In-situ self-assembly layered thermosetting resin-based system and composite material and preparation method thereof

Abstract

The invention discloses an in-situ self-assembly layered thermosetting resin-based system and a composite material and a preparation method thereof. The layered composite material is obtained on the basis of intermolecular force and reaction kinetics temperature conditions, on one hand, the problems that a large number of inorganic filler is used for achieving the flame retardance of thermosetting resin, and the mechanical property of the material is remarkably reduced due to the fact that a large number of inorganic particles are used are solved; on the other hand, on the basis of close kinetic reaction temperature conditions among the thermosetting components and reaction behaviors with the thermoplastic components, the phase separation structure of the thermoplastic components is effectively controlled, and a layered domain containing the thermoplastic components is formed. Compared with the traditional layered structure composite material, the layered structure composite material prepared by the method has the advantages of simple process, no need of external force control, low inorganic filler content, excellent mechanical properties and the like, and is more suitable for material performance development requirements in the fields of aviation, spaceflight and electronics.

Description

Technical Field

[0001] This invention relates to a functional high-performance thermosetting resin-based composite material and its preparation method, belonging to the field of functional and high-performance resins and composite materials. Background Technology

[0002] The cyanate ester / epoxy / bismaleimide (CE / EP / BMI) ternary copolymer system possesses excellent mechanical strength and heat resistance, making it highly valuable in aerospace, electronics, and other fields. However, it still suffers from drawbacks such as resin matrix brittleness and flammability. Therefore, toughening modification and improved flame retardancy can significantly expand its application range. Modifying thermosetting resin systems with thermoplastic components often significantly improves their toughness and impact resistance. However, the addition of high-heat-resistant thermoplastic components significantly reduces the processability of the thermosetting resin system and introduces numerous defects into the resin matrix, while the addition of low-heat-resistant thermoplastic components significantly reduces its heat resistance and strength. Inorganic fillers can improve the flame retardancy and impact resistance of thermosetting resins, but only high contents of inorganic fillers can impart excellent flame retardancy. Furthermore, the dispersion and agglomeration problems of inorganic particles severely limit the effectiveness of inorganic particle modification of thermosetting resin systems, preventing the full realization of their advantages. Therefore, it is of great significance to study how to effectively improve the acquisition of high-performance thermosetting resin systems by utilizing the advantages of inorganic fillers and thermoplastic components. Summary of the Invention

[0003] This invention is based on a thermosetting CE / EP / BMI resin system. It utilizes vinyl-terminated polyphenylene ether telechelic polymer (PPE) and aminographene (NH2-GO) to modify the brittleness of the thermosetting resin system. On one hand, the reactive thermoplastic component and aminographene (NH2-GO) respectively achieve the toughness and flame retardancy of the thermosetting resin. On the other hand, based on the hydrogen bonds and π-π bonds between NH2-GO and between the triazine rings formed by the polymerization of NH2-GO and CE, a layered structure material containing NH2-GO layers and thermoplastic PPE layers is constructed through self-assembly. This achieves excellent flame retardancy of the thermosetting resin with a small amount of NH2-GO. Furthermore, by controlling the phase separation structure of PPE through the reaction of double bonds in PPE with CE and BMI, and by using near-close temperature reaction conditions for CE, EP, and BMI, a composite material system with excellent mechanical properties is obtained. The layered composite material obtained by this invention is formed based on intermolecular self-assembly, and compared with existing layered composite materials, it has the characteristics of low inorganic filler content and simple molding process.

[0004] To achieve the above objectives, the technical solution adopted by the present invention is as follows: A method for preparing an in-situ self-assembled layered thermosetting resin-based system includes the following steps: adding vinyl-terminated polyphenylene ether to a mixture of cyanate ester resin and epoxy resin, then adding bismaleimide resin, and then adding aminated graphene to obtain an in-situ self-assembled layered thermosetting resin-based composite material system.

[0005] An in-situ self-assembled layered thermosetting resin-based composite material is prepared by curing the above-mentioned in-situ self-assembled layered thermosetting resin-based system.

[0006] In this invention, the mass ratio of cyanate ester resin, epoxy resin, bismaleimide resin, vinyl-terminated polyphenylene ether, and amino graphene is 100:20-25:20-25:10-40:0.05-3.

[0007] In this invention, the cyanate resin includes one or a mixture of bisphenol A type cyanate resin and bisphenol E type cyanate resin.

[0008] In this invention, the epoxy resin includes one or more of the following: glycidyl-based epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, hydrogenated bisphenol A type epoxy resin, phenolic epoxy resin, polyfunctional glycidyl ether resin, glycidyl ester type epoxy resin, and special epoxy resin.

[0009] In this invention, the bismaleimide resin includes N,N'-(4,4'-methylenediphenyl)bismaleimide or its derivatives.

[0010] In this invention, the number average molecular weight of the vinyl-terminated polyphenylene ether is 1000-3000; the amino graphene is tetraamine graphene.

[0011] The in-situ self-assembled layered thermosetting resin-based composite material prepared by this invention has a layered structure, wherein the outer layer contains graphene and the inner intermediate layer contains polyphenylene ether.

[0012] This invention discloses the application of the above-mentioned in-situ self-assembled layered thermosetting resin-based system or in-situ self-assembled layered thermosetting resin-based composite material in the preparation of functional materials.

[0013] This invention involves weighing cyanate ester (CE) resin and epoxy (EP) resin into a reactor, heating and stirring, then adding vinyl-terminated polyphenylene ether (PPE), continuing stirring, then adding bismaleimide (BMI), and finally adding amino-graphene (NH2-GO). The mixture is stirred to obtain a CE / EP / BMI / PPE / NH2-GO prepolymer system. After degassing this system, it is poured into a mold and cured for 5-10 hours at 180℃~220℃ / 2h according to a temperature program, resulting in a layered thermosetting resin-based composite material with an outer layer containing NH2-GO and an inner layer containing PPE. The content of each component is as follows: cyanate ester (CE) resin: 100b; epoxy (EP) resin: 20-25b; bismaleimide (BMI): 20-25b; polyphenylene ether (PPE): 10-40b; amino-graphene (NH2-GO): 0.05-3b (b is by weight). The beneficial effects of this invention are as follows: The layered composite material of this invention is obtained based on intermolecular forces and reaction kinetic temperature conditions. On the one hand, it avoids the problems of using a large amount of inorganic fillers to achieve the flame retardancy of thermosetting resins, and the significant decrease in the mechanical properties of materials caused by the use of a large amount of inorganic particles. On the other hand, based on the close kinetic reaction temperature conditions between thermosetting components and the reaction behavior with thermoplastic components, the phase separation structure of thermoplastic components is effectively controlled, forming layered domains containing thermoplastic components. The layered composite material prepared by this method has advantages such as simpler process than traditional layered composite materials, no need for external force control, low inorganic filler content, and excellent mechanical properties, making it more suitable for the material performance development needs of the aerospace and electronics fields. Attached Figure Description

[0014] Figure 1 SEM images of the fracture surfaces of samples from Example 1 (a, a', a"), Comparative Example 1-1 (b, b'), Comparative Example 1-2 (c, c'), Comparative Example 1-3 (d, d'), and Comparative Example 1-4 (e).

[0015] Figure 2 DSC curves of single components of CE, EP, PPE and BMI and their mixtures (a) and DSC curves of mixtures of CE, EP, BMI and CE / EP / PPE / BMI with NH2-GO.

[0016] Figure 3 Example 2: SEM image of the fracture surface of the sample.

[0017] Figure 4 Example 3: SEM image of the fracture surface of the sample.

[0018] Figure 5 Example 4: SEM image of the fracture surface of the sample. Detailed Implementation

[0019] This invention discloses a method for preparing an in-situ self-assembled layered thermosetting resin-based system and its composite material. The steps are as follows: Cyanate ester (CE) resin and epoxy (EP) resin are weighed into a reactor and stirred at 140-180℃ for 0.5-2h. Then, vinyl-terminated polyphenylene ether (PPE) is added and stirred for another 0.5-1h. Next, bismaleimide (BMI) is added and stirred for 0.5-2h. Then, aminographene (NH2-GO) is added and stirred for 5-20min to obtain a CE / EP / BMI / PPE / NH2-GO prepolymer system (an in-situ self-assembled layered thermosetting resin-based system). After removing air bubbles at 150℃, the system is poured into a mold and cured according to the temperature program 180℃ / 2h + 200℃ / 2h + 220℃ / 2h to obtain a layered thermosetting resin-based composite material with an outer layer containing an NH2-GO layer and an inner layer containing PPE components. The contents of each component are as follows: cyanate ester (CE) resin: 100b; epoxy (EP) resin: 20~25b; bismaleimide (BMI): 20~25b; polyphenylene ether (PPE): 10~40b; aminographene (NH2-GO): 0.05-3b (b is a unit of weight).

[0020] In the above technical solution, the CE resin is one or a mixture of bisphenol A type cyanate resin and bisphenol E type cyanate resin; the EP resin includes glycidyl-based epoxy resins (such as bisphenol A type epoxy resins (such as epoxy resins with grades E-51, E-44, E-20), bisphenol F type epoxy resins (such as epoxy resins with grade NPEF-170), bisphenol S type epoxy resins, hydrogenated bisphenol A type epoxy resins, phenolic epoxy resins, polyfunctional glycidyl ether resins (such as resorcinol bisglycidyl ether type epoxy resins, bisresorcinol formaldehyde tetraglycidyl ether), glycidyl ester type epoxy resins (such as diglycidyl isophthalate, 1,2-epoxycyclohexane-4,5-diglycidyl ester), and special epoxy resins (such as phosphated epoxy resins, brominated epoxy resins); the bismaleimide resin is N,N'-(4,4'-methylenediphenyl) Bismaleimide and its derivatives.

[0021] In the above technical solution, vinyl-terminated polyphenylene ether (PPE) includes vinyl-terminated PPE with different number average molecular weights, such as vinyl-terminated polyphenylene ether with number average molecular weights of 1100, 1500 and 2200.

[0022] In the above technical solution, the amino-based graphene (NH2-GO) is a tetraamine-functionalized graphene.

[0023] The composite material prepared by this invention has a three-layer structure, wherein the outer layer (or upper and lower layers) contains a graphene structure and the middle layer contains a PPE component; the composite material has high mechanical strength and excellent flame retardant properties.

[0024] The following specific experiments illustrate the technological advancements of this invention. The raw materials used are existing products, and the specific preparation operations and performance tests are conventional techniques. In the experiments, b is the unit of weight, g.

[0025] The flexural strength of the material was tested using an electronic universal testing machine according to the national standard GB / T 2567-2021; the glass transition temperature (Tg) was tested using a dynamic thermomechanical analyzer at a frequency of 1 Hz and a heating rate of 3°C / min; and the flammability was tested using a cone calorimeter.

[0026] Aminated graphene (NH2-GO) is a commercially available aminated graphene (Nanoinnova Aminated Graphene TEPA).

[0027] Example 1 Bisphenol A cyanate (CE) resin and epoxy resin (E-51) were weighed into a reactor and stirred at 150°C for 1 h. Then, vinyl-terminated polyphenylene ether (PPE) (number average molecular weight 1500) was added and stirred for another 1 h. Next, N,N'-(4,4'-methylenediphenyl)bismaleimide (BMI) was added and stirred for 2 h. Then, aminographene (NH2-GO) was added and stirred for 10 min to obtain the CE / EP / BMI / PPE / NH2-GO prepolymer system. After degassing at 150°C (30 min), the mixture was poured into a mold and cured according to the temperature program 180°C / 2 h + 200°C / 2 h + 220°C / 2 h to obtain a layered thermosetting resin-based composite material with an outer layer containing NH2-GO and an inner layer containing PPE. The contents of each component are as follows: cyanate ester (CE) resin: 100b; epoxy (EP) resin: 25b; bismaleimide (BMI): 25b; polyphenylene ether (PPE): 23b; aminographene (NH2-GO): 0.12b.

[0028] Comparative Example 1-1 Bisphenol A type cyanate ester (CE) resin and epoxy resin (E-51) were weighed into a reactor and stirred at 150℃ for 1 h. Then, N,N'-(4,4'-methylenediphenyl)bismaleimide (BMI) was added and stirred for 2 h. Subsequently, amino-graphene (NH2-GO) was added and stirred for 10 min to obtain the CE / EP / BMI / NH2-GO prepolymer system. After degassing at 150℃ (30 min), the mixture was poured into a mold and cured according to the temperature program 180℃ / 2 h + 200℃ / 2 h + 220℃ / 2 h to obtain a thermosetting resin-based composite material. The contents of each component were as follows: cyanate ester (CE) resin: 100 bp; epoxy (EP) resin: 25 bp; bismaleimide (BMI): 25 bp; amino-graphene (NH2-GO): 0.12 bp.

[0029] Comparative Examples 1-2 Bisphenol A cyanate ester (CE) resin and epoxy resin (E-51) were weighed into a reactor and stirred at 150°C for 1 hour. Then, vinyl-terminated polyphenylene ether (PPE) (number average molecular weight 1500) was added, and stirring continued for 1 hour. Next, N,N'-(4,4'-methylenediphenyl) bismaleimide (BMI) was added, and stirring was carried out for 2 hours to obtain a CE / EP / BMI / PPE prepolymer system. After degassing at 150°C (30 minutes), the mixture was poured into a mold and cured according to the temperature program 180°C / 2 hours + 200°C / 2 hours + 220°C / 2 hours to obtain a thermosetting resin-based composite material. The contents of each component were as follows: cyanate ester (CE) resin: 100 bp; epoxy (EP) resin: 25 bp; bismaleimide (BMI): 25 bp; polyphenylene ether (PPE): 23 bp.

[0030] Comparative Examples 1-3 Bisphenol A type cyanate ester (CE) resin and epoxy resin (E-51) were weighed into a reactor and stirred at 150°C for 1 hour. Then, N,N'-(4,4'-methylenediphenyl)bismaleimide (BMI) was added and stirred for 2 hours. After degassing at 150°C (30 minutes), the mixture was poured into a mold and cured according to the temperature program 180°C / 2 hours + 200°C / 2 hours + 220°C / 2 hours to obtain a thermosetting resin-based material. The contents of each component were as follows: cyanate ester (CE) resin: 100 lb; epoxy (EP) resin: 25 lb; bismaleimide (BMI): 25 lb.

[0031] Comparative Examples 1-4 Bisphenol A cyanate (CE) resin and epoxy resin (E-51) were weighed into a reactor and stirred at 150°C for 1 h. Then N,N'-(4,4'-methylenediphenyl)bismaleimide (BMI) was added and stirred for another 1 h. Vinyl-terminated polyphenylene ether (PPE) (number average molecular weight 1500) was added and stirred for 2 h. Subsequently, amino-graphene (NH2-GO) was added and stirred for 10 min to obtain the CE / EP / BMI / PPE / NH2-GO prepolymer system. After degassing at 150°C (30 min), the mixture was poured into a mold and cured according to the temperature program 180°C / 2 h + 200°C / 2 h + 220°C / 2 h to obtain a layered thermosetting resin-based composite material with an outer layer containing NH2-GO and an inner layer containing PPE. The contents of each component are as follows: cyanate ester (CE) resin: 100b; epoxy (EP) resin: 25b; bismaleimide (BMI): 25b; polyphenylene ether (PPE): 23b; aminographene (NH2-GO): 0.12b.

[0032] Reversing the order of adding polyphenylene oxide (PPE) and BMI, and adding BMI first, will cause the viscosity of the resin system to increase due to the polymerization reaction between BMI and CE. This will make it difficult for the subsequently added PPE to dissolve and it will easily agglomerate, weakening the interfacial interaction between PPE and the resin system. Consequently, the mechanical properties of the cured resin system will be significantly reduced, and the target layered structure will not be formed.

[0033] Figure 1 SEM images of the fracture surfaces of samples from Examples 1 and 1-1 to 1-4 are shown. Figure 1 As can be seen, Example 1 exhibits a distinct layered structure. Comparing Examples 1-1 to 1-3, the outer layer morphology of Example 1 is similar to that of Comparative Example 1 containing the NH2-GO phase, while the middle layer morphology is similar to that of Comparative Example 1-2. The fracture surface of the CE / EP / BMI resin system without added NH2-GO and PPE is very smooth. Therefore, the outer layer of the Example 1 sample is a resin system containing NH2-GO, and the middle layer is a resin system containing PPE. The high-magnification fracture morphology of the Example 1 sample is significantly rougher than that of Comparative Examples 1-1 and 1-2, and significantly rougher than that of Comparative Example 1-3. This suggests that the Example 1 sample can consume more energy during fracture, indicating that the material may have higher impact resistance. Comparative Examples 1-4 do not exhibit a layered structure, and the PPE is clearly unevenly distributed in the matrix.

[0034] Figure 2The DSC curves for each raw material component and its mixture are shown. From the DSC curves of CE monomer, EP monomer, BMI monomer, and PPE components, as well as their mixtures, it can be seen that the endothermic peaks of different systems are all endothermic peaks of the monomers and monomer mixtures. CE resin undergoes self-polymerization at 313°C. EP resin itself is difficult to chemically react at 300°C, and BMI monomer undergoes self-polymerization at around 248°C. PPE melts at around 250°C. The DSC curves for CE / BMI, CE / EP, CE / PPE, BMI / PPE, and BMI / EP show that EP, PPE, and BMI monomers can all react with CE; BMI resin can also react with PPE; and the mixture of EP resin and BMI resin lowers the melting point of BMI, promotes earlier self-polymerization of BMI, and can improve the processability of BMI. The addition of EP, BMI, and PPE to CE can lower the reaction temperature of CE and improve the processability of CE resin. This is evidenced by the lower reaction temperatures of CE / EP / BMI and CE / EP / BMI / PPE mixtures compared to pure CE resin. Figure 2 a). NH2-GO can promote the reactions of CE, EP, and BMI, but due to the very low NH2-GO content, its effect on the reactions of EP and BMI is not significant. However, it can significantly catalyze the reaction of CE resin. Clearly, the addition of NH2-GO can lower the reaction temperature of the CE / EP / BMI / PPE system. Figure 2 (b) This is mainly due to the cyanate ester groups (-OCN) in CE catalyzed by NH2-GO. It can be seen that for the composite material system prepared in this invention, when EP is added to CE, CE and EP polymerize; subsequently, when PPE is added, PPE continues to react with CE; and when BMI is added, BMI, CE, and PPE continue to react. Since the content of -OCN groups in CE is much higher than the content of reactive groups in EP, PPE, and BMI, a -OCN-terminated oligomer system is formed. Because PPE contains a large number of benzene ring structures and has a linear structure, when the system reaction temperature is high (>150°C), due to the tendency of the polymerization reaction kinetics, PPE is easily extruded into a linear (or fibrous) structure in the polymer system. Accompanied by the crosslinking reaction of thermosetting components, this linear (or fibrous) structure is easily fixed by the crosslinked network structure. Moreover, due to the large number of benzene ring structures in the polymer system, they easily form π-π interactions with the benzene rings in the PPE chain structure, that is, forming polymer layer domains with PPE as the structural center. When NH2-GO is further added, although it can react with the active groups in CE, EP and BMI (…), Figure 2(b) However, for the CE / EP / PPE / BMI prepolymer system, some active groups of EP and BMI have already reacted with the cyanate groups in CE. Furthermore, due to the participation of PPE double bonds in the resin system reaction, the polymer domains containing PPE chains have high viscosity. Simultaneously, the benzene rings in the polymer domains containing PPE chains form π-π interactions, making it difficult for NH2-GO to penetrate the CE / EP / PPE / BMI phase. NH2-GO can only participate in chemical reactions outside these domains and remain in the outer layer. In particular, the amino groups in NH2-GO rapidly crosslink with the outer -OCN groups and catalyze the crosslinking of -OCN groups, further restricting the diffusion of NH2-GO in the polymer system. In addition, further polymerization shrinkage and extrusion, hydrogen bonding between NH2-GO groups, and π-π interactions cause NH2-GO to self-assemble into a layered structure. After the curing temperature program is completed, a layered composite material with an outer layer containing NH2-GO resin and an inner layer of CE / EP / PPE / BMI is obtained.

[0035] Table 1 shows the mechanical properties, glass transition temperature (Tg), time to ignition (TTI), maximum heat release rate (PHRR), and average heat release rate (AHRR) data for samples from Examples 1 and 1-1 to 1-4. As can be seen from Table 1, the layered composite material of Example 1 exhibits superior flexural strength and impact strength compared to the comparative Examples 1-1 to 1-4. This is mainly attributed to the graphene layer structure on the surface of the Example 1 sample, whose high modulus and layered structure contribute to increased strength and inhibited crack propagation. Due to the promotion of resin system component reactions by PPE and NH2-GO and the high modulus of graphene, the Example 1 sample exhibits a slightly higher Tg than the comparative Examples 1-1 to 1-3 samples. Furthermore, because the PPE component in comparative Example 1 is more uniformly distributed than that in comparative Examples 1-4, Example 1 exhibits superior mechanical properties compared to comparative Examples 1-4. The data in Table 1 also show that the sample of Example 1 has a higher TTI and lower PHRR and AHRR than the samples of Comparative Examples 1-1 to 1-3, indicating that the sample of Example 1 has better flame retardant performance. This is mainly attributed to the layered structure of the sample of Example 1. Due to the graphene layer structure of its outer layer, its high heat resistance and barrier properties can effectively isolate and protect the internal structure of the material. In addition, its high char content will form a char layer on the outer layer, which effectively protects the internal structure and delays the combustion of the material.

[0036] Table 1. Mechanical and thermal properties of samples from Example 1 and Comparative Examples 1-1 to 1-3

[0037] Example 2 Bisphenol A cyanate resin (CE) and epoxy resin (E-51) were weighed into a reactor and stirred at 150°C for 1 h. Then, vinyl-terminated polyphenylene ether (PPE) (number average molecular weight 1500) was added and stirred for another 1 h. Next, N,N'-(4,4'-methylenediphenyl)bismaleimide (BMI) was added and stirred for 2 h. Then, amino-graphene (NH2-GO) was added and stirred for 10 min to obtain the CE / EP / BMI / PPE / NH2-GO prepolymer system. After degassing at 150°C (30 min), the mixture was poured into a mold and cured according to the temperature program 180°C / 2 h + 200°C / 2 h + 220°C / 2 h to obtain a layered thermosetting resin-based composite material with an outer layer containing NH2-GO and an inner layer containing PPE. The contents of each component are as follows: cyanate ester (CE) resin: 100b; epoxy (EP) resin: 25b; bismaleimide (BMI): 25b; polyphenylene ether (PPE): 30b; aminographene (NH2-GO): 0.20b.

[0038] Comparative Example 2-1 Bisphenol A cyanate resin (CE) and epoxy resin (E-51) were weighed into a reactor and stirred at 150°C for 1 hour. Then, N,N'-(4,4'-methylenediphenyl)bismaleimide (BMI) was added and stirred for 2 hours. Subsequently, amino-based graphene (NH2-GO) was added and stirred for 10 minutes to obtain the CE / EP / BMI / NH2-GO prepolymer system. After degassing at 150°C (30 minutes), the mixture was poured into a mold and cured according to the temperature program 180°C / 2 hours + 200°C / 2 hours + 220°C / 2 hours to obtain a thermosetting resin-based composite material. The contents of each component were as follows: cyanate resin (CE): 100 bp; epoxy resin (EP): 25 bp; bismaleimide (BMI): 25 bp; amino-based graphene (NH2-GO): 0.20 bp.

[0039] Comparative Example 2-2 Bisphenol A cyanate resin (CE) and epoxy resin (E-51) were weighed into a reactor and stirred at 150°C for 1 hour. Then, vinyl-terminated polyphenylene ether (PPE) (number average molecular weight 1500) was added, and stirring continued for 1 hour. Next, N,N'-(4,4'-methylenediphenyl) bismaleimide (BMI) was added, and stirring was carried out for 2 hours to obtain the CE / EP / BMI / PPE prepolymer system. After degassing at 150°C (30 minutes), the mixture was poured into a mold and cured according to the temperature program 180°C / 2 hours + 200°C / 2 hours + 220°C / 2 hours to obtain a thermosetting resin-based composite material. The contents of each component were as follows: cyanate resin (CE): 100 bp; epoxy resin (EP): 25 bp; bismaleimide (BMI): 25 bp; polyphenylene ether (PPE): 30 bp.

[0040] Table 2. Mechanical and thermal properties of the samples from Example 2 and the comparative examples.

[0041] Example 3 Bisphenol A cyanate resin (CE) and epoxy resin (E-51) were weighed into a reactor and stirred at 140°C for 2 hours. Then, vinyl-terminated polyphenylene ether (PPE) (number average molecular weight 1100) was added and stirred for another 1 hour. Next, N,N'-(4,4'-methylenediphenyl)bismaleimide (BMI) was added and stirred for 2 hours. Then, amino-graphene (NH2-GO) was added and stirred for 20 minutes to obtain the CE / EP / BMI / PPE / NH2-GO prepolymer system. After degassing at 150°C (30 minutes), the mixture was poured into a mold and cured according to the temperature program 180°C / 2 hours + 200°C / 2 hours + 220°C / 2 hours to obtain a layered thermosetting resin-based composite material with an outer layer containing NH2-GO and an inner layer containing PPE. The contents of each component are as follows: cyanate ester (CE) resin: 100b; epoxy (EP) resin: 25b; bismaleimide (BMI): 25b; polyphenylene ether (PPE): 15b; aminographene (NH2-GO): 0.05b.

[0042] Comparative Example 3-1 Bisphenol A cyanate resin (CE) and epoxy resin (E-51) were weighed into a reactor and stirred at 140°C for 2 hours. Then, N,N'-(4,4'-methylenediphenyl)bismaleimide (BMI) was added and stirred for 2 hours. Subsequently, aminographene (NH2-GO) was added and stirred for 20 minutes to obtain the CE / EP / BMI / NH2-GO prepolymer system. After degassing at 150°C (30 minutes), the mixture was poured into a mold and cured according to the temperature program 180°C / 2 hours + 200°C / 2 hours + 220°C / 2 hours to obtain a thermosetting resin-based composite material. The contents of each component were as follows: cyanate resin (CE): 100 bp; epoxy resin (EP): 25 bp; bismaleimide (BMI): 25 bp; aminographene (NH2-GO): 0.05 bp.

[0043] Comparative Example 3-2 Bisphenol A cyanate resin (CE) and epoxy resin (E-51) were weighed into a reactor and stirred at 140°C for 2 hours. Then, vinyl-terminated polyphenylene ether (PPE) (number average molecular weight 1100) was added, and stirring continued for 1 hour. Next, N,N'-(4,4'-methylenediphenyl)bismaleimide (BMI) was added, and stirring continued for 2 hours to obtain the CE / EP / BMI / PPE prepolymer system. After degassing at 150°C (30 minutes), the mixture was poured into a mold and cured according to the temperature program 180°C / 2 hours + 200°C / 2 hours + 220°C / 2 hours to obtain a thermosetting resin-based composite material. The contents of each component were as follows: cyanate resin (CE): 100 bp; epoxy resin (EP): 25 bp; bismaleimide (BMI): 25 bp; polyphenylene ether (PPE): 15 bp.

[0044] Table 3. Mechanical and thermal properties of the samples from Example 3 and the comparative examples.

[0045] Example 4 Bisphenol A cyanate resin (CE) and epoxy resin (E-44) were weighed into a reactor and stirred at 180°C for 0.5 h. Then, vinyl-terminated polyphenylene ether (PPE) (number average molecular weight of 2200) was added and stirred for another 0.5 h. Next, N,N'-(4,4'-methylenediphenyl)bismaleimide (BMI) was added and stirred for 0.5 h. Then, aminographene (NH2-GO) was added and stirred for 5 min to obtain the CE / EP / BMI / PPE / NH2-GO prepolymer system. After degassing at 150°C (30 min), the mixture was poured into a mold and cured according to the temperature program 180°C / 2 h + 200°C / 2 h + 220°C / 2 h to obtain a layered thermosetting resin-based composite material with an outer layer containing NH2-GO and an inner layer containing PPE. The contents of each component are as follows: cyanate ester (CE) resin: 50b; epoxy resin (E44): 10b; bismaleimide (BMI): 10b; polyphenylene ether (PPE): 10b; aminographene (NH2-GO): 0.3b.

[0046] Comparative Example 4-1 Bisphenol A cyanate resin (CE) and epoxy resin (E-44) were weighed into a reactor and stirred at 180°C for 0.5 h. Then, N,N'-(4,4'-methylenediphenyl)bismaleimide (BMI) was added and stirred for 0.5 h. Subsequently, aminographene (NH2-GO) was added and stirred for 5 min to obtain the CE / EP / BMI / NH2-GO prepolymer system. After degassing at 150°C (30 min), the mixture was poured into a mold and cured according to the temperature program 180°C / 2 h + 200°C / 2 h + 220°C / 2 h to obtain a thermosetting resin-based composite material. The contents of each component were as follows: cyanate resin (CE): 50 bp; epoxy resin (E44): 10 bp; bismaleimide (BMI): 10 bp; aminographene (NH2-GO): 0.3 bp.

[0047] Comparative Example 4-2 Bisphenol A cyanate resin (CE) and epoxy resin (E-44) were weighed into a reactor and stirred at 180°C for 0.5 h. Then, vinyl-terminated polyphenylene ether (PPE) (number average molecular weight of 2200) was added, and stirring continued for 0.5 h. Next, N,N'-(4,4'-methylenediphenyl)bismaleimide (BMI) was added, and stirring continued for 0.5 h to obtain the CE / EP / BMI / PPE prepolymer system. After degassing at 150°C (30 min), the mixture was poured into a mold and cured according to the temperature program 180°C / 2 h + 200°C / 2 h + 220°C / 2 h to obtain a thermosetting resin-based composite material. The contents of each component were as follows: cyanate resin (CE): 50 bp; epoxy resin (E44): 10 bp; bismaleimide (BMI): 10 bp; polyphenylene ether (PPE): 10 bp.

[0048] Comparative Examples 4-3 Bisphenol A cyanate resin (CE) and epoxy resin (E-44) were weighed into a reactor and stirred at 180°C for 0.5 h. Then, N,N'-(4,4'-methylenediphenyl)bismaleimide (BMI) was added and stirred for another 0.5 h to obtain the CE / EP / BMI prepolymer system. After degassing at 150°C (30 min), the mixture was poured into a mold and cured according to the temperature program 180°C / 2 h + 200°C / 2 h + 220°C / 2 h to obtain a thermosetting resin-based material. The contents of each component were as follows: cyanate resin (CE): 50 bp; epoxy resin (E44): 10 bp; bismaleimide (BMI): 10 bp.

[0049] Table 4. Mechanical and thermal properties of samples from Example 4 and Comparative Examples 4-1 to 4-3

Claims

1. A method for preparing an in-situ self-assembled layered thermosetting resin-based system, characterized in that, Vinyl-terminated polyphenylene ether was added to a mixture of cyanate ester resin and epoxy resin, followed by the addition of bismaleimide resin and then amino-based graphene to obtain an in-situ self-assembled layered thermosetting resin-based composite material system.

2. The method for preparing the in-situ self-assembled layered thermosetting resin-based system according to claim 1, characterized in that, The mass ratio of cyanate ester resin, epoxy resin, bismaleimide resin, vinyl-terminated polyphenylene ether, and amino graphene is 100:20-25:20-25:10-40:0.05-3.

3. The method for preparing the in-situ self-assembled layered thermosetting resin-based system according to claim 1, characterized in that, Cyanate ester resins include one or a mixture of bisphenol A type cyanate ester resins and bisphenol E type cyanate ester resins.

4. The method for preparing the in-situ self-assembled layered thermosetting resin-based system according to claim 1, characterized in that, Epoxy resins include one or more of the following: glycidyl-based epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, hydrogenated bisphenol A type epoxy resin, phenolic epoxy resin, polyfunctional glycidyl ether resin, glycidyl ester type epoxy resin, and special epoxy resins.

5. The method for preparing the in-situ self-assembled layered thermosetting resin-based system according to claim 1, characterized in that, Bismaleimide resins include N,N'-(4,4'-methylenediphenyl)bismaleimide or its derivatives.

6. The method for preparing the in-situ self-assembled layered thermosetting resin-based system according to claim 1, characterized in that, The vinyl-terminated polyphenylene ether has a number average molecular weight of 1000-3000; the amino graphene is tetraethylenepentamine functionalized graphene.

7. The in-situ self-assembled layered thermosetting resin system prepared by the preparation method of the in-situ self-assembled layered thermosetting resin system according to claim 1.

8. An in-situ self-assembled layered thermosetting resin-based composite material, prepared by curing the in-situ self-assembled layered thermosetting resin-based system according to claim 7.

9. The in-situ self-assembled layered thermosetting resin-based composite material according to claim 8, characterized in that, The composite material has a layered structure.

10. The application of the in-situ self-assembled layered thermosetting resin matrix system of claim 7 or the in-situ self-assembled layered thermosetting resin matrix composite material of claim 8 in the preparation of functional materials.

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