminoacrylate were mixed at 40 °C and 500 rpm for 2 h to obtain mixture A-4.

[0105] At 25 °C and 800 rpm, 8 kg of isobornyl acrylate (IBOA), 0.79 kg of initiator (a mixture of 0.55 kg of photoinitiator 907 and 0.24 kg of photoinitiator 819), and 0.1 kg of trimethylolpropane triacrylate (TMPTA) were added to mixture A-4 to obtain mixture B-4.

[0106] The mixture B-4 and functional additives were mixed using a gravity planetary mixer under a relative vacuum of -0.03 MP to obtain the final composition.

[0107] Example 5:

[0108] Aminoacrylate (CAS No. 7659-38-3): Polyimide component: And its precursor polyamic acid, viscosity 12000 cp

[0109] Photoinitiator TPO: 2,4,6-Trimethylbenzoyl-diphenylphosphine oxide Functional additives: 0.05 kg of defoamer BYK-051, 0.05 kg of leveling agent TEGO-450, 0.01 kg of tackifier TT-935

[0110] Under the condition that the inert gas ventilation rate was 2 L / min, using N-methylpyrrolidone as the reaction medium, at a reaction temperature of 50 °C and a stirring rate of 250 rpm, diphenyltetracarboxylic dianhydride was added to p,p'-diaminobiphenyl, with the molar ratio of anhydride / diamine = 1.5 / 1, and a polycondensation reaction was carried out for 3 h to obtain the polyimide component. The synthesized product was a mixture of polyimide and its polyamic acid precursor.

[0111] The reaction flask was purged with N2 for 10 min, and 79 kg of the polyimide component and 12 kg of aminoacrylate were mixed at 40 °C and 500 rpm for 2 h to obtain mixture A-5.

[0112] At 25 °C and 800 rpm, 8 kg of isobornyl acrylate (IBOA), 0.79 kg of photoinitiator TPO, and 0.1 kg of trimethylolpropane triacrylate (TMPTA) were added to mixture A-5 to obtain mixture B-4.

[0113] The mixture B-5 and functional additives were mixed using a gravity planetary mixer under a relative vacuum of -0.03 MP to obtain the final composition.

[0114] Example 6:

[0115] Aminoacrylate (CAS No. 7659-38-3): Polyimide compound: And its precursor polyamic acid, viscosity 10500 cp

[0116] Photoinitiator 2959: 2-Hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone

[0117] Photoinitiator ITX: Isopropylthioxanthone

[0118] Photoinitiator EDB: Ethyl 4-(N,N-dimethylamino)benzoate Functional aids: 0.05 kg defoamer BYK-051, 0.05 kg leveling agent TEGO-450, 0.01 kg tackifier TT-935

[0119] Under the condition that the inert gas ventilation rate is 2 L / min, using N-methylpyrrolidone as the reaction medium, at a reaction temperature of 70 °C and a stirring rate of 200 rpm, add biphenyltetracarboxylic dianhydride to p-phenylenediamine, with the molar ratio of anhydride / diamine = 1.3 / 1, carry out polycondensation reaction for 2 h to obtain a polyimide component, and the synthesized product is a mixture of polyimide and its polyamic acid precursor.

[0120] Replace the reaction flask with N2 for 10 min, and mix 79 kg of polyimide component and 12 kg of aminoacrylate-containing at 40 °C and 500 rpm for 2 h to obtain mixture A-5.

[0121] Add 8 kg of isobornyl acrylate (IBOA), 0.79 kg of initiator (a mixture of 0.6 kg of photoinitiator 2959, 0.09 kg of photoinitiator ITX and 0.1 kg of photoinitiator EDB), and 0.1 kg of trimethylolpropane triacrylate (TMPTA) to mixture A-5 at 25 °C and 800 rpm to obtain mixture B-4.

[0122] Use a gravity planetary mixer to mix mixture B-5 and functional aids under a relative vacuum of -0.03 MP to obtain the final composition.

[0123] Example 7:

[0124] Aminoacrylate-containing (CAS No. 7659-38-3): Polyimide component: And its precursor polyamic acid, viscosity 10500 cp

[0125] Photoinitiator 2959: 2-Hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone

[0126] Photoinitiator ITX: Isopropylthioxanthone

[0127] Photoinitiator EDB: Ethyl 4-(N,N-dimethylamino)benzoate Functional additives: 0.05 kg defoamer BYK-051, 0.05 kg leveling agent TEGO-450, 0.01 kg tackifier TT-935

[0128] Under the condition that the inert gas flow rate is 2 L / min, using N-methylpyrrolidone as the reaction medium, at a reaction temperature of 70 °C and a stirring rate of 200 rpm, add diphenyltetracarboxylic dianhydride to p-phenylenediamine with a molar ratio of anhydride / diamine = 1.3 / 1, and carry out polycondensation reaction for 2 h to obtain a polyimide component. The synthesized product is a mixture of polyimide and its polyamic acid precursor.

[0129] Replace the reaction flask with N2 for 10 min, and mix 69 kg of polyimide component and 18 kg of aminoacrylate-containing at 40 °C and 500 rpm for 2 h to obtain mixture A-7.

[0130] Add 17.74 kg of 2-hydroxyethyl acrylate (HEA), 1 kg of initiator (a mixture of 0.8 kg of photoinitiator 2959, 0.1 kg of photoinitiator ITX, and 0.1 kg of photoinitiator EDB), and 0.15 kg of trimethylolpropane triacrylate (TMPTA) to mixture A-7 at 25 °C and 800 rpm to obtain mixture B-7.

[0131] Mix mixture B-7 and functional additives with a gravity planetary mixer under a relative vacuum of -0.03 MP to obtain the final composition.

[0132] Example 8:

[0133] Aminoacrylate (CAS No. 7659-38-3): Polyimide component 1: And its precursor polyamic acid, viscosity 11200 cp, obtained by referring to the method of Example 1.

[0134] Polyimide component 2: And its precursor polyamic acid, obtained by referring to the method of Example 3, viscosity 10300 cp

[0135] Photoinitiator 907: 2-Methyl-1-(4-methylthiophenyl)-2-morpholin-1-one

[0136] Photoinitiator 819: Phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide Functional additives: 0.05 kg defoamer BYK-051, 0.05 kg leveling agent TEGO-450, 0.01 kg tackifier TT-935

[0137] The reaction flask was purged with N2 for 10 min, and 40 kg of polyimide component 1, 39 kg of polyimide component 2, and 12 kg of aminoacrylate were mixed at 40 °C and 500 rpm for 2 h to obtain mixture A-8.

[0138] At 25 °C and 800 rpm, 8 kg of 2-hydroxyethyl acrylate (HEA), 0.79 kg of initiator (a mixture of 0.55 kg of photoinitiator 907 and 0.24 kg of photoinitiator 819), and 0.15 kg of trimethylolpropane triacrylate (TMPTA) were added to mixture A-8 to obtain mixture B-8.

[0139] The mixture B-8 and the functional additives were mixed using a gravity planetary mixer under a relative vacuum of -0.03 MPa to obtain the final composition.

[0140] Comparative Example 1:

[0141] Aminoacrylate (CAS No. 7659-38-3): Polyimide component: And its precursor polyamic acid, viscosity 11200 cp, functional additives were obtained by referring to the method of Example 1: 0.05 kg of defoamer BYK-051, 0.05 kg of leveling agent TEGO-450, 0.01 kg of tackifier TT-935

[0142] The reaction flask was purged with N2 for 10 min, and 79 kg of polyimide component and 12.79 kg of aminoacrylate were mixed at 40 °C and 500 rpm for 2 h to obtain mixture C-1.

[0143] At 25 °C and 800 rpm, 8 kg of isobornyl acrylate (IBOA) and 0.1 kg of trimethylolpropane triacrylate (TMPTA) were added to mixture C-1 to obtain mixture D-1.

[0144] The mixture D-1 and the functional additives were mixed using a gravity planetary mixer under a relative vacuum of -0.03 MPa to obtain the final composition.

[0145] Comparative Example 2:

[0146] Polyimide component: And its precursor polyamic acid, viscosity 11200 cp, obtained by referring to the method of Example 1

[0147] Acrylic resin: Neocryl B-885

[0148] Functional additives: 0.05 kg defoamer BYK-051, 0.05 kg leveling agent TEGO-450, 0.01 kg tackifier TT-935

[0149] The reaction flask was purged with N2 for 10 min, and 79 kg of polyimide component and 12 kg of acrylic resin were mixed at 40 °C and 500 rpm for 2 h to obtain mixture C-2.

[0150] 8 kg of isobornyl acrylate (IBOA) and 0.1 kg of trimethylolpropane triacrylate (TMPTA) were added to mixture C-2 at 25 °C and 800 rpm to obtain mixture D-2.

[0151] The mixture D-2 and the functional additives were mixed using a gravity planetary mixer under a relative vacuum of -0.03 MPa to obtain the final composition.

[0152] Comparative Example 3:

[0153] Aminoacrylate (CAS No. 7659-38-3): Polyimide compound: And its precursor polyamic acid, viscosity 12000 cp, obtained by referring to the method of Example 3

[0154] Photoinitiator TPO: 2,4,6-Trimethylbenzoyl-diphenylphosphine oxide

[0155] The reaction flask was purged with N2 for 10 min, and 79 kg of polyimide component and 12 kg of aminoacrylate were mixed at 40 °C and 500 rpm for 2 h to obtain mixture C-3.

[0156] 8 kg of isobornyl acrylate (IBOA) and 1 kg of initiator TPO were added to mixture C-3 at 25 °C and 800 rpm to obtain mixture D-3.

[0157] Comparative Example 4:

[0158] Polyimide component: And its precursor polyamic acid, viscosity 11200 cp, obtained by referring to the method of Example 1

[0159] Photoinitiator 907: 2-Methyl-1-(4-methylthiophenyl)-2-morpholin-1-one

[0160] Photoinitiator 819: Phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide

[0161] The reaction flask was purged with N2 for 10 min, and 79 kg of polyimide component, 20.11 kg of isobornyl acrylate (IBOA), and 0.79 kg of initiator (a mixture of 0.55 kg of photoinitiator 907 and 0.24 kg of photoinitiator 819) were mixed at 25 °C and 800 rpm to obtain mixture D-4.

[0162] Comparative Example 5:

[0163] Polyimide component: And its precursor polyamic acid, viscosity 11200 cp, obtained by referring to the method of Example 1

[0164] Epoxy resin: E51

[0165] 79 kg of polyimide component and 21 kg of epoxy resin E51 were mixed at 25 °C and 800 rpm to obtain mixture D-5.

[0166] Performance Test:

[0167] 1. Photocuring: Irradiate with a 365 nm UV lamp for a certain period of time until the composition presents a gel state (Gel: Generally refers to the time required for a liquid resin or glue to change from a flowing liquid state to a solid gel at a specified temperature). Therefore, it is the time when it cannot flow at the same glue amount and the same inclination angle at 100 °C.

[0168] 2. Thermal curing: Perform thermal curing under an O2 atmosphere <100 ppm and at a temperature of 30 °C.

[0169] 3. Coefficient of thermal expansion (CTE): The resin film sample was cut into a spline of 13 mm * 5 mm, and a TMA4000 tester was used with a heating rate of 5 °C / min, and the values in the range of 50 - 200 °C were used as the measured values. The sample was heated once in the TMA before testing to remove the relaxation effect.

[0170] 4. Cross-cut test method: Spin-coat and cure the film sample on a silicon wafer; use a knife and a cross-cut board to make cross-cuts. (Cross-cut size: 1 mm × 1 mm); use a special test tape for adhesion and peeling, and observe the test results. (Tape model: 3M Transparent tape); if the edge of the cut is completely smooth and there is no peeling on the edge of the grid, the adhesion is considered to be qualified and is indicated by 5B. If there is small peeling at the intersection of the cut and the actual damage in the grid area is ≤5%, it is indicated by 4B. If there is peeling at the edge and / or intersection of the cut, and the area is greater than 5%-15%, it is indicated by 3B. There is partial peeling or large peeling along the edge of the cut, or some grids are peeled off in whole pieces. If the area of ​​peeling exceeds 15%-35%, it is indicated by 2B. If there is large peeling on the edge of the cut / or some squares are partially or completely peeled off, and the area is greater than 35%-65% of the grid area, it is indicated by 1B. If there are pieces of paint falling off at the edges and intersections of the lines, and the total area of ​​the peeling is greater than 65%, it is indicated by 0B.

[0171] 5. Film thickness: Use MX63 (OLYMPUS) film thickness meter to test the film thickness at different points, and judge the flatness based on the uniformity, that is, the standard deviation U% of the test film thickness; uniformity / flatness% = (test maximum value - test minimum value) / (mean value*2)×100%.

[0172] 6. Tensile strength / elongation: Using RTI-1225 (A&D) model tensile machine, at a tensile rate of 50 mm / min, test 5 groups of data with a film thickness of 5um±0.5um and a 5cm×1cm effective length, and take the average value.

[0173] 7. Leveling performance test: Place 1 mL of sample on a circle with a diameter of 1 cm, and determine the time required for the sample to contact the circumference by placing it for a moment; <1s is excellent, 1-5s is good, 5-10s is fair, 10s-20s is poor, and >20s is very poor.

[0174] Table 1, Examples 1-8 Components (kg) and Performance Results

[0175]

[0176] Table 2, Comparative Examples 1-5 Components (kg) and Performance Results

[0177]

[0178]

[0179] It can be seen that the present application connects acrylate to polyimide through chemical reaction, which can form a dual-curing system of light curing and heat curing. Moreover, the thermal expansion coefficient is much lower than that of epoxy resin / polyimide composite materials, and the toughness is much greater than that of epoxy resin / polyimide composite materials; the tensile strength is much higher than that of acrylic resin / polyimide composite materials.

[0180] The specific embodiments of the present invention have been described in detail above, but they are only examples, and the present invention is not limited to the specific embodiments described above. For those skilled in the art, any equivalent modifications and substitutions to the present invention are also within the scope of the present invention. Therefore, all equivalent transformations and modifications made without departing from the spirit and scope of the present invention should be covered within the scope of the present invention.

Claims

1. A polyimide composition, characterized in that: Comprising a polyimide component and an amino-containing acrylate, wherein: The polyimide component is a polyimide having a repeating unit of the following structure (I), or a precursor of a polyimide having a repeating unit of the following structure (II), or a mixture of the polyimide and the polyimide precursor: Wherein, the polyimide component has an anhydride group at least at one end; The amino-containing acrylate is selected from one or more of the following structures: Wherein, R1 is a tetravalent organic group, R2 is a divalent organic group, m and n are both positive integers ≥ 1, preferably: m is selected from an integer of 1-50, preferably an integer of 2-45, more preferably an integer of 3-40, more preferably an integer of 4-30, more preferably an integer of 5-20, more preferably an integer of 6-15, more preferably an integer of 7-10; preferably, n is selected from an integer of 1-10, more preferably an integer of 1-8, more preferably an integer of 1-6, such as 1, 2, 3, 4, 5.

2. The polyimide composition according to claim 1, characterized in that The R1 is selected from one or more of aliphatic hydrocarbons and aromatic hydrocarbons, and is preferably a tetravalent organic group of C4-C60, more preferably a tetravalent organic group of C5-C50, more preferably a tetravalent organic group of C6-C30, and may be selected from the following structures: One or more of .

3. The polyimide composition according to claim 1, characterized in that R2 is selected from one or more of a chain aliphatic hydrocarbon with or without branching, a cyclic aliphatic ring, and an aromatic ring, more preferably a C2-C60 divalent organic group, more preferably a C3-C50 divalent organic group, more preferably a C4-C40 divalent organic group, more preferably a C5-C30 divalent organic group, more preferably a C6-C25 divalent organic group, more preferably a C8-C20 divalent organic group; Preferably, the R2 is preferably an aromatic ring, which may be one or more aromatic rings, or more than one aromatic ring connected by M, and the M may be one or more of NH, O, S, Si, CO, COO, and CONH; Preferably, the branched chain may be an R group substituted with or without an X group, the R group may be a single bond, or may be a carbon chain containing or not containing heteroatoms, the carbon chain may be a C1-C10 carbon chain, more preferably a C1-C8 carbon chain, more preferably a C1-C6 carbon chain, more preferably a C1-C4 carbon chain, such as an alkyl group; X is selected from one or more of a halogen atom, a hydroxyl group, a nitro group, an amino group, and an aldehyde group; Preferably, the carbon chain containing heteroatoms means that at least one C atom in the carbon chain is replaced by a heteroatom, and the heteroatom may be one or more of the following structures: -O-, -S-, -NH-, -CO-NH-, -CO-, -COO-; Preferably, R2 can be selected from: -CH2-CH2-、-CH2-CH(CH3)-、-CH2-CH2-CH2-、 -CH2-CH(CH3)-CH2-, -CH2-C(CH3)2-CH2-, -CH2-(CH2)2-CH2-, One or more of -CH2-(CH2)3-CH2-, -CH2-(CH2)4-CH2-, etc.

4. The polyimide composition according to claim 1, characterized in that In terms of weight percentage, in the polyimide composition, the content of the polyimide component is 10-90wt%, more preferably 20-88wt%, more preferably 30-85wt%, more preferably 50-80wt%, more preferably 60-75wt%, more preferably 65-70wt%; preferably: the viscosity of the polyimide component is 5cp to 25000cp, more preferably 10-20000cp, more preferably 20-15000cp, more preferably 50-10000cp, more preferably 100-8000cp, more preferably 500-5000cp; In terms of weight percentage, the content of amino acrylate in the polyimide composition is preferably 5-30wt%, more preferably 8-25wt%, more preferably 10-20wt%, and more preferably 12-18wt%.

5. The polyimide composition according to claim 1, characterized in that: The polyimide composition may further include an acrylic acid reactive monomer. Preferably, in the polyimide composition, the acrylic acid reactive monomer content is 1-25wt%, more preferably 2-20wt%, more preferably 5-15wt%, more preferably 8-12wt% by weight. Preferably, the acrylic acid reactive monomer structure is Wherein, R4 is H or methyl; R3 is one or more of a saturated carbon chain, an unsaturated carbon chain, and a cyclic structure, for example, a C1-C10 carbon chain, a C3-C12 cyclic structure, such as R3 is one or more of a methyl group, an ethyl group, a propyl group, an ethylene group, a hexylene group, and isobornene; And one or more of the saturated carbon chain, unsaturated carbon chain, and cyclic structure may contain a Y substituent, and the Y substituent may be one or more of a hydroxyl group, a halogen atom, a nitro group, and an aldehyde group; Wherein, p is a positive integer, preferably 1-4, more preferably 1-3, more preferably 1-2; More preferably, the acrylic reactive monomer may be one or more selected from methyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 1,6-hexanediol diacrylate, and isobornyl acrylate.

6. The polyimide composition according to claim 1, characterized in that: The polyimide composition may further include an initiator. Preferably, in the polyimide composition, the content of the initiator is 0.01-10wt%, more preferably 0.05-8wt%, more preferably 0.1-5wt%, more preferably 0.12-3wt%, more preferably 0.15-1.5wt% by weight. Preferably, the initiator is a photoinitiator, for example, the photoinitiator is selected from 4-phenylbenzophenone, benzoin diethyl ether, benzoin dimethyl ether, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone, 2-hydroxy-methylphenylpropane-1-one, 1-hydroxycyclohexylphenyl ketone, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, 2-methyl-1-(4-methylthiophenyl)-2-morpholinyl-1-propanone, ethyl 4-(N,N-dimethylamino)benzoate, isopropylthioxanthone and one or more combinations thereof.

7. The polyimide composition according to claim 1, characterized in that: The polyimide composition may further include a crosslinking agent. Preferably, in the polyimide composition, the crosslinking agent content is 0.01-5wt%, more preferably 0.05-3wt%, more preferably 0.1-2wt%, more preferably 0.15-1.5wt%, more preferably 0.2-1.2wt%, more preferably 0.3-1wt%, more preferably 0.5-0.8wt% by weight; preferably, the crosslinking agent may be one or more of polyol acrylate or polyol methacrylate, and the polyol refers to at least two Polyols, such as diols, triols, tetraols, etc.; more preferably, the polyols can be one or more of ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, trimethylolpropane, pentaerythritol, propylene glycol, diethylene glycol, polyethylene glycol, polypropylene glycol, xylitol, and sorbitol; for example, the crosslinking agent can be one or more combinations of hexanediol diacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, and polyethylene glycol dimethacrylate.

8. The polyimide composition according to claim 1, characterized in that: The polyimide composition may further include an auxiliary agent, especially a functional auxiliary agent. Preferably, in terms of weight percentage, the auxiliary agent content in the polyimide composition is ≤5wt%, more preferably ≤4wt%, such as 0.01-3wt%, more preferably 0.05-2.5wt%, more preferably 0.1-2wt%, more preferably 0.5-1.5wt%; Preferably, the auxiliary agent includes one or more of a defoamer, a leveling agent, and a tackifier; more preferably, in terms of weight percentage, in the polyimide composition, the defoamer content is preferably 0.01-1wt%, the leveling agent content is preferably 0.01-1wt%, and the tackifier content is preferably 0.01-1wt%; More preferably, the defoamer is selected from one or more combinations of BYK-021, BYK-024, BYK-028, BYK-051, BYK-A530, BYK-141, BYK-1795, SAG-4865, TSA-750SH, TEGO-810, and TEGO-805; More preferably, the leveling agent is selected from one or more combinations of BYK-302, BYK-333, BYK-346, TEGO-410, TEGO-450, and DC-57; More preferably, the tackifier is selected from one or more combinations of BYK-428, BYK-4511, and TT-935.

9. An acrylate group-terminated polyimide, characterized in that: The polyimide is obtained by amidation or imidization reaction between the terminal anhydride group of the polyimide component of claim 1 and the amino group of the amino-containing acrylate of claim 1.

10. A method for preparing the polyimide composition according to claim 1, characterized in that the steps include: In an inert gas environment, at a first preset temperature, the polyimide component and the amino-containing acrylate are mixed; Preferably, under an inert gas environment: At a first preset temperature, a polyimide component and an amino-containing acrylate are mixed to obtain a mixture A; at a second preset temperature and a preset rotation speed, an acrylic monomer, an initiator, and a crosslinking agent are added to the mixture A; More preferably, under an inert gas environment: At a first preset temperature, a polyimide component and an amino-containing acrylate are mixed to obtain a mixture A; at a second preset temperature, an acrylic monomer, an initiator, and a crosslinking agent are added to the mixture A to obtain a mixture B; Mixing mixture B and functional additives under a preset vacuum degree; More preferably, the first preset temperature is 20-50°C, preferably 25-45°C, more preferably 30-40°C; more preferably, the polyimide component and the amino-containing acrylate are mixed under stirring conditions, more preferably, the stirring speed is 100-1000rpm, preferably 200-700rpm, more preferably 400-600rpm; More preferably, the second preset temperature is 20-35°C, preferably 23-23°C, more preferably 25-28°C; more preferably, the mixture B is mixed under stirring, and more preferably, the stirring speed of the mixture B is 300-1500rpm, preferably 500-1000rpm, more preferably 600-900rpm; More preferably, the preset vacuum degree is -0.01 to -0.08 MPa, preferably -0.01 to -0.07 MPa, more preferably -0.01 to -0.05 MPa; More preferably, the method for obtaining the polyimide component comprises: Acid Anhydride Carry out polycondensation reaction with diamine H2N-R2-NH2 monomer; preferably, the polycondensation reaction is carried out at 0-100°C, more preferably at 20-90°C, more preferably at 40-80°C, more preferably at 50-60°C; preferably, the molar ratio of anhydride to diamine is >1, more preferably 1.1-2.5, more preferably 1.3-2.2, more preferably 1.5-2, more preferably 1.6-1.8.

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